Il.

IT,a~~l
.'
'<~'.- ~',,:- :.;,-Y"':( :-':.:-.~;~:1
:-::~... .Introduction
,-": ' .- .:"
~;;~1
._.- ..

. Yvt>S Edern

Even though petroleum has been known since the dawn of civilization, its uses
remained limited until the 19th century. Its medicinal, plugging and combus-
tion properties (e.g, Greek fire and lighting) were recognized. However, it was
produced on a small scale (surface occurrences, seepage) and processing was
non-existent.
Although the domestication of horses and the use of water and wind energy
made for significant achievements during the Middle Ages, it was only in the
late 18th and early 19th century that great inventions showed how human
energy could be multiplied by the development of machines. The steam engine
rapidly reached its limits due to coal's lack of flexibility and adaptability. For
the industrial revolution to continue and particularly to become a reality of
daily life, it needed an abundant, low-cost, adaptableenergy source. This is
precisely what petroleum began to provide in the second haJfof the 19th cen-
tury, and this is when refiners began to face numerous challenges.

1.1 Coping with Challenges (1850-1915)

Crude oil is difficult to use as it occurs naturally, but after fractionation certain
cuts have specific properties which make them easier to use. For example. as
opposed to crude oil, a heart cut called kerosene or lamp oil bums completely
with a bright. smokeless flame. This simple fact prompted constant demand
from 1850 on. However, it was the invention of the internal combustion engine
in 1862, burning natural gasoline instead of coal gas. that made the demand for
petroleum products really take off.
The first challenge in the early days of the petroleum industry was to meet
this demand. Drillingwas developed and the first boreholes drilled by Colonel
Drake in Titusville in 1859 were to supply the required amount of oil. The sec-
2 Cr.aprer I mreccacu:,

ond milestone was to fractionate crude oil into specific cuts as performed by
batch distillation until 1910. when the first continuous-operating boilers
appeared. It was not until 1925that the first distillation unit with a furnace and
column came into being in the United States.
Two cuts from crude oil. lamp oil and natural gasoline or gasoline were par-
ticularly in demand, especially from 1890 on with the birth and then boom of
the automobile industry. But what about the other cuts? There were two solu-
tions:
Develop specific uses. This was the case for diesel oil with the invention
of the diesel engine in 1896. and fuel oil instead of coal on warships from
1900on (space heating only became common around 1930).
Modify the proportions of the various cuts obtained by distillation.
Undoubtedly a more flexible solution. as it does not rely on the different
uses growing si".:l~~tanequsly.
Implementing this second solution was to be the third challenge for the
refining industry and would ensure its development during the first half of the
20th century. Readjusting quantitative balances was only the first step. In
actual fact, the properties of cuts obtained by direct crude oil distillation were
not totally satisfactory in meeting increasingly stringent end" use require-
ments. For instance. improved performance for the internal combustion
engine entails higher compression ratios. which cause knocking and engine
damage with straight-run gasoline. The fourth and last challenge to be faced
during this period was meeting new quality requirements.

1.2 Developing Processes (1915-1940)

Whether to correct quantitative or qualitative imbalances, the oil industry
evolved from separation to molecular rearrangement processes. Initially,
molecular rearrangements were mainly thermal in nature (thermal cracking to
modify quantitative balances and thermal reforming for qualitative balances).
They quickly reached their limits: low selectivity. poor yield. severe techno-
logical requirements due to high pressure and temperature. along with short
production cycles. "
A discovery by a French chemist was to allow the transition to a second
much more efficient phase. The research done by Paul Sabatier, which won
him the Nobel prize in 1912.showed that certain metals and metal oxides pro-
mote cracking reaction.selectivity. Thanks to research by another Frenchman.
Eugene Houdry, the first industrial catalytic cracking unit came on stream in
the United States in 1936. It was followed shortly afterward by the first indus-
trial catalytic reforming unit, which started up in 1939, once again in the
United States. It was able to boost the octane number of an average gasoline
cut by 30 to 40 points.
The two major oil industry processes were then operational and were soon
supplemented by other more specific, even more selective processes, I?articu-
 1

1
larly to meet the needs of the Second World Wareffort. Operating crackers and!
reformers causes massive amounts of gas to be produced and the idea of usingl
them was soon afoot. Two processes, polymerization in the presence of P~OS-l
phoric acid and alkylation in the presence of sulfuric or hydrofluoric add'i
yield high octane gasoline from petroleum gases. They were to undergo rapid
development in the United States in order to produce the huge quantities of I
aviation fuel required when the Americans entered the war. I
All these innovations gave the oil industry a taste for molecular rearrange- I
ments and scientists wasted no time in understanding and explaining them. I
Researchers were soon to reveal the immense wealth of petroleum-based I
products and their use as feedstocks for synthesis chemistry. In 1920in the I
Lnited States, Union Carbide and Standard Oil produced 75 tons of petroleum- 1
based synthesis chemicals - and petrochemistry was born. It experienced a -
boom during World War ll, providing primary products for the manufacture of
substitutes for natural products. Even though American industry was I
deprived of its natural raw material supply sources, it was able to adapt and I
change so as to support an unprecedented war effort. As a result, a war that I
might otherwise have gone on for ages was cut short. and U.S. technological I
and economic superiority was established once and for all.
In less than a century. the oil industry had thus shown its extraordinary 1
capacity to adapt. It had provided fuels for engine and other combustion uses,
as well as the primary products required to keep abreast of technological I
progress and benefit a vast majority of the population. At the same time. sci- I
entific progress had made petroleum research more effective: I
After the United States, Canada and Mexico, Europe with Russia and I
Romania, the Middle East with Iraq, Iran and Saudi Arabia opened up to oil pro- I
duction. The growth in consumption bears witness to the extreme flexibilityof .I
this new source of energy. In actual fact, world consum.Ption would more than 1
double every ten years over a long period (Table 1.1). Up to then, the.United
States accounted for around two-thirds of the petroleum activity worldwide.
The leading role of oil in meeting the world's energy needs was obvious and I
was due to: I
effective petroleum research:
easy transportation and storage; 1
flexible and adaptable industrial plant that could respond suitably to
evolving increasingly numerous and diversified uses. 1
All this was possible only because technological innovation made the most
efficient implement available at each stage of oil production, transportation 1
and processing. Adaptability along with production growth ensured oil indus-
try development at ever decreasing costs for over a hundred years and would 1
contribute significantly to post-war economic development. The dominant
role played by oil was also to reveal its dangers. With the interdependence of
;:>roducers and consumers, oil began to play an eminently political and strate- 1
gic role which was to generate new conflicts and imbalances. Once again. the
oil industry would be strongly incited to offset these imbalances. 1

1
4 C!'.aCler 1 INTRCDt:CT:ON

Year tfyear

1860 100000
1870 800000
1880 4 000 000
1890 10000000
1900 20 000 000
1910 44 000 000
1920 97000000
1929 205 000 000
1938 282 000 000
,-- :

T'bk'i
1.1 . World consumption.

1.3 Oil and Growth (1940-1973)

From 1945 to 1970. the oil industry was to contribute significantly to the
reconstruction and industrialization of European and Asian countries that had
been hard hit by the war. Oil companies and processes developed in the
United States crossed the Atlantic and the Pacific. Western Europe and Japan
alike reproduced the American model and improved on it. Although there were
no fundamental changes anywhere near as important as the development of
catalytic reforming and cracking processes during the preceding period. some
significant evolution did occur:
new catalysts were developed;
hydrogen emerged as a refining agent in several processes:
- isomerization of light gasoline.
- hydrodesullurlzatlon,
- hydrocracking,
- hydroconversion.
Between 1945 and 1970 world oil consumption experienced an upswing.
mainly due to geographical extension:
t/year
1950 525000000
1960 1 050 000 000
1970 2336000000
Oil prices were at their lowest: $1.80 per barrel for Arabian Light. which
was still ten times its production cost. Some worried about this exponential
growth (Club of Rome), while others wanteo a new organization for producing
and distributing mining royalties (OPEC). International tension (Six-day war)
was favorable to action by producing countries, which unilaterally decided to
triple prices in November of 1973, then to further double them in January of
1974. The barrel of Arabian Light was at $12. Once again, the oil industry in
general and the refining industry in particular had another challenge to cope
with.

1.4 Oil and Crisis (1973-1990)

Consumption oUhe different oil fractions was to be durably affected by the
sixfold increase in prices:
when substitution was possible, oil products were replaced by alterna-
tive compounds;
when no substitution could be made, energy savings became the target.
The result was a drop in stove and furnace fuel consumption (heavy fuel oil
and space heating oil), and a slowdown in the growth of motor fuel (gasoline.
diesel oil and jet fuel) and petrochemical feedstock consumption.
Consequently, with the same or even heavier crude oils. the refining industry
had to manufacture more and more light. highly processed products to replace
heavy. less sophisticated ones. The processes existed, their implementation
was only a question of time and money. since investments are very high espe-
cially for an industry in the midst of a crisis.
Some processes evolved between 1970 and 1990. Reformers became semi-
regenerative then regenerative. crackers became more efficient with increas-
ingly heavy feeds. and more importantly, catalysts became more selective.
This period was especially marked by evolution in refinery flow schemes. l.e,
in the process line up. The simple TR (topping-reforming) refinery scheme of
the seventies became TRC (topping-reforming-cracking) at the end of the
decade and TRCY (topping-reforming-cracking-visbreaking) early in the eight-
ies. The addition of alkylation, of isomerization to offset the low quality of
gasolines sent to the cracker led to the TRCYAI scheme of the nineties.
Combined with this set up there were desulfurization units for gasolines.
diesel oil and even jet fuel.
The consequence of this evolution is a modification in the proportions of
products manufactured. From a conventional Arabian or Iraqi type crude. the
production slate went
from: to:
20%gasolines 30'?~ gasolines
35%middle distillates 45":, middle distillates
35%heavy fuel oil 15',\, heavy fuel oil
10?6 miscellaneous 10;', miscellaneous
6 c.oa=:e: Ir';;:;::C"'CilON

Two opposing results were then seen: a reduction in distillation capacity

and an increase in conversion capacity. All of these changes took place in an
unstable environment and a depressed economic situation, particularly for the
refining industry.
Three new crises broke between 1979 and 1991. In 1979 the barrel went
from S18.30 in January, to 526 a year later, to $32 in November of 1980, and
then hit 534 in October of 1981.Then in 1986,oil refining, a highly capital-inten-
sive industry with long but unavoidable lead times, experienced a far-reaching
reverse trend. In January of 1987, the barrel was at $17.85 and then fell to
510.60in September of 1988.The conflict in the Gulf pushed prices up again to
.1 fever peak of 536 in September of 1990. '....ith a dramatic drop to S17 when
hostilities ended and a price swinging between $13 and 520 ever since.
All throughout this disturbed period, the refining industry showed its
extraordinary ability to adapt and evolve despite disappointing .economic
results and uncertainty as to the future. The Gulf war underscored the strate-
gic advantage of having an efficient refining sector. In actual fact, the destruc-
tion of the refining capacity of Kuwait and Iraq made more of an impact that
the loss of their crude oil production capacity.
Additionally, exponential consumption growth broke with the previous pat-
tern during this same period: from 2 336 000 t/year in 1970,to 3 042000 in 1980,
to 3 101 000 in 1990. The oil industry was no longer a growth industry but a
mature one, i.e. in a phase of adaptation and diversification. New horizons
were opening up. I

1.5 The Future

The oil industry has played a leading part in the major events of the past
i 50 years. It has kept up with the great discoveries and thereby made eco-
iornic development possible. Petroleum products are manufactured from an
:bundant raw material with a low production cost, that is easy to transport
end store. Meeting the most varied requirements, they are present in our daily
ves and have often become synonymous with comfort and quality of life.
The downside is of course not absent from the picture: oil and politics, oil
.nd the environment. However, for a long time yet to come oil willhave a deter-
ninlng influence in the developed world and perhaps even more so in the
leveloping countries. As such, some changes are already making themselves
elt and others can be glimpsed in the distance. The refining industry will have
a respond to increasingly stringent quality requirements, particularly with
espect to environmental concerns, and has already made good progress in
.ils area.
Oilis a fossil fuel and therefore of limited availability, but it can still provide
-onsiderable resources, either through access to new production zones (deep
ffshore), improved recovery ratios, or production of unconventional oils. The
ew oil resources will be increasingly heavier, whereas end use demand will
focus more and more on light products (molor fuels, petrochemical feed-
stocks, liquefied gases) and a few specialty products (bitumens, lubricants).
Conversion of heavy products to light ones is already well under way and wiU
pick up speed in the years to come. The time is bound to come soon when
refineries will no longer produce any heavy fuel oils.
Product quality will have to meet increasingly stringent standards, what-
ever the nature of the initial processed crude. Complete elimination of impuri-
ties. such as sulfur, heavy metals. etc . will become the rule. Products' chemi-
caJ composition will be subject to regulation. at least by hydrocarbon family,
along the same lines as the regulation of their physical characteristlc.s. ::30me
examples of possible new regulatory measures are reduction of aromctlcs,
elimination of polyaromatics, limiting of olefiDs. conversion of naphthenes
(because of their poor octane and cetane numbers). These operations will give
specific importance to paraffins. particularly in their isomerized form, whose
properties can meet higher quality specificatioos.
Table 1.2, showing the varying HIC ratios KCording to molecular weight
and hydrocarbon family, gives an idea of the type of solutions that will be
needed. Motor fuels, the most highly processed products which contain
between 5 and 20 carbon atoms. will have to achieve an HIC ratio of between
0.li5 and 0.200. This can be done in several different ways depending on the
nature of the hydrocarbons under consideration. Carbon can be eliminated
i~m the heavy fractions (HIC limitof 0.166) by using crackers or cokers, while
olefins, naphthenes and aromatics can be hydrogenated by hydrotreating.
~Iore particularly, a combination of the two processes in the form of hydroc-
racking or hydroconversion gives maximum fleubility in the choice of feeds
and in the quality of end products. HydrocrackiDg and hydroconversion yield
high added value products. not by eliminating residues or wastes but by
enhancing the value of all the petroleum cuts as a whole. This is the most eco-
nomical solution in terms of the raw material resource base.
All these processes exist and are already being implemented. However,
since they are due to take on ever more importance, their performance will
have to be improved by developing more sophisticated, active and selective
catalysts to allow less demanding operating conditions (pressure. space veloc-
ity. etc.).
In any case. hydrogen will become more and more of a focal point and a
basic necessity in the refining industry of tomorrow. Hydrogen production
potential resides in hydrocarbons whose HIC ratio is greater than motor fuel
requirements. l.e. the paraffinic C, to C4 The C3 and C4 fractions have specific
uses (stove and furnace fuels, motor fuels. petrochemistry). The C1 and C2 will
be supplied by refinery gases or by natural gas. Probably the best utilization
value for natural gas, including from the standpoint of the environment. is not
to bum it as is done today, but to use it in the future as a source of hydrogen
:0 upgrade petroleum product quality. The future should bring about a grad-
uaJ change in the current compentton between oil and natural gas as general
purpose fuels. Competition should be replaced by a complementary relation-
ship for the production of increasingly sophisticated motor fuels.
8 Ctl8Dl8r 1 INTRODUCTIOI.

Paraffins
Olefios I Aromatics
and naphthenes
I
C1 I CH4 : 0.333
C2 I C2Ho : 0.250 CZH4 : 0.166
C3 CJHs : 0.222 C3" 6 : 0.166
C. C4H IO : 0.208 C.H8 : 0.166
c, CsH 1Z : 0.200 CsH IO : 0.166

C6 C6H I4 : 0.194 C6H I2 : 0.166 C6H 6 : 0.083

C7 C;HI6 : 0.190 C;H1 : 0.166 I C;Hs : 0.095
CIO ! CI(,H~~ : 0.183 CJOH 20 : 0.166 I CIOHJ4 : 0.066
CIS CIsHJ2 : 0.1i8 C15H 30: 0.166 i -
C20 CwH4Z : 0.175 CzoH40 : 0.166 I -
Cn.(n -+:c)
..... -
I"' "CnH~+2 : 0.166 CnH2n : 0.166 CnH2JH;: 0.166
" Table
1.2 Hydrocarbon families.
Varying Hie ratios (weight).
-

The already complex TRCVAlI refining flow scheme seen in the early
nineties will undergo further change toward even greater sophlstlcatlon.
Under the heading of topping. a refinery today can not do without a crude dis-
tillation unit supplemented by vacuum distillation. Operating conditions dur-
ing later processing are better adapted to specific narrow cuts than to wide
ones. However. direct crude hydroconversion can easily be imagined. it would
eliminate all impurities right from the start (including sulfur. thereby prevent-
ing corrosion in downstream units) and directly give the Hie ratio corre-
sponding to the target products. .
Reforming has two essential functions: improving octane number and pro-
ducing hydrogen. Even if aromatics - highlyappreciated in petrochemistry-
are contested as motor fuels. the reformer is indispensable as a source of
hydrogen. The regenerative reformer allows higher and more constant pro-
duction over time.
The cracker and visbreaker are low selectivity processes that are destined
to be gradually replaced by the hydrocracker and residue hydroconversion.
After modifications to improve its thermal equilibrium. the cracker will still
have a part to play in converting hydroconverted residues.
Alkylation and isomerization, which yield "ideal" molecules. are the pro-
cesses of the future. Implementation, especially for alkylation, is sometimes
difficult. Replacing liquid catalysts (hydrofluoric or sulfuric acid) by solid cat-
alysts would be a welcome improvement. These two units yield specific

1. Topping, reforming, cracking, visbreaking, alkylation, isomerization.

 Chap:er '- INTRODUCTION. 9
,;'

molecules rather than the wide cuts produced by the other units and in this
aspect they are similar to petrochemical units. This evolution will have other
applications, as can already be seen in the manufacture of oxygenated motor
fuels (MTBEor ETBE: methyl and ethyl tertio butyl ether). Other pilot or indus-
trial plants for the production of very high-performance diesel oils are becom-
ing a reality. They are based on the use of the raw material's chemical proper-
ties. whereas refining mainly built its development on the range of physical
properties.
Two compounds will be critical for this new trend. Hydrogen is the first, as
even regenerative reformers will no longer suffice. Partial oxidation, in partic-
ular of gases or heavy residues by steam, will be needed to supplement pro-
duction. The second is selective, efficient catalysts so as to limit the severity
of operating conditions.
The evolution of tomorrow's refinery will not be .confined to strictly
petroleum processes. Energy production, whether electricity or steam, is an
important item in plant cost and reliability. Cogeneration, especially from
heavy residues which may be untreated or previously desulfurized, demetal-
Iized or even gasified, will be common in refineries. All of these changes will
mean increasingly complex refineries, and therefore require huge investments,
which will only be possible for refineries of a certain size.
The major consequence will be a much more environmentally friendly
product quality. The elimination of sulfur. heavy metals and polyaromatics will
be concentrated in the refining stage instead of being dispersed in final con-
sumption. However, the recovery and end use of certain products will con-
tinue to be a problem and will require new refinery features. The refinery itself
will also have to comply with new more stringent constraints in its relation-
ship with the environment. However, concentrated local problems are bound
to be easier to solve than dispersed ones.

1.6 Conclusions
After having survived numerous crises which have shown its adaptability, the
refining industry is today an efficient and dynamic industry. It will have new
challenges to deal with in meeting the demands of the future. Solutions will
undoubtedly be mostly along the same lines as the ones we are used to today,
but they will have to be more selective and efficient. They will focus the reso-
lution of collective problems, such as energy conservation and environmental
protection. in the refinery. As such, it will be necessary to mobilize the inno-
vative capacity of all those who contribute to make the industry function prop-
erly: in the field of processes and catalysts. as well as in unit design and oper-
arion. The job is a considerable one and resources are often inadequate -
compared to the sometimes excessive demands. However. it is an exciting
challenge that should aC~ivate and energize the best skills as it has always
done in the past.
 Basic Principles Governing
Chemical Changes"

Jean-Pierre lVauquier

Stoichiometry
Thermodynamics of Chemical Reactions
Chemical Kinetics

The purpose of this chapter is to remind the reader of a number of basic prin-
ciples related to chemical changes. We will deal with the points below briefly
put thoroughly enough to help the reader understand the other chapters in
this volume:
stoichiometry (material balances associated with chemical changes);
thermodynamics of chemical reactions (variations in enthalpy and in
Gibbs energy accompanying chemical changes);
chemical kinetics (reaction rates involved).
In no way do we aim to duplicate more complete coverage of these subjects
which can be referred to if the reader requires a "more.in-depth understanding
of any given topic. The corresponding bibliographical references will be men-
tioned in the body of the text.

~.l Stoichiometry and Associated Parameters

The term stoichiometry is reiated to the expression of material balances and
10 the conservation of mass during any non-nuctear chemical change. whether
it involves one or more reactants or one or more reactions.
Generally speaking, a stoichiometric relation is expressed as follows:
;= 1.S (2.1)
"","ilh:
A. molecular species-of rank i
\', stoichiometric coefficient of species Ai
S total number of species
 By convention:
"reactants" have a negative stoichiometric coefficient;
"products" have a positive stoichiometric coefficient;
"inerts", solvents, catalysts, etc. have a zero stoichiometric coefficient.
An evolving system can be described in general by a set of several stoi-
chiometric relations:

;= 1.5 i> l,R (:!.:!)

where:
j reaction of rank j
vij stolchlometrlc ~~effjcient of component Ai in reaction j
R 'total number of reactions
As a descriptive example of such a system, the set of stoichiometric rela-
tions below can describe the methane steam reforming reaction, without tak-
ing any possible side reactions into account:

-CH 4 - 2 H20 + 4 H2 + CO2 = 0 (2.3a)

-CH 4 - H20 + 3 H2 + CO = 0 (2.30)
-CO - H20 + CO2 + Hz = 0 (2.3c)

The fact that expressions (2.3a), (2.3b) and (2.3c) are not independent is
not particularly significant. since it is the rate of the reaction act itself that
counts as will be seen later on. Anyway, the reaction as such is probably not
described, or is only accidentally described, by one of the relations listed
above. It is important to emphasize one point: since a stoichiometric relation
is only a material balance, it can not say anything about the actual feasibili~y
of the reaction as proposed. It can say even less about the rate at which the
assumed change would occur.
In the same way as molar balances are written:

IVijA i =0 (2.2)

elemental balances can also be written:

i= 1,5 j =l,R k= 1, (2.4)

in this expression:
ik number of atoms of element k in component Ai
E total number of elements involved
Accordingly, there will be Ex R elemental relations that will have to be com-
plied with simultaneously.
 Chapcer 2. BASIC PRINCiPlES GOVEFWING CHEMICAL CHANGES 13

The methane steam reforming example shows that:

Equation 2.3a can be broken down as:
-c + C =0
-4 H -4 H + 8 H =0
-20+20=0
Equation 2.3b as:
-c + C =0
-4 H - 2 H + 6 H =0
-0 + 0=0
and Equation 2.3c as:
-c + C=O
-2 H + 2 H =0
-0-0+20=0
which makes precisely 3 x 3 = 9 elemental relations complied with simultane-
ously.
In the case of complex reaction feeds consisting of petroleum cuts or
;~ctroleum residues, moles will no longer be identifiable, except on a few rare
occasions. Only elemental balances can be written and they will have to be
complied with as per the accuracy allowed by sample representativity and
analyzer performance. This will be the case, for example, of the following ele-
ments: C. H. 0, S, N, Ni, V.
An intermediate case is when the components of a cut can be grouped
together in families: aromatics, paraffins, naphthenes, etc. The lumping tech-
nique. which will be discussed later on (see Section 2.3.3.6) can be used to
follow a reaction by observing the changes in the families. For example, in a
catalytic reforming operation, hydrogen production is' Closely related to the
increase in the "aromatics" family. Quasi-stoichiometry can thus be estab-
.ished by combining elemental balances and balances by families.

: .1.1 The Concept of Advancement (or Molar Extent)

Advancement (or molar extent). which should not be confused with conver-
sion. defined later on in Section 2.1.2, can be used to quantify the variation in
the number of moles of components, reactants or products that take part in
the reaction. It is of no interest as regards elements. since their quantity does
not vary.
For a closed system and a single reaction, advancement is defined by the
-::;fJ!ar extent" ~:
(2.5a)

n, amount of species Ai (mol)

n.. initial amount of species A. (mol)
 For an open system, as are most of the reactors in the oil industry, advance-
nent or "molar extent" ~' is defined by:
(2.5b)
vith:
F; molar flow rate of species Ai (mol/s)
F;o inlet molar flow rate of species Ai (mol/s)
With the preceding definlttons.j; is expressed in moles and ~' in moles per
econd. ~ and ~' can be negative if the stoichiometric relation has been writ-
.en in the reverse direction from the one in which the reaction actually pro-
Jresses.
Sapproaches - ni/vi and;' approaches - Fia/V i when the reaction is com-
"Jlet,,:.
. . the case of a set of R reactions, relations 2.5a and 2.5b are written:
n,=nio + I vi/c,j (2.6a)

t.-r; +I vi/t.j (2.Gb)

Although the concept of advancement (molar extent) is quite useful in

molecular stoichiometry, it is of little interest for complex systems where
moles are elusive entities. Here, the concept of "conversion- will be used
instead, at least as far as reactants are concerned. I

2.1.2 Conversion, Selectivity, and Yield

In a closed system, the conversion of a reactant Ai is designated by:
(n -n.)
X=_'o__'_ (2.7a)
nio
and in an open system:
(F -F)
X=_Jo__J_ (2.7b)
r;
':onversion is dimensionless and is frequently expressed in %.
for petroleum cuts, characterized by distillation range for example, a con-
version can generally be defined unambiguously. Take for example the case of
cracking a 550C + residue. The cracking (or conversion) ratio at the cracking
reactor exit is equal to:

x = mass flow rateof 5SOC feed - mass flowrateof 550C+ residue in tile reactor effiuent
mass flowrateof the feed

Product selectivity expresses the (molar or mass) amount of the product

obtained over the theoretical amount that could be expected if the reaction
were totally oriented toward getting this product alone.
 Chapter2. BASIC PRINCIPLES GOVeRNING CH~MICAL CHA/I;GES 15

With the example of cracking the 550C+ residue, gasoline mass selectivity
is equal to:

s= mass flow rate of CS_ 80 gasoline in the emuen~__.-:-~~_

mass flow rate of feed - mass flow rate of 550'C + residue in the effluent

Accordingly, if the feed were processed to produce only gasoline exclu-

sively, selectivity would be 100%.
Product yield expresses the amount of the product obtained over the
amount of feed processed.
The gasoline yield in the preceding example is:

Y =mass flow rate of gasoline in the effluent

----m-as-s-f1-o..;.w-r-a-te-o-ff-e-ed----

This gives the basic expression:

Y=SxX (2.8)

The yield is equal to the product of selectivity and conversion.

However, great care is required in expressing the terms selectivity and
yield, for authors differ as to their meaning. For example, selectivity is some-
times defined as the ratio between the mass flow rate of one product and that
of another one, or as the ratio between the quotient of mass flow retes of two
products and that of theoretical flow rates. Additionally, no confusion should
be made between overall conversion and conversion per pass, or between
oeerall yield and yield per pass.
In Figure2.1 there are two material balances lnvelving a chemical change
that can be schematically represented by: ..

H(heavy) ~ MCmedium) ~ ~light)

The material balances are fictitious, shown only to illustrate the definition
of conversion, selectivity and yield.
In case A M and L are separated before recycling the non-converted part
of H and purging amount E:
conversion per pass of H =(129 - 39)/129 = iO%
overall conversion of H =(100- 10)/100 =90%
selectivity for M in relation to H = 45/90 =50%
selectivity for L in relation to H =45/90 =50%
yield per pass of M in relation to H =45/129 =35?~
yield per pass of L in /elation to H =45il29 =35%
overall yield of M in relation to H = 45/100 =45?6
overall yield of L in relation to H =45/100 =4576
 Chapter 2, BASIC PRINCiPlES GOVERNING OEAIICAL CHANGES 17

It is easy to imagine that overall conversion can exceed conversion per

pass by a great deal, and even reach 100% if amount purged E approaches zero.
The overall yield can then come close to, if not attain, the selectivity value.

2.2 Thermodynamics of Chemical Reactions

The two thermodynamic parameters to be considered when analyzing the
thermodynamics of chemical reactions are enthalpy H and Gibbs energy G.
Generally speaking, the variations in enthalpy and in Gibbs energy associated
with a chemical change will have to be assessed so as to draw the relevant
conclusions for the heat balance and for the equilibrium advancement.
It should be noted that there is absolute continuity between the thermo-
dynamics of physical equilibria and that of the chemical reaction. This is why
the reader is requested to read through Chapter 4, Volume 1 (Methods for the
Calculation of Hydrocarbon Physical Properties) and Chapter 2, Volume 2
(Thermodynamics. Phase equilibria) before approaching the subject pre-
sented here. In this way, he or she will be familiar with the different concepts
used in thermodynamics. Other references [40,31] could also be consulted for
~ more thorough understanding of the topic.
First and foremost it is important to define two concepts: the standard
state and the origin of enthalpies.
a. The Standard State
The standard state of a component corresponds to the ideal gas state under
an absolute pressure of 1 bar and is identified by the exponent ". It does not
imply a reference temperature.
Table 2.1 lists the standard states that are most commonly adoptedfor ele-
ments in tables. .

Element Standard state

Carbon Crystalline. graphite form

Hydrogen Biatomic molecule
Oxygen Biatomic molecule
Nitrogen Biatomic molecule
Sulfur Crystalline. orthorhombic form

"""'1' Table .
I
2.1 Standard state of a number of elements.

b. The Origin of Enthalpies

:tis known that the origin of enthalpies can be chosen arbitrarily. Consultation
0i available data suggests choosing elements in their standard state as the
 A. Separation of Land M before recycle

[TI] = 39
M=45
L =45
I

B. Separation of L before recycle

II rJgUre
2.1 Conversion per pass, overall conversion. selectivity, yield per pass and overall
yield.

In case B. M is not separated, It is recycled with the non-converted part

011-1:
, conversion per pass of H = (136 - 40)/136 = 70%
> overall conversion of H =(100 - 4)/100 =96%'
) selectivity for L in relation to H = 92/96 = 96%
> yield per pass of L in relation to H = 92/136 =68%
) over~1l yield of L in relation to H = 92/100 =92%
origin of components' enthalpies. This procedure proves to be very conve-
nient when heats of reaction are to be evaluated.

2.2.1 Enthalpy Variation Associated with a

Chemical Reaction
The enthalpy variation associated with a chemical reaction measures the heat
released or absorbed during a chemical change. It is obtained from the evalu-
ation of partial molar enthalpies of each of the components.

2.2.1.1 Partial Molar Enthalpy

By definition, the partial molar enthalpy of a component Aj at temperature T
and pressure P inCl. mixture with other components is written as follows:
(2.9)

It can be evaluated by the following expression, provided the convention

on standard state and the choice of a reference temperature To are taken into
account:
hr(A j) = (MlDro(A;) + [hTCA;) - hhCAj)] + hf(A j) + h(Aj) (2.10)
(~()ro (A;) is the variation in standard enthalpy of formation from the ele-
ments at reference temperature To.
[hr(A;) - hh (Aj) ] is the standard enthalpy variation between temperatures
To and T.
h;(A;) is an enthalpy corrective term to be considered if the state is dif-
ferent from the standard state. If the conditions laid down correspond to the
(liquid or solid) condensed state, the term contains the heat of condensation.
h (A;) is a term that takes into account the contribution of component Aj
to the heat of mixing. It is generally a relatively insignificant term that is diffi-
cult to estimate, and this is why it is frequently omitted.

2.2.1.2 Heat of Reaction

For a system characterized by the stoichiometric equation:

L vjA j = 0 (2.1)

the quantity MlR.Tis called the heat of reaction at temperature T, such that:
(2.11)

where hr(A;) is the partial molar enthalpy of component Aj

The tables available generally give access to standard heats of formation at
a reference temperature To and to molar heat capacities Cp(A;) [20, 28, 36, 37,
45,46J.
 Chapter2. BASIC PRINCIPLES GC1IISNING CHEMICAL CHANGES 1S

This allows calculation of:

T
[hi-(A;)- hhCAj)} =I [C;CAj dT )
To
and consequently estimation of:
T
hi-CA j) = CMI,)ToCAj) +I [C;CA;)} dT (2.12)
To
In particular, at reference temperature To:
hToCA;) =CtlliDToCA;)
and the standard enthalpy of reaction is defined by:
(M-IR)To =r V;(Mli)ToCA;) (2.13)
It can likewise be shown that:
CMfFJT= L v. (Mfi)T(A j) (2.14)
Generally speaking, at moderate pressure (a few bars), the terms corre-
sponding to hP(A;) and hM(A;) can be disregarded. This is true except when
the chemical change involves a change in state, as will be seen in the example
tJelow.
This frequently means that the reference to the standard state is elimi-
nated:
(2.15)

2.2.1.3 Example of Calculating Reaction Endlalpy Variation

Given the isopropanol dehydrogenation reaction: --..
CH3-CHOH-CH3 -+ CH3-CO-CH;+ Hz
liquid at 298 K gas at 433K gas at 433 K
The enthalpy variation corresponding to this reaction is calculated. The
thermodynamic data used are the ones published by the Thermodynamic
Research Center [37}. The reaction indicated can be broken down into three
parts:
1. CH3-CHOH-CH3 (liq., 298 K)
-+ CH3-CHOH-CH3 (gas. 298 K) (vaporization)
A298 = +45,396 J

2. CH3-CHOH-CH3 (gas, 298 K)

...,. CH3-CO-CH3 (gas. 298 K) + H2 (gas. 298 K)
(..lliR)298 =(llii)298 (CH3-CO-CH~
+ (..llif)298 CH:0 - (~(CH3-CHOH-CH~

=-217150 + 0 + 272295 =+55 145 J

 3. CH3-CO-CH3 (gas, 298 K) + H~ (gas, 298 K)
-7 CH3-CO-CH3 (gas, 433 K) + H2 (gas, 433 K)
433

f
(.ilig,298~433K) = 298 [Cp(CH3-CO-CH0 + Cp(Hv 1dT= +15 585 J

There is a total of:

.ili =+45 396 + 55145 + 15585 =+116 127 J
In conclusion, for each mole of isopropanol that reacts according to the
conditions indicated, the system will require an input of 116 127 J. This is a
highly endothermic reaction.

2.2.1.4 Case of Complex Systems Defined by a Set of

Several Stoichiometric Relations
The enthalpy variation corresponding to reactionj, whose advancement is ~j'
is equal to (~h !;j, and the enthalpy variation corresponding to all the reac-
tions taking part in the change is equal to:
(2.16)

This of course implies that the reaction can be broken down into its differ-'
ent component parts and that the corresponding advancement values can be
assigned to them with enough accuracy. As mentioned earlier, this can be
quite difficult for reactions involved in refining operations. The difficulties can
be circumvented in certain cases. For example in hydrodesulfurization, expe-
rience shows that the elimination of a sulfur atom requires 2.7 moles of hydro-
gen on the average (depending on the nature of the sulfur compounds).
Moreover, the disappearance by reaction of a mole of hydrogen releases
approximately 60 kJ (depending on the nature of the bonds that need to be sat-
urated) (Thonon in [44]). The desulfurization ratio can therefore be readily.
linked to the heat released, or to the temperature increment of the reaction
stream going through the adiabatic reactor.
The appropriate correlations for different cases (catalytic cracking, hydro-
cracking, oligomerization, reforming, etc.) can be established without too
much difficulty, at least approximately, by designing model systems and apply-
ing the principles mentioned above to them.

2.2.2 Gibbs Energy Variation Associated with a

Chemical Reaction
The Gibbs energy variation associated with a chemical reaction allows the
position of the chemical equilibrium state to be situated between reactants
and products for specified operating conditions. It also enables the position to
be expressed by a value: the equilibrium constant.
 Chapter 2. BAsIC PRINCiPLES GOVERNING CHEMICAL CHANGEs 21

2.2.2.1 . Law of Mass Action

Given the equilibrium reaction:
A + 2B::; C or more generally L ViAi =0 (2.1)
The law of mass action, which defines how far the reaction can go, is writ-
ten:
[el
K = [AJ(Bj2 and more generally K =n [Ad V ; (2.17)

where [ ] stands for a concentration, a partial pressure, a mole fraction, a mass

fraction, etc. depending on what was chosen as unit of mass density.
!\very high Kvalue means that the-reaction can go right to the end. It can
be considered complete from a thermodynamic standpoint. This in no way
predicts the reaction rate, which may be zero if there is no means of activating
it selectively or initiating it (e.g. by combustion).
A very low K value means that the reactions advances little. This does not
mean that it is not feasible, since difterent solutions can be imagined to over-
come this thermodynamic difficulty. Some examples are: wide disproportion
among reactants, removal of one of the products as it is formed, separation of
products and recycling of the unchanged reactant, etc.

~.~.2.2 Calculating the Equilibrium Constant

The equilibrium constant is related to Gibbs energy variation by the following
formula:
(AGR>r=- RTin K' (2.18)
where: KO =n(f;/f;OY'j (2.19)

The first problem consists in evaluating (AGR)r' It can be shown that, for a
reaction represented by the stoichiometric relation L ViA; =0:
(2.20)

(ilGnr(A;) is the variation in standard Gibbs energy of formation for com-

ponent A;. In tables, (~Gf)T(A;) is seklom found directly, however it is easier
to find out or estimate CilGf) To(A;), (AFlOTo (A;) and Cp(A;). The most common
To is 298 K.
It is then possible to calculate (MiR)r:

(2.21)

which can often be simpl~fied to:

(.:lGR)r = (j/ffJro - T(.lSVT.) (2.22)

as long as I V; Cp(A;) is small. which is usually the case.

 When (.1GR)r, and therefore K=. have been estimated. the "concentrations"
of the different components at equilibrium should be specified.
The following was defined:
(2.19)
with:
f; fugacity of component Ai in the mixture at equilibrium
f;0 fugacity of component Ai in the standard state
Fugacity f;0 is equal to 1 bar by definition of the standard state. Fugacity f;.
also expressed in bars, can be evaluated either in the liquid or in the vapor
state depending on the problem data (see Vol.2, Chapter 2).
If the gas phase is involved:
(2.23)

Pyi = p, is the partial pressure of component Ai (to be expressed in bars)

~Y is the fugacity coefficient in the gas phase
If the liquid phase is involved:
(2.24)
where:
Pf is the vapor pressure of component Ai (to be expressed in bars)
Xi is the mole fraction of component Ai in the liquid phase
y;L is the activity coefficient of component Ai in the liquid phase
When component Ai has no definite vapor pressure (supercritical state),
the Henry relation is used to express f;L:

(2.25)
where 'Je; is the Henry constant for component i. The equilibrium between
phases is obviously considered to have been achieved for these estimates and'
therefore:

It is also possible to express the equilibrium constant in terms of mole frac-

tions, partial pressures or molar concentrations:
KG = n(f;/f;)Vi= n(Py;,Y/f;)VI
=(P/1)r. v; n(+nv; Ky
=n (Y)viKp (2.26)
Note that Kp defined in this way is dimensionless and that at a relatively
moderate pressure:
 The following can also be written:

KG =n(f;/ft)v; =nCI1x;y;Llfj)v; =n(P7/1)v; ncy;L)Y;Kx (2.27)

.. n- n.l n x-
and. additionally since C; = ...!. = -'-' = --!.., vm being the average molar
V vt, vm
volume, the result is:

KG =n (11/I)V; n (YiL)V; (v~)rV; K~ (2.28a)

for a liquid phase, and:

KG =(P/I)~V; n (,n V
; (v~) !v; K8 (2.28b)

for a gas phase.

Note that K~ and K8 are not cimensionless, as long as L v; * O.

~.~.2.3 Application Example

Use the example of isopropanol dehydrogenation:

a. Calculating the Variation in Standard Gibbs Energy

Given that the reaction is carried out in the gas phase at 433 K at an absolute
pressure of 1 bar. The TRC tables [37} give:

=
(tllif)298 (CH3-CO-oI:i) -217 150 j
(tllii)298 (CH3-CHOH-CH:i) -272 295-J =
(tllij)298 (Hv =0 (elements' heat of formation is zero
at any temperature)
(.lGf)298 (CH3-CO-oI:i) =-152716 J
(ilG f)298 (CH3-CHOH-CH:i) =-173 385 J
(ilGj)298 (Hv =0 (true at any temperature)
The following is calculated first of all:

(tlliR)298 = -21; ISO + 272 295 = +55 145 J

then:

(ilG R) 298 =-152 i16 + 173 385 =+20669 J

and:

(~ RJ298
~, = (.llipJ~ - (~GiD298 = +115.69 J/K
298
 Using Kobe et als C; (Ai) data [20), the following is then calculated:
(~GR)433 = 55 145
433
+
f
298 4.184(i.i83-1.8871O-2T+ 1.3i51O-5~-0.3-l61O-8T3)dT-433x 115.69

433
- 433
f298
[4.184 (7.783 - 1.88i1Q-2T + 1.3i51O- 5T2 - 0.346.10-8 T3)] dT,fT
.

The result is:

(j,G R) 433 =55 145 + 1 452 - 50095 - 2770 =+3732 J
Using the simplified relation:
(L\G R) 433 =(MfR) 298 - 433 (~R)298
would give:
(L\G R) 433 =55 145 - 50095 =+5 050 J
b. Calculating the Equilibrium Constant KO
(,1GR)-l33 =- R x 433 In KO
The result is: KO =0.35
K _ 0.35
and therefore:
p- nccpy)\';

For example the law of corresponding states and the general graph for
determining fugacity coefficients like the one found in most thermodynamics
reference works [17] are used to calculate C}")\'( An equation of state, such as
the Soave Redlich Kwong or the Peng Robinson equations (see Vol. 2.
Chapter 2) can also be used.
In the case under consideratlon, since the pressure is low arid the temper-
ature is moderate, the following is found:

and therefore: Kp iO!! KO =0.35

c. Maximum Molar Extent
If the initial system were made up of no moles of isopropanol and kno moles of
inerts, the composition at.equlllbrlurn can be estimated which corresponds to
the maximum molar extent Se' At equilibrium, by definition of Se' there are:
~ moles of hydrogen
l;e moles of acetone
no- ~e moles of isopropanol
kno moles of inerts.
 C/I6pref' 2. 8AsJcPRINC6'l.ES GOVERNING CHEMICAL CHANGEs 25

Partial pressures at equilibrium will be:

. 110-1:
P. (isopropanol) = . p
(1 + k)no + <;.

P. (acetone) = 1;.. P
(l+k)Ilo+<;'

P. (hydrogen) = (l
+
k~no+".~ P
P. (inerts) =by difference with P
~ For P = 1 bar. by application of the law of mass action:
~!
K p =0.35 = {(l +k)no+~} (no-I;.)
the result being:
!' = no IV (0.35k)2 + 1.89(1 + k) - 0.35 k}
.... 2.70

I l.e, for no =10 and k =0.5:

I;. = 5.62 mol
For 10 moles of isopropanol and 5 moles of inerts at an absolute pressure
of 1 bar and at 433 K, at equilibrium there wiD be:
5.62 moles of acetone
5.62 moles of hydrogen
4.38 moles of isopropanol
5.00 moles of inerts .
a total of 20.62 moles

This short exercise shows that for a reaction occurring with an increase in
the number of moles, it is advantageous to reduce the pressure in order to
boost the potential advancement at equilibrium. Dilution by an inert is also an
asset in this case. Cracking is a ideal illustration of this situation in the refin-
ing industry. Hydrotreating operations exhibit just the opposite.

2.2.2.4 Variatioa in the Equilibrium Coasant with Temperature

On the basis of:
(2.18)

it can readily be shown-that:

d(lnK') -(j}{~JT
(2.29)
delfT) = - R -
 oy plotting In K' versus I T. a curve is obtained which is practically a
iight line. Its slope is - (~~JIR as long as (MiRJ can be assumed to be
ariant in the temperature range under consideration. For an exothermic
etten ~R) < 0). the slope is seen to be positive and consequently the
.ie of the equilibrium constant decreases when the temperature increases:
equilibrium moves backward. The situation is just the opposite of course
endothermic reactions.

~.5 Complex Systems Defined by a Set of

Stoichiometric Relations
. each reaction taken separately with its stoichiometric expression. the fol-
..ing can be determined:
(2.20)

As a result, each reaction j can be associated with a variation in Gibbs

ergy and therefore with an equilibrium constant. When the aim is to know
~ equilibrium state of the system taken as a whole, a system simultaneously
:Iuding the following must be solved:
S linear balance relations of the type:

i=I,S i=I,R (2.5) ,

R non-linear relations of the type:

i= 1,5 i= I,R (2.19)

This procedure is very cumbersome as soon as the number of stolchlo-

etric relations becomes significant. It then becomes necessary to resort to
uch more efficient methods of minimizing Gibbs energy [33].

2.3 Conclusion
iernical changes that occur during refining operations involve muitiple reac-
.nts involved in multiple crisscrossing reactions. Lumping, t.e, grouping. by
.rnilles of reactants and reactions. is required. Lumping is very common in
hemical kinetics (see Section 2.3.3.6) and in determining equilibria between
hases (see Vol. 2, Chapter 2 [II D, but seems to be less commonly used in
hemical equilibria. It is often possible to situate the theoretical limits of a
hange, at least qualitatively, based on the behavior of a few model com-
-ounds that are representative of all the compounds and take part in a limited
.umber of determining reaction paths.
The influence of temperature, pressure and dilution parameters on the
-quillbrium position can then be examined for each of the reactions. This will
;ive a Quickrough idea of the assumed equilibrium positlon according to the
exo- or endothermic nature and the overall increase or decrease 01 the num-
ier of moles during the change.
 In actual fact, the problem is not so much to define the equilibrium position
accurately. It is rather to work out which activation method (thermal Or cat-
alytic) will help approach equilibrium reasonably quickly under satisfactory
selectivity and stability conditions. To take the example of catalytic reforming,
thermodynamics dictates that it is advantageous to operate at low pressure
and high temperature (highly endothermic change, increased number of moles
and in particular significant hydrogen production byaromatization).
Actually, all efforts have been focusing on developing active. selective and
stable catalysts which are compatible with thermodynamic requirements.
Moreover, as mentioned before. a thermodynamic constraint difficulty can be
overcome in many refining processes by limiting conversion, creating dispro-
portions in the initial mixture, diluting. eliminating one 01 the products as it is
formed, or even by changing process conditions. etc.

2.3 Chemical Kinetics

Mass balances and heat balances associated with reaction molar extent (or
conversion) have been written and conditions 01thermodynamic equilibrium
have been examined. Now the rate of change should be discussed, if the
change is feasible. This is the aim of chemical kinetics. which incorporates the
time dimension. Belore defining the lormal expressions of reaction rate. the
main features of a chemical reaction will be analyzed:
the nature and location 01the reaction phase:
the means of activating the reaction and the active intermediate forms.

2.3.1 Nature and Location of the Reaction Phase

In a reaction environment involving one single gas or liquid phase, the prob-
lem of location does not arise. In contrast, when the environment involves sev-
eral phases. the chemical change is usually seen to occur either in one 01the
phases. at the interlace between two phases or in the vicinity of this interlace.
For instance in a hydrotreating process. the gas phase contains most 01 the
hydrogen co-reactant, the liquid phase contains the compounds to be treated
and the solid catalyst activates the reaction. The place where the reaction
actually occurs is here the solid-liquid interlace or rather on the surlace of the
porous solid impregnated with a liquid saturated in hydrogen. The physical
mechanism of entering into reaction means that the hydrogen goes from the
gaseous to the liquid phase and that the components in this liquid phase
(induding the hydrogen) reach the active sites of the catalytic surlace. so that
the reaction per se can occur at its own specific rate. The reaction's location
is by no means insignificant. If a reaction is disturbed by a physical process
upstream from the reaction site. the process will obviously have to be identi-
fied and every effort will have to be made to correct it. This is particularly
important when laboratory results are transposed in order to build an
industrial unit. Examples of chemical kinetics thrown off by physical
processes will be shown later on, along with the consequences of such
disturbances.

2.3.2 Methods of Activating Chemicaillcactions.

Active Intermediate Forms
The two main ways of activating chemical reactions involving hydrocarbons
are raising the temperature and implementing a catalytic substance. Both
methods can even be combined. When the only activation method consists of
increasing temperature. the active intermediate fonns are generally radicals.
When catalytic substances are implemented. the active intermediate forms
can be carbocations (also termed carbonium or carbenium ions) or neutral
molecules in an adsorbed state. The temperature method can also generate
other active forms such as coordination organometallic complexes. carban-
ions, enzymic ferments [24, 29].
In the relining industry, carbocations are involved in catalytic reforming,
catalytic cracking, hydrocracking, alkylation, isomerization, polymerization
and etherification reactions. Radicals are brought into play in visbreaking, cok-
ing, steam cracking and partial oxidation. Neutral adsorbed molecules are
observed in hydrogenation, hydrodesulfurization, hydrodenitrogenation and
hydrodemetallization. Oligomerization of olefins uses soluble organometallic
complexes.
The nature of the active intermediate forms is related to that of the cata-
lysts which are (or are not) implemented and to the operating conditions
used.

2.3.2.1 Carboc:ations
It has already been mentioned earlier that a large number of refining opera-
tions involve carbecatlons. They are indispensable in-triggering reactions and
are produced by using catalysts, usually of the solid, "acid" type. The cata-
lyst's acid sites can be of two kinds: Lewis and BrOnsted. A variety of treat-
ments. particularly with steam, can be used to transform Lewis sites into
Breasted sites. The nature, strength and distribution of sites can be highly
variable from one catalyst to the other. Generally speaking, the hydrocarbon
molecule is adsorbed on an electron receiver site that it reacts with to form a
carbocation:
I I
-C-H+ A"receiversite -+ _C4!;+AH
I I
carbocation
The carbonium ion formed in this wayan the surface can then evolve in dif-
ferent ways. It can be:
desorbed restoring the receiver site to its original status,
 desorbed losing a proton that remains on the receiver site thereby form-
ing an alkene,
rearranged by migration of the positive charge along the chain Qi-shift)
to the most stable position (tertiary C; is more stable than secondary CS ,
which is more stable than primary C E).
The ion modified in this way can in tum follow the paths indicated previ-
ously. It can:
be rearranged by migration of a chain element. lor example a methyl
group (CHJ-shift. PCP branching),
react with another molecule to effect a charge transfer or an addition,
be cut in ~ position with respect to the carbon carrying the positive
charge.
These possibilities can be used to explain the behavior of hydrocarbons
involved in reactions qualitatively (as well as quantitatively. to the extent that
the kinetics specific to elemental steps can be accessed). The conventional
reaction scheme of iso-alkane alkylation byalkenes [32] is presented below as
an example.
The initial carbocation is provided by propene reacting with an acid site:

Then there is a charge transfer onto an lsobutane molecule:

CH3-CH :-CH3 + CH3- yH-CH3 -+ CH3-CHz-CH 3 + (CH~3 C E

CH3

This tertiary ion is more stable than the initialsecondary ion. It reads with .
a propylene molecule:

CH3
:
which gives the following by H-shift: CH3-C-CH-CHz- CH3

CH3

then. by CHJ.shift:
 Afterward. there is another charge transfer with isobutane:

This provides the main product, 2-3 dimethylpentane. and the tertiary car-
bonium ion that allows the cycle to start over. As a whole. the reaction is writ-
ten:
CH~=CH-CH3 + CH3:"'yH-CH3 ~ CH3 - y H -
yH-CH 2-CH3

CH3 CH3 CH3

if the very small amount of propane produced during the initiation step is dis-
regarded.
Side reactions are possible. even if they are not thermodynamically pro-
moted:
C-C-C-C-C~C-c-C-C-C~ C-c-c-c-c
I I I I I I
C c C C C c
CH"ShJlI, C-c-t-c-C charg~) C-C-C-C-C
I I transfer I I
c C c C
24 dtmethylpentane, by-product

For these reactions to take place. it is indispensable for the alkane to be

branched so that the relay carbocatton is stable enough. Note also that the
carbocations do not leave the surface of the catalyst. They are an adsorbed
form of the relevant molecules and all the changes occur in constant contact
with acid sites.

2.3.2.2 Radicals
Radicals are formed by homolytic cleavage of a C-C or C-H bond. while car-
bocations are formed by heterolytic cleavage. The different steps of radical
processes are:
Initiation
R-R' ~ R + R' for alkanes and alkenes
 ('J ~ ("I biradical for cycloalkanes
R~ R
A aa'
rry
~R
~ rQ!
~R'
+ H' or R for alkylaromatics

Propagation
R' + R' ~ R + R"
Termination
RO + R" ~ R-R'
Thermal cracking of n-heptane [101 serves to illustrate this process, with
the various differentsteps shown in Figure 2.2-
Radical schemes differ widely from carbocatlon schemes in their results. In
particular:
the short 013. CzH; radicals may generate large amounts of light gases;
the cleavage always occurs in the side chain for alkylaromattcs, whereas
, it takes place flush with the aromatic ring for carbocatloas:
radicals do not lead to isomerization of the skeleton, there are no
branched products other than those already present in the feed;
thermal cracking of alkanes can produce u-olefms.
Speight [34J and Pines [291 have shown clearly the characteristic differ-
ences between the two reaction schemes when both are possible.
Greensfelder et aI. [15J have analyzed the reaction mechanisms of the two
schemes for pure hydrocarbon cracking in detail.

2.3.3 Formal Chemical Kinetics

By convention. a reaction rate is defined by monitoring the appearance of a
product or the disappearance of a reactant versus time in a reactor that is spe-
cially designed so that the measurements can be made under the best possi-
ble conditions. The kinetic data required to calculate and rationally perform a
chemical reaction come from laboratory experiments. so the design of the
experimental reactor is of critical importance. The size is generally of little sig-
nificance. However.it is indispensable for the experimental reactor to resem-
ble as closely as possible one of the three types of ideal reactors that will be
defined and discussed below. This allows the results to be analyzed rigorously
to see whether the kinetics observed is actually representative of the chemi
cal phenomenon that is proposed for definition and quantification. Due to
inadequate precautions. there are still too many instances of spurious transfer
limit phenomena skewlng conclusions on the characteristics specific to a
chemical change.
 I Termination I

., I
l.
I
., I
RH + /c~,/\ //CH,' \ /CIl,
'\. __
ICH, + /
CH,
'\ /
CH,
'\ _
,CH,
+ I"" __
CH,
I
CH,
+'CH

\
'CH, CH, CH, CH, CH, 'CH, CH, CH, CH, 'CH, CH, CH, >

/ '\
I

\ / \
Inillation

CH, /CH, CH.

+ R
~
CH, CH, CH, CH, short
Initial reactant
I

!'"
RH + ,--<C,\ /C,\ XC~
CH. VH CH, CH,
<
CH,

/
CH,
CH

"
CH.
r< / '<
CH.
CH, ICH,
CH
CH,

+ /
CH,
CH,
'\
-CH, CH,
+ CH.--------

I
CH,
CH.
+
1-
ca, _ _~_ _ I

CH, CH, CH, CH CH, CH, CH. 'CH,

RH+ / ":'< '\.1'\ _ I \ + ' \ /"-. --." + \ - __
CH, CH. CH, CH, CH, CH, CH. CH, CH, CH,

'\ CH, CH, CH, CH CH, CH I

RH+ I 'XI '\/( '\ ---.. 1'\ />; + '\
CH, CH, CH, CH, CH, CH. CH, CH,

Propagation
, -
Fi~"re I---------------------~---------~-~----------------'

2.Z /(lIclit.'ul.St.:I,ellw of ,,-/wlllalie cruckilll-: (J(J). UcuctiuII/Uutlll~I x un' ill "'O/d churucter (t""yl"1h', '''-''I'}'h-,W, 111I"'11('-1. IWHf,'/w}, Iw,,",-,w-' J.
'---_.
 Three types of reactors, corresponding to three idealized models, can be
used to determine the reaction rate. They are as follows:
the stirred discontinuous reactor. or batch reactor;
the stirred continuous reactor, abbreviated as CSTR (continuous stirred
tank reactor):
the continuous plug flow reactor (pFR: plug flow reactor).
To the extent that the experimental reactor used corresponds to one of
these three types. it will be possible to determine the reaction rate and study
the parameters that influence it. Note that the expression of rate per se does
not depend on the reactor chosen since the actual reaction is conditioned only
by local values of composition, pressure and temperature. Consequently, if
two studies of the same reaction carried out in two different reactors lead to
different rate expressions, it means that one of the reactors (or both of them)
can not be considered as sufficiently dose to the ideal type it simulates.
At first glance, the batch reactor might be considered inappropriate for
studying continuous processes, which are the most common type in the oil
industry. This is not exactly true. For example bitumen blowing is a discontin-
uous operation, and coking is likewise carried out until the reactor is filled
with coke. In hydrodemetallization operations. each grain of catalyst can be
considered as a batch (or rather semi-batch) mtcroreactor, accumulating
metallic deposits with time. Furthermore. each mlcrograin of catalytic crack-
ing catalyst gets gradually covered with coke as it moves upward in the FCC
riser before it is regenerated by combustion. In addition, any start up or shut
down operation. any change in operating conditions in any continuous unit
brings the time factor into play (real time and not average reactant residence
time). In conclusion, besides the fact that the batch reactor is a remarkable
implement for studying reaction kinetics. the discontinuous nature of certain
refinery operations should not be disregarded. . .
The following section anticipates somewhat on the respective characteris-
tics of the three types of reactors. Expressions of reaction rate that might be
established for a reaction occurring in the homogeneous phase will be exam-
ined. then other cases will be discussed later on.

:.3.3.1 Defining Reaction Rate AcconlinC to the

Type of Reactor Used
a. Batch Reactor
This case deals with one single reaction. whose molar extent is observed ver-
sus time in a batch reactor of volume r.
At time t. for reactant .-1,:
l2.5a) and (2.7)

At t +:It
n, -e- sn, = n,,, ... v, (~ - ~) = n", (I - (X, ...:lX,))
irom which the following is taken:
dn; d~ (dX,)
dt = "i dt = -n i dt
d~
2 is the extensive rate of reaction
dt

..!.. d~ is the intensive rate of reaction, or simply the rate

V dt
It is commonly designated r:

r=..!.. d; = -nio
V dl v;V
(dl(,)
dl
(2.30)

dX; = -v;rV
dl nio

The relation can be used in both directions:

r can be determined by measuring the molar extent or the conversion
versus time;
if r is known, the conversion versus time in a reactor of volume V can be
determined.
The situation is not quite so simple when reactant A; is involved in several
-eactions, as shown below:

dn, -e- d:'j , ( -<IX; )

-=1V"-=L,vrV=n. - -
dt -qdl 'II '. dl

can not be expressed as a function of dXJdt because:

dX; = -Iv;jIjV
dt dn;.
This example shows that molar extent is a more complex concept than con-
.erslon. However, conversion will have to sulfice in many cases and the rate
.iII then be the overaJl average rate at which reactant A; disappears.

J. Continuous Stirred Tank Reactor (CSTR)

:-he molar flow rate F, of substance A; is expressed:
when there is one single reaction. by:

(2.5b) and (2.ib)

The subscript e refers to the inlet and s refers to the outlet of the reactor:

(2.31)
 when there is a set of reactions, by:
F,. =F;" + LVijS;
Fi"X
L.vij'j =overall average rate = -V i

c. Plug Flow Reactor (pFR)

For one single reaction:
with a volume covered V. the molar now rate of substance At is expressed by:

F, = F" + v;i;' =Fi" (1 - X;) (2.5b) and (2.ib)

with a volume covered V + d V, it is expressed by;

F, + dF, =F,.+ Vj(S' + d'; ') =F,. (I - (Xi + dX;))
Le.:
dF,
dV
=v(d!;')=_F..
'dV
(dX
"dV
i
)

and:
(2.32)

For several reactions:

For one-phase systems such as the one examined here, the intrinsic rate r
is generally expressed in mol/(sm3 ) . However other expressions will also be
found later on. for example when a solid catalyst is implemented or when it is
impossible to account for the number of moles. .

:.~.3.: Expressinl tbe Intrinsic Kate ,.

Experimental measurement provides the value of r, or rather a series of values
of r. depending on the experimental conditions used. Based on these expert-
mental results, an attempt is made to establish the fonn of expression of r.
For reactions in homogeneous phase, the most general form of expression
is:

or: (2.33)

with n standing (or a produft of factors.

The arrows above 13 and k refer respectively to the reaction taken in the for-
ward direction and in the reverse direction.
 At equilibrium. r = 0 and the conventional thermodynamic relations are
found:
Kc ;: ~ and V, = 13: - if,
k
~j is termed the partial order of reaction for component Ai (which may be
radically different Irom Vj)' It is a dimensionless number. which mayor may
not be an integer and has a low value (0 to 2).
k is called the rate constant. Its dimension depends on the values 01 ~,.
Note that if the driving forces of the reaction are expressed in terms of con-
centrations. the equilibrium constant corresponds to Kc. ff the driving forces
were in partial pressures. it would be Kp and ifthey were expressed in the lorm
of mole fractions. it would be K, or Ky , depending.
Frequently, only the part corresponding to the forward direction is seen:.
r= k n (C,)~i
without arrows. This means that, taking the value of (,lG R)rinto account. equi-
librium is still quile lar away and so the reverse reaction can be disregarded

2.3.33 Expressing Reaction Rates with

Element Mass Concentrations
The case where the only values accessible are element mass concentrations i~
frequent in relining, particularly in treatments designed to purify leeds by
eliminating unwanted elements (S. N, Ni,V, etc.). It is quite possible to express
a reaction rate with respect to a tracer element. precisely the one that is to be
removed. In a hydrodenilrogenation operation on a petroleum cut. the reac-
tion rate will be expressed lor example in kg of nitrogen eliminated per kg 01
catalyst per hour. For a dillerential catalytic reactor volume (With plug flow)
the balance is written as shown below:
'{2.34)
with:
PL density of the liquid feed. measured at inlet conditions (kg/m3 of liquid)
QL nquid feed flow rate. measured at inlet conditions. considered to be
constant (m 3 01 liquid/h)
N mass fraction of nitrogen in the liquid (-)
V volume of the bed (m3)
Pc density of the bed (kg 01 catalyst/m 3 of bed)
r reaction rate [kg 01 nitrogen/(kg of catalyst.h))
Equation 2.34 obviously can not be solved unless a rate equation is avail-
able that has been obtained independently or by internal processing of results,
for example: .
r= keN) (PH) (2.34)
PHz is the local hydrogen partial pressure (in bars).
 II the reactor is Isothermal and isobaric, and the hydrogen flow rate is sul-
, liciently high lor Plit to be considered as a constant, expression 2.34 can be
integrated and the following is obtained:

In!!.- =-k Pc PH ~ =-k Pc ( Plit ) with QL = WH

No PL' QL PL WH V

Pc ( PH, ))
N =No exp ( -k Ii;:- WH (2.35a)

Conversion X:\"could just as well have been introduced and expressed as:
No-N
X~=--
No
dN
ctx:\"= - No

and conversion would have been obtained versus space velocity:

Pc ( Pflo
x:\" =1 - exp ( -k PL VH )) (2.35b)

, This example aflords an opportunity to introduce space velocity. WH,

which plays a leading role among operating conditions for chemical processes
with catalysts. As seen before. space velocity is the volume flow rate of feed
taken at inlet conditions over the volume of catalytic bed (normally packed).

2.3.3.4 Temperatare's Influence on Reaction Rate.

~tivad_ Energy

It is often said that the rate 01 a chemical reaction doubles whenever the tern-
peratureis raised by 10'C. This statement is slightlymisleading. since the mar-
gin of variation is in fact much wider. However. it does underscore the consid-
erable influence of temperature, on thermally activated reactions as well as on
the others. The influence 01 temperature makes itself felt via the variation in
the reaction rate constants k.
Reaction rate constants, whose dimensions depend on partial orders of
reaction, vary with temperature according to the Arrhenius equation:
(2.36)
or:
(2.3i)

The term " which appears in Eq. 2.36 is called activation energy and is gen-
erally expressed in J/mol.'ar even in kl.rnol. R. the ideal gas constant. is equal
to 8.31 J/(mol.K). Written as in Eq. 2.37. the expression recalls a form known in
thermodynamics as the Clapeyron-Clausius equation.
 Likewise. the constant Ii is expressed as a function 01temperature by:

d(ln k) "
d(lfT) =-Ii
The result is that:
s ==-
Kc = rz:
k;; exp (-E)
--
k ko 8T .

d(ln Kc) -E
del/T) =~
Since thermodynamics states that (see Section 2.2):
. d (In KO) (AHFJr
d(llT) =- - 8 - (229)

considering Eq, 2.28 relating Kc and KO, consequently:

MiR ;;:;E- (2.38)

Therefore. as an initial approximation, the heat 01 reaction is equal to the

dillerence between the reaction's activation energy in the forward and in the
reverse direction. Generally speaking, the activation energy 01a chemical reac-'
tion ranges between 40 and 200 kljmo!. Any value outside this range should be
considered questionable. A low observed value in particular is almost always
indicative 01a diffusion limit skewing the chemical reaction as such. Activation
energy of thermally activated reactions is also frequently higher than that of
catalyzed reactions. This is not surprising since one 01the Iunctions of a cata-
lyst is precisely to lower the potential barrier that separates the reactants
from the products (Eschard and Wauquier [44]).
It is ofien preferable to use the Arrhenills equation in a different form. In
actual fact. ko called the frequency Iactor, is the value of the reaction rate con-
stant that would correspond to an infinite temperature. The concept is there-
fore somewhat abstract. To overcome thiS conceptual difficulty. another reier-
ence temperature To is often chosen which can be:
the initial temperature 01 a reaction carried out in a closed system;
the average temperature of the cooling fluid used to cool the reaction
vessel;
the feed inlet temperature in a continuous reactor;
any other appropriate temperature.
Equation 2.36 is then written:

k T = k To exp ( ~ U~
o
- )) (2.39)
2.33.5 Expressing Reaction Bates for Reaction' Involving a
SC!lid Cataly't

Chemical reactions activated by a solid catalyst make up a very large category

which warrants a separate analysis. As mentioned earlier, the first im:nediate
consequence is that the reaction space Is restricted to the surface of the solid
catalyst. Taylor introduced the concept of 'active sites' on the catalyst sur-.
face. Langmuir and Hinshelwood developed a theory of that bears their name
which can account lor the great majority of experimental results obtained in
heterogeneous catalysis. Hougen and Watson [Ii) utilized this theory and
developed a series of reaction rate expressions commonly called LHHW [38..
39\. According to this theory, the total number of active sites is considered to
be distributed homogeneously on the catalyst surface. The term catalyst sur-
face means both the outside and inside surface area of the catalyst grains, with
the inside area being much larger due to the porous nature of the catalyst. If
the sites are distributed homogeneously, a fact that generally holds true, there
is proportionality between the number of active sites and the catalyst surface
area. Additionally, proportionality is considered to exist between the catalyst
area and its mass. As a result, reaction rate will usually be expressed per unit
of catalyst mass.
The example below will show how an LHHW expression is established. The
computation takes into consideration the function of active intermediate
forms in the reaction as examined in Section 2.3.2. without any contradiction.
Generally speaking, the different steps in a catalytic reaction are as follows:

The reactants approach the catalyst surface. The approach is governed

by mass transfer laws. while the penetration in the pores is dictated by
intraparticle diffusion laws (see Vol. 4).
The reactants are adsorbed.
The adsorbed reactants react with each other-and sometimes with non-
adsorbed ones.
The products are desorbed.
The products move away from the catalyst surface.

Each of these steps proceeds at its own rate, and together they make up the
overall reaction rate. One step can otten impose its rate and it is then said to
be limiting in the process. Under these conditions, all the other steps are con-
sidered as non-limiting, meaning that they have reached the equilibrium state.
This assumption allows the system to be solved easily. In the example devel-
oped below. the first situation to be examined is where the rate is not limited
by mass transfer. Only the other steps will be considered. along with the sub-
steps if they seem useful.
Given the catalytic.
. reaction:
characterized by an equillbrium constant K c such that:
CJ. C~.
Kc = - -
CI.C:!e
with the subscript e indicating equilibrium.
This reaction can be broken down into several steps. Among others. the fol-
lowing reaction process is possible.
AI is adsorbed:

where:
a is a free active site
Ala is a site occupied by Al
~ is the adsorption rate constant for AI
kl is the desorption rate constant for AI
~/~ =b l is the adsorption coefficient for AI
Note that the adsorption process can be likened to the formation of a car-
bocation. if this active intermediate form is involved (the case of acid cata-
lysts).
The carbocatlon undergoes changes (H-shift. CH3-shilt. etc.):
t;
AI a ==r Ba
k;
where Ba designates a site occupied by B.
kz/k; =02 is the stability equilibrium constant between the two types of
carbocations.
-, The transformed carbocation reacts with a co-reactant coming from the
homogeneous phase:
k;
Sa + A 2 =; A 2Ba
k;
with k;/k; =~. which can be considered as the adsorption coefficient of com-
poundA 2
, The new carbocatton undergoes changes:

~
A 2Ba ~ A 3A4a
~
~/~ = equilibrium constant for reaction 04'
 Chapter2. BASIC PRINCJPI.ES Gov!RNrNG CHEMICAl CHANGes 41

One of the products (A:i)is released:

k;
A3A 40' ==;. A 3 + A 40'
k;
with "ii"s/ks = bs which can be considered as the adsorption coefficient of com-
pound A3"
The second product A.J is released and the acid site is restored to its ini-
tial state ready to continue the cycle:

k;
A 4 (J =:;. A 4 + 0-
~
with ~/ko =b6 coefficient of adsorption A 4
Supposing that the limiting step in the process in the adsorption of Air the
rate can be deduced as equal to:
r= Ii;{Ad fa] - k; [Ala]
with the brackets [ Jrepresenting concentrations:
[Ad concentration of Al in the fluid phase surrounding the catalyst
(d] concentration in free sites. expressed for example in the number of
sites per m2 of catalytic surface area or per kg of catalyst
[AId] concentration in sites occupied by AI'
All the other steps, as mentioned earlier, are considered as being con-
stantly in their equilibrium state:
k;[A1a] =k;[Ba]

k; [AzJ[BcrJ =k; (A:!Ba]

~ [A!B (J ] = ~ [ASA.l o ]

~ [A3A ..o ] = ~ fA3J[A..c ]

~ [A.d[0'] =k; [A..cr]
Based on these equality equations, the "concentrations" in different
adsorbed substances can be defined:
k;; .
= -=- fA.d(cr] =b6[A4 Hcr]
k6
40 Cha/Jrer2. SASIC PRINCiPLESG:;::=lNING C..,E.'.r.::;4L c-s-.sss

characterized by an equilibrium constant Xc such that:

C31!C4e
Kc==-
Cl eC2e

with the subscript e indicating equilibrium. .

This reaction can be broken down into several steps. Amongothers, the fol-
lowing reaction process is possible.
Al is adsorbed:

where:
0' Is a free active site
AlO' is a site occupied by AI
k; is the adsorption rate constant for Al
IJI is the desorption rate constant for Al
k;f7it = b, is the adsorption coefficient for Al
Note that the adsorption process can be likened to the formation of a car-
bocatlon, if this active intermediate form is involved (the case of acid cata-
lysts). I

The carbocatlon undergoes changes (H-shift, CH3-shift, etc.):

~
AIO' -==;. Ba
k;
where designates a site occupied by B.
BO'
k;/"ii; = a2 is
the stability equilibrium constant between the two types of
carbocations. .'
.) The transformed carbocatlon reacts with a co-reactant coming from the
homogeneous phase:
Ii;
B<J+Az =::::;. AzBcr
k;
with"k;I"k; =b3 which can be considered as the adsorption coefficient of com-
pound As
~ The new carbocation undergoes changes:

A2BO'
~ A
~ 3A 4O'
i4
7i.t/k4 = equilibrium constant for reaction a4'
 One of the products (Avis released:

k;
A3A4 0' =::; A 3 + ..4.0
~
with ils/k; = bs which can be considered as the adsorption coefficient of COm-
pound Aj,
The second product A-t is released and the acid site is restored to its lnl-
tial state ready to continue the cycle:

~
A 4 0' =; A 4 + cr
~
with k;.1kr; =b6 coefficient of adsorption A4
Supposing that the limiting step in the process in the adsorption of AI' the
rate can be deduced as equal to:

r = k;[Ad [cr] - k;{AI 0']

with the brackets [ ] representing concentrations:
(Ad concentration of AI in the fluid phase surrounding the catalyst
[a] concentration in free sites. expressed for example in the number of
sites per m2 of catalytic surface area or per kg of catalyst
[Ala] concentration in sites occupied by AI_

All the other steps, as mentioned earlier, are considered as being con-
stantly in their equilibrium state: .
=k; [Ra]
Ii; [A1H B a ] =k; [A2Ba]
~ [A2Bcr I ;: ~ [A3A..a I
~[A3A~crJ =k;[A3)[A-\<J]
k;. [A4Ha) =kr; [A4 G ]
Based on these equality equations, the "concentrations" in different
adsorbed substances can be defined:

~
=-=- [A 4J{a] =bdA 4][a J
kG
42 C~aoter 2. BASIc PRINCIFi..ESGOVERNING Cn=~.:;AL CHANG!"$

[Ba]

Additionally, the balance of active sites must be complied with, conse-

quently:
[aoJ = [a] ~ [A4a] + [A 3A4a] + [A2Ba] + [RO'] + [Ala]

where [0"0] represents the initial site concentration, which is constant for the
catalyst. The rate expression therefore becomes:

However, at equilibrium r =0, so:

and therefore:

(2.40)

The form of the denominator DEN is usually very complex. The important
thing is the fact that the denominator can sometimes be reduced to one if [GJ
remains close to [GoJ, l.e, if there are surplus active sites compared to the
requirements of the reaction per se, so that there is no competition for differ-
ent species to be adsorbed.
This case is not overly Tare. Under these conditions, the expression of rate
is reduced to:

(2.41)

with:
r in mol/(s.kg of catalyst)
k;[O"oJ in m3/(s.kg of catalyst) in the present case
 Developing this example affords an opportunity to show the possible influ-
ence of a mass transfer limit. If the same reaction is used, but considering this
time that it is limited by the transfer of molecule AI from the homogeneous
phase to the catalyst, the following can be written because of the equilibrium
state of all the other steps in the process:
[AIls < [Ad
[A2ls = [Azl
[AJ]s =[AJJ
[A]MA.ds
[A41s = lA.d and Kc = {AIls[AzJs

where the subscript S means on the catalyst surface: Therefore:

r= ksAs ([Ad _ [AdS) = ksA s (lAd _ [AJJ[A 4 l ) (2.42)

Pc Pc KdA 2]
with:
, reaction rate in molt(s.kg of catalyst)
ks mass transfer coefficient in mls
I Pc catalyst bed density in kg of catalyst per m3 of bed
As fluid-solid interfacial area in m2 of outer grain surface area per m3 of bed
Expression 2.42 looks just like 2.41, and this poses the problem of discrim-
inating between models, i.e. of choosing the most probable model.
Fortunately, it will be easy to determine the dominant process in the present
case simply by examining the rate variation with temperature. Chemical pro-
cesses such as chemisorption (characterized by k;) are much more sensitive
to temperature than physical ones (characterized here by the transfer coeffi-
cient ki). As a result, the experimental activatioo .energy value will allow an
unambiguous conclusion to be drawn.
The situation can prove to be more complex if the reaction is limited by
both the adsorption rate of Al and the transfer rate of AI' In this case. to the
extent that DEN can be reduced to one, it is shown that:

(2.43)

This discussion was initiated on the subject of carbocatlons, but it can

obviously be integrally transposed to other cases of adsorbed active forms.
Hydrogen is commonly found in a great deal of petroleum processing and is
a special case. Its molecular size is small. it readily produces protons and has
Particular physicochemical characteristics. All these features give hydrogen
adsorption properties that are radically different from those of hydrocarbons.
Generally speaking. hydrogen does not take part in the competition to occupy
the same sites as hydrocarbons. It has its own specific sites in the immediate
vicinity of those occupied by hydrocarbons. The fact that the order of reaction
for hydrogen is often close to one can then be explained simply if the reserved
sites are assumed to be numerous compared to the number of hydrogen
molecules required for the reaction. If this were not the case and if the number
of reserved sites were limited. all the sites would constantly be occupied
and zero order of reaction would be observed for hydrogen. However, a mass
transfer limit could also skew the conclusions as to the hydrogen reactant's
participation mechanism.

2.3.3.6 OVerall Kinetic Behavior of Groups of Compounds

The petroleum feeds entering the main refining units (catalytic reforming, cat-
alytic cracking, hydrocrackmg, visbreaking, coking, etc.) are made up of a
great many components. Many of them are reactive, either independently or
associated, and the primary products themselves are often reactive.
Processing as a whole therefore involves thousands of reactants, thousands of
elementary reactions and thousands of products. It is seldom possible, except
in the case of light cuts, to identify the different components. Even more so, it
is almost impossible to describe the behavior of each of them and the reaction
procedure quickly becomes inextricable. Consequently, the reaction process
usually needs to be simplified by grouping families of compounds together, or I
lumping. Lumping has long been the subject of in-depth study and seminars
have been devoted to the topic [6J. After analyzing the various papers pub-
lished to date (1994), we have been able to distinguish three trends, repre-
sented by three different categories of researchers.
Q. The Theorists
Using specified synthetic feeds (defined by discrete or continuous values for
properties) and a pre-established reaction procedure with aU the values of
kinetic parameters (discrete or continuous), these researchers have attempted
to determine the most appropriate groups by calculation according to feed
composition and process operating conditions [1-5,9, 12,13,14,16,21,23,25,
26,27,43}. .

b. The Practitioners
Faced with industrial constraints in managing processes, these researchers
have constructed models. They were initially rudimentary with a few carefully
selected groups and designed to find adequate tools to run and optimize oper-
ations. As they have been utilized with time, the models have become more
complicated and the number of groups has increased, particularly in order to
account for.the properties of the products obtained [18, 21, 42}.
c. The Visionaries
Under this heading we have placed researchers who, being informed of the
respective advances made by theorists and practitioners and having Identified
the difficulties of the task, have chosen a completely different approach. Based
 Clwpter 2. BASIC PRINCRES GO'.'ERf'/ING CHEMICAL CHANGES 45

on the fact that reaction procedures involve a limited number of elemental

steps and that these steps are governed by simple kinetic laws, they consider
that it will soon be possible to deal with the problems of processing complex
mixtures without resorting to lumping. This is currently valid for simple syn-
thetic feeds, but will naturally only really become feasible through -the con-
stant progress made in theoretical chemistry (understanding elemental mech-
anisms), in analytical chemistry (identifying individual compounds, both
reactants and products), and in applied mathematics. The growing power and
speed of computers will also help develop this approach [7, 10.41].
In the present state of the art, the three trends remain valid and substanti
ate each other.
As an example of the first approach, the research by Golikeri and Luss [14 J
can be mentioned among a host of others. They demonstrate that, for a set of
first order, parallel, independent reactions with different kinetic constants and
activation energies, the overall activation energy observed depends on the
conversion and the temperature. For low conversion, the overall activation
energy is close to that of rapid reactions, whereas for high conversion, it is
close to that of slow ones {38, 39]. Their demonstration illustrates precisely
the risks in attempting to reconstruct reaction processes by measuring the
activation energy.
I The second approach can be exemplified by the catalytic cracking model.
It was very rudimentary initially and included three groups of compounds
[42], but then gradually filled out and finally ended up as a model involving
eleven groups [18]. The same holds true for the catalytic reforming model {30].
Several authors have noted an important fact: it is not necessary to define a
large number of groups in order to describe the kinetic behavior of a change.
whereas a lot of groups are required to predict product properties {22].
Accordingly, although it would be quite possible to lump n-paraffins and
isoparaffins together in a catalytic reforming kinetic system, it is preferable to
dissociate them since the octane number of each of their end products is too
different.
The third trend can be illustrated by the research on hydrocracking of n-
paraffins on a dual-tunction catalyst [35]. After identifying the different ele-
mental reactions possible for the carbocations and breaking them down into
single events via the activated complex theory, the kinetic constants were esti-
mated and the results of the virtually complete model were compared suc-
cessfully with experimental results.
A successful lumping operation carried out on a given type of reactor (e.g,
batch or CSTR) can hold some surprises when an attempt is made to imple-
ment it on a different type (e.g, plug flow reactor). This shows the impact of
extra-kinetic mechanisms on the reaction process (diffusion. dispersion, mass
or heat transfer), which are sometimes difficult to circumvent given the
unknowns involved in tha intrinsic kinetics governing the procedure [8].
As a concrete illustration of the lumping problem. we will examine a typical
situation that experimenters might come up against. Table 2.2 gives a set of
results obtained in a pilot hydrodesulfurization unit. At fixed temperature and
hydrogen partial pressure PH" the desulfurization rate of a gas oil cut is mea-
sured versus the space velocity (hourly flow rate of gas oil at 15'C per catalytic
bed unit of volume). In actual fact. the variable PH.lspace velocity appears in
the table. This implicitly means that the reaction his been shown to be of first
order for hydrogen partial pressure and that there is no problem of hydrogen
diffusion limitation.

"HOS

o o
5 87.4
10 96.3
15 98.2
20' 98.8
,...---
Tabl. f-------'------------1
2.2 Results of hydrodesulfuri;;atiOtl tests.
PH,=40bar. T=36S'C

There are several ways of interpreting these results:

Consider all the sullur molecules as a single group. Under these condi-
tions, an apparent order can be observed for the sulfur element equal to
1.4,and the rate expression is written:
r= kSl.4 with k., 7.2 h- I
with:
r in kg of sullur eliminated per hour and per kg of catalyst
S In % wt of sulfur in the cut
-, Consider the whole system as being made up of at least two distinct
groups: one comprising molecules that are easy to desullurize (rnercap-
tans, sulfides, disulfides) and the other composed of more stubborn ones
(thiophenes).
The two groups are assumed to react independently:

rl = hiS. and rz = kzSz

The first group contains 95% of the total Initial sulfur and its rate con-
stant can be estimated at 24.1 h- I . The second one contains 5% of the
total initial sulfur and its rate constant can be assessed at 3.6 h-I . The
assumption would of course be reinforced U the results of feed analysis
could corroborate it.
 CMPlIIN 2. BASIC" PRtNCIPtES GOVERNING CHEMICAL Ow.GES 47

Consider more than two groups and attempt to introduce a greater

degree of sophistication - an effort that is, however, bound to fail
because there are not enough experimental results available, especially
for low conversion. This last comment is generally applicable. It is point-
less to try to construct an elaborate model if the results available, or
those expected to be available at the outcome of an experimental pro-
gram of reasonable duration and cost, are insufficient in quantity, accu-
racy or variety.

2.3.4 Classifying Chemical Reactors

The chemical reactor, the enclosure where the chemical.change occurs, is the
heart of the chemical processing units found in oil fefineries, metallurgical
complexes as well as chemical and parachernical plants. Because of the diver-
sity in size and shape of the various reactors, it might seem pointless to try to
classify them. However, all of them have in common the fact that their function
is to carry out a chemical change. Consequently, by referring to the main char-
acteristics of a chemical reaction, it should be possible to define a number of
criteria that would serve as a basis for classification. In actual fact, no sys-
tematic analysis of how the reactors work can be performed until they have
b'een classified into a number of properly characterized types that industrial
reactors can be identified with.
First of all, we will examine the classification criterion involving the nature
of the phases present. A primary distinction will be made between the follow-
ing:
One-phase systems: gas or liquid
Two-phase systems: gas-liquid, liquid-liquid, liquid-solid (whether cat-
alytic or not), gas-solid (whether catalytic or oot)._
Three-phase systems: gas-liquid-solid (whether catalytic or not).
The second classification criterion will be laid down to a certain extent by
the practical requirements of operating the chemical process, for example dls-
continuous or continuous operation. The fact that most processes imple-
mented in refining are continuous was pointed out earlier, so the focus will be
mainly on this type. However. what is termed semi-conttnuous operations
(continuous for part of the reactants or products. discontinuous for the rest)
are not uncommon. Some examples are regeneration of catalysts by in situ
combustion and production of petroleum coke.
The two operating modes mentioned above can be characterized in a dif-
ferent way. Systems operating discontinuously are said to be non-stationary,
while those operating continuously are termed stationary. An outside
observer will see the composition of the reaction environment change con-
stantly during a discontinuous operation, whereas a periodic snapshot of a
continuous reactor wiU not show any significant changes as time elapses.
In multi phase systems, it is not impossible to have a phase "imprisoned"
inside the reactor (Le. implemented discontinuously), while another phase
48 Chaor~ 2 B~sIC PRINCIPlES GOViiRNlNG CHEMiCAL C,...wGS

will be let into and out of the reactor continuously. This is the case for most
flxed bed catalytic reactors. A product may also accumulate gradually inside a
reactor, while the reactants and at least part of the products flowcontinuously.
This is the case for example for coking and hydrodemetaUization. Common
practice dictates that operations using a solid catalyst be considered as gen-
erally continuous processes and this can be seen in Table 2.3.
When continuous operations are examined more closely, two main types of
flow can be identified which give rise to two types of models. They were men-
tioned earlier with respect to the reaction rate: plug flow and stirred tank reac-
tors. Continuous plug-flow reactors or models quite close to them are very
common in relining operations. The two types of flow are widely dissimilar as
regards structure and will influence how a chemical change occurs inside the
reactor in Widelydiiferent ways.
The changes in a chemical species entering each model reactor can be
imagined. In a tubular plug-flow reactor, the chemical species will advance
along the tube at the same time as its environment and be gradually trans-
formed. Arguably, what is established is a continuous and decreasing concen-
tration profile of the reactant considered from the reactor inlet to the outlet.
This is why this type is sometimes called a concentration gradient reactor. In
contrast, the reactant entering a stirred tank reactor is suddenly thrust into an
environment whose composition is identical everywhere to that of the outgo-
ing stream. As a result, at the reactor inlet there is a concentration disconti-,
nuity in the incoming stream, whereas the concentrations of the various chem-
ical species are uniform in all of the reaction environment in the reactor. This
type is sometimes called a uniform concentration reactor.
An intermediate case between the two ideal models is the staged reactor,
made up of a series of stirred zones. Instead of a sudden concentration dis-
continuity at the reactor inlet, there will be a series of lesser discontinuities at
the inlet of each of the stirred zones. In practice, the vessels found in industry
will not exhibit all the characteristics of the ideal models, but to the extent
that they are sufficiently close, their operatlon will be analyzed on the basis of
the ideal model with added corrective terms if necessary.
A fourth classification criterion is important whenever a multiphase sys-
tern is involved: the direction of phase flow. The same as for separation appa-
ratuses (see Vol.2), there will be three possible types of phase flow:co-current
stream, counter-current and cross-current,
Another reaction characteristic will often have a determining influence on
the reactor-structure and outside appearance: the thermal effect, unavoidably
associated with any chemical change. Here again there are two extreme mod-
els: isothermal and adiabatic reactors. However, the wide diversity in thermal
exchange media does not allow for classification on the basis of this criterion.
Table 2.3 summarizes this discussion and presents a number of reactions
classified according to the criteria mentioned. Other classification criteria
could be contemplated, based for example on the severity of operating condi-
tions (temperature, pressure) or on the size-In fact, experience shows that the
classification in Table 2.3 is satisfactory in meeting the needs of designers and
 Operation mode
1---------
Phases present Continuous
Discontinuous
Tubular Staged Stirred tank
----~--

.. .... . ..
One-
phase
...
Gas

Liquid
--
... * Solution .. Steam cracking

Urea production .. Solution ...... Esteriflca'tlon

.....
polymerization polymerization
- --
-----~-- ..- ., ~

(lUll + IIqllld .... Fennentnrlon CO;!lind I-I~O ... .. Cyclohexane ..... Blologlcal treatment
..
ahsnrpnon IOWN oxidation atwater
.~-.----~-~---~--

LIquid + llquld Oleum ... Ester hydrolysis .... Emulsion .... Nitration
sutlonatlon polymerization of aromatics
Multi-
phase
-~._-

Fluids + solid
(c'al lysl)
....
of aromattcs
---
Hyclmw'natlons
willi Sllsp~!I\(I~\d
..
....
.. Fixed bed
Moving IlC!t1
.. Staged [luldlzed
Iwtl
.. .... Fluidized bed or
slllipcndc!c! cntnlyst
-----

Fluids + solid
reactants
...
cntalyst

Catalyst
regeneration
I
I
i

.. Moving bed
(blast furnace)
-
.. Calcination of ores ... Fluidized bed
combustion
'llY cllll\hulition
_.. ~._-_. ,--.- -+-
Indkllllon 01 how Ire(lllently eachtype of reactor Is found;
seldom or Vf!ry seldom Industrially; ** ouen fouud;
~-- -_
... ..
.... preferred.
'--
Tilillc
Z.l Classification of reactors (witll some typical examples of applicatiol/s (38, 39]),
users. who already know that there are numerous variations anyway. For oil
refining as such, the most common model is the multiphase, continuous, plug-
flow reactor with co-current fluids.

2.3.5 General Formulation of Mass and

Enthalpy Balances
2J.5.1 One-Phase Systems
First of all the relatively simple case of the reaction phase consisting of a sin-
gle fluid, gas or liquid, will be examined.
Given a volume element ~ VoC reaction phase, assumed to be homogeneous
in composition and temperature (~V is chosen as small as necessary so that
this condltlon is complied with). For any species A; contained in this volume
~ V, a molar mass balance can be written in the following form:

dn; = F- _ F: + L\VY v..r, {=1,5 j=I,R (2.44)

dt 'e'. -') )

~
'e. n., F,.
I,

~V

with:
n, amount of matter of species Ai (mol)
Fj molar flow rate of species Ai (mol/s)
AV volume element (m3)
r reaction rate (mol/(s.m3))
time (s)
e inlet
outlet
Ukewise, the overall enthalpy balance can be written:

da: nh-) -
- _ ' _ ' =IFh-IF-h/+qL\V
-
(2.45)
dt 'e 'e '. s

with:
Iimolar partial enthalpy (J/mo!)
q enthalpy transfer rate (from the outside to volume AV) (J/(s.ml))
Absolutely general for one-phase systems, expressions 2.44 and 2.45 are
obviously applicable to the ideal reactors defined previously, and this is pre-,
cisely their main advantage. The only condition is to clearly identify in each
case the extent of the aV domain for which the temperature and composition
can be considered homogeneous (Fig. 2.3).
I

l Figure
1.3
D

lQIwne parts taken as a basis for material balances in the various ideal
1mCtVr; /38, 391.

a. Discorrtinuolls or Batch Reactor (Fig. 2.3A)

Here, ll. V extends to the whole volume if it is sufficiently agitated and therefore
.lV,. V. Additionally, there is neither inlet nor outlet during the reaction so
0. =0. =o.
Expresstoa 2.44 is reduced to:
dn
dti =I vij1jV (2.46)

and expression 2.45 is reduced to:

,
d(~n;iiJ =qV (2.47)
dt
 0)':; Cha~:e~ 2 I;;Asrc t"RINCIPLES <iOVERNING GHEMIC,:'_ C.-;';NGS

b. Semi-Continuous Reactor (Fig. 2.3B)

Here, either Fi or F, is not equal to zero and can vary with time. This needs to
be taken into ~ccou~t. In contrast, .1V = V.
c. Continuous Stirred Tank Reactor (CSTR) in
Steady State Conditions (Fig. 2.3D)
Here. .1V can be extended to the whole volume (.1V == V). The term dnJdt
becomes zero when steady state operation is established and consequently
expression 2.44 becomes:
Fie - Fi. + I \'~"jl' = a (2.48)
and expression 2.45 becomes:
r F,)iie - r FiJii. + q V = 0 (2.49)

d. Continuous Plug Flow Reactor (pFR) (Fig. 2.3C)

Here, volume .1V is reduced to an infinitesimal element d V. The general equa-
tion applied to this volume element is therefore written:
dn.
df == (Fj)v- (fj)V+dF+ dVrVij'i

Under steady state conditions dn;/dt =0 and the result is therefore the
expression characteristic of this type of reactor: '
dF-
-
dV' =2:vr
I))
(2.50)

2:d(Fh.) =q
I ,
(2.51)
dV
A comment should be made about enthalpy balances, however. Although
the general expression is faultless, iLstili has the drawback of hiding tbe heat
of reaction. term MfR' Expression 2.51 is transformed so that the ~ terms
show up explicitly. We willdemonstrate how to proceed to this transformation
for a PFR reactor in steady state conditions:

d (FJiJ = dF, h. + dhi F

dV ev: dV 1

dfj d~'
dV =I.v ij dV

dh; _ dh; dT _ c. dT
dV - dT dV - P, dV

Finally;noting that L: vijhj == L~. the result is:

{
2: F-I C,. -
i dV
+LdT} {Mf.. -d~'}
J dV
- q =0 (2.52)
with:
Cp molar-heat capacity (J/(mol.K))
~ heat of reaction j O/(mol of reactant Ai'under consideration))
This form offers two advantages: the heat of reaction shows up and the
essential characteristics of isothermal and adiabatic reactors can be visual-
ized as well. For adiabatic reactors. q = 0 and the heat of reaction (produced.
or absorbed) causes heating (or cooling) of the reaction stream. For lsother-
mal reactors (dT/dV = 0), the heat of reaction must be offset by thermal
exchange with the system's environment (q 0). '*
General expressions 2.44 and 2.45 can not be used as is when only the mass
fractions of the elements or of the chemical families. and not the moles. are
accessible. They have to be transformed. The general mass balance ezpres-
sian becomes:

(2.53)

with:
PP density of the fluid (assumed to be constant) (kgfm3)
Q volume flow rate (m3{s)
w mass fraction (-)
rM; reaction rate for reactant Ai (kg/(s.m3)

The forms of expression showing MlR are preferred for writing mass
enthalpy balances. expressed this time in J/kg of reactant Ai' For a PFRreactor
this will give the following for example:
(2.54)

with:
Q volume flow rate (m3/s)
Xi conversion of reactant Ai (-)
Cp~( mean heat capacity of the reaction stream (J/(kg.K
MlR heat of reaction (J/kg of Ai)
V volume of reactor covered (m3)

~.3.5.2 Multiphase Systems

a_ Systenrs with a fluid and a Solid Catalyst
The reaction site is the catalyst surface. Catalyst surface area and mass are
proportional. The reaction rate is typically expressed in mol/(s.kg of catalyst)
and the general mass ba~ance equation becomes:

-d~ =F -F +.lM ~ vsr. (2--)

.;;10
dt '. I. - 'f J
.Mf being the mass of catalyst contained in .1I/...lollI ~ V could be called the
mass concentration of catalyst (kg/m3). If the catalyst grains are contiguous
and form a continuous bed, .1..\f' ~ V becomes the density of the bed Pc
There is no reason why the reaction rate' can not be expressed by unit of
catalyst surface area, of particle volume or of bed volume. However, to avoid
any confusion it seems preferable to express the rate in moltes.kg of catalyst)
or in kg/(s.kg of catalyst) if the molar entities are not accessible.

b. Systems Consisting of Two Fluids (Usually Gas and Liquid)

and a Solid Catalyst
This case is very common in refining. Since the site of the reaction as such is
still the catalyst surface, the rate will be expressed once again in malt(s.kg of
catalyst) or in kg/(s.kg of catalyst). Usually the reactors will be' continuous
ones, and so it is expressi?n 2.50 that is applied in the form:

(2.56)

with:
rj in mol of reactant AJ(s.kg of catalyst)
F, in molar flow rate of the phase containing reactant A j (molls)
or:
(2.57)

with:
'M; in kg of Ai per s and per kg of catalyst
QF being the volume flow rate of the phase containing the reactant A j
under consideration
Expression 2.57 has already been used previously in the example of hydro-
denltrogenatlon of a petroleum cut (see Section 2.3.3.3). Any limitations on
gas-liquid, liquid-solid transfer and transfer limitations inside the catalytic
solid should of course be taken into account if need be (see Vol. 4).

c. System Consisting of Two Fluid Phases (LiquidLiquid or Gas-Liquid)

Generally speaking, the reaction is located in one of the phases, either inside
it, close to the interface or at the interface itself. One of the reactants is usu-
ally contained in the reaction phase and the co-reactant is in the other phase,
hence the critical importance of the co-reactant's transfer to the reaction
phase. The reaction rate is expressed as a transfer rate accelerated by the
chemical reaction. The resulting equations are then similar to transfer equa-
tlons, p'rovided that an acceleration factor is introduced, whose vaJue is
directly related to the rate specific to the chemical reaction itself.
A discussion of the different cases is beyond the scope of this chapter (see
Vol. 4). Let us simply mention that if the reaction is located inside one of the
phases, it will be advantageous to increase this phase to a maximum in the reac-
tor. In contrast. if the reaction is located near the interface. the interfacial area
per reactor unit of volume should be maximized by any appropriate means.

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2 Aris R.. Gavalas G.R. (1966) On the theory of reactions in continuous mix-
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 Philippe Courty

Industrial catalysts are at the heart of refining processes and determine the
way they will evolve in the future [1, 2]. Catalytic processes are developing
Increasingly at the expense of thermal ones and the discovery of new catalysts
spurs the development of new processes.
, Rich in carbon and hydrogen, crude oils naturally contain numerous impu-
rities: heteroatoms, sulfur, oXygen. metals (traces) such as vanadium, nickel
and sometimes arsenic. Crude oils are made up of a number of individual com-
pounds: paraffins. aromatics, cydoparaffins, heterocyclic structures whose
molecular weight varies from 16 to several thousand (asphaltenes).1n contrast
with the extreme diversity of crude oils and their components, there are the
increasingly stringent s pecifications on refinery products, the constant change
in world demand and the constraints on discharge combined with environ-
mental issues.

3-1 The Place of Catalytic Processes in Refining

The first refineries were based on physical fractionation processes (Fig. 3.1).
The first catalytic unit came into operation around 1927 (hydrogenation) and
was then followed by catalytic cracking processes (Houdry, 1937). aliphatic
aIL-ylation, hydrotreating and finaDy catalytic reforming (platformmg, UOP.
1950). At that time, world refined oil product consumption was less than
0.6 billion tons per year. Consumption.quickly quintupled and reached 3 billlon
tons per year (1992). At the same time. the refining industry's energy require-
ments grew tremendously. Today the worldwide cost of refining catalysts is
about 1.7 billion per year, l.e. less than 0.5% of the value of refined products.
Table 3.1 shows the breakdown in terms of tons and corresponding costs.
From the standpoint of value. reiiDing catalysts account for 33% of the world
market. coming just after environmental protection catalysts (40%).
 Etherification
A-

1.0
Reforming

Hydrotreating
O.B
0
OJ
~ ~ Catalytic
-g .s 0.6 cracking
U ~
"0
"0
<:l 2
o
.!:
~ "0
a: .s 0.4
Q

Qj
ex: Batch
distillation
'0.2

1850 1900
r 19~ 2000

Catalytic processes
emerge: 19351940

IF~,re I
Historical overview of refining catalysts.
LJ
Processes t/year 106 IT/year
1. Solid catalysis
# Catalytic cracking . 440000 5500
Hydrotreatlng 80000 2800
Sulfur production (Claus) 20000 200
Hydrocracking 8000 600
Reforming 5000 450"
Isomerization 1000 150
Other processes 12000 200
Subtotal 566 000 9900
2. Uquid catalysis
(lnorganlc acids) 2000000 800
3. Grand total 2566000 10700
Not including the cost of recoverable precious metals.
.....r - -
Table
3.1 World refining catalyst market (IF?, 1994).
.....-..-
 The refining industry's requirements are constantly evolving: more and
more petroleum is processed into high added value products: motor fuels,
petrochemical feedstocks and lubricants. The tranSportation industry is a
driving force behind this development (reformulatiOIl of gasollnes, kerosenes
and diesel oils), which has become possible because of the regular progress in
processes and catalysts. The changing speclflcatlons o~ motor fuels (gasoline
and diesel oil) and on heavy fuel oil bear witness to thls fact (Table 3.2). The
same constraints exist and will be more and more preValent for other fuel prod-
ucts, In the area of processes and catalysts. requirements involve (fable 3.3):

hydrofining processes;
catalytic processes to convert the bottom of the barrel;
processes to upgrade FCC, refonning and hydrocracking products.
Further needs also include:
Lower process operating costs and investmellts (especially for hydroc-
racking and residue hydroconversion processes) along with improve-
ment on present time performance (for example ill hydrocracking middle
distillate selectivity).

Current Possible delleJo p me n t 2006-2020

situation
19961998 Europe IUnited States" California

Premium gasoline
RON(clear) 94-98 95-98
i
MON (clear) 85-88 85-88
.1
Benzene (% vol)
Aromatics (% vol)
2-5
30-50
s1
20-30
!. - . -0.95
24
-or.;; 1
or.;; 25
OIefins (~{, vol) 10-30 9.2 =s;6
5-10 1.' 185 ,.. 40
Sulfur (ppm) 50-100 3D-50
Oxygen C:' wt) I < 2.8 between
2.1 1.8-2.1
2.1 and LH
Diesel oil 1

Sulfur (ppm) 450-500 3D-50

Cetane number 49-51 53
Polyaromatics (% vol) 9-11 210
Heavy fuel oil
Sulfur (% wt) 2-4 0.5-1
Nitrogen (% wt) i 0.5-0.; , 0.3-0.5
Except for California.
L:
limit
__ defined bv drivabilitv.
J-

- --------
..--.....
Table
3.2 ; The changing quality of motor fuels and heacy fuel oil.
 Objective Processes Involved Aims
I I
Purify feeds and pro-I Hydrorefining ilmprpved sulfur. nitrogen. metals
ducts i and asphaItenes elimination yield

Convert the bottom

of the barrel
Hydroconverslon of
vacuum resids, then
I More active and selective catalysts
with lower production costs
FCCor hydrocrack-
ing !
Upgrade product Catalytic reforming Increased MON. RON, cetane num-
Quality (gasolines. ber, and hydrogen yield
diesel 011) FCC Decreased benzene. sulfur, nitro-
gen and aromatics contents
Reduce investments All existing proces- Reduced operating pressure
and operating costs ses.-mainl)' resid hy- Increased activity, selectivity and
droconversion and lifetime for catalysts
hydrocracking
Improve existing pro- FCC and downstream New decyclization catalysts for
cesses processes naphthenes and naphtbeno-aro-
mattes (production of isoparaffins
and of mono alkylnaphthenes)

Control emissions
Aliphatic aU.;ylation
Claus process
New solid catalysts
Improved sulfur recovery and
higher SOx and NOs conversion
.
Decrease discharges Purification of efflu-
ents and of FCCand Decreased particulate emissions
thermal power sta-
non flue gases
Produce hydrogen Partial oxidation Reduced soot formation
of resids
Steam reforming of Lower temperature
gases (CH~, LPG) Improved Hzselectivity
Table
3.3 Uses of retining catalvsts.

New processes and/or innovative catalysts: for example the development

of new naphthene decyciization processes to produce isoparaffins from
the hydrocracking gasoline cut or high-cetane diesel fuels from FCC
LCO's. A solid catalyst with superadd properties for aliphatic alkylation
would be appreciated to replace conventional inorganic catalysts (H~04'
HF, etc.). .
~ More eHicient emission control (SOX' N0X' particulates) and reduced dis-
charges (retreating of spent catalysts, water pollution control).
11 Improved hydrogen production.
 C1wptar3. INDUSTRIAL CATALl'STS 63

This list takes future needs into account. With investment costs having
quadrupled with reference to 1970 costs, refinery energy consumption that
could reach 13%and quintupled production costs, the refinery of the 21st cen-
tury will require high-performance non-polluting processes based on innova-
tive catalysts. The general objective is and will remain to produce quality
products at the lowest cost by means of technologies and processes with min-
imum emissions and discharges.

3.2 Classifying Catalysts

3.2.1 Active Elements, Promoters
The available body of catalyst classifications can be broken down into two
groups: empirical based on acquired experience and scientific based on
explicative correlations I.
An example of empirical classification is given in Table 3.4. It distinguishes
on the one hand the active elements causing homolytic or radical activation
(metals, sulfide or oxide semi-conductors). On the other hand there are the
active elements responsible for heterolytic (or ionic) activation of hydrocar-
bons (insulating oxides). Families of reactions correspond to these different
'types of solids.
Other more specific empirical classifications are available for families of
refining reactions. For example. the.hydrogenating activity ofmetals, sulfides
and oxides bas been classified according to the target type of hydrogenation
reaction (e.g. hydrogenation of aromatics, polyaromatics, alkylaromatics,
oleflns, oxygenated compounds. etc.) or even the type of unsaturated bond
under consideration. Similar correlations exist in acid catalysis.
Explicative correlations, the basis for scientllic classifications, are gener-
ally fewer ill number. They relate catalytic properties of the active elements
alone or associated with the intrinsic properties of the active solid, or with the
interaction properties that the solid exhibits with the reaction medium. espe-
cially with the properties characterizing adsorption and desorption, which are
fundamental in heterogeneous catalysis.
As an example. the "d" type fraction (%) of the metal bond and the average
interatomic distance (exposed faces) of metals have been related to their
intrinsic catalytic properties (for instance in hydrogenation). Another example
involves adsorption properties. Usually the more exothermic the adsorption
of a reactant (I.e. the more negative the adsorption enthalpy), the more stable
the adsorbed complex and the weaker the catalytic activity [3]. Thus the reac-
tion rate usually decreases with the adsorption enthalpy of the most adsorbed

1. They invoh~ the active el~ments .actlve phases) of catalysts. whether hyperdispersed
mono or multimetalJic aggregates on a support. or oxide. sulfide active phases or even the
association of these different phases.
 64 Chatll~ 3 INDUSTRIAL CATALYSTS

Reaction families Examples r

Product class
Ii I
Metals' Hydrogenation
Dehydrogenation
Fe, Co, Ni
Ru,Rh,Pd
I
Homolytic activation of Hz. CO,
Nt, hydrocarbons, heteromo-
lecules
Hydrogenolysls
Oxidation
} Ir, Pt
Cu.Ag
R-C -/.H
R-C ./. C-R' NH3 synthesis 1 Fe

Sulfide and oxide semi-conduetors I Oxidation

The same homolytic activation Reduction CuO. ZnO. Cr203
as with metals ! Hydrogenation
(heterolytic activation is possible
in some cases)
Dehydrogenation
Cyclization
) V20S ' MoO)
Fe203' CoO. NiO

MoSz WSz
Desulfurizatlcn
Denitrogenation } COg$s, Ni3SZ
RuSz

Acid and insulating oxides Hydration Acid zeolites

Heterolytic activation Dehydration
R-C +-;-C-R'
Mechanism by carbonium or
Isomerization
Oligomerization
} SiOz-AI:P3
A1 z0 3 (+ CI or F)
H3P04' H~04 J
carbenium ion
Alkylation ~ HzS0 4 HF, AJCI 3
Cracking -+ SiOZ/AlZ03
Acid zeolites
,-r---
Table
3.4 Example ofsolid catalyst classification.
0....-..-

reactant or with that of a simpler molecule that exhibits a functional analogy

with it.
In the absence of data on adsorption enthalpy. the formation enthalpy of
the sulfide or oxide has been correlated to their catalytic properties. For exam-
ple inhydrotreating petroleum feeds (Fig. 3.2). the classification resulting from
empirical correlations is roughly the same. The sulfides associating Mo and W
with Co and Ni as well as ruthenium sulfide are in fact the most active
hydrotreating catalysts.
The last example involves acid catalysis (catalytic cracking, isomerization.
alkylation, etc.) where the essentially heterolytic hydrocarbon activation step
forms carboionic species. By analogy with catalysis by complexes. the prop-
erty taken into account is basically acidity, characterized in terms of site den-
si ty or strength.
Active phase catalytic properties can be radically modified by adding pro-
. meters, sometimes only as traces. For example in hydrorefining, molybde-
 ~ 3. INOUSTRJAL CATALYSTS 65

num's catalytic activity is enhanced by adding Ni or Co (Fig. 3.3). Ukewise in

selective hydrogenation on palladium, the adsorption properties of unsatu-
rated molecules are fundamentally changed by a .very small proportion of IB
metals: the activity, selectivity and stability of the corresponding catalysts are
highly improved.

109
80 CoNI
NilMo
60
ColMa
en 40
............
N
x Au
E
;n-
o
x 20
'C
.!!!
Q)
:>
c:
0
o
- 10
m
Q 0.8
'0
en
CP 0.6
'3
(,)
CP
0 0.4
~

0.2

Ti

100 200 300 400

liH' formation (kJ/mol metal)

figure:
3.1 Hydrodesulfurization ofdibenzothiophene at40frC HDS activity per m J ofsin-
gle and double sulfides of transition metals rersus the fonnation enthalpy of
the corresponding sulfides (-If.
Activity cersus Ihe acerage formation enthalpy of the nco sulfides under
considenuion.
Actiuity cersus the enthalpy of the binary sulfide.
c JleaslJTel7fenton a CoJlo catalyst.
 A

A
qa

~
a .0

...
.

'0
E

0..
.9
ro
Ci;
0.
i!:-
:2u
0:(

Mo~\> = constant

Promoter content (arbitrary units)

"j A
8 s:
I
ro 0.8
"0 Mo% = constanl
..

0 0.6

:E
'0
E
a 0.4
ro
z-
Q;
a.
0.2

:2 .+
u
0:(

0
0.2 0.4 0.6 0.8 1 1.2
Atomic ratio NVMo at.

Hydrotreating active phases (NiMoS). DecomJing the small particles of MoS~

with a promoter (Ni. Co. etc.) considerably increases the activity referred to
the Ma sites. A. Simulation of the activity ooriation. a: activity of a Mo site.
qa: promotion (actor; activity of a promoted site. B. Experimental results
(hydrogenation ot toluene 6 MPa. 3S0"C. space velocity 2 n:') {8]. =
 ~ 3. fMJUSTRIAL C4TAt.l'ST.S 67

3.1.2 Main Types of Refining Catalysts

The active phases of refining catalysts are seldom of the bulk type, and are
usually dispersed on an oxide support. Organometallic complexes should also
be mentioned.
Bulk catalysts are exclusively made up of the active phase. 1bis is the case
for Claus catalysts (transition alumina and/or titanium oxide), for heteroge-
neous oligomerization catalysts (solid H3P0 4 silica-alumina, zeolites) and for
the supports of some bifunctional catalysts, which are genuine co-catalysts. (t
is also the case for the chlorinated y or 11 alurninas used as supports for light
paraffin isomerization or reforming catalysts.
Supported catalysts constst of an active phase dispersed under control ~
on a previously shaped oxide support. This is the case lor example of catalytic
reforming catalysts made up of approximately 0.5% platinum and a promoter
dispersed on a chlorinated '( alumina support. In contrast to bulk catalysts, the
use of a pre-shaped oxide support allows control of its genesis and especially .
the optimization of its textural, structural, mechanical and morphological
properties.
A third category of catalysts are those resulting from a unit operation com-
bining shaping (see Section 3.4.2.1) and the addition of an active phase or pre-
cursor salts. This category can also include co-mixed hydrorefiniog catalysts,
catalytic cracking catalysts - genuine "composites" obtained after spray dry-
ing - and some heterogeneous catalysts obtained by oil-forming of a mixture
of zeolite and alumina hydrogel.
"Homogeneous" catalysts are produced from organometallic complexes
interacting with an appropriate solvent medium. They are added in trace
amounts in the reaction medium. They are used especially in light olefin .
oligomerization for motor fuel production, in gasoline and kerosene sweeten-
ing and In the finishing treatment for Claus reaction effluents. .
Table 3.5 summarizes the main active phases of refining catalysts. Except
for liquid acids for aliphatic alkylation. these catalysts are complex liquids or
solids whose preparation is discussed in detail in Section 3.4.

3.3 Catalyst Characteristics and Properties.

The economics of catalytic processes in refining are highly dependent on cat-
alysts properties and more specifically on their characteristics. 1be user. the
process licensor and the catalyst manufacturer attach a great deal of impor-
tance to monitoring them. The licensor and the manufacturer endeavor to
ensure their reproducibility by accomplished quality control of preparation
and skilled characterization techniques.

2. :\Ia'dmum dispersion. i.e. maximum accessibility to active atoms. is not always a desir-
able property. Example: selective hydrogenations.
.~
Precesses
Melnls Sulfides Oxides
Acid solids
Zeoliles
Inorganic
acids Complexes
Acid
resins en
co
~-~-----~ --~~ -._~-- -- -
Reforming PI,He, lr, 511 Chlorinated alumina, KL zeolite
._---- ----- 9
Iscmertzatlon Pt ZrOrSO~-- Chlorinated alumina. zeolites r;
Calalytlc crackilll:: La 2OJ Cc0 2 USY, ZSM5
f-- ------ --- _,._. ___ T
~
<.,
-- --- ~
Alkylalloll ? H250_1 (j

Oligolllcrizat ion Silica-alumina II ZSM5

IIF
~-

11:11'0.\
~~ . "---.'---
Nmi),,\1 EI:1
--~~
~_._. __ .
I:
III
:11
i~
C)
H mordenlte AICI:I _ x Etx }.
.--
Etherification Sulfonaled resin 11
~-

~
Hydrocraclclng

Ilydroconverslon
Pt, PIPd NiMoSx
NiWSx
NIMoSx
Alumina
slllca-alumina
Alumina
USY
SAPO
(V zeolite)
.- --_._ ..
L _ _ _ _ _ _ _ _ _
_.- ---_.-~----..........-..-'-'

-- ~~-_ .. _-_.~-~
....

Ilydrollen production NI, cu Cr,AI Alumina

Rh or magnesia
- .. _..-.
Sweetening Na,K Alumino- Cn Ilhthnillcynnillc
silicates lIlI charcoal
---_...-
Hydrotreatlng
(NI M.}
CoW S
Alumina
silica
(V zeolite)

Fe
Acid gas treatment,s Alumino Complexcd I It.
silica lind/or 1\ It. metals
Ti0 2 Ironcomplexes _~ _ _ _ _ . o __

These active phases can also contain 1~\IIl.melallh! elements III small proportions which have a promoter ellcel.
Thelollowing can be mentioned among others: Group lllboron, IV silicon, Vphosphorus, VI sullur, Vllllluorlnc, chlorine,
It Alkyl or alkoxy.
~
3.3.1 Basic Catalyst Characteristics:
Three basic features characteriZe the catalyst's action: activity, selectivity and
stability (Table 3.6).

..

Properties Definition

Activity The catalyst's capacity to activate the transformation of a feed

into products. It is expressed in:
kgof reactant converted per kg(or liter) of catalyst per hour
% of reactant converted
rnol-g 01reactant transformed per g of ca!alyst per second
mol-gof reactant transformed per m2 of catalyst per second
molecules of reactants transformed per site per second

Selectivity The catalyst's capacity to activate the transformation toward

the required product among all the possible ones
It is expressed in per cent with respect to the reactant fraction
converted (or products formed)

,Stability This is expressed by the period (minutes, hours. months, years)

during which the catalyst retains the specified activity and/or
W- I target selectivity
I Table
Basiccatalystproperties{5].
IL3.6-

Catalyst activity expresses reactant transformation rate under given oper-

ating conditions in several different ways. Good activity means a high reaction
rate with two possible advantages: either a small amount of catalyst can be
used or operating conditions can be less severe. especially the operating tem-
perature which can be relatively low.
Catalyst selectivity characterizes the aptitude to activate reactant trans-
formation towards the required product among all those that could be formed.
High selectivity allows a good yield of the required product to be achieved and
reduces side reactions to a minimum.
Catalyst stability is defined by the period during which its activity and
selectivity remain unchanged. In actual fact. these properties change to a
greater or lesser extent with time. The causes of catalyst deactivation will be
dealt with in Section 3.5.1.

3.3.2 Intrinsic Char;1cteristics

Activity, selectivity and stability are the result of two main types of intrinsic
characteristics.
 Struc~ properties: the quality of sites dispersed on the active surface.
which gove(IlS catalysis as such, is determined by the characteristics of the
accessible active phase (structure, local chemical composition, defects).
These chafj;1.cteristics in tum determine the intrinsic characteristics of the
accessible ,ites (nature. strength. density. stability. etc.).
Textural properties: these properties govern the possibility of reactant
access (by diffusion) to the above-mentioned sites as well as the possibility of
evacuating the reaction products outside by diffusion. Catalyst texture is
determined by the total specific surface area. the active specific surface area
(expressed in per cent of accessibility for dispersed metals), the accessible
pore volu[11e, and the interconnectivity of the pore network. Figure 3.4 shows
and quantifies the relationships between porosity range and particle size.

~
~
Micfopores Mesopores Macropores

2nm 100 nm 5 000 nm

: Particle : Micrograin : Catalyst
I (rnicrocrystallile, I (assembly I grain
: molecular : of elementary : d p > 5,000 nm
: aggregate) I particles) I (assembly
I \ : of micrograins)
: 1.5 < dp <50 nrn : 100< d p<5000nm: 0.005< d p< 10mm
I I I
I I I
I I I
,..icropores: Mesopores : - Macropores :
0< 2 nm : 2<0< 50nm : 0> SOnrn :
I I I

.----
0.1 2
I
I I
10
I
II
50100
I
1000
I
I

10000
I
nm
(1 A) (1 J.lrn)

l.- Figure
3.4 Make up of a catalyst groin: relationship between particle size and porosity
range (IUPAC definition).

3.3.3 Non.Catalytic Characteristics

Here the subject is basically the morphology of the catalyst. along with its
mechanical and thermal properties.
 The external morphological features - shape and granulometry :..... are dic-
tated by the technology of the process where it is used. A spherical shape is
recommended for entrained or ebullatlng fluid beds. whereas in a fixed bed,
extrudates, beads orpellets, or particular shapes (rings, monoUths)are used
when a minimum pressure drop is required. .
Mechanical properties: During its lifetimethe catalyst is exposed to a num-
ber of different mechanical constraints (production, transportation, storage,
loading into the reactor, unit start up and shut down which cause settling, uti-
lization in the unit, unloading, off site regeneration, reloading, etc.) with the
resulting breakage, abrasion and attrition. Actual use in the unit is sometimes
a critical period. especially when the catalyst circulates. Resistance to
mechanical degradation is therefore an important property and should be
monitored. -
Thermal properties: When reactions are highly endo- or exothermic, good
thermal conductivity allows temperature gradients to be limited in the catalyst
grain and bed, thereby promoting the heat transfer. U the catalyst is to func-
tion as a heat carrier (in catalytic cracking for example) it should have maxi-
mum heat capacity: the heat energy stored during coke combustion will be
returned. during the reaction, thereby offsetting its endothermicity.

3.3.4 Determining Basic Catalytic Properties

When the reaction rate expression is already known, activity is characterized
by the overall rate constant and selectivity by the ratio between two rate con-
stants [3]. Allthese constants, along with the stability study, are determined
in a micropilot under conditions as close as possible to industrial practice.
The feeds used can be either model molecules or industrial feeds.
Performance can be determined:
In a discontinuous system such as a "Grignard"type apparatus operating
at constant pressure (open reactors) or at variable pressure (closed reac-
tors) by depletion of a reactant (Rg. 3.5). This equipment is particularly
. suited to the kinetic analysis of the chemical transformation and can
quickly help to determine the influence of contact time.
Continuously in fixed bed reactors with a concentration gradient. either
of the rnicropilot type (l to 2 g of catalyst) or of the pilot type (10 to 100 g
of catalyst).
Such equipment (Fig.3.6) gives indications on performance stability versus
time and allows a quick study of the influence of the main operating parame-
ters (temperature, pressure, space velocity (GHSV or UfSV). nature of the
feed, etc.).
This simplified presentation mainly involves screening tests between dif-
ferent catalytic formulas and summarizes the acres to Taw kinetic data. It is
evidently necessary at this stage to operate on micrograins of catalyst and to
select the appropriate operating conditions to achieve the chemical reaction
state. exclusive of extra- or intragranular diffusional limitations [3J.
72 CI>aDlrJ INDUSTRIAL CATALYSTS

3 4 3

Figure

IU Simplified flow scheme of an open reaction system lor liquid phase

hydrotreating.
1. Calibrated hydrogen storage. 2. Downstream pressure regulator. 3. Pressure
indicator. 4. Pressure sensor. 5. Autoclave (200 bar). 6. Thermocouples.
7. External heating. 8. Hydrogen input. 9. Sampling system. 10. Stirring'
mechanism.
This type of equipment is used to study the chemical kinetics of liquid phase
reactions.

Whatever the test equipment under consideration, test results must be val-
idated on the basis of mass balances adjusted over the reactor. Carbon. hydro-
gen, sulfur etc. balances supplement the mass balance and make the results
easier to express.
Following this first step, the catalyst's industrial performance needs to be
defined under test conditions representative of the industrial process. This
means that the following points have to be taken into account:
mass and heat transfers,
) flow hydrodynamics of the reaction phase(s) in the catalytic bed,
testing with feeds representative of those used in the industrial unit's
operation.
These tests are generally carried out in large pilot plants containing one to -
25 liters of catalyst. They usually operate by partial conversion with the
untransformed reactants recycled to the reactor so as to better represent an
industrial unit.
 Gas feed Reaction zone Tank
(Iurnace-reactor)

~J1
H;.!

.n. N;.!
Flowralc
control

F rl
-. - ~

I-I
-_.Q i

!ol

f
Liquid leed Feed pump Liquid-gas
separation ~
~
~
~
--1 Fi~lIro: r-
~.(lt\ How sclunne of" cuuilys: I('.~I pilot (cutatest) running On
ii1
Slide of a catalyst test pilot running on
1/ C{ll/lillllll//); basi. a continuous basis. (j
 \\ben the catalyst is being developed, this body of information is of course
Indispensable. However, determining catalytic properties must also include
characterizing appropriate physicochemical and mechanical properties. The
objective is to identify any potential defect in the catalyst and eventually get
the appropriate activity-property correlations so as to control catalyst prop-
erties.

3.3.5 Physicochemical Properties

3.3.5.1 Texrural Properties and their Determination [3]
Whatever the catalyst genesis, the catalyst particle is made up of an assembly
of micrograms which in tum consist of interlocking elementary particles
(rnlcrocrystallltes, molecular aggregates). The micrograins and elementary
particles compose the rigid architecture of the grain's pore network where
macro-, meso- and micropores can be distinguished (Fig. 3.4).
The maln textural properties measured are the specific surface area (in m2
per g" of catalyst), the pore distribution and specific pore volume (tncm'' per g
~~~YS~ ,
In specific area, a distinction must be made between:
the total surface area, measurable by a non-selective physical adsorption
technique and
the accessible active surfac.e area (metals, sulfides), measured by a selec- ,
tive chemical adsorption technique, and if necessary followed by back
titration of active sites.
Q. Overall Specific Area

The most common method is the BET (Brunauer, Emmet, Teller) based on
physical adsorption of an inert gas (N2' Kr) at constant temperature, close to
the adsorbate's liquefaction temperature. The measurement principle is to
identify the p!Po ratio (Fig. 3.7) corresponding to the formation of a single
layer, to deduce the adsorbed volume Vm froll'l the linear transform and finally
to divide it by the molecular volume VM of the adsorbate.
This will give: S= o-,Vm/V:\IS
with:
0- the area of the adsorbed molecule (16.2 A2 for N2)
X Avogadro's number
b. Accessible Active Surface Area
The bonds involved in chemical adsorption are much stronger than for physi-
cal adsorption. The chemical adsorption isotherms are of the Langmuir type 3.

3. The adsorption isotherm expresses the variation in the coverage rate or the surface ver-
sus PIP. The Langmuir isotherm corresponds to a homogeneous surface whose adsorp-
tion properties do not vary with the coverage ratio.
 Chspter J. IM:JusTRIAL CAWYSTS .- 7S

A
Area of an adsorbed moleculea

Vm : volume adsorbed 10form a single layer of gas with a molecularvolume V..

S=ax v..x,.'((a=162 A fornitrogenatnK)

V..

number of moletUes making up the single layer

B c
Adsorption isollerm Linear transform
-_P_- (g.cm- 3 )
V(Po- F?

~r
PIPa PIPo
L----l...-.-----'-_...1.....--.L-_
0.35 o 0.2 0.4

The horizontal plateau corresponds to the single layer of adsorbate, which is

used to calculate V.. (adsorbed volume). The stoichiometry n of the
chemisorption reaction being known (number of metallic atoms required to
chemisorb a molecule of adsorbate), the accessible number of surface atoms
s
.v is deduced:
Vm
Ns = -nA
v:\!

Then. with the surljace area Sa of a metal atom (calculated by taking into
account the relative density oi the exposed crystallographic faces):
Sm = ;'VsS",
76 Cna::l~r 3. INDVSTRIAL CAT':'LYS:'$

B (+) Millivolts

500
135
400
120

105 350

300
90

75 250

200
60

45 150

30
-I 100

15 ~iJ 50

o
o 20 40 60 80 100 120 140 160 180 200 minutes

Total area 1.477512 107 Vol. ads. (em3) ;; 7.53 PE. (g);; 1.0062
Area of standard peak .. 290 800 Vol. ads. cm'fg :: 7.482 =
VB (cm3) 0.5306
Calcination, sulfurization. activation.chemisorption of oxygenon a CoMo catalyst

Figure
3.8 X Sorb chemisorption apparatus (A) and dynamic oxygen chemisorption on a
Procatalyse HR 306 sulfide 'catalyst (B). Based on a dynamic adsorption tech-
nique with katharometric detection. the multifunctional apparatus is used to
study the solid-adsorbate interactions. In addition to oxidations or reductions
under programmed temperature and thermodesorptions of various gases, the
apparatus can be used to determine the accessible active surface area by
dynamic chemisorption (Hz. OJ).
 These two parameters - overall specific area and accessible active surface
area - can be determined by a static (volumetric) adsorption procedure or by
a dynamic procedure with katharometric detection. Figure 3.8 describes an
industrial chemisorption apparatus ex
Sorb) and the measurement of the
accessible active surface area for an industrial sulfide catalyst by dynamic
oxygen chemisorption.

c. Measuring Pore DiMribution

By nitrogen adsorption. The nitrogen adsorption isotherm (at -183C) is
used to determine pore size distribution with the Kelvin relation [4J.
By mercury porosimetry: a technique based on the Washburn Jurin equa-
tion that states that any non-wetting liquid can penetrate in the pores of
porous materials by means of a pressure P exerted on the liquid: -
2ycos e
rp = --p--
with:
r p pore radius
y surface tension
e meniscus junction angle (140' for Hg)
Given the values of T and 8:

0.75 X 104 p:= 2 000 bar r=3.75 om

r. ( nm) =~---
P P (bar) P =4000 bar r= 2.00 om

Mercury does not penetrate spontaneously into the pores of the solid and
the previous equation shows that an increasing pressure P fills increasingly
smaller pores of radius T, with a volume of mercury Vp (the solid was degassed
in a vacuum beforehand).
Figure 3.9 presents the cumulative pore distribution of a catalyst with
bimodal distribution. The photo in the figure (by transmission electron micro-
scope) shows the macropore structure. in this case called "chestnut husks",

d. Measurement of Totol Pore Volume

Mercury picnometry (carried out at atmospheric pressure in a porosimeter)
determines grain density dg by measuring the volume u' of mercury displaced
by a weight of solid p', The specific volume Vg of the grain is deduced (solid +
pores) in cm3.g- l The grain density is expressed by d'l = l/Vg
Helium picnornetry (bellum penetrates into all the accessible pores what-
ever their size) yields the specific volume Vs of the non-porous fraction of the
solid in cm3.g-1 by a similar reasoning process. The skeletal (or structural)
density of the solid is expressed by ds = Ih s. The total pore volume ~!Pt is by
definition:
78 CflBo:er 3. INCJSTFlIAL C';-";'.XS:::

100

90
j"
CI
80 Cumulative curve
"'E
0

g 70

(l)
c 60
:5
(5
> 50
i 40
Derivative curve

!!
.;:;
1!!
:) 30
E
:)
(J
20
30nm
10

10 103 1()4
Pore (iameter (nanometers)

IF~.eel
U Residue hydrotreating catalyst. Pore distribution curoes by mercury porosime-
try and description of the macropore sites by scanning electron microscope.
The catalyst tnesoporosity is centered on 30 nm (derived curve) and its macro-
pore network is delimited by a needle-shaped struclUre (chestnut husks, with
needles of 0.5 to 2 um). The large total pore 1J0lume (J.OScm7/g) (cumulative
curve) allows the catalytic act to go on despite /he coking process and the
deposition of asphaltenes and heavy metals.

3.3.5.2 Structural Properties [5, 6}

Catalyst structural characterization includes bulk properties and surface
properties.
a. Bulk Properties
Table 3.7 lists a number of techniques and presents lhe properties that they
determine. Once the catalyst composition has been defined by elementary
analysis, emission spectrometry or X-ray fluorescence, Xray diffraction
reveals the type of crystallized phases present and even
allows the average
size of elementary crystallites to be evaluated. The Castaing.microprobe anal-
ysis gives the dlstrtbution of elements in the grain. Scanning electron
microscopy gives valuable information on the morphology of the catalyst's
small particles and its microtexture (on a scale of 10om). Transmission elec-
tron microscopy and its associated techniques (X-ray spectroscopy, mlcrod-
iffraction) are used to define the composition of elementary crystallites and
their crystallographic structure (on a scale of 0.7 to 4 nm) by microanalysis.
Theother techniques mentioned are used in more specific cases. For example.
NMR of 29Si allows a good approximation of the SijAIratio to be determined in
the structure of some zeolites. .

1
Technique Property determined
I
Elementary analysis (qualitative and quantita- Bulk composition
nve) .
Emission spectrometry; X-ray fluorescence

X-ray diffraction Crystallized phases

Crystallite size
lectronic microscopy and associated tech- Morphology and size of elernen-
niques (X-rayspectroscopy. microdiffraction) tary particles; particle compost-
I tion and crystalline structure

Castatng microprobe Variation in composition inside

. the grain (on a scale of a square
, micron)
!
i Xuclear magnetic resonance Chemical environment of elements
j ~Iossbauer spectroscopy
!Infrared and ultraviolet spectroscopy Characterization of. existlng che-
\ EXt\FS (extended X-ray adsorption fine-struc- mlcal bonds
ture analysis) ". -
Programmed temperature reduction (oxlda- Identification of reduction steps
1 tion) (of oxidation) and measurement
of reduced (oxkfrzed) propor-
tions
. Combination of gas chromatography and mass
spectrometry (GCjMS)
I Analysis and characterization of
volatile elements

Table I
3.7 Ii Techniques used to determine "bulk" properties of catalysts (Excerpted
_ from (Sf).

b. Surface Properties
Table 3.8 lists some of the'techruques used to characterize the catalyst's sur-
face properties. Heterogeneous catalysis is a surface phenomenon. hence the
surface characterization is of prime importance. This explains why this
domain is currently developing fast [6J. Since no single technique can give a
80 c.~a:J:e, 3 INOUSTRIAL CATALYSTS

complete description of the active surface, several methods are usually com-
bined to get a significant characterization of its properties. Chemisorption of
probe molecules carried out close to reaction conditions (T, P), combined with
the characterization of slte-absorbate interactions by Fourier transformed
infrared spectroscopy have recently enabled progress to be made. In contrast.
surface characterization techniques using ultra high vacuum (e.g. XPS, UPS.
Auger) give results that are hard to correlate with the steady state of the cata-
lyst in the presence of reactants under the reaction operating conditions.

Technique : Property determiDefl

Auger spectroscopy
-
Photoelectron spectroscopy'(UPS, XPS) ICh~mical
tIes .
identity of surface spe-'

SIMS (secondary ion mass spectrometry) I Surface composition

Programmed temperature desorption I Chemicalid~ntity of adsorbed sur-

Flash desorption ; face species
Chemisorption and thermodesorption of bases ! Surface concentration and
(NH3 pyridine) ,
strength of acid sites

Chemisorption and thermodesorption of acid Surface

gases (COV
I concentration
I strength of basic sites
and

Infrared and ultraviolet spectroscopy in the pre- I Characterization of chemical inter-

sence of adsorbates actions between Sites and
adsorbates
EXAFS (extended X-ray adsorption fine-struc- Atomic structure of surfaces and
ture analysis) - adsorbates

Electron microscopy Chemical identity and structure of

surfaces

Isotopic marking of reactants (or of catalysts) Chemical origin of adsorbed

species, elementary reaction
mechanisms
.....r - - -
Tableau
3.8 Some techniques used to determine catalyst surface properties (&r:erpted from
"----
IS}).

This is why the catalyst's surface properties are still often characterized by
reactions on model molecules along with appropriate cherntsorptlon tech-
niques. Figures 3.9 and, later on, 3.12 and 3.14 give some specUk examples of
structural characterizations of catalysts.
I
 ChBprsr 3. /NOIJS1RIN.. C4TAOST$ 81

33.5.3 Morphology and Mechanical Properties

Solid catalysts can be classified in three main categories:
Granulated catalysts (0.5 to 10 mm) in the form of pellets. extrudates or
tablets. especially adapted to fixed bed technologies (moving bed tech-
nologies mainly use bead-shaped catalysts, for example in' continuous
reforming). -,
Micropellet catalysts (50 to 100 urn) adapted to fluid bed technologies
(for example catalytic cracking).
Catalysts in small particles (1 to 30 urn) processed as suspensions in a
liquid phase that is inert toward reaction conditions (for example, hydro-
genations).
Manufacturers and users ha~e developed simple but varied empirical
methods of evaluating catalysts' mechanical characteristics. Although the
methods are empirical, they seldom disagree with each other. .Itis indispens-
able for measurements to be carried out on a sample that is representative of
the catalyst under consideration.
a. Average Crushing Strength (ACSJ
The method is generally implemented on 50 catalyst grains chosen at random
so as to have a representative average statistical value. Each grain is subjected
to increasing load until it is crushed. The force corresponding to the breaking
point is recorded. Compressive force is expressed in kg/mrrr" for extrudates
(pressure applied along the generatrix) and in kg for spherical grains. For
spheres, note that the Hutt relation is applicable:
F
-=c
{drJ2
with:
F crushing force
dp diameter
C constant

b. &d Crushing Strength (Shell Test)

This method is valid only for grains smaller than 6mm in size. A specified mass
of catalyst is placed in a standard metal cylinder and increasing pressure is
applied in stages on the catalyst by means of a standard metal piston. The
fines obtained at the various pressure stages are sieved and weighed. The %of
fines versus crushing force (kg) curve is plotted and the crush resistance is
determined by the pressure P (bar) corresponding to 0.5% fines formed (the
base of the cylinder has an area of 6 cmZ).

c. IFP Attrition Resis!ance Jfethod

This is a severe test in which the catalyst is placed in the cells of a steel ball
microgrinder (0 =65 cml). It is then subjected to intense alternative stirring
82 C,~_ler 3. INDUSTRIAL CATALY$~$

(700 cycles/min, 40 mm stroke) during 5. 10 or even 15 min for the most resis-
tant products. The percentage of fines formed is measured.
d: Specific Attrition Tests for Fluid Bed Catalysts
Many tests for determining the attrition resistance of fluid bed catalysts have
been described. Most of them work according to the same principle and differ
only in the equipment used, the operating conditions applied and the duration
of the test.
Under controlled pressure. a flowof air is made to go through a perforated
plate. The air flow rate is sufficient to fluidize the catalyst in a vertical tube
Cd = 2.5 em, h ::: 50 em). The impacts between particles generate fines which
are recovered in a specific apparatus and weighed. Depending on the models,
the operation can last from a few tens of minutes to 24 hours or more.
Theseexamples aim to give a brief description of the evaluation of a cata-
lyst's mechanical properties", but for further details the reader is advised to
see reference [3J.

3.4 Preparing the Catalyst

3.4.1 Methodolog}r. Optimizing the Formulation
The development of a catalyst consists first of all in selecting the active phases
best suited to catalyze the reaction under study. As indicated in Section 3.2.1,
the choice of active phases is based on experience (empirical or scientific cor-
relations), on possible analogies (activation of similar catalytic reactions) and
on exploratory research results.
The next step aims to identify which initial reactants include or prefigure
the desired active phase, then to design an operating mode and finally to
implement it. It is crucial at this stage to carefully define the target and to iden-
tify the physicochemical methods which will.be implemented (in.addltton to
the test reaction) in order to validate the result. If the active phase is of the
supported type or if the catalytic reaction is bifunctional, a similar methodol-
ogy will have caused the support phase to be selected or prepared before-
hand.
Once an initial result has been obtained and the active phase has been
characterized, the required catalyst qualities are ranked: catalytic, physico-
chemical and mechanical properties. The most critical are singled out and the
key preparation unit operations are listed. To the extent possible, the textural
and structural properties that can be correlated to performance are identified.
At the same time, on the basis of published data and initial kinetic experi-
ments, a simplified approach to the reaction mechanism is used to identify the
limiting steps and the possible inhibiting effects. In particular, it is used to
define the level of diffusional limitations.
At this stage, the activity and selectivity of an initial catalytic formula have
been established and performance stability has proved satisfactory. Then the
evolution of the active phase (and/or the support) should be assessed in the
reaction medium and if possible its stationary state should be characterized
(Fig. 3.10).
The catalytic formula under study can now be considered valid and a num-
ber of correlations can be established linking its catalytic properties. th'e
intrinsic characteristics of the active phase (and/or the support). the.prepa-
ration conditions. then the pretreatment conditions in the reactor and the sta-
bilization conditions in the reaction medium.
Preparation-characterization-test correlations will serve as a basic guide-
line for optimization later on (Fig.3.10) of:
the active phase composition,
the choice of support phase.
the preparation procedure.
the procedure for pretreatment in the reactor then for testing.
As soon as laboratory formulation has been optimized and the catalysis
results have been validated in a continuous pilot 00 a real feed. it will be pos-
sible to scale up the operating mode to produce a pilot test batch of catalyst
(10 to SO liters) and then to begin optimizing the operating conditions of the
Juture production process. This will result in a representative pre-industriaI
sample which will be tested in a large pilot unit.

.3 Formulation Components:
(support + activeelements)

//'/ j
Operating parameters
Preparation
unit steps
,

.
AA
,

.\

\
,
Characterization ..-,- - - - - -..... Test Catalyticproperties
~"" ,/,',.

Physicochemical properties '" Correiations- -' --

mass.surface area Behaviorin the
samepropertieson _ reaction medium
stabilizedlreaction" catalyst

Figutt ;
3.10: Development of catalytic formulas.
84 enaoler 3. INDUSiA/AL C.4TALYS:"$

3.4.2 Basis for Preparing Catalysts: Unit Operations [3,5)

The aim is to produce a catalyst at the lowest possible cost, consisting of the
required active agents, with the desired surface area and porosity, external
morphology and necessary mechanical properties for the process technology
under consideration.
The choice being made between different possible manufacturing methods:
bulk formulation, impregnation on a preshaped support or comalaxed
together with a support precursor then shaped (see Section 3.2.2), the result-
ing manufacturing technique will be based on a sequence of unit opera-
tlons.The number and sequencing order of these operations must be opti-
mized to minimize' the manufacturing cost and obtain the most
higH~performance and reproducible product possible. Table 3.9 lists the main
unit operations and Figure 3.11 describes their sequencing.

1. Precipitation
2. Aging
3. Filtration
4. Washing
5. Hydrothermal transformations
6. Thermal treatments (drying. activation)
7. Grinding
8. Forming process
9. Thermal treatments
10. Impregnation
11. Malaxing
12. Miscellaneous forming processes
- -Table ~ ....J

3.9 The main unit operations in catalyst

manufacturing.

It is impossible to present the status of what is now known about prepar-

ing industrial catalysts, or more precisely, about catalytic engineering of unit
operations within the scope of this discussion. References [3, 5, 7] can be con-
suited for further details.
The following will be examined by way of examples:
shaping supports -and catalysts,
preparing supports, their properties,
catalysts impregnated on supports.
 C!'apt 3. 1MJUS1RlAL cATALYSTS 85

Unit operations Means of action

pH, concentration, Textule

temperature, nature Strucue
of ions, dunItion Homogeneity

pH, tempe1llture, salt Textule (porosity),

Salts (whether (exchange) purity
?~~~~:-~?~~i... ---,:....---, Salt content, Homogeneity, texture
introduction mode (solid,
nuid), pH, temperature,
rheology

Temperature, humidity FurtherfonTling unit operation:

homogeneous and reproducible

'----,......;----'~-: Tablening, extrusion

(screw. piston, etc).
Mechanical properties
Texlule (porosity).
crushing. spray drying, morpholOgy
oil-forming.
bowl granulation

{See above) Textule

Strucll.m
HO~

.. See calcination

Nature, concentration Dispersion of active

01 the solution. pH. phases (macro- and
, !~ third solvent microscopic)

~~lIon
!.i'! { ir~
Temperature, humic.ry,
atmosphere, pressure.
duration
Disper.;ion of metals,
Comalaxed ~~ Precipitated salts aid active OXides
catalysts --- Activation -----~ catalysts Rapid actIievement of

.
Impregnated
or supports
steady state

catalysts

Figure
3.11 Main unit operations encountered in a catalyst mamlfaetrlTing flow scheme.
 86c~ 3, INDUSTRIAl. C..T.;LYS:-S

3.';'.2.1 Shaping Supports and catalysts

The choice of the catalyst shaping process is generally the result of a compro-
mise after a set of constraints has been studied, particularly with respect to:
The characteristics of the catalytic process (catalyst slurry, fixed, circu-
lating or fluid bed), which dictate morphology (powder, particles), grain
size (from 1 urn to 10 mm) and specific macroscopic properties (for
example, grain size, abrasion, attrition or flow properties).
The intrinsic characteristics of the solid that is to be shaped (erys-
tallinity, chemical reactivity, plasticity, etc.).
Economic imperatives (cost of the shaping process).
For instance, rheological properties of suspensions (spray drying), pastes
(extrusion, co-mixing, oil-forming), or moist powders (extrusion, agglomera-
tion as pellets) depend basically on the intrinsic physicochemical properties
of the' precursor under consideration.
During the shaping unit operation and during the subsequent steps (matu-
ration, washing, drying and thermal activation), the choice of technique is also
limited by the possibility of activating the elementary particle surfaces so that
bonds are formed between them causing sufficient cohesion among the grains
of the final product.
Even though good progress has been made in rationalizing several shaping
processes, this essential step is often a question of industrial know-how:
Dry powders (after their grain size has been adjusted) are -shaped by
tabletting (or compacting); moist powders more often by agglomeration
in pellets (bowl granulation). Tabletting requires a degree of plasticity
for each elementary particle, while bowl granulation requires chemical
reactivity so that stable bonds (or sets of bonds) can be established
between particles and allow agglomeration.
Pastes obtained by adding sufficient water into powders are generally
extruded (0.5 to 20 mm scale). They must be homogeneous and exhibit
rheological properties suited to the process (additives. etc.),
After indispensable preliminary mixing, hydrogels and humidified pow-
ders are shaped in a "press" type apparatus (Ior extrusion diameters
-- 2 mrn), In the most common case (non-Newtonian fluids: pastes with
thixotropic properties 4), extrusion is carried out in a screw-type appara-
tus (single screw or double screw in the more difficult instances):
scale ;;t 0.5 mm, The screw apparatus often allows mixing and extrusion
to be combined in a sequence.
, Suspended solids can also be shaped by spray drying or by ell-forming. '
In spray drying (10 to 700 urn), the suspension is sprayed in a hot air cur-

4. Their dynamic: viscosity decreases when the shear rate increases, then comes back to
the initial value when the paste (or the extrudate that has been formed) remains
motionless.
 rent (2So-300C). The mlcrodroplets formed by means of a nozzle or a
turbine are instantaneously transformed into solid micropeUets. A unit
operation of fluid betllbermal activation can followthis particular "dry-
ing + shaping" step. 'Ibis technology is used in preparing FCC catalysts.
In the oil-forming operation, the suspension (usually a hydrogel. at least
in part) flows drop bydrOp in an appropriate reaction medium (for exam-
ple a hot inorganic oiI). The hydrogel coagulates and can be partially
transformed into xerogel by evaporation of water. The washing operation
allows the unwanted anions and/or cations to be exchanged and/or
eluted and then the product is dried and thermally activated (grain size
scale after activation: 30 Jim to 5 mm). Table 3.10 presents the different
forming processes for refining supports and catalysts. "'

Particle
0.02-0.5 8.05-4 0.1-10 0.5-8 2--10
size (mm)

Process Spray drying on forming Bowl granulatioJ Extrusion Tablettlng

00.5-8mm 02-10mm
I=O.5-IOmm /:0/2t00
Products Micropellets Beads Pellets Cylinder Cylinders
monoliths
Attrition ~good Average -;
Good Fairly good Averagefalr
resistance lDacellent
Production
Low High Low Low High
cost
Fluidized bed

Process
Entrained
OrcuJaling Fixed bed
nuidlzed bed Fixed beef . F.. xed bed (mulli-tubular
technology .mngbed
Catalyst reactors)
slurry

Area or
application
Catalytic
cracking
Continuous
catalytic
HOT
Reforming
Claus sulfur
I .z,
Isomerization
Hydrogen
production
~n refinin~g_-,l
(fCC) monning
;....- ,-- unit -,-Hydrocraddng"",,--- ----,
\
: Table I
~ Catalyst forming proasses.

3.4.2.2 Preparing SuppOl'lL Properties

Refining catalyst supports consiSt of alumina. silica, silica-alumina or tita-
nium oxide. They can also contain some zeolites (mordenite, Y zeolite. ZS:\15.
etc.),
They are characterized by:
high chemical purity;
88 CflaDler 3. INDUSTRIAL C..;r~rs~

morphology, grain size distribution and texture suited to the process

chemistry:
- surface acid-base properties,
- ion exchange properties,
- mechanical properties suited to the process technology;
economic feasibility that allows significant production.
To give an example, alumina supports are prepared by means of four main
processes [7]:
flash thermal treatment of a hydrate.
precipitation by acidification of an alkali aluminate,
precipitation by neutralization of an aluminum salt,
hydrolysis of an alkoxlde,
Precipitation of an alkaline aluminate by a strong acid-aluminum salt:
3AlO 2 + AP + + 6 H20 -+ 4 Al (OH)3
. . -"7
has been studied in depth. As for any precipitation (or coprecipitation), super-
saturation of the medium is controlled so as to adjust the nucleation rate with
respect to the growth rate, and control the number of small particles of alu-
minum hydrate formed and their crystalline organization. Likewise, by adjust-
ing the stationary precipitation conditions - pH, temperature, concentration,
type of anion, etc. - several hydrate structures (bayerite, boehmite, pseu-
doboehmite) and several textures can be achieved.
After filtration, maturation and washing (Fig.3.11), the alumina hydrate can
be shaped by extrusion (or by oil-forming). k will give transition aluminas with
acid properties (11, .., J used as supports for hydrorefining catalysts.
The activated alumina surface consists of a combination of aluminum and
oxygen atoms that are coordlnatlvely unsaturated. Respectively, they consti-
tute the Lewis acid and basic centers. Depending on operating conditions
(especially temperature and water partial pressure) these vacant sites are
occupied by hydroxyl ions (formed by dissociative adsorption of water or by
adsorbed water molecules). In this way, Bronsted acid and basic centers are
formed, which are fewer on alumina than Lewis centers.
Surface hydroxyls (Fig.3.12a and b) can be characterized by infrared spec-
troscopic analysis, or more accurately by adsorption of probe molecules
(Table 3.8) then infrared spectroscopy or thermodesorption [7]. Not very
acid, with a surface density ranging from 5 to 12 OH per nm 2, these surface
hydroxyls are at the origin of the ion exchange properties described below and
also allow grafting of organometallic ligands (Fig. 3.13).

3.4.2.3 Catalysts Impregnated on a Support

The active phase' of many refining catalysts (reforming, isomerization,
hydroreftning, hydroconversion, etc.) is at least partly deposited by impreg-
nation on a preshaped support (or by impregnation of a hydrogel support
 cr~prf!'3. INDUSTRlALCArALYSTS 89

3900 3800 3700 3600 3500

Wave length (an-')

I b (3 785-3800 cm-t) la (3 760-3 780 em-I) II a (3 730-3735 em-I)

faees (100), (110). (111) faces (110), (111) face (111)

Infrared spectrometric characterization and surface modelling of a cubic

gamma alumina (speci1icsurface area =135 m 2 g-I). From [6].

Figure I
3.12b: Alumina h.,..droxylationand hydration equilibria.
~ (1) Lewis acid site (3) Bronsted acid site
(2) Lewis basic site (4) Bronsted basic site

precursor then mixing and shaping in sequence). A precursor salt of the active
agent is deposited on the support and then thermally decomposed. thereby
yielding the desired active phase.
90 CnafJ,er 3. iNDUSTRiAL CAT~''S'S

A. Grafting

8. Anionic exchange (acid medium) Alz03: pH 5-9

MgO: pH < 12

C. Cationicexchange (basic medium) Alz03: pH ~9

Si0 2 : pH ~2

Figure
3.13 Grafting or ion exchange on an oxide support.
The surface tiydroxyts. of an amphoteric support can read in a non-aqueous
medium with an organometallic compound (A). Or they ron be ionized differ-
entlydepending on the pH in an aqueOU$ medium. With on acid pH (B), the
support is an anionic exchanger, fixing anions (Cl- PtCl/- etc.). With a basic
pH (e), the support is a cationic exchanger, Iixing cations (Na" Pr(NH:J r)"
Each support is characterized by its isoelectric point (eqU/libn"um pH in an
aqueous medium) where exchange properties are at a minimum.

In impregnation without interaction, the support is simply welted by the

precursor solution (by spraying or immersion). The solution penetrates the
pore network, gradually filling it (in a few minutes to a few hours). The three
characteristics of the method are:
Its exothermicity (heat of adsorption).
The high pressures developed in the pores, since part of the air initially
present is trapped by the liquid and compressed. The Young-laplace law:

J1P = !!:. cos a

Tp

(y: surface tension, e: junction angle of the meniscus, rp: pore radius)
shows that pressure can reach several hundred bars in the mesopores
with Tp < 10 nm. Under such pressure the support particles can burst.
The duration of impregnation. The solution penetrates very rapidly by
means of capillary forces (a few minutes), but its diffusion is slowed
down in the meso- and micro pore network (Fig. 3.4) by dissolution and
diffusion of the trapped air. .
 During the operation of solution equidlstribution, then subsequent matu-
. ration and drying, the active phase precursor becomes deposited (supersatu-
ration, acid-base reactions, et~.).
mimpregnation with interadioo. the support is immersed in an excess of
solution containing the precursor salt. The salt interacts with the surface as
shown in Figure 3.13. . .
Interaction can consist in (Fig. 3.13A) formation of a chemical bond
between the precursor and the support: the interaction is then a grafting.
In this way it is possible to fix silicon from tetraethoxy silicon or tin from
tetrabutoxy tin in a hyperdispersed form. Later on. thermal activation
releases the organic frag!l1ents and forms the surface oxide molecule.
Precursor-support interaction can also be ionic in nature, of the acid-base
type for example. This is the case for anionic (Fig. 3.13B) and cationic
(Fig. 3.13C) exchanges. A competitor ion (CI- for PtCI,2-, NHt for
Pt(NH:Jl+) is generally added to the reaction medium in order to control
exchange kinetics and get homogeneous distribution of active elements
in the grain in a hyperdispersed form. The support-anchored hyperdis-
persed phases are obtained after drying and thermal activation.
Figure 3.14 (transmission electron microscope photograph) shows
nanopartides of Pd anchored by cationic exchange on zeolite crystallites.

3.5 Catalyst Regeneration

3.5.1 Catalyst Deactivation
A significant loss in activity and/or selectlvtty usually means that the catalyst
is unloaded or regenerated in situ.In any case. the 'decreased performance cor-
responds to a smaller number of sites accessible for catalysis as such. It may
be irreversible or reversible. Atoss in activity can be offset by increased oper-
ating temperature. for example a lO~C increase in operating temperature-
(3OQ-310'C) compensates for a 25% drop in activity if the apparent thermal
increment is 84 kJmol- 1 Independently of the reversible or irreversible nature
of deactivation, M.Twigg [51 mentions three main causes:
physical causes,
poisoning by impurities.
poisoning by reactants or reaction products.

3.5.1.1 Physical Causes

The agglomeration of crystallites by sinterlng is the principal physical cause
of catalyst ageing. Sintering causes a significant decrease in the active surface
area (metals, sulfides) and sometimes in the total specific area (oxide sup-
ports). Breaking. attrition or abrasion of catalyst grains causes greater pres-
sure drop (fixed bed) or production of fines (moving and fluid bed). that make
continued industrial operation impossible.
 Electron microscopy (enlarged x 400 000). Transmission eleCIrfM microscope
photograph showing small particles (Pd) from 2 to 10 nm deposited on crys-
tallites of Y zeolite.

Plugging of the outside macropores by feed impurities is also one of the

causes of deactivation. More generally, a malfunction in the industrial unit is
often at the root of physical deactivation (running under inappropriate oper-
ating conditions, thermal runaways, etc.).
Sintering has been studied in depth and industrial catalyst formulations are
designed to control it or, in some cases of catalysis by metals" to make it
reversible by redtsperslng metallic sites.
Two major mechanisms are proposed to explain sintering of the metallic
phase. The first involves crystallite migration; the particles move: on the sup-
port surface and coalesce to form larger ones. The second assumes that metal-
lic aggregates dissociate into atomic or molecular species. The species
migrate on the support surface and are captured by stationary aggregates.
 Cllalller 3. INDUSTRIAL CATAL't'SJS 93

Generally speaking, the two mechanisms coexist. AJong with them, the effect
of interactions between the active phase and the support slow down sintering.
Sintering of the support causes its texture, and even its structure, to
change with a decrease in free energy. Two extreme cases can be considered
[3}. sintering with constant pore diameter (with shrinkage of the solid) and
sintering with constant pore volume (no solid shrinkage). In both, the sup.
port's specific area becomes smaller.

3.5.1.2 Poisoning by Impurities

Table 3.11 gives a non-exhaustive list of refining catalyst poisons. Poisoning
occurs if the impurities interact more stronglywlth the active surface than the
reactants and if the interaction is irreversible (otherwise the term would be
inhibition).

Poison Catalysts for:

I
Coke
Organic sulfur corn-
pounds including H~
Organic nitrogen com-
pounds and NHJ
Oxygenated compounds
lncluding CO, H20 et O2
Polynuclear aromatic
compounds
Asphaltenes and resins
Nickel-vanadium
Iron
Sodium (potassium)
Acid and bifunctional metal-acid catalysis. hydrore-
fining
Hydrogenation. dehydrogenation. reforming. C~1i
isomerization, steam reforming. low-temperature
CO conversion
Acid and bifunctional metal-acid catalysis: refer-
mingo isomerization, catalytic cracking, hydro-
cracking, oIigomeriz~tion
CS-C6 isomerization. reforming. alkylation. oUgome-
rization, Claus sulfur unit
I
Acid or bifunctionaL metal (sulfide)-acid catalysis
I
Hydroconversion of residues, hydrocracklng, cataly-
tic cracking
Hydroconversion of residues, hydrotreating, cataly-
tic craclcing, reforming, isomerization, acid and
bifunctional, metal (sulflde)-acid catalysts

Arsenic Reforming, catalyttc cracking, hydroconversion of

! residues
Phosphorus I Reforming. hydrogenations
:
Halogens ) Steam reforming. low-temperature CO conversion
'--
Table
3.11 Solid catalyst poisons in refining.
94 C1"~Ofer 3 INDUSTRIA!,. CATA!,.YS~S

Since poisoning modifies active sites, it can either affect activity (number
of sites) or selectivity (certain sites) or both.
The poisoning effect is specific to a catalytic formulation: For instance in
bifunctional metal-acid catalysis (reforming, isomerization), chlorine is an
acidity promotor (it also makes the platinum more thioresistant). However, it
is a poison for other metals (Ni in steam reforming, Cu in low-temperature CO
conversion and methanol synthesis).
The poison's distribution in the catalyst particle and in the catalytic bed (in
a fixed bed) is determined both by poisoning kinetics and the mobility of the
poison. The poison is said to be "reversible" if it can be eliminated without any
memory effect subsisting in the site's catalytic properties. Note that in indus-
trial units, an accidental event may cause poisoning. For example, the contents
of the associated amine washing scrubber may be sucked into the bed of a cat-
alytic desulfurization unit.._

3.5.1.3 Poisoning by Reactants or.. by lte:i:CtiOD Products

Deactivation by coke deposit is the most common example of this category. It
has been the subject of a great deal of research mentioned in [3] and [5}.
Reversible for catalytic cracking and catalytic reforming catalysts, it is limited
in other processes by adjusting the acid properties of the support. the lntrin-
sic properties of the active phase and the operating conditions. For instance
in hydrocracking, high hydrogen partial pressure is used to avoid dehydro-
genation which would form coke precursors.
An organometallic compound present in a residue which is a hydrotreating
feed can react with H2S to form a sulfide that modifies the catalyst's proper-
ties. The presence of arsenic in certain petroleum fractions is a very well
known example of this.
In selective hydrogenation of the olefinic C2 cut. acetylene, an impurity in
the feed, can be selectively hydrogenated. However, It can also form unsatu-
rated oligomers (green oils), whose heavier components poison the catalyst.
Obviously, these different causes of deactivation do not usually act inde-
pendently. For instance, M. Twigg {5] mentions poisoning of nickel-base cata-
lysts used in naphtha steam reforming by arsenic and sulfur. Poisoning of
nickel crystallites lessens their hydrogenating activity, unsaturated corn-
pounds are formed and the catalyst is rapidly covered with coke.

3.5.1.4 Other Causes of Deactivation

It is difficult to classify certain physicochemical changes in the catalyst into
one of the three preceding categories. Catalytic properties are also altered in
the following ways:
, modification'S in composition (surface, bulk): the loss of the bimetallic
effect in catalytic reforming is an example;
~ deaJumination of zeolites with an irreversible loss of activity, as in cat-
alytic cracking;
 ~ 3. INDusTRIAL CATAll'S7S 95

1. of an active element by sublimation (for example: Re207. RuO.t). by

gas-phase formation (for example Ni(CO),J. by elution (C1 2 in the pres-
ence of water in reforming 'or isomerization) or by accidental leaching.

3.~.2 Regeneration Methods

3.5.2.1 Transformation of Refining Catalysts in the
llcaction Medium
Generally speaking. solid heterogeneous catalysts undergo profound changes
between the time when they are loaded in the reactor and the time when they
reach a state of "equilibrium under operating conditions" in the reaction
medium. For instance. in the specific case of catalytic cracking. the unit has to
. be started up with a "balanced catalyst" (Le. a used catalyst), which is then
gradually replaced by fresh catalyst. Directly starting up with new catalyst
would cause excessive and prohibitive formation of coke. A much more com-
plex case is that of the hydrorefining and hydroconversion catalysts whose
active hydrogenating phase at equilibrium is essentially made up of sulfides.
The sulfurization of mixed crystallites (CoO or NiO + M003 or WOJ + additives)
dispersed on a support changing them into small particles of MaS:! {or WSV
"decorated" on the comers and edges with cobalt or nickel sulfide is particu-
l'\lrly complex [8]. In fact these nanoparticles (optimum size 3.5 iim) interact
with the support and any possible additives. This is why the genesis of the
"sulfur" species and the control of chemical interactions during changes must
be thoroughly mastered.
These few examples show that industrial manufacture of a catalyst is gen-
erally followed by one or more unit steps of in situ preparation in the reactor.
The end result is a balanced catalyst and scientific control of these unit steps
is the licensor's responsibility.

33.2.2 8q:enerating the Industrial Catalyst

At the end of an initial run. a large number of industrial catalysts require regen-
eration. In some industrial processes - catalytic cracking, continuous regen-
eration catalytic reforming - regeneration is one of the steps of the process
and needs no specific action. In most of the other processes, the problem
arises of regenerating the catalyst either on site, l.e. without unloading it. or
off site using the services of specialized companies.
Table 3.12 shows a number of unit operations that can be carried out in the
unit. but which are increasingly being performed off site. Off site operating
conditions are better controlled. SO regeneration time is much shorter. The
development and diversification of off site services means a significant
increase in the number of effective stream days for industrial units in most
refineries.
For example, the simplest industrial regeneration consists in removing
coke. When the reactor is of the flxed bed type, this unit operation can cause
problems if carried out in situ. Even in the presence 01lean air, the risks are
96 Chapter 3, INDUSTRIAL c..l.TAL~STS

high that the temperature will rise and active species will be slntered..Offsite.
one of the industrial methods consists in using a rotating furnace of the
Rotolouvre type [9] with the catalyst flowing in a thin layer and radial diffusion
of lean air. This original technology allows the thermicity of the combustion
reaction to be controlled. The catalyst's initial activity is restored without
altering the accessibility of active sites. The other unit steps described in
Table 3.12 are and will continue to be carried out increasingly off site.

On slte i Off site :

(in situ) (exsilu)
I
Coke combustion X X
"

Reducti9n X X (byH~
Presulfurization X
Reai sullurlzation X (X) *
Chlorination X X
Oxychlorination with
redlspersion of metals X (X) *
Being developed (1995).
~
I Table
3.12 Regenerating spent catalysts.
L-.

3.5.2.3 Reprocessing Spent Catalysts [2)

The amount of solid catalysts used annually in refining is estimated today
(fable 3.1fto be 566 000 1. Added to this is some 2 000 000 t/year of sulfuric
acid.
The fate of spent catalysts is increasingly becoming a current problem due
to a legitimate concern about environmental protection.
Some catalysts, such as the Claus process aluminas and catalytic cracking
catalysts, are partly recycled (cements, building construction materials) or
stored on an appropriate site. However, site storage is becoming more and
more costly ($80/t in California for FCCcatalysts). Those with a precious metal
base have been reprocessed and the metal recycled ever since the beginning
for obvious reasons: the reprocessing cost is negligible compared to the mar-
ket value of the product (pt, Pd, etc.),
Hydrorefining and hydroconversion catalysts and more particularly those
designed to purify, then convert the bottom of the barrel are made up of heavy
metals. They contain even more heavy metals (vanadium, nickel, arsenic) com-
ing from the feed at the end of their lifetime. Other products designed for puri-
fying feeds are polluted by mercury, another toxic element. It is important to
 Oa:::~ 3. INDUSTRIAL CATALYSTS 97

have appropriate reprocessing methods, and hydro- and pyrometallurgical

technologies developed by the mineral chemical industry have been adapted
to the purpose. Figure3.15 [9] describes a recycling process for hydrorefining
catalysts that can separate and recover the metals and alumina with high
yields.
In the near future it is highly probable that catalyst reprocessing will be
generalized. Today's economic conditions are not particularly favorable to
reprocessing, but future laws on spent catalyst transportation and storage
could profoundly change the present situation.

Alkaline solution Solid

AI, Mo, V, P, As AI. Si, Ni, Co

1 !
~.P.As~. ~$ag:~
Solution - Matte
Mo,V Ni.Co

LjepaLj I
Mo V Ni Co
L--~ .;. . ----'
Figure I
3.15 I Eurecat process flow scheme for recycling spent hydroretining catalysts [9].
-..--J

3.6 Conclusion
Table 3.13 summarizes the continuous action involved in developing a new cat-
alyst from fundamental research to industrial achievements. It goes without
saying that the table is in no way dogmatic and that some sequences can be
inverted.
98 CMDler 3 INDU:;TRJAL CATALYSTS

I Selecting active agents. Laboratory studies

Detailed analysis of the chemical transformation (desirable and unwanted reac-
tions. thermodynamic and kinetic data). '
Usting of possible active phases (analogies, scientific correlations. literature.
patents).
Definition of it lest reaction. choice of a testing tOOl and analytical methods.
Exploratory n:search to select the most appropriate active phases. initial stabi-
lity tests.
Preliminary choice of a support (selection tests).
Phystcochenu-at characterization of active phases.
Fundamental research on aging, regenerability.
Fundamental ~tudy of reaction kinetics and reaction mechanism approach.
industrial property rights: freedom to use the active phase.
Technical and economic study.

2 Developing the Indusbial catalyst

Preparation uf the model active phase and the s\Jpport: parametric studies.
Validation of vatalytlc properties: test reactions. pilot tests on real feeds.
Acquisition of all the kinetic data required for kinetic modelling (kinetics at grain
level, at bed lvvel) and validation of the reaction mechanism (characterization
of adsorbed Illtermediate forms).
Studies on fonning unit operations (bulk) or final support selection (impregna-
ted, cornalaxi-uj with respect to the process approach under consideration.
Characteriz31lon of physicochemical and mectJaIlical properties of new and
aged catalysts Rationalization of preparatrcn-charactertzatton-test correlations.
Studies on Conditioning in the reactor and optimization of catalyst start up and
stabilization l"ondltions.
Final specific.llion of the industrial support and drafting of operating procedure
lor pilot catalrst manufacture.
Production 01 pilot batch and catalyst valldation by long duration tests on real
feeds.
Setting up correlations and modelling the reaction.
Catalyst utiliz.u ion patents and "Ireedorn to use" studies.
Spent catalyst reprocessing studies. patents.
Industrial production and Qualification of the average batch.

J Implementing i"duslrial catalysts in the selected process

Choice and 0lllimization of technology (e.g. circUlating bed).
Choice and OPtimization of reactor.
Choice and optimization of start-up and operatUtg conditions.
Industrial mo\lel. development of an expert system.
Final optlmlzai ion of the catalyst/process as a whole.
Process patents. process integration patents, freedom to use the catalyst uncer
process conditions in the process technology.
Table r--------------_--------_-.J
3.13 Develol':ng cataiyus: from fundamental research 10 industrial actueoeme-ns.

Industrial catalysts are and will remain a strategic product. As a result, the
search for innovation in their manufacture and in the technologies that use
them is intense worldwide: membrane reactors, reactors combining fractiona-
tion and a catalyzed reaction. monolithic catalysts. Meanwhile, scientific
understanding of catalysis as such is becoming increasingly thorough: e.g.
progress in in situ characterization techniques, molecular modelling of the site
and its interactions with the reaction medium. Finally, catalysts and processes
can not be disassociated. A better understanding of the interactions between
all the molecular changes along with accomplished kinetic modelling of reac-
tion procedures should yield elaborate reactor models and expert systems to
improve the operation of industrial units and ultimately optimize catalyst uti-
lization.

R.eferences
Martino G. (1994) Prospects in oil refining. Bull. Soc. Chim. France 131,
444-451.
2 Martino G., Courty Ph., Martilly C. (1997) Perspectives in oil refining. In:
Handbook of Heterogeneous Catalysis, Ertl G., Knozinger H., Weitkamp J.,
I Vol. IV, 1801-1818. YCH.
3 Le Page J.F.et al. (1987) Applical Heterogeneous Catalysis. Editions Technlp,
Paris.
4 Chiavelli RR In: Catalysis and Surface Science, Heinemann M. et Somorjai
G. eds., 21, 61-87, Marcel Dekker Inc.
5 Twigg M.V., Catalyst Handbook. 2nd Edn., 23. Wolfe Publishing Ltd.
6 Haller G.L, Sachtler W_\l.H. (1994) Catalyst characterization:
structure/fonctlon. Catalysis Today 22,261-280. ",
7 Poisson R.. Brunelle J.P., Nartier P. (1989) In: Catalyst Supports" and
Supported Catalysts. Theoretical and Applied Concepts. Stiles A.B.,
Butterworths.
8 Kasztelan S. (1991) Relations entre proprietes catalytiques et structures
des catalyseurs supportes abase de molybdene. Ph. D. thesis, Paris. Edi-
tions Technip.
9 Berrebi G., Dufresne P., Jacquier Y. (1994) Resources Conservation and
Recycling 10, 1-9.
 ._j

CatalYtic Reforming

Germain Martino

Today most refineries are equipped with catalytic reforming units. The pro-
cess serves to produce high octane gasoline stocks from "naphtha" cuts con-
sisting mainly of straight-run gasolines. In addition. it provides the hydrogen
required by the refinery for hydrotreating other cuts.
-.

4.1 Importance of the Process in Making Up

tbe ."Gasoline poor
4.1.1 Gasolines
Gasoline specifications have evolved a great deal during the past 20 years and
will surely be modified yet again in the future. For example, developed coun-
tries have seen the gradual removal of lead. the introduction of oxygenated
compounds (alcohols and ethers). the decreasing of allowable sulfur content
and the introduction of regulations involving distillation curve configuration:
vapor pressure and end point. Discussion is under way to make certain gaso-
line specifications more stringent. For instance, the motor octane number
(MON) is increasingly taken into account along with the research octane num-
ber. The values chosen obviously depend on the car population existing in a
given location. As an illustration. Table 4.1 lists the main administrative spec-
ifications in effect for Eurosuper in the rust ofJanuary 2000.Developments are
expected with respect to the maximum allowable sulfur (:E; 50 ppm). the
mandatory presence of oxygenated compounds (oxygen content ~ 2% wt),
and a more stringent Iimi~ on total aromatics (:e< 30% wt), Also expected is a
reduction in the end point in order to lower the heavier aromatics concentra-
tion along with a limit on high volatility C~-C6 olefin concentrations, whose
effect on ozone production has been demonstrated.
 Properties Values j
RVP (kPa) max 60
Distillation (% vol min)
at lOO'C 46
at 150'C is
Benzene (% vol max) I
Aromatics (% vol max) 42
OIefins (% vol max) 18
Oxygen content (0/.. wt max) 2.8
Sulfur max (ppm) 150
Lead (gil max) 0.005
....--
~ Table 1--------,-----------------------'
4.1- Main specifications for Eurosuper (January 20(0).
~

4.1.2 Motor Fuel Stocks

The gasoline pool is built up from a number of stocks whose octane numbers
are listed in Table 4.2. Isopentane, FCC gasoline, which accounts for a large
weight per cent of the pool however, as well as isomerate have RON values
lower than 95. Light paraffins (butanes and isopentane), alkylates, ethers and
reformates have MaN values higher than 85. As a result. except for ethers and
alkylates, relorrnates are the only stocks produced in large amounts which
meet both RON and MON requirements.
A reform ate consists of (fable 4.3) normal or branched paraffins and espe-
cially aromatics, most of which have Iewcr than 10 carbon atoms. Olefin and
naphthene concentrations are lower than 1% wt except for low pressure refer-
mates which approach 1% wt. Note that with RON =98, the aromatics concen-
tration is close to 70% wt. The octane in a reformate is generally previded by
C,cIO aromatics and by light isoparaffins, especially Cs' This is because the
C6, C7 and Cs isoparaffins are not very branched as will be seen later on, and
so they have a low RON. The -end point (Table 4.3b) is limited. usually to
around 205~C. to comply with the corresponding gasoline specification, but
mainly to prevent large-scale formation of naphthalene derivatives which
color the reformate and cause rapid catalyst deactivation.
The reforrnate is basically made up of CoCIO aromatics, but increasingly it
is limited to Ci , Cs and ego The aromatics concentration is directly related to
the desired research octane number. Note that refonnates do not contain any
sulfur (S :so; 0.1 ppm).
 ~ 4. CATAlYTIC REFOFftM; 103

Stock RON MON

Butane 95 92
Isopentane 92 89
Ught gasoline 68 67
Medium pressure reformate 94 85
Low pressure reformate 99 88
Heavy reformate 113 102
Total FCC gasoline 91 80
Alkylate 95 92
Isomerate 85 82
Dimate
. 97 82
MTBE 115 99
ETBE 114 98
_.....---
Table
4.2 Octane numbers (RON and MON) of motor fuel stocks.
~

Number I
of carbon oP iP P 0 I N A Total
atoms 1i ",

4 0.57 0.57
5
6
t I
1.51
1.69
2.5
2.37
3.97
8.42
3.88
5.66
10.92
I
!
OJ
0.16
0.35
0
0.19
0,4
2.34
14.16
3.98
8.35
25.83

I
8 1.16 4.91 6.07 0.44 0.34 26.28 33.13
9 0.26 1.04 1.3 0.08 0 21.08 22.46
10 0.07 0.28 0.35 j 0 I
0 4.76 5.11

Total
11 0
7.76
0.02
21.01
0.02
28.77 I
I
0
1.13
i
!
0
0.93
0.55
69.17
0.57
tOO
nP: normal paraffins. iP: branched paraffins. P: total paraffins
0: olefins. I'C: naphthenes. A; aromatics.
.....:---.
Table
, 4.3a i Characteristics of a lou: pressure ff!formate. Analysis (:t uit per family and
number of carbon atoms).
RON = 98
Sp.gr.d~5 = 0.85
{
S ~ 0.1 ppm.
 104 Chap,,,, 4. CATALYTIC RER)RMING

% distilled GC
1

IBP 56
5 83
10 92
20 103
30 113
40 121
50 128
60 135
70 : 142
80 150
90 160
. 9~ 168
EP 194

% distilled 98.4
% residue 1.5
% losses 0.1

Characteristics of a low pressure retormate.

ASTMdistil/ation (see \0/. I, Section 4.1.3.1).
RON : 98
Sp.gr.d~5 : 0.85
{S ~ 0.1 ppm.

4.1.3 The Catalytic Reforming Process

Roughly speaking, the process is designed to produce aromatics having 6 to
10 carbon atoms, with the largest proportion possible limited to 7, 8 or 9. As
such, the initial feeds contain paraffins and naphthenes with an equivalent
number of carbon atoms. Table 4.4a gives the composition of two typical
extreme feeds: one with 63% weight paraffins and the other with 63% weight
naphthenes. Note that the amount of aromatics in these two straight-run dis-
tillation feeds is lower than 15% weight. The overall properties of the two feeds
are given in part (b) of Table 4.4. The RON is low: 50 for the paraffinic feed and
66 for the naphthenic feed. The molecular weight is approximately 115. Le,
centered on Cs. The boiling points: IBP= 90 e and EP == 160C limit C6 and CUI
G

concentrations. Sulfur is present in the feeds in the range of 500 and 350 ppm.
These sulfur values are representative of straight run feeds (SR) corning from
atmospheric distillation of the crude. Values lower than 100 ppm are found in
. a few particular crudes (Hassi Messaoud, for example), These SRfeeds contain
limited amounts (a few ppm) of nitrogen (arnines) or oxygenated compounds
(phenol or carboxylic acid). In some cases, traces 1 ppm) of metals or met-
 ~ 4, CATALYTIC ReFORMING 105

alloids can be found depending on the origin of the crudes. For instance, mer-
.cury and, more seldom, arsenic are found in some crudes.

P N A
Paraffins Naphlhenes Aromatics

Feed (a)
C5 - -
2.30
-
C6 5.49 0.41
C7 16.83 5.80 3.18
C8 21.38 8.27 6.80
C9 17.26 5.95 3.08
CIO 2.59 0.63 -
Total 63.55 22.95 13.47
Feed (b)
C5 0.16 0.27 -
C6 3.31 5.78 0.20
C7 6.13 14.24 120
C8 9.79 14.47 3.54
I C9 3.89 17.14 4.29
CJO 3.59 IU7 0.88
Total 26.81 63.0T 10.10
w-::-:-:-
IT.bl.
4.4a Characterislics of two rypical feeds. Analysis by family and by number 01
L-- carbon atoms, expressed in % wt.

If the "octane barrel" requirements can not ~met by reforming heavy

naphtha (9Q-160 C), it may be necessary increase to the amount of feed pro-
G

cessed in reforming, by using cuts distilling in the same range, produced in

conversion units and having an overly low octane number. For instance, vis-
breaking or coking gasolines can be sent to reforming. In comparison with SR
feeds, they are characterized by a high olefin and acid sulfur content and
larger amounts of nitrogen compounds. Hydrocracking gasoline is another
feed, it is clean. free of sulfur and nitrogen compounds, but it is mainly made
up of cyclopentane-structure naphthenes and isoparaffins. FCC gasoline heart
cut is another possible feed. It is characterized by significant olefin and aro-
matics concentrations as well as by the presence of molecules containing het-
eroatoms such as S or N.
If there is no light paraffin isomerization process in the refinery, it is tempt-
ing to send part of the light gasoline to reforming. The end point of the feed
can be raised, if gasoline pool specifications so allowand if the duration of the
reforming run length - shortened as a result - remains within acceptable lim-
its.
 Paraffinic (a) Naphthenic (b)
II (Arabian tight)
I (Nigeria)
I
I
RONclear 50 I 66 i
PIN/A (% vol)" i 66.8 21.8 11.4 I 29.3 61.85 8.85
N + 2 A** I 44.6 I 79.55
ASTM distillation (%)
IBP 92 88
5 103 102
10 106 107
30 115 115 I
50 ! 123 123
!
70 133 132
90 147 145
95 152 150
EP
Average molecular weightl
i 155 161
119
114
sp.gr.dJ5 I 0.733 0.763
S (weight ppm) I 500 350
I

PIN/A % paratrlns/naphthenes/aromalics.
.. N+2A % napnthenes + 2 (% arom;ltics).
r--l
Table
4Ab Overall characteristics of fICO typical feeds.

Figure 4.1 shows how catalyt ic reforming is integrated in a refinery that

includes a light gasoline (Cs-e,J isomerization and a catalytic cracking unit,
and whose option is maximum gasoline production without reforming FCC
gasoline, however. Here catalytic reforming provides over one-third of the
gasoline pool.

4.2 Process Background

4.2.1 Past and Present
With the rapid development of automobile use in the thirties. gasoline demand
increased both in quantity and in quality. Catalytic cracking came into being
and thermal reforming processes became common for gasoline cuts produc-
tion. A large number of catalytic reforming processes were operational even
during the Second World War. They used catalysts with alumina as a support
and chromium or molybdenum oxides as active elements and molybdenum
 - - - - - - - - - - - .. - I

C'-C 3

C'-C 4

RON MON %wt

c, 93 81 3.8
I&o-C
89 87 1.8
Ughl gasoline

C'-C 4

Light naphtha
----+
IReformate
~
98 87 37.2

I Dimate
96 61 4.3

97 94 5.5
t
~

~
-~

Relidue
---
MTBE
Light gallno
116
93
10[
81
2.6
34.5
f
_
--r
Heavy naphlha
94 81 10.5
~

1 ....
l;jl:llrc
4. I Catuiyttc reformillg integrated ill (J refinery: base case. ..,o
oxides could be doped with cobalt. They were implemented in fixed or moving
bed reactors.
There were a good 50 when the first major turning point in process tech-
nology appeared in 1949. At that time UOP developed the "platformlng" pro-
cess based on a platinum catalyst on chlorinated alumina. running at pres-
sures of approximately 70 bar. The catalyst was regenerated in the unit after a
few months' operation. This is why the process was called seml-regenerative.
A number of processes based on the same type of catalyst (Pt/chlorinated
Al:P3 or Pt on silica alumina) came on the market afterward. Cyclic regenera-
tion with swing reactors was developed by Exxon.
Catalysts were improved in the fifties and sixties and operating pressures
were lower - some' 30 bar - before bimetallic catalysts made an appearance
in the late sixties. A new stage was reached and operating pressures of some
10 bar became possible.
Inthe early seventies, the third major modification occurred: the introduc-
tion of continuous regeneration with reforming units running at approximately
10 bar. In the late eighties. even lower pressures were achieved: 3 bar.
Naturally these changes meant more severe operating conditions, higher
RON and space velocity and an effort to get better yield. Today catalytic
reforming is the aromatics and hydrogen producer in a refinery,

4.2.2 Future [13, 14)

The future of catalytic reforming is partly related to the constraints that envi-
ronmental regulations will continue to introduce. At first glance, an overall
capacity standstill can be expected in the developed countries. or at best a
slight increase. There will be an unquestionable trend toward units that will
produce less benzene and more Cs+ and hydrogen. In contrast, China. India
and other Southeast Asian countries will install new capacity.
The future belongs to continuous reforming units operating at low pressure
on narrower feeds, with a higher initial boiling point and a relatively low end
point (EP :so; 160c C). and highly selective catalysts producing a maximum
amount of hydrogen. It is not likely that refineries will be producing gasoline
without a catalytic reforming unit. even in a 15 to 2Q-yeartime frame.

4.3 Data Overview

4.3.1 Reactions Involved [3. 4. 7,8]

In an initial analysis. catalytic reforming consists in producing aromatics from
naphthenes and paraffins, basically C7 Cs and C9 as selectively as possible.
 Chapter of. CATALYTIC REFoRMiNG 1 09

4.3.1.1 Reactions in Detail

A more thorough analysis can be made by considering the research and motor
octane numbers of hydrocarbons with 7 carbon atoms (fable 4.5). Only highly
branched oleflns and paraffins along with aromatics have satisfactory RON
and MON values tor the present-day gasoline pool (RON 95, MON85). Slightly
brilDChed paraffins and naphthenes have values that are too low.
TheRON of paraffins in general and of mixtures at thermodynamicequilib-
rium at 480C presented in Figure 4.2 decreases as the number of carbon
atoms increases. Only mixtures with 4 or 5 carbon atoms give satisfactory val-
ues. Aromatics values remain high whatever the number of carbon atoms.

Straight dlain paraffins

o Iso + normalparaffinsat equilibrium at 480C
o Aromatics

100

z
o0::

50

Of---'---'------'---IlL---.\---.:.----'-_
3 4 5 6 7 8 9 10
Nunber of carbon atoms

j fi:ve
1,
.." 4.2 I Research octane number (RON) versus the number of carbon atoms of-
linear paraffins and their mixture at equilibrium at 480 C, as well as that of
G

aromatics.

To get a satisfactory ~octane number, the reactions that need to be carried

out in reforming are therefore to convert the hydrocarbons in the feed into a
mature ot aromatics (CoC9) and isoparaIfins (C4-CJ . The presence of paraf-
fins with a number of carbon atoms greater than 5 is a drawback.
110 ChlIDler 4. CArAt-ro.::; REFORMliVu

I
Compounds RON MON
1 I
i~1 0
1 0
I
!
!~ I
!
42
I
-

;~ 56 46
I
I
~ I
I
89 !
!

I
~
;
Paraffins
91 88
C,H16
I
I

j~ 83 -
I~ 83 -

!) 65 69 f

Ii ~
112

54
101

-
Glefins
C1H t ( ~ 94 -
>(,/"/".. 105 -

Naphthenes
CiHt (
I
~ - 41

Aromatics
6 I
75 it

CGlts-CH 3

I-----
Table
120 104

4.5 Research and motor octane numbers of some compounds with seven carbon
'---
atoms.
 ~ -f. CATALYTIC fiEFoI:uNG 111

4.3.1.2 Reactions catalyzed by PtlChlorin3ted Al1.03

All present-day catalysts are derived from platinum on chlorinated alumina.
Bimetallic catalysts (platinum associated with another metal) today exhibit
the same basic properties, but with some improved properties which justify
their industrial use in modern units. ..
The required reactions are indicated in Table 4.6 and illustrated by hydro-
carbons with 7 carbon atoms. TIley are dehydrogenation of cyclohexanic
naphthenes, isomerization then dehydrogenation of cyclopentanic naph-
thenes, isomerization of paraffins and finally dehydrocycJization of paraffins.
Although dehydrogenation of paraffins does not contribute to producing
octane, it is an indispensable reaction, as it is involved as an intennediate step
of dehydrocyclization and .isomerization.

4H
Reactions Stoichiometry
(kJ/mol)

Dehydrogenation O~@+3H'(') a) -209

n- or i-C;H16;::: n- or i-C,HI4 + H2 (b) b)-126

Isomerization-
dehydrogenation
G~6~@:3H'
(c) (a)
c) +15

Isomerization I tK:,H 16 -;= i-C,H lli +10

i of paraffins

Dehydrocyclization
n-C;H16 -;=
+4H 2
-260

I
i-C,HIS -;= @ +4Hz I
l
I

Table ~
4.6 Reactions to be promoted, illustrated b.v ttydrocarbans with seeM carbon
atoms.
112 CnalJ1er4 C;'TALYTIC REFORt.::f.3

Platinum on alumina catalysts implemented under reforming conditions

catalyze a number of other side reactions (fable 4.7):
first of all certain reactions that do not require hydrogen such as dis-
proportionaUon of toluene to benzene and xylenes or alkylation of aro-
matics by olefins. The second reaction yields products with more carbon
atoms than the reactants.
Reactions of hydrogenolysis, hydrodealkylation and hydrocracking
which yield products lighter than those present in the feed (methane.
ethane, propane, and butanes, etc.). .
Finally, coke is laid down. a condensed form of the molecules that are ini-
tially present. It is a solid that is very rich in carbon and poor in hydrogen. It
is formed by a large number of successive reactions: alkylation, cyclizatlon,
dehydrogenation, etc.

Reactions Stoichiometry
I All

Dlsproporttonation z@o=@+@ - Athermic

Alkylation @+Ol~n~r Exothermic

Hydrogenolysis and/or
hydrocracking ~ 0 6-+~,
0,

n- or i -C;H 16
.. Exothermic

CH,4 + n- or i-C6 H14

CzHj; + n- or j..CSH I2
C3HjJ + n- or iC..H1O

Hydrodealkylation
@+H2~CH'+@ Exothermic

Coking Probably from polyaromatics obtained by

alkylation and cyclization
,-'---
Table
4.7 Other reactions that occur at the same time as the reactions to be promoted on
'--
the selected catalyst. illustroted by hydrocarbons with seven carbon atoms.
 Chapt"'''_ CATALYTIC REFORMING 113

The reforming catalyst also has other functions that are complementary to
those mentioned above. For instance, in the presence of hydrogen it catalyzes
hydrodesulfurization, hydrodenltrogenatlon, hydrodeoxygenation, hydrode-
halogenation and hydrodemetallization reactions as indicated in Table 4.8.
Note that volatile species: H~. NH3 H20 and HX are generally formed at high
temperature from heteroatomic compounds. while the metals are laid down on
the catalyst.

Reactions Stoichiometry AH

Desulfurization
. 0 + 4 HZ-+C4H 1O+ HzS Exothermic
S

Denitrogenation 0+N
5 If, ... n-C,H" NH,+ Exothermic

3
Deoxygenation ROH + '2 Hz-+ RH + H2O Exothermic

O2 + 2 Hz-+ 2 H2O Highly exothermic

Dehalogenation RX + H2 -+ RH + HX Highly exothermic

ex ..
o, Br)
n
Demetalflzation MRII + 2" Hz -+ n-RM + ~
(M .. Hg, As. Pb .) -'.
,r---"l -
I Table 1
I 4.8 , Other reactions catalyzed by Pt/AI;/J:/CI.
i.,~I

4.3.2 Reaction Thermodynamics [9, lOI

4.3.2.1 'I1aerma1 Effect of Reactions
As indicated in Table 4.6, the reactions that produce aromatics, l.e, dehydro-
genation and dehydrocyclization. are highly endothermic (Mf> 200 kJ/mol),
as is dehydrogenation of paraffins to oleflns (Mf > 100 kJ/mol). In contrast,
paraffin. naphthene and aromatics isomerization reactions are only slightly
exothermic em
== 10 to 15 kl/rnol). The aromatics transalkylation reaction is
also very slightly exothermic..-\11 the reactions that consume hydrogen are
highly exothermic (Tables 4.i and 4.8), and the same holds true for the aro-
matics alkylation reaction by olefins.
4.3.2.2 Thermodynamic Equilibria
All reactions that consume hydrogen and yield light molecules are complete
up to temperatures of 600C and over. In contrast, all the desirable ones in
reforming are equilibrium reactions in the. 300 to 60CrC range. '
Figure 4.3 shows that increased temperature is detrimental to formation
of the most highly branched paraffinic structures, i.e. those that have the
best octane numbers. As a result:
- the best operating conditions to achieve a maximum amount of useful
isomers are situated at T < 100cC. and the pressure has no effect on the
equilibrium;
- cyclopentanic naphthenes prevail at T > 500C.
For paraffin dehydrogenation, the variations in free energy (t\G) of reac-
tion change very little from e6 to C9- Figure 4.4 gives the mole fraction of
heptenes at equilibrium for various hydrogen pressures. At 5OOC, it goes
from 0.035 to 0.07 when the total pressure goes from 15 to 3 bar.

FIgUre
4.3 Variations in the distribution of paraffins with 7 carbon atoms at thermody-
namic equilibrium.
 ~.t. CATALYTIC REFoRMwG 115

:::::::!!!=::=:::::::::.
0.8 ~:.~~.,:..~.:.: '. 15bar
' , , , , _
E -'. "':~: 11 bar
2 rK;7 ~'7bar
g
"3
0- "'3 bar
Q) 0.6
'i
c
.2
ti
~
Q) 0.4
(5
:E

0.2 3 bar
7 bar
11 bar
15bar

480 520 560 600

T(C)

Figutt:
4.4 Dehydrogenationequilibrium of n-neptane t?n-heptenes.

Dehydrogenation of cyclohexanic naphthenes is highly influenced by the

hydrogen partial pressure. For instance, as indicated in Figure 4.5, at
40 bar over 10% of the cyclohexane remains present at equilibrium. while
at 5 bar total conversion is achieved from 500'C on. Replacement of the
aromatic ring by alkyl groups at Iso-condltlons moves the equilibrium
toward more thorough dehydrogenation:
- low hydrogen pressures and high temperatures promote aromatics
production. Light feeds require processing at higher temperatures in
order to achieve the same conversions.
For n-paraffin dehydrocyclization, the equilibrium is more complex.
Along with olefins (not shown in Figure -4.6), it involves isoparafflr:s.
cyclohe..xanlc and cyclopentanic naphthenes. aromatics and hydrogen of
course. To convert over 90% of the heptanes at 500'C, pressures lower
than 10 bar are requtred,
116 ChaotlH 4. C,.;TALY7'IC REF01IMlNG

,
~
+
E -- O+=@+3H
z Z

0.1

0.05

0.01

450 500 550 T(OC)

Figure
4.5 Influence oftemperature and pressure on the mole fractions of naphttienes pre-
sent at equilibrium for hydrocarbons with 6 and 7 carbon atoms.

100

75
Q+H z

tf.
'0
~ 50
C1H,6 ==: o !t
f1
25
T=500"C
e +4H 2

Figure
4.6 Variation in the mole fraction of C; hydrocarbons versus PHt
 ChaP/!' 4. CAW-YTlCREFoRMING 117

Figure 4.7 shows that at soooC with a total pressure of lO'bar C1 and C9
paraffins are transformed into aromatics but the conversion is limited for
C6 and C7's:
- dehydrocyclisation requires high temperatures which increase with
the lowering of the number of carbon atoms of the feed.

100

III 75
0
~
E
2
III
'0 50
t!-
o
::E
25

400 450 500 550 ' 600

T(OC)

'. F
r;u.;iguree I Influence of the number of carbon atoms on the mole fraction of aromatics at
~ equilibrium versus T'C loTPH~ = 10 bar.
6. C6: .. C7 ; 0 Ca; C9' -

. fJ.2.3 Conclusions
The thermodynamics of the desired reactions determines operating condi-
tions: high temperature. around 5OOC and hydrogen pressure as low as possi-
ble. Since the reaction produces hydrogen. the minimum pressure is deter-
mined by the desired aromatics conversion.

4.3.3 Catalysts [2. 3]

of.3.3.l Type
All current catalysts are deri ved from platinum on chlorinated alumina as
introduced by VOP in l~49.
a. Platinum on Chlorinated Alumina
A few hundred tons of this type of catalyst are still being used in the world.
Table 4.9 gives its main characteristics.
 Characteristics Average values

Support Yo: alumina

Impurities: I'
alkalis + alkaline earths + iron (ppm) I <500
Specific surface area (m 2{g) 150-250
Total pore volume (cm 3/g) 0.5-0.8
Pore diameter (nm) 8-10
Chlorine content (% wt) 1

LPlatinum content (% wt)

Extrudate or bead diameter (mm)
0.2-0.6
1.2-2.2

iThbi:l
~ Main characteristics of Pt/AIPJ catalysts.

The base is Yc alumina, chlorinated at approximately 1% wt. The specific

area ranges from 150 to 250 m2/g, and the pore volume from 0.5 to 0.8 cm3ig.
Consequently, the average pore diameter is approximately 10 nm. The alumi-
nas used are very pure and the alkaline metals, alkaline earths, iron etc..
always account for less than 500 ppm on new catalysts and usually less than
100 ppm. The amount of platinum is on a downward trend, usually ~anging
between 0.2 and 0.6% wt. The catalyst is implemented in the form of .beads
(fixed and moving beds) or extrudates (fixed bed), approximately 1.2 to
2.2 mm in diameter.
In addition to the properties of the support and the amount of platinum. it
is crucial to make the most of the small amount of platinum (cost of
platinum == $IS/g) on the catalyst. As such, each platinum atom should be
accessible to the reactants and therefore should be in unit amounts of the
smallest size possible. A gram of platinum well dispersed on the surface of an
alumina will represent an area of approximately 260 m2 and wiU have maximum
hydrogenating or dehydrogenating activity as indicated in Figure 4.8. If on the
contrary non-optimum operations are carried out during catalyst implementa-
tion, values lower than 100 m2/g of platinum will be obtained and the catalyst
will be approximately three times less active.
Dispersion D is defined by the ratio between the real area and the theoret-
lcally possible area per gram of platinum. The theoretical area can be achieved
on industrial catalysts. A reduction in activity is directly proportional to the
variation in D for dehydrogenation (Fig. 4.8). For dehydrocycIization (Fig. 4.9)
it varies in the same way but in a more complex manner.

b. Bimetallic [12]
The first bimetallic catalysts were introduced in the late sixties. They consist
of platinum associated with another metal (iridium, rhenium, tin or germa-
nium). While maintaining acceptable run duration, they have allowed activity
 I P(bar) T("C) ~(moI) WHSV

.~
He
1 115 20 20 it
1 300' 5 8.5 ~
I
s:
<D
7 :1:...
U
(5
6 ..
5
~
c
.( .2
asc
3 cD
CI
e
'0
2 >-
.r:.
cD
0

o 50 100 150 200 250

m2 /g Pt
I I
o 50 Dispersion (%) 100

I I
Ego
4.8 Influence of dispersion on hydrogenaling-dehydrogenating activity, Example of
hydrogenation of benzene to cyclohexane and the opposite reaaion.

to be boosted at identical operating conditions (Ir), operating pressure to be

lowered with the same run duration (Re), or low pressure yields to be
improved (Sn and especially Ge, seldom used today). The use of Pt/Re is now
most common in semi-regenerative processes and Pt/Sn in moving beds.
The standard second metal content is shown in Table 4.10. Depending on
these concentrations, catalyst properties can be adapted to the unit's operat-
ing conditions. An interaction between two metals, whose properties and
chemistry are widely different, must be achieved on the scale of the nanome-
ter and this is the manufacturers' secret
To achieve interaction between the two metals. the first thing is to get the
best equidistribution on the micrometric scale. It can be seen by means of a
Castaing microprobe. Figure 4.10 shows the example of a platinum/tin catalyst
on chlorinated alumina seen along a bead diameter.
The effects of different metals on performance have not been publicly
quantified. since there is no non-proprietary literature available. However, it
can be stated that the different elements do have a positive effect. although
the effects differ. The following properties are involved: stability of dispersion
over time, modification of coking resistance. change in selectivity and. espe-
cially for high concentrations of iridium. a significant effect on activity,
120 C~ler 4. CATALYTIC REFORMING

'0
2
n-C~Hle-~
o A
Dispersion Pt 1 0.4
1.5 Carbon ("10 wt) 1.5 15

T= 470C
PHC =2.2 bar
PVAJ 203
'0'" rate at PH: =18 bar
o'-- ...... -'-- ....- -'- . . . . ._ ___=.

o 5 10 15 20 25
PH, (bar)

Figure
4.9 Denydrocyciization rate (r) of n-neptane uersus the dispersion percentage of
the metals.

o 330 660 990 1 320 1 650

Bead diameter (lim)

Figure
4.10 Distribution profiles (Pt. Sn, Cl) by microprobe.
 0Iap:er 4. CATALYTIC REFCRMING 121

Second metal COnceJllntiOD ('Yo wt)

Iridium OJJ2to020
Tm O.os to 0.50
Rhenium 0.20 to 0.60

~~
Standard second metal content values tn
bimetallic catalysts.

Figure 4.11 illustrates the influence of elements such as tin, indium, rhenium
and iridium on the evolution in the platinum surface over time as compared
with platinum alone. In all cases, the effect is highlypositive. This is why these
elements have been selected for numerous industrial catalysts.
Figure 4.12 shows the variation in octane number in a constant tempera-
ture test versus time. In these operating conditions - feed end point very high
and test duration short - deactivation is related only to coke formation
(lnd/or coke toxicity with respect to activity. The bimetalliccatalyst, here plat-
inum-rhenium. proves incomparably more stable than the monometaJIic one.
The other "second metals", Sn and Ir, give the same type of effects.

1.00 T=6OO'C
~=2lJXllkg-1 h- 1
*Pt-lr
Opt..Jn
0.75
a: PtRe
OPt
d
"0 "" Pt-Sn
S
Q.
cD 0.50
;2
:1
\II
0
0
-c

I 1 ! I to
o 10 20 30 40 50
Tme(h)
L--- __
Figure.
4.11 Effectof different metals on platinum sintering underhydrogen pressure.
122 C/lapter4 CATALYTIC REFORMING

105

100

Feed, {ASTM: 95 ~ 2OO;C

naphtha PIN/A: 50 - 42- ~Q vol
95
P';dObar
T=500C
HtHC = 4 moVmoI
WHSV =2.5 (h- f)

o 50 100
Tme(h}

I Figure
4.12 Compared stability of mono-and bimetallic catalysts (PtIRe).

Figure 4.13 illustrates the effect of metals on selectivity, measured by the

hydrogenolysis of hexanes to light products. Depending on the hydrogen pres-
sure, activity drops for platinum, but at low pressure platinum-rhenium proves
to have less of a cracking effect-than platinum alone. In contrast- tin kills all
hydrogenolysis activity and consequently leads to more selective catalysts.

4.3.3,2 Reaction Mechanisms [1, 7.8)

The platinum on chlorinated alumina catalyst has two functions: a hydro-
genating-dehydrogenating function provided by the platinum and an acid func-
tion provided by the alumina. The two functions are indispensable in promot-
ing the desired reactions (fable 4.11).
Most catalytic reforming reactions are well understood today: dehydro-
genation and hydrogenolysis take place on metals. isomerization and hydroc-
racking require metallic and acid sites, disproportlonatlon and alkylation are
promoted by acids alone.
Dehydrocydization is not as well understood. Nevertheless, although plat-
inurn alone can promote the reaction, acid sites also seem to be involved when
the dehydrogenated species have been generated on the metal (Fig. 4.14).
 Ct:aprer4. CATALY11C ReFORMING 123

(n+iso) CsH 14 == C$ ReIPt

T=35O"C (atoms)
HzIHC = 3 moVmoI o 0
(J 1
Pt and Pt-Re/~03
2

i
.'
o
". " 4
10 20

Figure I
~ Hydrogenolysis of hemnes in the presence of bimetallic catalysts.

Reactions Mechanisms Active sites ....

t I
Dehydrogenation M Pt
Dehydrocycfization M Pt
and
B Pt and Pt s A
Isomerization B Pt +A
Hydrocracking B Pt +A
I
Hydrogenolysis ~l Pt I
! t
Disproportionation/a1kylation I M A
Coking ! M Pt or A
and
j B Pt +A
~I: monofunctional "Pt: platinum
B : bifunctional A: acid
L -----,
Table
4.11 ! Reaction mechanisms.

Coking is the most complex reaction. Metals alone or acids alone cause
coking in the presence of hydrocarbons at high temperature. The acid function
alone causes rapid coking, as observed for example in catalytic cracking, but
the presence of platinum limits this type of coking.
 P : paraffin
p Ne AR AR : aromatic
M M o: olefin

~Ns~
DO : diolefin
TO : triolefin
p
Ns : naphthene
cyclopentanic
H+ Ns
JfM ~ Ns
It
: naphthene
cyclohexanic
MW
0 AR NOs : naphthene
H+ Ne
M cyctopentenic

H- NOs : naphthe
NOs
JfM cyclohexenic
~ Jf MH+ MOOs : substituted

~,
cyclohexadiene
DO AR
NO e
M
M : catalysis
by the metal
JfM H : catalysis by
TO NOO e AR the acid function
H+ M MH : bifunctional
catalysis

IFigure
I4.)4
I Reaction routes incoloed for aromatization.
L-J

In catalytic reforming, an operation where gaseous hydrocarbons are in

contact with the catalytic solid, the reaction occurs on the surface of the solid
as long as temperatures remain lower than 550~C. Above this, thermally actl-
vated homogeneous phase reactions can take place. On the catalyst surface
~ (Fig. 4.15) there are a large number of adsorbed species that are dehydro-
genated to a greater or lesser extent, either on the metal or on the acid part of
the support. The adsorbed species change by isomerization, cyclization or
cracking and are then desorbed. Note that there is naturally also adsorbed
hydrogen whose function will be discussed in the following section.

4.3.3.3 Hydrogen's Action [II)

Hydrogen is not involved as a reactant in most reactions, except for
hydrogenolysis and hydrocracking. It is involved in the reactant and product
adsorption-desorptlon equilibrium and as a product of equilibrium reactions.
It limits the conversion of certain hydrocarbons.
a. Product Yield and Quality
The impact of hydrogen on reformate quality is related mainly to the presence
of more or fewer residual naphthenes. However, the principal effect is the pres-
 Gas n-Paraffrn
phase

Adsorbed
phase

-H+
returning
tosuppor1 'II
Initial Isomerization Isomerized

/r0300n (2) carbocatlon

II '"
-.
"Coke" ~cracking ~cracking
Cyclized
carbocation

+Ughter ~I
caroocatlon /
. Cr

Coke Cycles

Aromatic + 4H 2 Ught
(DHCy) obtained isoparaffin

(1) Development of initial carbocations;

(2) Development of second generation carbocancns.
Conversions areas follows:
- Paraffins = isoparaffins
- Paraffins - 1 H2 consumed by cracking
2 (or n) light isoparaffins;
- PaIaffins ;:::::!' aromatics + 4 H:2 4 H2 produced by cyclization
- Theinside of the box concerns the adsorbed phase
- Theoutside of the box concerns the gas phase
- InsKle the box. circled items <:om!Spondto species adsorbed on the platinum
- On mettalic siles. the followingreaction also occurs;
naphthenes - aromatics + 3 H2
- )~} standsfor a hydrogen whoseconsumptionor production balance is zero.

Figure
~.15 Essential changes in paraffins on the catalyst surface.
ence of olefins. which can go up to more than 1% when the process is run at
pressures lower than 5 bar. Reformate yields are modified by a conjunctton of
thermodynamic and kinetic effects. As illustrated in Figure 4.16. this can be
measured at high octane numbers by 2 or 3 extra yield points when the pres-
sure goes down from 20 to lObar for example.

83

~~
82
S-
al
ell
sa: 81 ;0

~<'6
~
q~
80
c.:t
79

Middle East naphtha

78

97 98 99 100 101 102 RON

I'~~I
4.16 Effect of pressure on retortnate yield.

b. Effects on Reaction Kinetics

The kinetics of heterogeneous reactions is generally very complex and this is
particularly true for the dehydrocyciization reaction. Figure 4.17 illustrates
this with the variation in dehydrocycllzation rate of n-heptane at 470"Cversus
the hydrogen pressure PH. for different hydrocarbon partial pressures. Note
that, depending on PH., there is a maximum whose ordinate and abscissa
depend on the hydrocarbon pressure. Hydrogen is involved in generating
unsaturated species on the catalyst surface (it limits formation of overly unsat-
urated species that could develop solely into coke and would block part of the
catalyst), but also by the fact that it is adsorbed on the catalyst, thereby block-
ing certain sites that are no longer available to activate reactions.
The dehydrocyclization reaction rate can be expressed in the following
furm: .
p. x pS/2
r= kK P H2
[A + BPU; + CPH2Pp + DPr!22 + EJ1,l
 Chap/e( 4. CATALYTIC REFoRMING 127

where:
It is the reaction rate constant
K is a composite constant of adsorption equilibrium for paraffin P and
hydrogen Hz
A. B. C. D, E involve adsorption constants for dehydrogenated species
and hydrogen
Pp is the paraffin partial pressure
PHt is the hydrogen partial pressure
K. A, B. C, D. E are dependent on the temperature, the catalyst used and
the hydrocarbon under consideration
This equation shows that hydrogen exerts a complex action on the dehy-
drocyclization rate. Even though the equations are simpler for other reactions,
hydrogen pressure is always a parameter that influences reaction rates. It can
modify the rates of two competitive reactions differently and consequently
influence selectivity.

T= 470C
,
coo 1.0
PtlAI20 3
OJ =
C 1.5%wt
I PMC (bar)
~

'0 ~ 0.5
.s o 1
s
'5 0.5
5
III
~
'15
III
iii
a::
o 10 20

'--f--'-
I Fa:are
--------------------------'
l-tli I Dehydrocyclization rate I.:ersas hydrogen pressure.
C-----J

Asan example, Figure 4.18 shows the variation in methylcyclopentane con-

version, either to benzene which has a high RON, or to C6 paraffins which have
a lower RON. versus hydrogen pressure for three different catalysts: platinum.
platinum-tin and platinum-rhenium, At a hydrogen pressure of 25 oar. benzene
is fanned twice as fast as hexanes, while at i bar, it is formed five to six times
faster with platinum and platinum--rhenium and 12 times faster with platinum-
tin.
 (8 e
10
y ~(iso+n)C6
Pt-MlAl 203
PtIM (atom) = 1
8 C = 2.5%wt
M
So A
6 PI 0
Re

2 PHC>.=2bar

;~;-----------------------------'
Figure'
. 4.18 i Influence of hydrogen pressure on the selectivity of metttyicydopentane
_ _~! conversion.

c.. Effect on Coking

As indicated above, hydrogen influences polyunsaturated species concentra-
tions on catalysts. It therefore limits the average concentration in intermedi-
ates likely to develop into coke. For instance, the time required to lay down an
~amount of coke on a catalyst is determined. 1.5% wt in Figure 4.19. The time is
seen to increase very quickly as the molar ratio H2/heptane rises at constant
total pressure. In an initial analysis. the coke formation rate from a reactant i
can be expressed by the following formula:

where:
kc; is the coking rate constant
Pi is the partial pressure of compound i
PH2 is the hydrogen partial pressure

Experimentally, n is close to 2.
Catalyst aging due to coking In an industrial unit running at constant RON
means that the temperature has to be raised more or less quickly to maintain
 Chaptet4 CATALYTIC REFORMING 129

15% wtofC
on PtlAl 203

T=S10"C
10
p= 5 bar
WHSV =3.5

o 5 10
H2 I HC (moVmol)

Figure,
~ Effect of hydrogen pressure on coke {ormation rate.

performance as time goes by. Figure 4.20 gives a schematic idea of the varia-
tions that could be observed for different hydrogen pressures with hydrocar-
bon pressure remaining constant. By going from 20 to lfl bar, the time that can
elapse between two regeneration operations is divided by four.

4.3..3.4 Poisons and Inhibitors [~I

The catalytic reforming catalyst can be affected by adsorption of inhibitors

and reversible or permanent poisons. The behavior is different depending on
the function under consideration: metallic or acidic.
a. J/etallic Function
Platinum can be poisoned by the presence of organic sulfur which is converted
into H~. HzS is adsorbed reversibly with an equilibrium reaction on the metal
as shown by the equation:
Pt + H~.s ~ ?tS + Hz
Platinum sulfide is practically inactive.
The metals or metalloids in the feed - arsenic due to crude origin. lead
due to improper refinery operations or mercury when electrolytic hydrogen is
used - are adsorbed irreversibly on the platinum. The same is true for the
130 c.'W1:er":. C,:'T,l.D;.:; REFORMING

o'" pressure (bar)

RON", constant

o 3 5
Time (arbitraryunits)

Figure
....20 Influence of pressure on catalyst stabiiay:

coke formed during the reaction. Figures 4.21 and 4.22 illustrate the effect of
lead and coke on activity in cyclohexane dehydrogenation with a platinum on
alumina catalyst. Activity is reduced by a factor of 5 by 1 000 ppm of lead or
1% wt of coke.

b. Acidic Function
The support's acidic function is reinforced by the presence of chlorine on the
catalyst, generally approximately 1%. The function can be inhibited by bases,
nitrogen compounds for example, or destroyed by coke. In addition, the AI-CI
bonds created by the action of chlorine on alumina are not stable in the pres-
ence of water or ammonia. They are broken as shown by the diagrams in
Figure 4.23.
From a practical standpoint, the loss of acidity makes itself followed by a
drop in isomerizing, cracking and dehydrocydization activity. For instance,
the rnethylcyclopentane to benzene conversion reaction requires prior iso-
merization to cyclohexane, and the loss of chlorine diminishes this activity. It
can be restored by injecting chlorinated derivatives such as CCI4 or
CCI 2 =CCl2 , which are converted into Hel with hydrogen as indicated in Figure
4.24. If the elution of chlorine by water is not offset, dehydrocyclization activ-
ity falls much more quickly than in the absence of water. This is illustrated by
Figure 4.25.
 40

iii
>-
iii
iii
o-@ +3H~
o
I
~
i'
.c .,
~
o o
'0
E 10
o

1 000 2 aoo 3 000

Pb (ppm we)

gFigure
~ Influence of lead on the dehydrogenating acticity of platinum..

0-0 +3H 2

PtlAl 203

P=1bar
T=3CO:C
H;HC '" 5 moVmcl
WHSV=57

2 3 4 5
Coke(% wt)

Figure
~.22 Effect of coke on dehydrogenation rote.
 [ -,~~~]-H~+NH3_
A

o CI

AI-OH
/

8 -, -,
Al-CI A1-0H
/ /
0 H2O ;::=. 0 +HCI
-, -,
AI-OH J14-0H
/ /
'-...--1-- -1

Figure
4.23 Schematic chlorine elution reactions.

The action of ammonia is reversible as shown in Figure 4.26. The dehydro-

cycllzatlon rate of n-heptane is divided by 5 in the presence of small amounts
of ammonia (37 ppm), but when it is eliminated from the feed, the initial activ-
ity is gradually restored. This is true only to the extent that processing has
lasted a short -time, otherwise a compound to generate HCl would have to be
injected.
Coke is a permanent and irreversible poison and coke accumulation lowers
dehydrocyclization activity. The drop is significant between 0 and 1% coke. but
even between 1.5 and 4.4% it is approximately a factor of 2 as indicated in
Figure 4.27.
 C(--@)
2.5 Ptl A1 203
=
C 2.8o/ewt
T=470DC
calCl!' PHC =2 bar
c
.2 o wilh CCle injection
U
:l 2.0 withoutCCle injection
s
'C

I
C
Q)
N
C
.8
1.5
.E
;:.
:~
u<II
I
.::
iii
Q; 1.0
a:
ira '= activity at P~ =18 bar
without CC1c injection
0.5 ~_-..1- _ _'---_.f..-_-..1-_-L _

o 5 10 15 20

: Figure
I 4.24 Ettect of acidity on metiiylcyclopemone aromatization.

1 PtlAl 203 catalyst

2 PtlAI203 catalyst (wet test)
I
o 50 100
TIme (h)
:.-.
Figure i
4.15 ! Influence of uxuer on dehydrocyxiization acticity.
 n-C7 ~@+4H2
T= 470~C Pw;; =2.2 bar PH2 = 17.8 bar
1.0
I
I
I
pure n-C7 I n-c;
I
amine II
-I- pure n-C7
~ I (37 ppm N) \
I I
x I I
I
~ I
I
~ I
10
iii 0.5
o
a-2-o- : I
I
I
I
, I
I
1
~ I
I
t
I
.J::
I I
I I
"0 I

i~
..

I I
0
0 10 20 30
Time (h)

Influence of ammonia on the dehydroc)'cli=ation rate.

~C7Hl~ - - ~ T =470'C
P HC =2.2 bar
Ptl A/:P3

2 '0 =rate of reaction at PH,. =18 bar

Coke (%wt)
o 1.50
4.40

o 5 15 25
p~ (bar)

Figure
'.21 Influence of coke on the dehydroeyclization rate.
433.5 1lgeneration [21
Reforming catalysts normally become deactivated by coke deposit. In a fixed
bed operation,approximalely l or 2 atoms of carbon out of 1 million in the
feed are laid down on the catalyst in the form of coke. AdditionaH1. as time
goes by platinum dispersion normally decreases very slowly. This develop-
ment can be accelerated byvarious incidents such a chlorine loss for example
or the presence of hot spots in the catalytic b e d . "
Regeneration consists irst of aU in burning the coke off the catalyst; coke
concentration can go up to 20% on a PtjRe. The platinum crystallites
also have to be reconverted into precursors that will allow the initial
catalyst activity to be restored after reduction. The operation is schemati-
cally shown in Figure 4.28. It involves an oxidizing attack which forms volatile
chemical species of platinum (probably PtCI2 2 AlCI:J.The species then react
with the support hydroxyls to restore the surface complexes of the new cata-
lyst.
The problems posed are mainly related to temperature control to prevent
reduction of the support's specific area and keep platinWn crystaUites from
developing to a size such that they can no longer be redispersed C$' > 5 nm).
Alumina supports are stable in normal conditions of use. Coke combustion,
especially if the concentration is high, can cause localized hot spots
tr 700C) that can degrade the alumina irreversibly. It loses its area and con-
sequently (Fig. 4.29) its activity, but this modification fmthermore causes a
lessening of mechanical strength. This means that dust is formed, which is
detrimental for proper operation of the catalytic bed.
Small platinum crystaDites can be redispersed readily in the presence of
chlorine and oxygen. However, generation of large crystallites should be
avoided by keeping a chlorine level of some 1% weight on the catalyst as
shown in Figure 4.30.

4.3.3.6 Kinetic: Data

The reforming operation kinetic data are quite numerous for the monometallic
platinum-based catalyst, but only few exist for bimetallic catalysts.

Q. Monometallic Pt Catalpt
Platinum-based catalysts have been used between 20 and 70 bar. In this range,
as indicated in Figure 4.31. the naphthene dehydrogenation rate varies little
with pressure. Dehydrogenation is the fastest reaction, some 7 to 8 times
faster than paraffin or cydohexanic naphthene isomerization. Cracking, the
sum of hydrogenolysis and hydrocracking reactions, is promoted by raising
the pressure, whereas debydrocydization is slowed down. Both are around
30 times slower than dehydrogenation.
The coking rate decreases very quickly with increased hydrogen pressure:
the apparent kinetic order versus hydrogen is greater than -2. This rate is
approximately 2 orders of magnitude smaller than that of the other reactions.
 000
o I I I 0
00000 "00000/
o - ()()()OO - 0
~8888
1IIIIl
o-6~)OO-O
I / / / I

CI 0 0 -0 CI
C/\ I I I / CI
-'00000'- , -.
o_~_o
0- _0
I~/I

A'CI~ 000
I I I
000
0 - \..""\0000 - 0
o -\.'0000- 0
/ / / I I

000
~:::. .=~I:(AICI3)=)
I I I Cl-. .-0 C1-. .-Cl
()()O ,..,. pt -. ....... Pt - .

O=~OO-O
0=
_~
99-77-777/ ~ 7 / ; / /
0
0
I
- 0
I
0
I

Figure
4.28 Schematic diagram ofplatinum redispersion to~: .>x)'Chlorinu.[ion.
 ChI/ptfN 4. CATALYTIC REFORMING 137

.. 1.00 500C
So
600C

700C
0.75

750C

0.50

Space velocity: 100 lit-I tr l (dry air)

0.25

o 20 40 60 80
Time (h)

Changesin the alumina surface area V1SlIS time and temperature.

5 (m2 {g PI) D
t, f Spacevelocity:'2 000 1/t"IJrf ~

~ 1.12 1.21 CI(%wt) 1~04' -. ~

1 ! ! -1
-::---0,.....-------0
......
200 f- e !.

- 0.5

100 ~
0,0 : with CCI4 injection
: without CCI4 injec:lian

I I I I
o 10 20 30 40
Trme(h)
Figure
-1-.30 Changesin the platinum surface area in an oxidizing atmosphere,
138 Chaorer 4. CATALYTIC R:.=:;ii,WNG

Dehydrogenation
2

8 Isomerization
c"
0 ~ C~C~~~.
~

~~:~".~'
C
ell
01
e
} ..- ~
Ci
-0 -,

~ 0 '.
:> .............~~~
~

Figure
4.31 Various reaction rates versus hydrogen pressure.

Apparent activation energies (Fig. 4.32), or rather the thermal increments

measured for these reactions are widely different. For hydrogenation it is
around 42 kllmol, while for dehydrogenation it is approximately double. Since
these reactions are rapid, they are often limited by diffusion. Isomerization
activation energy is of about 100 kJ/mol, whereas the value for dehydrocy-
cIization is around 150 kllmol and for cracking about 190 kl.rnol. This is why
cracking prevails over the other reactions, thereby lowering the C5+ yield,
when the monometallic catalyst ages and is consequently operated at a higher
temperature. Coking, a complex reaction, has a high activation energy
(150 kl/rnol), As a result, the higher the operating temperature, the faster
deactivation occurs.
All reaction rates involved in reforming vary according to the number of
carbon atoms. For instance in dehydrocyclization, conversion of n-e 6 is very
slow, approximately one-tenth of that or n-e 7, which in tum is around three
times lower than n-e\(} (Fig.4.33). Likewise, cracking of n.(s is about four times
slower than that of n.(lO'
b. Bimetallic Catalysts
Bimetallic catalysts have a more complex behavior. In their range of operation,
the reaction rate for dehydrocylization can reach a maximum depending on
 CNQtw 4. C~TAJ.YTIC fiEFoRMING 139.

Hydrogenation 42

510 450
T(=C)
~!

- ~ j/nRuence 01temperauueee reaction rate.

1.0

o
C,-C,+C i _ 1
- CZ+C._ 2
""",-C 3+C'_3

o 6 8 9 10
Number of carbon atoms

~
4.33 Influence of the number 01carbon atoms on reaction rate.
hydrogen pressure. Figure 1.34 shows that for the dehydrocyclization reaction.
platlnum-lridtum is the most active in the 10-30 bar range. platinum and plat-
inum-rhenium are fairly close. but that platinum-tin is less active. At low hydro-
gen pressures. platinum-tin activity is the highest. except for platinum-iridium
which is not used at low pressures for other reasons.

Pt-M catalyst
M: Pt= 1:3
T= 470C
PH(; = 2.2 bar
M=lr ~
Ah --+-
2: 2 Au .0.
x Re .--6--
~
>.
Pt alone .._.-
iii Sn .0(>.-
iii
0
Ge -
I In .-4-
~ Pb
, -0-
s:
a
...

o 10 20

r---l;..- --'
l Figure i
I
1 4.34 I: Variation in dehydrocyclization rate versus catalyst formula and hydrogen
L-J pressure.

The low-pressure advantage of platinum-tin is also found in dehydrogena-

tion of naphthenes (Fig. 4.35). Here Pt-Ir and Pt-Re tum out to be better in all
cases than platinum alone.
Finally. for the conversion of n-heptane into toluene and light products, the
important point is that (Fig. 4.36) for platinum alone the ratio of dehydrocy-
clization (ED and cracking (ED activation energy is less than 1 whatever the
pressure range. Any increase in temperature causes a loss of selectivity,
In contrast. the ratio is slightly greater than 1 for platinum-iridium. The
same is true but more clear cut for Pt-Re and Pt-Sn,and for Pt-Sn even at low
 C~4. CATALYTIC REFORW:; 141

1
O+=!:@+3H2
2

5% coke
Ptlr o PtRe
o PtSn PI
30
~
X

I
Ol
"j
s: 20
"0
S
~
">
U
-c 10
..' ..-
.....'
.... ... .'
'

Figure
4.35 Variation in dehydrogenation rote versus catalyst formula and hydrogen.
pressure.

temperature. This explains why bimetallic catalysts maintain their C5+ selec-
tivity, or lose very little during runs, when operating temperatures are gradu-
aJIy raised.
Pseudo-kinetic models based on some fifty compounds and around a hun-
dred reactions have been developed. They can be used to rationalize most
observations.

4.3.3.7 Condusions
Catalytic reforming catalysts activate a large number of reactions whose exo-
!endothermicity, thermodynamics and rate are Widely different. They are sen-
sitive to impurities, so proper operation will require prior purification offeeds.
They produce coke at a slow rate. which is nevertheless too fast to allow sta-
ble operation. The coking rate can be stgniflcantly reduced by the presence of
hydrogen. As a result, it is advantageous to implement catalysts under the
highest hydrogen pressure compatible with reaction thermodynamics and
 Pi<:: =2bar PtSn
C=2%wt

1.5

Pt-lr

------Pt
0.5

o 10

Figure
4.36 Variation in selectioity vers::s metallic formula and pressure for various
catalysts and different H: pcrziai pressures.

with the specified objectives of run duration (SR reforming) or catalyst circu-
lation rate (continuous regeneration reforming). Furthermore, even though
they are increasingly selective, th~'y cause light by-products (Iuel gas or LPG)
to be formed, which have to be s~;'.trated from the gasoline.

4.4 Process Data

4.4.1 Operating Variables
The refiner's requirements are the ::-.asis used to define process data: reformate
quality (RON) and quantity, flow rate and type of feeds to be processed, at
least a few extreme feeds. The unit should not usually be shut down more than
once a year in the case of a fixed bed process. The process licensor will define
an optimum proposal on this basis: total pressure, hydrogen pressure, amount
of catalyst and its distribution in ~:'e reactors and finally operating tempera- .
tures.
4.4.1.1 Ddinidons
Total pressure is set once and for all in the design phase and is therefore
not an operating variable.
Hydrogen pressure is obtained by recycling part of the hydrogen pro-
duced. It is dictated by the molar H2Ihydrocarbons ratio at the inlet of the
first reactor. Only the hydrocarbons in the feed are taken into account.
Lighthydrocarbons contained in the hydrogen are not taken into account
in this ratio. In contrast, they help modify the reactant and hydrogen par-
tial pressure. Hydrogen purity is defined by the molar percentage of
hydrogen present in the recycle gas.
Feed Dow rate is a design value. The volumes of the 3 cr 4 reactors and
the total volume of catalyst are defined in such a way that at a reactor
inlet temperature (from 480 to 490*C), the required reformate RON per-
formance can be achieved at start up. The space velocity, LHSV and
WHSV, is defined in this way.
The reactor inlet temperature which yields the required octane at full
capacity at the beginning of the run is called TSOR (start of run). The tern-
perature at which the unit must be stopped at the end of the run is
termed TEOR (end of run). The second is often an operating temperature
limit related to metallurgy (Tinlet =:. 540 to 550'C) and can depend on
operating variables such as:
- a recycle gas that is too impure to provide sufficient hydrogen recy-
ding with the existing compressor;
- a Cs. yield that is too low, prompting the operator to stop the unit for
economic reasons. . .
The time elapsed between start up and shut down for regeneration is the
cycle length of the run. It is usually expressed iri months, but can also be
found in cubic meters of feed processed per kilogram of catalyst or bbi/ib.
Catalyst lifetime is the operation time between the first start up and
replacement with a new load of catalyst. It is expressed in years or some-
times in cubic meters per kilogram of catalyst. The decision to replace a
catalyst is made when its properties after regeneration are too different
from those of a new catalyst.
An operation is often defined by its severity. Low total pressure and
Hz/He ratio. high RON and space velocity bear witness to high severity.
This concept indicates how difficult the operation is.

4.4.1.2 Tempe:rat1ll'e

The operator bas very little freedom to act on an industrial unit in normal
operation. Temperature in fact is the only operating variable he can use to
adapt to changes in feed Qualityor to produce reformates of slightly different
quality (a few octane points). With time, temperature is raised gradually to off-
set the effect of catalyst deactivation by coking. The temperature variation
curve with time depends on the severity of an operation and naturally on the
catalyst quality.
At lso-conditions, a platinum catalyst alone or a bimetallic Pt-Re catalyst
will allow the required octane number to be achieved at approximately the
same starting temperature TSOR (Fig. 4.37). In contrast, the variation in tem-
perature during the run will be much faster with a monometallic catalyst. Run
duration can easily be shorter by a factor of 5 or 10 depending on the severity
of the operation.

TEOfi

0.;

0
U
1rI

~
h

TSOR

tz
TIme (arbitral'}' units)

i Figure
! 4.37. -
I Van'arion in temperature dun'ng a run.
~

Yield (Fig. 4.38) does not vary in the same way. Monometallic catalysts
show a drop in yield as soon as the temperature rises, while bimetallic C,;.-
selectivity remains the same practically until the end of the run. Note that
although platinum-tin is less stable at 10 bar than Pt-Re,it has the same behav-
ior with respect to yield.
The temperature TSOR required to achieve a specified RON is directly
related to the RON under certain conditions as indicated in figure 4.39.

4.4.1.3 Effect of Space Velocity

The operator sometimes modifies the space velocity to adjust to temporary
reformate needs or because of an interruption in supply. Figure 4.40 shows that
 Middle East naphtha
% Pt=O.35 P= 10 bar
H2IHC = 5 moVrnol
90 Space velocity =3
RON =98

~ Pl+ Re
85l==----..;...:.......;~..;..-.y}_--~~n
E:
C
;'80
o

75

70

Cycle (m3 of feedlkg of catalyst)

IR~re:
4.38 I variation in c; yield during the run.

beginning with a space velocity = 2 for example, an increase to 3 requires rais-

ing the reactor inlet temperature by SC to maintain reformate octane. In con-
trast, a drop to 1.5 allows the inlet temperature to be lowered by 6C. These
values may vary a little depending on the operating conditions and catalyst.

4.4.1.4 Effect of Total Pressure and BzJHC Ratio

The total pressure and the HdHC ratio influence two things: aging, i.e. run
duration. and yield. For a monometallic catalyst, the TSOR required and its vari-
ation with time versus pressure were presented in Figure 4.20. A decrease in
pressure has a very important effect on Us variation. The HdHC ratios also
have a significant impact on deactivation rate. The monometallic catalysts in
the seventies (Fig.4.41)worked at high ratios (7 to 8) to achieve stability com-
parable to the more modem catalysts with H2/HC =4.
Pressure also modifies yield (see Section 4.2.3.3) as shown in Figure 4.42
which gives variations in yield at the same RO:.\ for three different pressures
on a paraffinic feed (naphthenes 22?~ vol). Roughlyspeaking. 2 to 3 points are
gained when pressure goes from 30 to IS bar. whilegoing from 15 to 5 bar gives
4 to 5 extra points.
146 Ct"-apler 4. CATALYTIC RFORMING

102

98
a
II:

e
.~ 94
=
Feed constant
=
Space velocity constant
Ql
II: ~JHC=4
p= 10 bar
90

FiJ:Ure
4.39 Variation in octane number versus T5Ok-

+10

-10

2 3
Space velocity

FJ:ure
4.40 Influence of space velocity on reformale octane number.
 3

Catalyst 1995

4 8

Figure
..JA 1 Catalyststability versus H/HC
_ _I

Naphthenes '" 62~o

90 95 100 RON

Figure
4.H Influence of P and the feed on Cs yield.
148 ChaPlet 4. CATALYTIC REFoR',' '.3

4.4.2 Influence of Feeds

Feeds are defined either by the overall characteristics: Kuop. N + 2A. mp, EP
(Table 4.4b), or by the hydrocarbon family and number of carbon atoms
(Table 4.4a) as is done increasingly today. Naphthenic feeds give much higher
yield than paraffinic feeds (Fig.4.42). Table 4.12 summarizes the effects of cut
points on the different variables. The temperature TSOR increases if the initial
boiling points are low. The run duration is shortened by low initial boiling
points due to the higher operating temperature, and by high end points due to
the presence of coke precursors,
Initial boiling points that are too low, indicating the presence of a lot of C6
cause a large amount of benzene to be produced. Since light paraffins are hard
to convert, the desired octane will be achieved only by producing more C;_
aromatics. High end points reduce benzene production. but can cause substl-
tute naphthalenes to be produced. which in turn cause rapid catalyst coking.

Variable TSOR

I
Run
duration [@] ToIaI
aroJDatics

JBP '\. . i
I
IBP< IOOC / I -, / / i

EP /
EP < 180C
EP> 180C
-,
-, -
-,
-,
-, -
Presence or
naphthalenes
....r-----
Table
4.12 Influence ofIBP and P at constant space velocity and RON.
'--
-
4.5 Technology
The different technologies basically involve two types of reactor: fixed or mov-
ing bed.

4.5.1 Fixed Bed

This is the oldest technology.

4.5.1.1 Type of Reactors

In the beginning, the pressures used were greater than 50 bar and reactor pres-
sure drop had little influence in comparison with total pressure drop. This is
 Chapter 4. CI,DI/.tT/C REFORMING 149

why axial reactors (Fig. 4.43), which have simple internals and are therefore
less costly, were chosen to implement the process at the time. Radial ,reactors
made their appearance some time in the seventies at the same time as the
bimetallic catalysts that allow operation at pressures lower than 25 bar. Here,
pressure drop in the reactors became significant in relation to total pressure
drop. In addition, the cost of recycle hydrogen compression became a non-
negligible item.

Radial Axial

----------------------------'
'---'---';...'
iFigure
! 4.4-3 Reactortypes.

The evolution toward continuous reformingand the implementation of con-

tinuous catalyst circulation imposed the radial type of low-pressure drop reac-
tor once and for all. The trend toward a total pressure of 3 bar left no other
choice. >

Reactors are built of low-alloy carbon steel that can withstand hydrogen
corrosion and oxidizing atmospheres during regeneration and oxychlorination
operations.
150 Chap:,r4 CATALYTIC RE,":::;;',:lt,3

4j.1.2' Reactor Configuration

As mentioned earlier, catalytic reforming involves mostly endothermic and
equilibrated reactions whose rates differ by a factor of 50. A set of isothermal
reactors with a heat input could have been the solution, but it is expensive and
lacking in flexibility. The choice of adiabatic reactors in conjunction with fur-
naces was eventually made. Differences in rate between cyclohexane dehy-
drogenation, cyclopentane hydro-isomerization-dehydrogenation and paraffin
dehydrocyclization amount to a ratio of approximately 50/5/1. As a result, the
final configuration is a series of 3 or 4 furnace + reactor groups depending on
the type of feed: 3 for paraffinic feeds and 4 for naphthenic feeds.
Each furnace + reactor group (FigA.44) takes reaction rates into account. F,
is large and R1 small, while F3 is small but R3 is large. The figure also shows the
variation in temperature in the reactors: significant drop in RI smaller drop in
R2 and firially less variation in R3, where the endothermidty of dehydrocy-
clizatlon is partially offset by the exothermicity of cracking, since the two reac-
tion rates are comparable. The aromatics concentration rises gradually.
Catalyst distribution among the three reactors is usually 15% (R,), 25-30% (Ri)
and 55-60% (Ri).

4.5.1.3 Flow Scheme: Semi-Regenerative (SR) Fixed Bed

This type of process is given its name because catalyst regeneration causes
the unit to be shut down at the end of the run. The reactor configuration is the
same as described earlier (see Section 4.5.1.2). Ancillary units are designed to
allow optimum use of catalysts and to offset some of their drawbacks:
The catalyst is sensitive to impurities: nitrogen-, oxygen- and sulfur-con-
taining compounds and metals. Consequently, a feed purification section
must be provided. The feed is purified by hydrotreating, which blocks the
metals and produces ammonia. hydrogen sulfide and water, eliminated in
the purification section (Fig. 4.-15). The feed can be further treated on
molecular sieves to knock out the few ppm of residual water and also on
a sulfide compound trapping agent,
The catalyst becomes rapidly ,:eactivated in the absence of hydrogen.
Deactivation is considerably re.i uced by hydrogen, so high hydrogen par-
tial pressure is created CHiHC > 8 for monometallic catalysts) by com-
pressing and recycling part of the hydrogen produced during the reac-
tion. It may contain some lmpurtties: water, hydrochloric acid and
sometimes HzS, and needs to be dried, dehvdrochlorineted and desulfur-
ized on specific adsorbers. Such installations are mainly used during
start up but not only.
, Finally, the catalyst produces light C1 to C.. hydrocarbons in addition to
hydrogen, and they are separated from the reformate in a stabilization
section. Depending on the operating pressure, separation systems of
varying degrees of complexity will be implemented to get relatively pure
hydrogen and high gasoline recovery: a simple separating drum, recon-
tacting purification systems, ultra-cooling, etc.
A

\J
~ I
I I I
I I I
I I I
I I I
I I
I I I
I I I
I I I
I I I
I I I
R,~-R:!--r----R3-'
I I

c
Vol % R1 - : - R : ! - : - - - A3 - - - - - : .
I I I Aromatics
Po=60 r-----,-~ I I
I I
I
I
I
I
No=30 r
J
I
I
Ao= 10 Paraffins
I Naphthenes

A. Furnace (FJ F:. FJ ) and reactor (R/. R;:. R1} layout..

B. Variation in temperature in reactors RI R:. RJ
C. t'oriation in effluent composition (paraffins-naphthenes-aromaticsJ in the
reactors.
152 Cnaallff4. CATALYTIC REFOR.~ '.3

c:
.2
~
~
i5
~
~
~

:i:
>:
,..'"
c:<II a::;
E
<ii ~
~
!a.. ~
~
:c.
~
"
~
 C"~CIIt' 4. CATALYTIC REFORAMIG 153

4.5.1.4 Flow Scheme: Cyclic Fixed Bed

An initial solution was proposed by Exxon to avoid shut.ting down units by

using an extra reactor. With a complex valve system, three reactors can be run-
ning while the fourth is being regenerated. Here. the four reactors are of the
same size and are. located in position RI Rz, R3 alternatively (Fig. 4.46). This
line up requires installation of a regeneration system and does not always
allow the regenerated catalyst to be restarted in optimum conditions.

4.5.2 Moving Bed

4.5.2.1 Technologies
Although the moving bed was used on M0031'A)203 type catalysts before 1940,
use on platinum-alumina catalysts came into being only in the early seventies.
UO? put a continuous regeneration system (Fig. 4.47) on the market, where
three or four reactors are located one on top of the other. The effluent coming
out of each reactor goes through a furnace before entering the next one. The
catalyst moves downward by gravity from RI to R2 then R3, and loaded with
coke it is taken by a lift to the top of the regenerator. It goes through the regen-
I erator by gravity and is afterward sent back to the top of Rj The rest of the
unit flow scheme is very close to the fixed bed process.
The technology developed by IF? uses the conventional SR reformer.layout
of "side by side" reactors. The catalyst at the bottom of each reactor is raised
by lifts to the top of the following reactor. From the last reactor it goes to the
regenerator (Fig. 4.48) and then back to the top of the first reactor.
VOP regeneration is continuous, lFP's can be continuous or batch.

4.5.2.2 Advantages oftbe Moving Bed

The introduction of moving bed technology has had the following effects:
Reforrnates are produced with a very high octane number even from dif-
ficult feeds and without any run duration problems.
Units are operational all year round. regularly producing the hydrogen
that modem refineries constantly need.
Catalysts are less stable over time but more selective, making it possible
to improve yields.
Recycle rates are lower, thereby improving yields and reducing operating
costs.
Operating pressures are significantly lower and this is highly favorable to
gains in reforrnate and hydrogen yields.
Generally, as indicated in Figure 4.49, pressure has gone from P = 35 bar.
H2/HC = 7 to P == 3 bar. H2/HC = 2 with yield gains of nearly 10 points for C5..
and over 1% for hydrogen.
154 enaote' ~ CATALYTIC REFCB',';NG

- -,
t--.. , -N- --
I -
_I
'i-
~} - - - -,

o ~-- -,- - - - - - - -,- - - - -,- -------- ...

1II . '

~~
.-
I'
Y I
/'; :1-, I
,-_ / \, I
<z 2.. ,
I
I
1--,....--.,... - ~- - -I
I
I

...J
, I
, ,
t
,
I
I
I
f ,
I ,
}-M- -l
I
I
I
I
I
,
I
I
, 1
1
I
I
4xJ--
t
--j
?
I
,
I
I

,
I
"tJ
1lI
S
I .B:!
I
I
I 1CI
:5
"
~
"'l
I s:
I Q.
1CI
:3
I
I Z c
1------0-'"- -I><J- - - ...
~
~
~

~
Regenerator Reactor Furnaces Exchanger Separatqr Gas
recovery
r - ~ I I
, \ I
ni] I
\ I
I

I I
I I
I I
I I
I I

,
II
II

,I
I I

9. .I \., R4

6 -
- -' I
I
I J'
Feed

I'
,I>.

F
,.
R

.;il:lIn
Debutanlzer Furnace
!
-."'7 Cmrtimwl/.S regellerution reformer (lJOP: Piattormtng). ....
UI
UI
 Air

lift gas

COII/iIlLW(/S regcllemlieJl/ r('(orll/er (IFI': Oc/cmizillg). CCl/(J/y.~/ circulation reuenerak:

 CJ1aDcer 4. CATALYTIC REFORNING 157

I I
Unitwith monometaUic talalyst -

--V
6
----
/
4 /""
~ . f

.. V I
-: I
Unit .... bimetallic catalyst
2 t I
CCR wilblspecilic ca~t

o
5 10 15
I I
20 25 30 35
Total pressure (bar)
1--

i Figure 1--------------------------"'
i 4.49 Various types of reforming units.

4.6 Industrial Performance

4.6.1 Processes. Operating Conditiolts
There are still a number of catalytic reforming units working with a mono-
metallic catalyst in the world today. but most units use platinum-rhenium for
semi-regenerative fixed beds and platinum-tin for moving beds.
Operating conditions are summarized in Table4.13 for operating pressure.
H2/HC ratio, space velocity and octane number (severity). SR reforming units.
based on monometallic catalysts. are characterized by high operating pres-
sure, high H2/HC, low space velocity and rather low RON.
SRor cyclic operations on bimetallic catalysts are more severe: higher RON
and space veloctty. lower pressure and H2/HC.
The trend in continuous regeneration reforming is toward pressures of
3 bar, H:JHC =2 or Jess. octane numbers higher-than 100and space velocities
close to or even greater than 3.

~.6.2 Typical Yields

Catalytic reforming produces C5 gasoline, hydrogen. but also a little amount
of methane. ethane. propane and butanes. In the last few decades the yield in
158 en.ao/e, J. CATAl.Y11C RFORMING

Catalyst
j
I
p j H../HC ,Space velocity
(bar) . (mol/mol) I (m3/m3fh)
I RON
I
SR fixed bed Monometallic I > 25 >7 I 1-2 I 90-92
Bimetallic 12-20 4-6 I 2-2.5 91-98
Cyclic fixed bed Bimetallic 15-20 I 4 I 2 96-98
100-102
MoVing bed'
Continuous Bimetallic 3-10 2 I 2-3
> 104 for
aromatics
regeneration
........- .-- ! ' production
! Table I
~ Operating conditions for present-day processes.

target products, CST and H2 has risen gradually with pressures going down to
lObar and less and improved catalysts.
Table 4.14 gives an average product distribution from a paraffinic feed on a
bimetallic catalyst at 15 bar and RON = 98. The desired products account for
85%weight and the ones with lower added value represent less than 5%weight
(methane and ethane).

Products % wt/feed

H2 2.5
CH. 1.7
C;zH6 3.1
C3H g 4.2
(i + n) C4H lO 6.0
Cs.. 82.5
-
'- Table
4.14 Typical yields on a Middle

---- Eastern feed.

RON = 98 P::: 1S bar.

Figure 4.42 shows the changes in CS+ yield versus the desired RON, the
operating pressure and the type of feed processed. Lower pressure and more
naphthenes in the feed have a favorable effect. In this case, a CS+ yield
approaching 90% can be achieved for an octane number of 100. The value of
such results can be judged in comparison with the best case on this type of
teed: a perfect catalyst and optimum operation would give 94% reformate with
octane =around 106 and 6% hydrogen. .
 Chapre(4. CATAlYTIC R~ 159

4.6.3 Reformate Characteristics

A reformate totally free of heteroatoms (5, N, 0) is characterized by its RON,
which is the parameter fixed (or the run, and also by its end point. The end
point is determined in relation to local regulations which dictate the value for
gasolines (205C in france, 215C in some other countries). It is also deter-
mined by operating considerations since high end points cause more rapid
catalyst dea.ctJvation.
The research octane number is related to the aromatics concentration as
indicated in Figure 4.50. High pressure reformates contain few oletins.
However. in modern units running at low hydrogen partial pressure, there are
more and more olefms, as indicated in Figure 4.51. These olefins lower the
MON of gasolines and often make hydrogen purification more complicated.
During recent years, benzene has been ecologists' bugbear and the subject
of particular attention. Benzene production depends on the operating pres-
sure and target octane number for a given feed. Figure 4.52 shows that benzene
content in C5+ increases with hydrogen pressure and depends on the catalyst
used. It is produced not only by direct cycllzatton of C6 but also by
hydrodealkylation of higher aromatics. At iso-conditions, hydrodealkylation is
more significant on platinurtHbenium type catalysts than on platinum-tin. It is
promoted by hydrogen pressure.
I Moreover, the proportion of C6 in the feed, measured by the initial boiling
point is influential (Fig. 4.53).. If initial boiling point is lowered, the benzene
yield rises quite considerably.

85

1II 80
G

!2
!! 75
oS

.2
'i 70
E
0
G
'#- 65

60
95 100 110
RON
Figure
-t.;\) Relationship betuieen me ROS and the % aromatics in the refonnate.
 2 RON

\. 95
<:)
(ii \ -: 100
~
. V><105
e
.s A~'
w
.S: O~'
<s
'0
~
;if!.

.I------~------~--
l': Figure
j4.51
o

Olefin content in the reformate.

5 10
P~(bar)

j;
U 6
.s
m
c:
m
N
c: 5
m
.D
'0;>
r?- 4

3'--_--'-_ _'-- ......._ _"'---_......._ _"----"

90 92 94 96 98 100 102

I
,---,
f'. ....
4.52
I;---------------------------'
Benzene yield venus severity (RON) and operating pressure.
RON

The reformate distills between 40 and 205C (end point in France), but if
octane distribution is analyzed more closely versus distillation range. several
comments can be made. The octane number of light fractions (isomerized sat-
urated hydrocarbons) is relatively good and the same holds true for heavier
fractions that distill out after toluene (IIOC). In contrast there is an octane
 Chal*r4. CATALYTIC REFORAflftIG 161

gap (Fig. 4.54) for distillation temperatures between SO and 110C.The gaso-
line pool make up must take this refonnate property into account.

7
6
...

~
lap 65"C
(J' 5
0=

.E
Ql 4
c \~ 'QaJ
:ec 3

~
II)
.0
2
IBP =85C
~
'0
>
fI!.
0
90 92 94 96 98 100 102
RON
! Figure
.I 4.53 Benzene yield versusseverity (RON) and feed initial boiling P?int (lBl')
_I

RON

l~t
120

110

100,

90

80

70

60

50
35 65 95 125 155 185 215
T{"C)

Figure
4.54 Variation in RON cersus distillation range of reformate components.
162 Cl:a"le'~. CATALYTIC REFORMiNG

4.6.4 Run Duration. Lifetime

Seml-regeneratlve .reforming units are generally designed so that the run lasts
one year, so they are stopped only once a year for regeneration. A properly
operated and regenerated catalyst can easily undergo regeneration ten times
before being unloaded and replaced. Due to malfunctions during operation
(contamination by poisons for example) or simply because more efficient cat-
alysts are brought out, catalysts are replaced every 5 to 7 years on the aver-
age.
Catalysts in continuous reforming systems work under more exacting con-
ditions. They may be regenerated up to 100 times a year. As a result. the life-
time ranges from two to four years depending on conditions or use.

4.6.5 Special Runs

4.6.5.1 Maximum Aromatics Production
As mentioned earlier, reformingyields octane number by producing aromatics
and by extending severity to RON = 102 to 104, aromatics are concentrated.
Accordingly, catalytic reforming, along with steam cracking of gasolines, is
today the major source of benzene and xylenes (Table 4.15).

Feed (distillation range) Cq 60-103 70-150

Products % wt/feed .
Cs. 66.50 i2.5Q
Benzene 20.40 5.70
Toluene 27.50 25.70
Xylenes 3.10 25.70
~

C 9+ 0.70 7.70
Total aromatics 51.70 64.70
~--

I :a~~
U Maximum aromatics run. Middle Eastern type feed.
II

Certain aromatic hydrocarbons may be a specific production objective,

benzene for example, and more economical feeds than naphtha may be
needed, light gasolines or even LPG for example. In this case, it is possible to
use new processes such as Chevron's Aromax, VOP/BP's Cyclar or IFP's
Aroforming.
Aromax is based on a new generation of catalysts with platinum laid down
on a barium and potassium exchanged L zeolite. It is far superior to conven-
 Chapl4t 4. CATALYTIC Ruoiu.uNG 163

.
tlonal reforming with preferably linear C6 and C7 paraffinic feeds. It operates in
low pressure reforming conditions. Cyclar and Aroforming use catalysts of the
gallium type laid down on an MFI zeolite along with continuous catalyst regen-
eration. They are suited to LPG feeds and are characterized by considerable
hydrogen and aromatics production. as well as methane and ethane.
These processes are expected to penetrate the market very slowly. For the
time being a few industrial tests have been carried out with the Aromax type
process. Cyclar and Aroforming have remained at the stage of pilot plants in a
variety of sizes. The first Cyclar unit was to come on stream in probably 2001.

4.6.5.2 Maximum LPG Production

In countries that- consume large amounts of LPG,-there are reforming units
working at high pressure (40 bar) on more acid catalysts (presence of fluorine
or zeolites) designed for maximum propane and butane production, up to 30%
weight Naturally, this type of production occurs at the expense of C5+ and
especially of hydrogen yield. Hydrogen yield may be lower than 0.7% wt
(Table 4.16).

Products % Wf/feed

Hz 0.6
C1 + C2 5.2
C3 + C.. 27.1
CS+ 67.1
.----
'- Tableauf------:..---------'
4.16 Maximum LPG from a reiorming
unit. --

4.7 Economics [13, 14J

4.7.1 Catalytic Reforming' Capacity
Today there are around 600 refineries in operation in the world. Practically aU
of the ones that produce gasoline (some only manufacture lube oil stocks)
have one. or sometimes even two. catalytic reforming units. World reforming
capacity is some 400 Mt/year for an atmospheric distillation capacity of
around 3.6 Gt/year, Continuous regeneration accounts for more than 25% of
the reforming units. The geographical distribution is given in Table 4.17. North
America is the main user but Southeast Asia is developing its processing
capacity. France's throughput is 10 Mtjyear. Le, 2.5%of world capacity.
164 Chaorer 4 CATALYTiC RFC:;.:ING

Geographical distribution %

North America 42.0

Latin America 3.7
Africa 3.5
MiddleEast 5.5
Asia 18.5
CISand Eastern Europe 14.3
WesternEurope" 12.5
Total 100.0
Including France 2.5"....

. . . ,----r------------------------'
Table norld: 400
Catalytic reforming capacity. Mt/year: 3QOMt ofsemi-
4.17 regenerative or cyclic; JOO Alt of continuous regeneration (1998
t.--- figures).

4.7.2 Process Licensors

In the sixties a number of process licensors offered catalytic reforming pro-
cesses: UOP (platforming). Engelhard (Magnaforming), Kellog (Sinclair Baker).
IFP and various others. Today UOP and Iff account for 90% of the market in
new units. The cyclic process has only been applied to Exxon's Powerforrning.
Only VOP (pIatforming-CCR) and IFP (Octanizing-Aromizing)offer the continu-
ous regeneration process.

4.7.3 Investment. Operating Costs

4.7.3.1 Semi-Regenerative Catalytic: Refonaing
Table 4.18 shows the investments and utililies for a medium pressure.
800 000 t/year (RON =: 97) reforming unit. Fuel oil is burned mainly to heat the
feed and in intermediate furnaces, electricity is consumed by the recycle com-
pressor, and water by effluent cooling after the feed/effluent exchanger. The
steam produced in the furnace convection zone is exported.
The catalyst costs some 106 US$ excluding platinum. Common practice is
for the refiner to be the owner of the platinum and, when the catalyst load is
replaced. for him to pay for recovery. The cost of recovery (over 98% of the
platinum is recovered) is from 2 to 3 USS/lb of catalyst. The platinum is worth
Irom 15 to 50 USS/lb of catalyst depending on the content and market value.

4.7.3.2 Continuo," Catalytic Reforminc

Table 4.19 shows utility consumption and typical investments, base: West
Coast, early 1998, for a continuous regeneration type of catalytic reforming
 Operating pressure (bar)
I 15

Severity (RON) 97
Run (months) 12
Battery limit investments (106USS)" 30
Catalyst (loa USS)(excluding platinum)" 1
Utilities (per ton of feed)
Fuel oil (10' kJ) 1.3
Electricity (kWh)
Cooling water (m3)
I 4.5
8.9
I
HP steam exported (t) I -0.12
- Base: West Coast. 1998.
'---
Table
4.18 Economics. Semi-regenerative reforming (excluding preprocessing).
Capacity: 800 000 t/year. 15 bar. Feed: P;\"A ~;; r;o/60-30-1O.
'----

Operating pressure (bar) 3

Severity (RON) 102

I' Battery limit investment (10' USS") I 39
Catalyst excluding platinum (1()ti USS*) i 1.3
UWities (per ton of feed)
Fuel oil (106 kJ) 2.2
Electricity (kWh) 5.3
Cooling water (m3)
- 8.0
HP steam exported et) -0.03
Base: West Coast. 1998. ".
'----~'

: Table I
-+.19 I, Economics. Continuous catalytic refonnmg (e.lcludlng preprocessing).
Capacity: 800 000 t/year.

unit, with a throughput of800000 t/year, producing a reformate with an octane

number of 100 and working at a pressure of 3 bar.
Comparison with the semi-regenerative process (fable 4.18) shows that:
Investments and utilities consumption are higher. fuel oil consumption is
higher. since the reactions directly connected with selectivity are highly
endothermic. The added electricity consumption is because a larger
amount of hydrogen produced at a lower pressure needs to be recom-
pressed to network pressure. The larger investments are due to
increased furnace and compressor size on the one hand. and to the
intrinsic cost of the regenerative loop on the other.
166 Cr.aprer 4. CATALYT;= Hi:FORMJI\':;

Reformate and hydrogen yields are much higher. The greater hydrogen
yield more than offsets the higher operating costs and makes return on
investment more advantageous for continuous catalytic reforming.

4.7.33 Revamping Existing Units

Most new catalytic reforming units built today are of the continuous type. A lot
of existing non-continuous units can be revamped in various ways, with
options ranging from a simple change in operating pressure associated with
implementation of a more efficient catalyst, to retrofitting the whole reaction
section to transform it into a continuous system. Various combined or hybrid
solutions designed to reduce investments have been studied. They differ
mainly in the operating pressure of the fixed bed and of the continuous regen-
eration section. In an existing semi-regenerative unit, they consist of an added
reaction. section usmgtheconttnuous regeneration technology. This gives
some relief to the fixed bed section, which can then work at moderate or even
low severity. The final overall efficiency is achieved thanks to the regenerative
section. To the extent permitted by the major existing equipment, lower sever-
ity in the fixed bed section allows a reduction in operating pressure, thereby
giving improved yield while maintaining acceptable run durations.
Additionally, the finishing regenerative section, using a more selective catalyst
as explained earlier, gives the whole process significantly better efficiency.
What is termed a number 1 combined solution consists in incorporating an
extra furnace and reactor in the existing fixed bed reaction loop, the reactor
being equipped with the continuous catalyst regeneration system.
Modification in or replacement of some existing equipment (heat exchangers
for example) may be required in order to reduce the operating pressure low
enough to make the most of the operation while continuing to use the main
equipment (furnaces, recycle compressor).
What is termed a number 2 combination solution consists in keeping the
existing fixed bed reaction section and adding a new continuous regeneration
reaction section on the separator effluents. The new reaction section includes
a feed/effluent heat exchanger, a furnace, a reactor equipped with the contin-
uous catalyst regeneration system and another separator. The pressure in the
fixed bed section is reduced with little or no modification (it will therefore be
higher than for solution number I), whereas the pressure in the regenerative
section, which is independent here, will be very low,thereby improving yields.
An extreme retrofitting solution, called continuous regeneration, consists
in replacing all the reactors by continuous catalyst regeneration reactors and
keeping the other equipment as is, to the extent possible, especially the recy-
cle compressor. However, to get the most out of this solution, the pressure
must be reduced significantly. Pressure reduction and greater selectivity often
dictate modification in or replacement of other equipment such as furnaces or
heat exchangers.
Table 4.20 shows the operating conditions and yields that can be expected
from these djfferen~ revamping options. Starting with a conventional SR unit
 Chapter 4. CATAtmC ~ 167

-
Conventional
Solution I
CoatInuous
SR + continuous Solutioe %
SR regenenuioD
regeneration

RON 97 100 100 100 100

Pressure (bar eff.) 26 26 15 20/3 7
Run duration
(months) 12 6 12/collt. 12/cont. eont.
H2 yie ld
(% wtjfeed) 1.6 1.7 2.4 2.6 3.1
C5+ yield (% wt/feed) 78.6 76.3 81.9 83.$ 81.4
_.----
Table .
4.20 Operating conditions and yields.
'---

operating at 26 bar and RON = 97, it shows the impact on the unit of the change
=
to RON 100 without any modiflcatton, then the expected results with combi-
nation solutions 1 and 2 and finally with the continuous regeneration solution.
The change from RON =97 to 100 without modifying the unit reduces cycle
.life by half and lowers the reformate yield significantly. In contrast, revamping
solutions 1 then 2 and finally the continuous regeneration solution give
increasingly higher yields at RON = 100 than the base case at RON =97, while
maintaining the same cycle length.
Table 4.21 shows the investments and operating costs of the various solu-
tions for the same cases with a throughput of 800 000 tjyear. Going from RON
97 to 100 in the unit without any modification simply causes extra utilities .COO-

IConventional ISolution 11Solution 2 r Continuous

Solutions
! SR I ;regeneration
RON 97 100 I 100
-l' 100 100

Enhanced value of products!

base (10 6 USSjyear)*
- 11 13 22

Battery limit
(106 U5S)*
investments - 14 17 31

Catalyst (excluding platinum) I II

(10" USS)* J - 0.5 0.5 l.0
Utilities (106 USS/year)* I - 2.5 4.6 ! 4.9
* Base: West Coast. 1998.
---
Table;
~.21 : Incestmems and operating costs. (800 000 t/year unit using .'diddle Eastern
_ _i naphtha as feed).
168 Cllgorer4. C"iA!.YTIC R:=:;=:..3

sumption. The other solutions entail higher investment and operating costs
(utilities + catalyst), with a large percent due to recompression of the pro-
duced hydrogen. In all the revamping cases, higher margins due to enhanced
yields offset the higher operating costs and return on investment is similar for
each one. Note however that the continuous regeneration option does involve
considerable investment compared with a new unit, without providing the
same advantages, and this may limit its attractiveness.

4.7.3.4 Conclusion
Present-day developments will intensify the preference for continuous regen-
eration catalytic reforming. since it is often the only unit producing the hydro-
gen needed in the refinery for hydrotreating processes to continue running.

References
Montarnal R., Duhaut P. (1972) Reformage catalytique. In: Raffinage et
Genie chimique, P. Wuithier. Editions Technip, Paris, 775-815.
2 Le Page J.F. et al. (1978) Catalyse de contact. Editions Technip, Paris,
575-622.
3 Haensel V. (1955) The chemistry of petroleum hydrocarbons. Catalysis 2,
189-219.
4 Steiner H. (1958) Catalytic cydization and arcmatizatton of pure hydro-
carbons and petroleum naphtas. Catalysis 6, 495-S92.
5 Ciapetta EG., Wallace D.N., Heinemann H. (1971) Catalysis Reviews 5,
67158.
6 Riediger B. (1971) Die verasbeitung des Erd6ls. Springer Verlag. 510-566.
7 Gates B.C., Katrer J.R., Schuit C.C.A (1980) Chemistry of Catalysis
Processes. MacGraw-Hill, 184-324...
8 Germain J.E. (1969) Catalytic Conu. of Hydrocarbons. Academic Press. New
York.
9 Kurek W.S. (1971) A/ChE, Houston, 1-40.
10 Pines H., Haag W.O. (1960) JACS. 82-2471.
11 Bournonville J.P., Franck J.P. Hydrogen and Catalytic Reforming. In:
Hydrogen effects in Catalysis. Marcel Dekker ed., 1988, New York.
12 Bournonvllle J.P., Franck J.P., Martino G. Stud. Surface Sci 16.81 (1983)
13 Thery M. (1993) Petroieet techniques 380, [uin, 29--36.
14 d'Auria 1.1. et at. (1994) Petroleet techniques 388, juln, 46-51.
 !

~-5.--_-
Cat~I~~c. c.racldng
~_~~c l~~~ ~ < " ~ J.": .:;~ '"'
.. :". -!." .. . ~

Regis Bonifay
Christian Marcilly

Catalytic cracking works with high-molecular-weighthydrocarbons located in

a boiling range above approximately 350C. It breaks them up into lower-
molecular-weight hydrocarbons, mainly consisting of a gasoline cut ranging
'from C5+ to 200 or 220'C, at low pressure on an acid catalyst at a temperature
of some 500'C. It is today the leading refining conversion process in terms of
tons of feed processed and amounts of catalysts used.. "

5.1 Historical Overview [1-5]

The first attempts to reduce the molecular mass of heavy petroleum cuts. date
back to 1912.They were followed sometime around 1920by the development
of the McAfeebatch cracking process with AIel!as a catalyst, which was to be
used for 14years in the Gulfrefinery in Port Arthur.In 1923, a French engineer
named Eugene Houdry launched a study that led to the fixed bed catalytic
cracking process. The first unit started up in 1936 with a natural clay based
catalyst (montmorillonite). In 1940, the natural catalyst was replaced by a
more active and selective silica-alumina based synthetic one.
Catalytic cracking is much more rapid and selective than thermal cracking.
It allows lower operation severity, thereby considerably reducing secondary
reactions that produce gases, coke and heavy residues at the expense of gaso-
line. Moreover, the gasoline produced is of much better quality (the stability
and octane numbers are superior by far). As a result, the process quickly
became Widely used in refineries.
The process operating conditions are naturally chosen in a range favorable
to thermodynamics: a temperature over 450=C and a pressure lower than
2-3 bar. The catalyst working in these conditions without any outside input of
170 Cr;apler 5_ CATALYrIC CR;.CKING

hydrogen quickly gets loaded with coke. a poison for catalytic sites. It needs
to have the coke removed frequently by combustion so that it can recover its
activity.
The fixed bed Houdry process used 3 reactors working alternately in reac-
tion then regeneration with intermediate purges. SWitching back and forth
quickly between phases made the process complex and expensive. and
research was soon undertaken to improve on it.
Research work. intensified by the demand for gasoline during the Second
World War, started giving results in the early forties. The following new tech-
nologies were developed:
The fluidized bed process, or FCC (Fluid Catalytic Cracking). The first
PCLA unit (powdered Catalyst Louisiana) was commissioned in May 19-t2
in the Esso refinery in Baton Rouge, with a catalyst whose clay base was
ground up into powder.
"The moving bed process. The first Tee (fhermofor Catalytic Cracking)
then Houdriflow units started up at more or less the same time in 1943.
The most efficient technology, FCC, gradually gained ground the world over
and in 1990 over 95%of the units were workingwith the fluidized bed type pro-
cess. The few rare moving bed units still in operation today will gradually be
phased out and replaced by FCC. This is why this chapter on catalytic crack-
ing is exclusively devoted to FCC.

5.2 The FCC Process

5.2.1 Introduction
The typical feed going into the FCC is the vacuum distillate (VGD or vacuum
gas oll), whose initial boiling point is 350-380C and end point is approxi-
mately 550-560C. However, the refiner very often adds other stocks with a
comparable molecular weight that he wants to upgrade from various conver-
sion units such as visbreakinlti'coking and deasphalting, Ever since the early
eighties, the tendency has be~n toward heavier feeds by the addition of vary-
ing amounts (10 to 50%generally) of atmospheric residue CAR) 350+ or 380=C.
These feeds are converted in a few seconds in the FCC reactor on a solid
acid catalyst in the form of a fine fluidized powder. The cracking product yield
and quality obviously depend on the characteristics of the processed feed, the
operating conditions (480C < T < 550C, 1 bar < P < 3 bar, catalyst and feed .
flow rate) and the catalyst. A very wide range of products can be obtained,
ranging from light gases (C4- ) to very heavy fractions (liCD I: 350-550C,
slurry 2: 550C+) and even coke. Usually the most valued product is gasoline
with an average yield of some 50% weight in relation to the feed.

1. HeO: Heavy cycle oil.

2. Slurry: bottom of the fractionation column that can contain catalyst fines. .
 CNpI.5, CATALY7IC CRAcxrNG 171

5.2.2 Feeds and Products

5.2.2.1 Characteristics of Feeds

FCCfeeds are characterized by a number of properties that govern the yields,

the catalyst deactiVation rate and the operating conditions (fable 5.1).

~
A B C D
I

Type Hydrotreat.
Distillate Distillate Residue
residue

sp. gr. d15

-0.937 0.913 0.939 0.926
KuoP 11.67 11.91 11.86 12.00
Aniline point CC) 19 87.4 90.8 97.8
Molecular weight (gfmol) 458 450 612 510
Conradson carbon (% wt) 0.76 0.67 5.6 4.2
Sulfur (% wt) 2.20 0.90 0.90 0.35
Nitrogen (ppm) 1500 1400 2400 1000
Basic nitrogen (ppm) 425 455 688 335
Nickel(ppm) Ll 0.1 4.0 4.0
Vanadium(ppm) 1.5 OA 11.0 5.0
Hydrogen (% wt) 11.86 12.42 12.il 12.43
TBP distillation CC):
5%wt 358 340 370 347
10% wt -.384 363 396 378
30%wt C9 403 455 448
50%wt 476 443- "
508 506
70% wt 5D9 496 - 577 '576
90%wt 549 571 695 692
95% wt 566 615 719 733
Viscosity lOO:C (mm2s- l)
L...-;--
10.3 I

I
8.3 25.5 II 24.8

I Table I
~ Examples of FCC feeds.

The simplest property that directly influences yields is the feed's specific
gravity. For a given distillation range it indicates the degree of saturation of the
molecules. For instance, low specific gravity is evidence of high hydrogen con-
tent and the feed~s potential to be readily converted into high added-value
products such as gasoline and liquefied gases. In contrast, high specific grav-
ity is evidence of high aromaticity, the feed's resistance to cracking and its
 172 Cfl4.:xer S CATALYTIC CR,:,C.......;J

potential to give heavy aromatic oils such as LCO 3, HCO and slurry. The same
relationships are found when the feed is characterized by the aniline point test
which measures its aromaticity.
A number of properties which characterize the feed's degree of contami-
nation influence the thermal balance and the catalyst's stability. Conradson
carbon is the main indicator of the presence of residue. Generally an increase
in Conradson carbon also means an increase in the asphaltene and metal (e.g.
nickel and vanadium) content. High Conradson carbon is synonymous with
increased coke yield and regenerator temperature. The presence of metals at
the same time causes more catalyst to be consumed to maintain the same
activity, The indirect consequence of a higher regenerator temperature is
lower conversion (see Section 5.2.4).
Other properties influence the thermal balance directly and the yields indi-
rectly. They are the' distillation range and the viscosity. These two properties
affect the degree of feed atomization and vaporization in the reactor. High vis-
cosity and an overly high distillation end point explain the production of addl-
tlonal unwanted coke which leads to the increased regenerator temperature
and lower conversion.

5.2.2.2 Yields

Table 5.2 illustrates typical yields achieved on two different distillates whose
properties are given in Table 5.1.

5.2.2.3 Product Characteristics

Cracking product quality has a complex relati*nshiP to the feed quality. the
operating conditions, the catalyst properties and structure, and also to the
technology used. Table 5.3 illustrates the typical characteristics .of the main
liquid cuts obtained from an FCC. ..

5.2.3 Description of the Process

The catalytic cracking process consists of four sections:
the reaction section,
the flue gas treatment section.
the catalyst handling section,
the product fractionation section.

3. LCO: Light cycle oil.

 er.a:J:er 5. CATALYTIC CRACKING 173

~
A B
Type Distillate Distillate

HzS 0.80 0.38

Hydrogen 0.23 0.23
Methane 1.04 0.79
Ethane/ ethylene 2.86 2.02
Propane 1.30 1.10
Propene 3.60 3.90
n-Butane 0.60 0.80
iButan~ _ 1.20 1.68
i-Butene LiD 1.82
n-Butenes 4.00 4.38
Light gasoline (Cs-160C) 32.20 33.90
Heavy gasoline (l60-221C) 10.20 13.70
Wide range gasoline rc,
-221C) 42.40 47.60
LCO(221-350C) 18.00 16.30
HCO + slurry (350C+) 17.40 14.60
Coke 4.87 4.40

---r--r
100.00
L 100.00

LJ
I T:b:e II
Typical FCCyields during trItlXimum gasoline production (% wi).

5.2.3.1 Rea~tion Section

a. General Operating Principles
This section is the heart of the unit and. whatever the technology, it is basi-
cally made up of a reactor and a regenerator (Fig. 5.1). Because of the superfi-
cial velocity of air in the regenerator or of steam in the reactor stripping zone,
the catalyst ebullates and forms a dense phase clearly separated from the
dilute phase comprising the overhead in both vessels. In this way. levels are
established and can be controlled. The catalyst is kept in a fluidized state and
circulates continuously like a liquid between the reactor and the regenerator.
The fluidized bed process is characterized by very rapid operating dynamics.
Typically, the catalyst runs a co~te cycle in less than 15 min. Le, the reac-
tion, the separation of reaction products from the catalyst, catalyst stripping
and regeneration.
The fundamental operating principle of the FCC is based on the thermal
equilibrium achieved constantly between the reactor and the regenerator.
Catalyst circulation is the energy vector. it provides the energy required to
vaporize the feed in the reactor and to make the endothermic cracking reac-
tion occur. The energy comes from the regenerator where coke. a by-product
 174 C!vpr~5_ CAT"LYJ/C CflACKfNG

\
tight gasoline Heavy gasoline
I
!
(Cs-160"Q (l60-221"Q
I

Gasolines
sp. gr. 5 dl 0.727 0.856
Paraffins (% wt) 18.6 10.4
Olefins (% wt) 59.9 20.8
Naphthenes (% wt) 2.8 0.8
Aromatics (% wt) 18.7 68.0
RON clear I
94.0 92.3
MON clear ! 78.9 82.0
Vapor pressure (bar) 0.59 -
Sulfur wt) eX 0.027 0.148
Leo '.
(221-350C)
sp. gr. d~s 0.948
Cloud point rC) -18
Pour point 'C) -19
Cetane number (motor) 21.1
Saturated compounds (% wt) 13.8
OIefins (% wt) 4.3
Aromatics (% wt) 80.3 t
Vlscostty 20C (mrn-s") 4.5 I
Sulfur (% wt) 1.2
Slurry (350C')
sp, gr. d ~5 1.025
Viscosity 100e (mm 2s-l ) 7.4
Sulfur (% wt) 1.8
Sediments (% wt) * 0:15
Theiractlon that Is not soluble in hot toluene (ASTM 83)

IT,bl,!
L.r::":":"""l
5.3 Typical characteristics of FCCproducts (feed B, Table 5.1).

of the cracking reaction, is burned. The coke is laid down OIl the catalyst in the
reactor and deactivates it, so when the spent catalyst comes from the reactor
its acttvtty must be restored by eliminating the coke.
The thermal balance depends on the characteristics of the feed processed.
For feeds with low Conradson carbon, such as vacuum distillates, the coke
yield is too low to meet the unit's needs. Energy must be supplied to the sys-
tem by a feed preheater. For feeds containing a lesser or greater proportion of
residues, the energy available from coke combustion may prove to be exces-
sive and heat will have to be exported to make the process workable.
 To flue gas Reactor effluent to
treatment primary fractionation

Disengager

U/ i I S~am

Feed

Frh or
equilibrium
calalyst In
Riser
Fresh catalyst
make up module

Air Ix : I 1 ~ Slurry
.f'"
~
Recycle ~
~

nl:llfC
Compressor r
....
;: '.
5.1 I Reaction and catalyst handling sections.
176 CnaDler5 CATALYTIC C=;: ".3

The amount of catalyst in circulation controls the severity of the reaction

and in tum the conversion for a given feed. As a result, it is of utmost impor-
tance to maintain the equilibrium between the combustion and the reaction
thermal balance. This equilibrium determines the chemical kinetics of the con-
version reaction occurring in the reactor.
b. Control Systems
Catalyst circulation is generally controlled by two slide valves controlled by
two main regulators. The valve regulating the flow rate of regenerated catalyst
that is fed into the reactor is controlled by reactor outlet temperature. The
valve regulating the flow rate Qf spent catalyst to the regenerator is controlled
by the catalyst level in the stripper. Some older designs such as the E.xxon
model IVuse the pressure differential between reactor and regenerator to con-
trol catalyst circulation. This type of indirect control is much less accurate
than -the system using slide valves.
The pressure of the dilute phases in the vessels is regulated. The reactor
pressure is generally controlled by regulating the pressure of the drum at the
top of the primary fractionation column (see Section 5.2.3.4a). The regenera-
tor pressure is controlled by a double disk slide valve often associated with an
orifice chamber or a variable orifice.
c. The Reactor and the Regenerator
In all modem FCC plants. the reactor consists of several component parts.
each with a very distinct function.
The actual reactor is in fact a usuaJly vertical pipe (riser), whose internal
diameter is approximately 1 m. At the riser foot, very hot catalyst (680to
750C) returning from the regenerator is mixed with the liquid feed that
has been finely atomized by injectors (typically, the ratio of catalyst/feed
mass flow rates is 5 to 6). As a result, the feed is vaporized and cracked.
causing a sudden expansion in volume which accelerates the mixture to
a superficial velocity close t<? 15 to 20 mls, The residence time of the
hydrocarbons in the riser is approximately 2 s (on the basis of the
gaseous reaction products) and the reaction temperature at the top of
the reactor is kept in the 500 to 530C range, with an accuracy of 0.5'C.
The riser is connected to the dlsengager, where solids and gases are sep-
arated.
. The top of the riser generally features a primary reaction product-versus-
catalyst separation system. Separation must be as efficient as possible.
because post-riser cracking is detrimental to reaction product quality
and yields.
The gaseous products are then routed to a cyclone separator system for
final separation of entrained. catalyst fines by centrifuging. The vapor
coming out of the cyclones is then sent to the primary fractionation col-
umn while the recovered solids are sent to the catalyst stripper.
The catalyst coming from the primary separation system and from the
cyclones then flows into the stripper where the catalyst residence time is
 C1Yptw 5. CA'W.YTIC CRACKiNG 177

. approximately 1 to 2 min. Here steam contacts the spent catalyst

counter-currently in order to desorb and recover the hydrocarbons
entrained by the catalyst. Stripping efficiency is very important, because
any unrecovered hydrocarbons will subsequently be burned as coke in
the regenerator. This will only ralse the regenerator temperature need-
lesslyand cause a loss in yield. The stripped catalyst is then sent into the
regenerator under level control. .
In the regenerator, the air required for coke combustion is carefully dis-
tributed. The more coke laid down on the catalyst during the reaction, the
higher the regenerator equilibrium temperature. Most present-day FCC plants
work on the basis of total coke combustion, with the air now rate regulated so
that excess oxygen from 0.5 to 2.0%mol is present in the flue gases. This oper-
ating Diode also requires a platinum-based COcombustion promotor in order
to confine combustion to the dense catalyst phase and avoid the problems of
post-combustiOn in the dilute phase. Post-combustion, which can be explained
by the fact that the catalyst mass present in the dilute phase is too small to
absorb the combustion heat. can cause temperature to rise excessively and
damage equipment in the flue gas circuits.
The catalyst generally remains less than 10 min in the regenerator and
returns to the reactor with a resldual carbon content of less than 0.1%.
Some units still work on the basis of conventional regeneration, i.e, partial
combustion with insufficient oxygen. This operating mode, producing flue
gases with both CO and CO2, limits combustion exothermicity and the regen-
erator equilibrium temperature is established at approximately 650C. The res-
idence time required for regeneration is consequently longer for obvious
kinetic reasons. This type of regeneration does not usually allow the residual
carbon content to be lower than 0.3%.'
The catalyst fines entrained by flue gases are separated out by two stages
of cyclones before the gases leave the regenerator.

;.2.3.2 CatalJst Handling Section

This section (F"sg. 5.1) consists of two or sometimes three catalyst storage hop-
pers, one for spent catalyst and one or two for fresh catalyst(s). They are con-
nected to the regenerator by catalyst transler lines.The spent catalyst hopper
must be able to contain a volume greater than the unit's total catalyst inven-
tory. The voltJJDe is needed when loading the unit during start up or for emp-
tying the unit during shut down. Fresh catalyst hoppers are normally equipped
with catalyst transfer modules. small vessels featuring an automatic system
controlling air controlled transfer of specified amounts of fresh catalyst to the
regenerator.

i2.3.3 Flue Gas Treatment Section

This section (Fig. 5.2) may be of varying degrees of complexity depending on
energy optimization in the catalytic cracking unit and also on local environ-
mental regulations.
 ..
~
Superheated LP steam
.~
~...
To stack
Superheated HP steam
~
t Waste heat

:J
boiler ~
~
Regenerator ~
flue gases
III;
2Li

Boiler water

'----I
, I ..

~ LP steam from fractlonator

r--- .. HP steam from fractlonalor

TertialY
separator

Figure
5.2 I Flue gas treatmentsection
 The flue gases coming from an FCC regenerator contain a significant
amount of recoverable energy. The mechanical energy can be recovered by
expansion in a turbine placed directly at the regenerator outlet: The turbine is
generally used to drive' the combustion air compressor. Here a tertiary cyclone
system needs to be installed to separate out catalyst fines between the regen-
erator and the turbine and protect it against erosion as much as possible. After
expansion, the flue gases are routed to a waste heat boiler that produces high
pressure steam. If the FCC is operating in the partial combustion mode, the
boiler is replaced by a CO incinerator. It achieves final combustion of CO to
CO2 in order to recover the heat energy from combustion and meet CO emis-
sions specifications (100 to 500 ppm vol) for gaseous discharges.
In addition to CO specifications. environmental regulations mandate instal-
lation of further equipment to limit pollutant emissions such as:
catalyst dust (50 mg/Nm3 max),
sulfur oxides, sax, from burning the sulfur contained in coke (595 ppm
vol max),
nitrogen oxides, NOx from burning the nitrogen contained in coke
(340 ppm vol max).
Catalyst dust is usually separated out by an electrostatic precipitator.
Sulfur and nitrogen oxides can be eliminated by installing separate ancillary
units that will not be dealt with in this chapter.

5.2.3.4 Product Fractionation Sectior:

a. Primary Fractionation
The FCC reactor effluent is sent to a primary fractionation eoIumn (Fig. 5.3),
which separates a very wide range of products. These go from very light ones
such as butane, propane and gases to heavier ones such as LCO, HCO and
slurry, whose end point is approximately 650C.
The column's particular feature is that completely vaporized and super-
heated feed is let into the bottom. Heat must therefore be exported in the form
of circulating refluxes placed all along the column so as to balance liquid and
vapor streams.
The most important circulating reflux is for the slurry at the bottom of the
column. It is a critical circuit that operates With heavy oil containing catalyst
fines lost by reactor cyclones. It carries out several functions:
it achieves the initial "desuperheating" stage for the vapors;
it washes the feed zone efficiently 50 as to prevent coke deposition and
poor vapor distribution:
it subcools the slurry to prevent thermal breakdown which would cause
deposits of heavy polymerized products, thereby plugging up e.xchangers
and eventually causing shut down.
 CracklliJ gaS!)S
To primary 10compression .....
absorber
!

Hoavy g"s~ne
I
\II

~
~
~
()
Absorption od 10

~
secondary absorber
Heavy gasoline
circulating relluK Q
;;;
(,1

LCD circulating relluK

Absorplion LCD
oNback 10 stripper
secondary _Steam
absorber
, LCf
HCO
strippe(

r~l~
_Steam

Slurry
circulating tleo
relluK

Reaelor
effluent
Clarified 011 Recycle
10riser

Pritnury fmcticJIlatirm section.

 ~pters. CATAlYTIC CRAQlIilG 181

The slurry produced at the bottom of the column generally needs to be fil-
tered before being sent to storage. The filtered product is called clarified oil.
The HCO and LCO are two sldestrearns on the column. HCOis not usually an
end product. but is used as a purge or a barrier fluid in the bottom section. It
can also be recycled to the reactor during low conversion runs or to compen-
sate for insufficient coke production in the thermal balance. Gasoine and
lighter products are recovered from the drum at the top of the col una

b. Gas Concentration
The gas in the drum at the top of the main fractionation column is compressed
by the cracked gas compressor to a pressure ofapproximately 15 bar(Ftg. 5.4).
The high pressure gas is routed to the primary absorber where most of the C4
and C3 cuts are recovered. Absorption is usually carried out by the unstabi-
lized gasoline which is the overhead liquid in primary fractionation.
Sometimes debutanized gasoline is recycled at the top of the absorber to
improve its efficiency.
The gas produced by the primary absorber is then sent to a secondary
absorber where final C4 and C3 recovery is accomplished. The oil used for
absorption is either LCO or heavy naphtha. which is recycled to main frac-
tionation after absorption. The gas produced is dry sour gas and goes to amine
washing to remove H:zS. The treated gas is then finallysent to the refinery fuel
gas network. "
All of the liquid from the primary absorber is routed to a stripper where
deethanization and H~ stripping are performed. The bottom of the stripper is
sent to the debutanizer where gasoline stabilization is achieved. The product
from the bottom of the debutanizer is stabilized gasoline and goes to a sweet-
ening unit to remove mercaptans before storage with finished products. The
mixture of C3 and C4 cuts is recovered from the top and the liquid mmure is
sent first to amine washingin order to eliminate H~.then to a sweete.ling unit
for mercaptans removal.The sweet product is processed in the depropanizer
to separate the C4 from the C3 cut. The two products from the depropanizer
are pumped to the refinery's liquefied gas storage. Sometimes the fractiona-
tion train finishes off with propane/propylene superfractionation.

j.2.4 Thermal Balance

The thermal balance between reactor energy consumption and regenerator
coke combustion controls catalyst circulation. The data required to calculate
the thermal balance areas follows.
Reactor thermal balance
Heat consumption:
- feed preheating. vaporization and superheating,
- heat of cracking reaction.
- atomization and stripping steam superheating.
- reactor heat losses.
 Ac~ses
....
Gasoline from primary ~lIonoil ~
Crackedgaae. fractionallon reflux drum

Secondary
abso,ber i
~

(l
~
~
Compressor
1s1slage s~
:I:
(;1

Ughl gasoline

Gels cOllcentration SC(:';OIl.

 Heat inputs:
- coke adsorption,
- temperature drop in drCtltatlng catalyst from the regenerator.
Regenerator thermal balance
Heat consumption:
- combustion air preheating,
- coke desorption,
- regenerator heat losses,
- temperature increase in circulating catalyst from the reactor.
Heat inputs:
- coke combustion.
The thermal balance items show the importance of the catalyst in trans-
ferring heat from the regenerator to the reactor. The heat carried by the cata-
lyst is expressed as follows:

Qcat =Cdrc X Cpcat X (Treg - TreaJ (5.1)

with:
Celre weight of catalyst dn::ulated per unit of time (usually per hour)
Cpcat specific heat of the catalyst
Treg temperature of the regenerator dense phase
Treac temperature of the reactor
Since the unit's main heat source is coke combustion, the coke balance can
be related to catalyst circulation via the followingequation:
(5.2)

with:
Mcoke weight of coke produced per un it of time
.icoke (% wt of coke on the spent catalyst coming from the stripper) -
(% wt of residual coke coming from the regenerator)
Note that in practice the unit's coke production is determined by measur-
ing the combustion air flow rate and analyzing flue gases.
Additionally, if Rho defines regenerator combustion efficiency:

R = heat absorbed""by the catalyst x 100

ho heat produced by combustion

and Qcoke the coke's specific heat of combustion. the result is:
Qcat := .t/Ulke x Qcoke X Rh,/lOO (5.3)

or, using Eq. 5.2:

(5.4)
 Since the coke's specific heat of combustion and the regenerator's cc
bustlon efficiency are roughly constant, comparison of Eqs. 5.1 and 5.4 she
.that the temperature diCference between the regenerator and the react
varies as .!\:oke' In other words. for a given reaction temperature, the higher t
A coke ' the higher the regenerator equilibrium temperature and the lower t:
catalyst circulation rate. This will thus limit conversion of the feed.
The A COke parameter is extremely important It characterizes one of t:
essential properties of an FCCcatalyst: coke selectivity. It is used when choc
ing a catalyst according to thermal balance constraints on an industrial un
Catalyst Acoke values are determined in the laboratory (rnicroactlvity te-
MAT) on a relative basis by measuring the coke content of a catalyst that hi
operated under conditions similar to the optimum objective of the industri
operation (for example the coke yield corresponding to maximum gasolu
production) (Figs. 5.5a and 5.5b).-
Consequently, a catalyst with a low 6.coke will be chosen if the aim is to rnov
away from the regenerator temperature constraint and thereby be able to pre
cess heavier feeds to improve the unit's economics. In contrast. a catalyst witl
a high Acoke will be selected if there is a thermal balance deficit in the unit du.
to the feed's low coke yield.

5.2.5 Fluidbation and Pressure Balance

5.2.5.1 nUidizatioD
a. Catalyst Characteristics
FCC catalysts are characterized by a number of physical properties that influ-
ence the hydrodynamic behavior of fluidized beds (fable 5.4).
The catalyst's average bulk density (ABD) directly influences the density
observed in ebullatlng beds and in catalyst transfer lines. A higher ABD
will cause a higher fluidized system density and improve the unit's pres-
sure balance. For a given technology, this means an increase in pressure
differential on the slide valves that control catalyst circulation, and pro-
vides improved operation 1lexibility by boosting the margin available to
.adjust the unit.
Particle size distribution is monitored regularly during industrial opera-
tion, for it greatly influences fluidization quality and catalyst circulation
stability. The average particle diameter ranging between 65 and 70 !lID
and the fines content (particles with a diameter smaller than 40 lJm) are
usually checked. For example, if a larger average diameter and a smaller
fines content are observed at the same time during operation, it means
there is an abnormal catalyst loss. which may indicate a failure in cyclone
operation. A normal fines content for an equilibrium catalyst ranges from
10 to 12%.
The attrition rate characterizes the catalyst's mechanical strength. The
property is important, because an overly-soft catalyst will break up in
high velocity areas such as the riser, the cyclones and air or steam dis-
tributors. The catalyst fines formed in this way will be lost for the system.
 Ch__ S. CATALYTICCRACKING 185

55

50
j
~
"'C
Qj
's, 45
II
..
c
'5
(II
m
~
40

35 '--_--'-_ _. L . . - _ - - L_ _""""-_---L_ _..l-_---'-

3 4 5 6 7 8 9 10
Coke yie1d (0/0 wt)

i Figure I
I 5.5a I Coke yield (% un].

2.5

j
::l! CatalystA '
~ 2 i a Catalyst8
-'
<]B
i CatalystC

1.5

lL-_---l._ _..:.-_ _L-_---L_ _..l.-_--i_ _- l

3 4 5 6 7 8 9 10

L--
Figure
Coke yield (% wt)
--J

5.5b Classification of various catalysts according 10 the microaaicity test. JLtT.

 186 Cr>aorer 5 CATALYTIC CRACKIN::>

fresh Equilibrium
Characteristics
catalyst
I catalyst I
Chemical analyses ("/0 wt) If
AI~03 25.48
;
sio, 70.00
Rare earths (in oxides) 2.02
Fe:P3 0.46
I
K20 i 0.08
Ti0 2 0.77
i
Na20 0.35
loss on ignition to 1 OOO<C 16.70 1.25
Ni (ppm. wt) - 2040
V (ppm. wt): '. - 3140
Ni +. V (ppm. wt) - 5180
"V/Ni - 1.5
Physical analysis
BET area (m"2/f!J 1 260 142
I
Elementary cell CUCS) (A) 24.54 24.23
Pore volume (Nz. P/Po = 0.95) (cmJ/g) II 0.25 0.16
Pore volume (Hg, 35-530 A) (cmJ/g) 0.14 0.1I
Apparent bulk density (ABO) (gJcm 3 )
Particle size distribution (% wt):
I 0.82 0.87 1
I

0-20\lm 1.4 0.6

0-40\lm 24.5 5.9
0-60j.1m 55.5 32.5
0-801lm 76.9 6l.I
O-lOO\lm 93.4 84.5
0-150\lm 100 100
Average particle size (pm) 56.1 71.5 .
Attrition index (Davison Index) (%) 5.9
'- ,....--.--,

G 5.4 Comparison of the main physical properties of a fresh and

catalyst in an FCC unit. .
all equilibrium

b. Fluidization Curve
of
An FCC catalyst subjected to the superficial velocity a gas lorms an emul-
sion that is characterized by a fluidization curve determined with air at ambi-
ent conditions (Fig. 5.6). The curve establishes the relationship between the
superficial velocity and the apparent density of the catalyst/gas emulsion. It
can be used to distinguish between several systems when the superficial
velocity is increased from zero. .
 C/!apUlr 5. CATALYTiC CRACKING 187

-
{
01
~750
Z.
~
G)

600

450

300

150 Uw = minimumfluidization velocity

u". =minimum bubbling velocity

0.3 3 30 300
Fluitization velocity (cmls)

: Figure
'5.6 Typiml curveof changes in density versusfluidization velocity.

The starting point is the apparent bulk density (ABO), then fluidization
begins at the minimumfluidizationvelocity correspondlng to a few millimeters
per second. Beyond this, the density is first relatively stable, then slightly
lower. When the superficial velocity is under 3 mis, there is an ebullating bed
zone where a catalyst/gas emulsion coexists with gas bubbles. Finally, above
3 mls the density drops very Quickly and the entrained zone appears where
the catalyst is dispersed in the gas phase.

5.2.5.2 PrCS5Uft Balance

In an industrial unit, circulating the catalyst in steady state conditions requires
a stable fluidized system everywhere in the loop. As such, it is necessary to
supply the catalyst with gas continuously (generally air, steam or fuel gas
depending on the section in the unit) and keep it from getting deaerated, since
this would cause settling with a discontinuity in fluidization. If this condition
is met. then the Duidized catalyst behaves likea liquid and transmits pressure
as stated in the general Jawsof hydraulics.
For instance. a column of fluidized catalyst corresponds to a differential
pressure (Fig. 5.1):
M'=dxgxj}r
188 eNIDr s. C':'T;'LYT/C CRACKIN$

with:
.1P in Pa
d in kg/m3
g= 9.81 m/s 2
All inm
In practice. the difficult part is to keep the system properly fluidized in the
catalyst transfer lines. Accordingly. gas is injected in a regular pattern in such
a way as to offset the decrease in the interstitial volume occupied by the emul-
sion gas which would be the consequence of the compression effect of the cat-
alyst column. Without this precaution, compacting would occur, eventually
blocking circulation.

Pressure drop
aP

I
I
I
I 0.3 mis 0.8 mI$
; ~ -It :

I
I
I
I
I Gas flow
". I rate or

I < 0.1 mIs 4rrJs velocity

I
I Compact Fluidized
I bed bed Pneumatic
11
I transport
Y
Minimum
fluidization velocity
Gas

* Normal operating range for fluidized beds

Figure
5.7 Pressure drop ve~us gas velocity.
 ~s. CArALmcCRACKlN(; 189

5.2.6 Operating Variables. Conversion.,

and Cracking Severity
By .definition, conversion (CONY) of a feed is the percent of feed converted
into coke and products lighter than LCO or the residue (slurry):
CONY == 100- (LCO + Slurry)
CONY, LCO and slurry can be expressed in %vol or in % wt.
For a given feed, increased cracking severity meansan increased feed con-
version. Cracking severity is controlled by the kineticconditions achieved in
the reactor. so the higher the catalyst circulation rate. the catalyst activity and
the reaction temperature. the greater the severity. Feed conversion is there-
fore adjusted to.the required value by regulating the kinetic conditions and
selecting the operating variables accessible to the operator. T"ypicaJ changes
in yields versus conversion are illustrated in Figure S.8.
Contrary to a lot of other processes where the effect of a single operating
parameter on product quality and yield can be isolated, a change in a single
FCC operating variable causes one or more other operating variables to
change. This is the direct consequence of the thermal balance by means of
which the energy produced by coke combustion is transferred from the regen-
eratorto the reactor. for instance. if the reaction temperature is raised, the
-catalyst circulation is too, along with the reactor equilibrium temperature (see
Section 5.2.3.lb). Asa result, yields are influenced by the combined effects of
a simultaneous increase in three parameters: reaction temperature. catalyst
circulation and return temperature of regenerated catalyst.
The major FCC operating variables can be dividedinto two groups:
Independent variables directly adjustable by the operator:
- reaction temperature,
- preheating temperature,
- recycle flow rate,
- catalyst activity and selectivity,
- regenerator combustion mode (total or partial).
Dependent variables not directly accessible to the operator but never-
theless adjustable via independent variables:
- regenerator temperature,
- catalyst circulation flow rate,
- conversion.
- combustion air Oow rate.
The effect of changes in the main independent variables is as follows
(Fig. 5.9):
A higher reaction temperature causes an increase in:
- catalyst circulation.
- regenerator temperature,
- conversion.
- production of C'T C3 and dry gas.
- gasoline octane number and olefin content.
- LeO aromaticity,
190 ChaPter ~, CATALYTIC CRACKIN3

- coke yield slightly,

but increases or decreases the gasoline yield depending on the position
of the over-cracking point.
A higher preheating temperature with a constant reaction temperature
causes a decrease in: '
- catalyst/feed ratio,
- coke yield,
- conversion,
but increases regenerator temperature.

.l.
Yields

.75 CD Gasoline (Cs 220"C) 37.5

CutC~
@CutC;
@COke
G)

. ~:
. - -I-~

I ,
~
.. - - - - - -(,,: * : \ ~
Q)

"'o0"

/./
50 25
0
~
:2
.'E
>-
>
i (5

~
a
>

Cll * ,:
,S
(5
III
(IDI
AI
~
C'
III
/ C
cS'
in
'0
25 12.5 Qj
's,

oI I I ,I 10
20 40 60
Conversion(% vol)

Figure
5.8 I General seoerity-conoersion-yield relationship.
 Riser
g temperature (OC)
c.
. Regenerator
!2
!1! temperature (0C)

8
80 " ' , _ Preheating
_ _ .". temperature (DC)

--- '200

4.0,,-

75-
300

...............
r~

70
376 o~
~
i'S
4 5 6 7 c/o ~
Fi~lIrc
i
5.9 Typical retationships between the oarious opemting lmriables anti tlUI gasoline and coke yields (modetlin(J results).
......
CD
192 cn.orerS CATAI.Y71C CRACKlN3

5.1.7 Changing Technology

Ever since the first commercial fluidized bed catalytic cracking unit (pCL~
No.1: Powdered Catalyst Louisiana) was commissioned in May of 1942 in the
Esso refinery in Baton Rouge. the technology has not stopped evolving. par-
ticularly due to the progress made in catalyst design [6]. The first processes
used ebullatlng bed reactors because of the low activity of the catalysts avail-
able at that time. They were the result of development carried out mainly by
three companies:
Standard Oil Development Co. (SOD) developed a series of models that
eventually led to the famous Model IV in 1952 (Fig. 5.10). It became a
great commercial success due to the numerous advantages it provided:
operation was designed at relatively high pressure and velocity in vessels
located side by side..Moreover, the use of lJ-tubes for catalyst transfer
minimized the height of the structure and construction costs.
M.W. Kellogg Co. introduced theOrthoflow, or vertical streams concept,
in 1951. The principle is based on eliminating lateral catalyst movement
by using a reactor placed on top of the regenerator with a stripper
located inside the regenerator. The catalyst circulates in vertical piping
affording upward Gift) and downward (stand-pipe) movement. The flow
rate is controlled by plug valves that were also developed by Kellogg.
UOP introduced its "side by side" unit in 1945using a simplified catalyst
circulation scheme. Then in 1947, the stack configuration came into
being, where the reactor is placed on top of the regenerator. The spent
catalyst flows by gravity from the reactor to an external stripper and then
to the regenerator. The regenerated catalyst is lifted to the reactor by the
velocity generated in the lift line by feed vaporization.
In the sixties, progress made in catalyst activity led to various technologies
being adapted to riser cracking. For instance, Kellogg introduced Orthoflow C
which had two separate risers, one for fresh feed and one for recycling. UOP
kept its side by side technology, but built the reactor structure higher than the
regenerator in order to incorporate a riser.
Between 1970 to 1980 new advances in catalyst quality, especially
improved resistance to deactivation at higher temperature, prompted tech-
nologies to evolve toward operating conditions and materials that would
achieve lower residual carbon ratios after regeneration 0.1%).
In 1973. the Kellogg Orthoflow F process (Fig. 5.11) came on the scene,
which used two regeneration zones in the same vessel.
In 1978,UOP introduced the high efficiency regenerator concept (Fig.5.12).
featuring dilute phase combustion that eliminates a limiting step in combus-
tion kinetics: oxygen transfer between the emulsion and the bubbles.
In 1979.Exxon developed the Flexicracking process that uses a configura-
tion where the reactor is placed higher than the regenerator located beside it.
The reaction takes place in an outside vertical riser.
 FIIIO
gLlSOS 10 CO Reactor Cracking ellluenis 10
incinerator primary fractionallon

SIeam

Catalysl make up I---.-t--\

Air
Emergo~ ..
steam
Sleam

Steam

f
~

Feed ~
~

Secondary
To t cernpressor
FUll 011 FUll g'l,
i...
Fil:,m~
5.10
I condenser

Ess: Mode/IV FCC.

U)
w
194 C!laprer 5. CATALYTiCCRACKING

Cracking effluents
to fractionation

Flue
gases 10 ... 4__---
CO incinerator "----''t-h~

1------_ Steam

Transfer lUbes

Regenerator
with dual
combustion I
zone

Feed

11 .... Steam

Combustion air

Plug valves

Figu~1
5.11 I Kellogg Orthonow F FCC.
I
 Chapter 5. CATAl.YT1C CRACKIIG- 195

Flue gases to
energyrecovelY Cracking eftluenls
to fractionation
t

Disengager

!-"f---- Steam

C - : : J - - - - - - Feed

Combustion
air

Figure
5.12 UOP high efficiency FCC regenerator:
 196 Cna::xer5. CATALYTIC CRACKING

It was also at that time that the latest technological improvements were
seen:
Feed injection systems became more efficient with the appearance of
multiple injectors that provided both better coverage of the riser section
and better atomization' of the feed. The result was improved reaction
selectivity by reducing coke and dry gas production.
Reactor effluent/catalyst separation systems were designed to limit efflu-
ent breakdown reactions by confining the reaction to the riser and
decreasing post-riser residence time. The closed cyclones introduced by
Mobil-Kellogg were one of the technologies used for this purpose.

5.2.8 Residue Cracking

Process economics ~is increasingly prompting refiners to handle ever larger
amounts of residue in the FCC. This has required the development of specific
technologies suited to processing this type of feeds. The problems they pose
are due to their metal content and their increased coke yield.
More coke yield causes a problem in the thermal balance, because it raises
the regenerator temperature and entails introducing a means of extracting
heat from the regenerator to control the temperature. Two technologies were
developed to solve this problem, the first in the early sixties and the second in
the eighties:
A special exchanger that cools the catalyst, which needs to work with its
mechanical integrity preserved in a particularly abrasive environment.
The technology is proposed by Kellogg-Phillips (Fig. 5.13) and VO?, and
allows the regenerator to operate at low temperature. This limits the cat-
alyst's hydrothermal and metals deactivation kinetics.
The double regeneration technique developed by Total. Today proposed
by IFP-SWEC-Tota1 4 (Fig. 5.14), it is based on two-stage catalyst regenera-
tion. In the first stage a large part of the coke (60 to 70%) is burned at low
temperature with an insufficient amount of oxygen, thereby extracting
quite considerable heat due to the production of CO which is much less
exothermic than that of CO2, In the second stage combustion is finished
off with excess oxygen.
Double regeneration also protects the catalyst from deactivation by metals.
because vanadium migration is blocked by the reducing atmosphere in the
first regenerator. Furthermore, it is precisely in the first regenerator that most
of the water is eliminated (entrained from the stripper + combustion). It is one
of the essential components in the hydrothermal and metals deactivation pro-
cess.

4. Institut Franl;ais du Petrole-Stone and Webster-Total..

 ~ 5. CATALYTIC CRAcKING 197

Cracking effluents
to fractionation

Disengager_

Auegases
to energy
recovery ~
Reactor
(riser)

).4.-4---+--'+-- Steam

Stripper

!
Air distributors

Feed

Catalyst cooler
heat exchanger

Plug valves

:.-..--,~----------------------....;
Figure !
;.13; Residue cracking process. Kellogg-Phillips' HeacyOil Cracking, HOC
 Flue gases to
waste heat boiler

cracking effluents to
primary fractionation

External
cyclones _

Disengager

Second
regenerator _--1-+-_\

Regenerated
catalyst
withdrawal well

Air distributor --;.~

Rue gases to
CO incinerator

First regenerator

_ Reactor
(riser)

Air riser ----HI-~

Recyde

Air distributors ----FM=~F===K=j

Plug valve __'

Figure
5.14 Residue cracking process.IFP-Stone & WebsteT-Total~ R2R.
 a.pw 5. CATALYTIC CRAC/CIIIiG 199

5.3 Reactions, Reactivity, and Mechanisms

53.! Reactions [1.3. 7-48J
The reactions that occur In an FCC reactor are numerous and complex.
Basically,two groups can be distinguished:
Thermal reactions are inevitable at the high temperatures encountered
(.... 450C) and give rise to free radicals [1,8.11-14]. They occur in the
gaseous homogeneous phase but can be promoted in various ways by a
solid surface (silica, alumina. activated carbon, etc.) [12, 13]. They are
not selective and lead to the production of large amounts of very light
hydrocarbons such as methane, ethane and ethylene In the gaseous
C1-C. fraction. for this reason and because the resulting gasoline is of
poor quality (low octane number and inadequate oxidation stability), an
attempt is made to minimize them. Given their high activation energy,
these reactions are greatly favored by an increase in temperature.
Catalytic reactions are of heterolytic nature and involve short-lived reac-
tion intermediates of the carbocation type [8., 15-18] (mainly carbenium
ions). The presence of acid sites in the reaction medium helps promote
the formation of these carbocation intennediates considerably as
opposed to free-radical intermediates. It also greatly improves cracking
rate and selectivity (less very light gases produced and better quality of
the resulting gasoline).
The main heterolytic reactions involved in catalytic cracking are: isomer-
ization, p-scission, hydrogen transfer, .dehydrogenatton, and various conden-
sation reactions.

;.3.1.1 Isomeri~atioa and lJsd5sioa

These two reactions involve the participation of carbenium ions, whose initial
formation is still today a subject of debate.
a. Carbenium Ion Formation [3, 7, 13, 14. 19-21],
At least three hypotheses have been put forward:
Protonation of an olefin present in the reactants or produced previously
by thermal cracking:

Protonation of a paraffin (or a naphthene) to produce a carbonium ion

then its breakdown into a carbenium ion by elimination of a hydrogen
molecule:
200 (;traoe" 5 CA.TA1,.YTIC CRACKING

Roughly speaking the reaction is equivalent to extraction by the proton

of a hydride ion H- from the paraffin to produce a carbenlum ion and H2 o

Extraction of a hydride ion from the paraffin by a Lewis acid site (electron
receiver):

b. Isomerization of the Carbenium Ion [8, 13, 14, 16-18,22]

The carbenium ions present on the catalyst surface become rearranged more
or less quickly according to the Simplified diagram below:

CH z CHz CHz CH3 CHz CH 3 CHz CH3

/\/\/\/ /\ \/\/
CH3 CHz CH = CHz CH3 CHz-C oS CHz
A- A-
In this particular case, a secondary carbentum ion (5 +) becomes rear-
ranged to form a tertiary carbenium ion (T"). Among the three categories of
carbenium ions, primary or P" (the charged carbon has only one neighboring
carbon), secondary or 5 (2 neighboring carbons), tertiary or T+ (3 neighbor.
ing carbons), the order of stability is as follows:
tertiar~ T + > secondary 5 + > primary P +
Tertiary ions' greater stability allows their carbocatlons to occupy the cat-
alyst surface preferentially. It gives them a better chance of having a C-C bond
scission than secondary S+, and especially primary P+, carbocations.

c. f3-scission [7.8, 12, 14. 16-21,23-25]

The scission takes place in Pof the positive charge, at a rate depending on the
structure of the carbocation that reacts and of the one that is produced. The
greatest probability of P-scission occurs with the favorable configuration
below:
c c
I I
R1-c-c-C-R.. ~
I '&-

C
where cracking of a tertiary carbocation produces a smaller tertiary carboca-
tion.
 C/lapMr 5 CA1ALYTIC CRACKING 201

The cracking rate drops quickly in the following order [24-26]:

mechanism A:. T'" ~ T+
mechanism B1 or 8 2 : S+ ~ T+ or T+ -+ S'"
mechanism C: S'" ~ S+
mechanism 0: S'" ~ P+ or P+ ~ S..
In olefinic or paraffinic structures with little branching, isomerization reac-
tions precede those of j}-scission.
The maximum number of favorable configurations possible obviously rises
with the number of carbon atoms in the hydrocarbon. This is why long paraf-
finic chains are more reactive to cracking than shorter ones. Methane and
ethane production by j}-scission of long paraffins or olefins ts significantly
curbed since it corresponds to the formation of a highly unstable primary car-
bocation. Mechanism A (very favorable) of ~scission explains the large pro-
portion of branched structures in light C4 and C5 hydrocarbons produced by
cracking. The saturated C. cut is thus very rich in lsobutane (i-C4/n-C4 + i-C. -
80%). However, the number of branches in cracking products is always lower
than that of the initial carbocation. For instance, the tertiary 2,2,4-trimeth
I Iypentyl carbocation which has 3 methyl branches is converted by mechanism

A into isobutylene and an isobutyl carbocatlon. each one with a single branch.
As a result, paraffinic hydrocarbons with more than 5 carbon atoms present in
the C5 -220 cracking gasoline cut are not very branched. This partly explains
the moderate octane number of this cut.
Although Il-scission is the most commonly mentioned FCCcracking mech-
anism, a second mechanism should be listed as a reminder. Its influence is
probably slight with conventional FCCcatalysts: scission of the C-C bond in a
of the p~sitive charge ofa carbonium ion: .

d. Thermodynamic Aspect ofIsomerization and {J-Scission Reactions

Isomerization is an equilibrium reaction. For paraffins, any rise in temperature
is conducive to the formation of products that are less and less branched.
Consecutive isomerization of light slightly-branched carbocations with 5 to 7
(or even 8) carbon atoms is therefore not thermodynamically promoted by the
high temperatures normally used. Moreover, cracking kinetics adjusted by
operating conditions to optimize gasoline production is not very favorable to
consecutive isomerization. It does not allow an efficient approach to thermo-
dynamic equilibrium as far as isomers with at least two branches are con-
cerned [27]. For naphthenic structures, a temperature increase promotes
rings with 5 carbon atoms at the expense of those with 6.
202 Cha:J:e."5. CATALYTiC CRACKING

~scission is an endothermic reaction, thermodynamically favored at high

temperature and low pressure. It can be considered as complete for naph-
thenic and especially paraffinic and olefinic structures in FCC conditions.

5.3.1.2 Hydrogen Transfer [I, 7, 10, 16,20,28-32)

This reaction is critical in catalytic cracking, and roughly speaking consists in
transferring one or more hydrogen molecules from a saturated or partially
unsaturated hydrocarbon molecule to another hydrocarbon molecule that is
partially unsaturated. For example:
3 C5H IO + cyclohexane ~ 3 CSHJ2 +benzene
or:
2 i-e 4Hs + tetralinef -+ 2 i-e H
4 IO + naphthalene 6
This exothermic reaction is very much shifted to the right in catalytic crack-
ing conditions, and helps especially to decrease the overall endothermlcity of
conversions in the reactor. It is of heterolytic nature (carbenium ions) and
involves several elementary steps that entail a series of hydride H- and proton
H+ transfers from the donor to the receiving molecule. It is of the bimolecular
type and is promoted by any catalyst, such as a Y zeolite for example. capable
of increasing the reactant concentration in the immediate vicinity of acid sites.
As shown in the examples below, the reaction actually means a transfor-
mation of light olefins into paraffins (with a moderate average degree of
branching), and naphthenes, polynaphthenes or naphtheno-aromatics into
aromatics or polyaromatics. A substantial fraction of isobutane is thus pro-
duced from the cracking primary product isobutene. Figure 5.15 illustrates the
impact of hydrogen transfer on the gasoline's chemical structure. On the aver-
age, the result is a lower gasoline octane number, especially the research
octane number (RON). It also causes a slight decrease in the hydrogen content
in light and heavy gas oils, LCD and HCa, therefore detrimental to their qual.
ity, and an increase in coke production (highly condensed polyaromatics).

5.3.1.3 Dehydrogenation by Catalysis

on Metallic Compounds [33-39]
The dehydrogenating activity of purely acid catalysts is generally negligible.
even though some components of new catalysts, such as free alumina, exhibit
slight activity. Jt is the metallic contaminants - vanadium and mainly nickel-
in the feeds which confer most of the dehydrogenating activity to the catalyst
where they are laid down in quantity. Contrary to the previous reactions. dehy-
drogenation on metallic contaminants is of a free radical nature. It is thermo-
 Cha(JIw 5. C4TAt.YTIC CRACKING 203

Silica-alumina Zeolite
lowTH high TH
100

- - Naphthenes
I-

- Naphthenes ~

- H transfered
from naphthenes
~

Cycflcs
~
to olefins
Aromatics
50 - Aromatics
I-

- - -
Jletlns
-
- Olelins - Non-cyclic$
- Paraffins
Paraffins -
10

'"'-I
I 5.15
i
Difference in composilion between FCCgasoiines produced on amorphous siI-
ica-alumina and on a 2OIile.
m: transfer of hydrogen.

dynamically promoted by an increase in temperature and a drop in pressure.

Dehydrogenating activity accelerates the process of converting the feed's
poIynaphthenic or naphtheno-aromatic compounds into polyaromatic coke
precursors. It also contributes to enriching gases (CtTin molecular hydrogen,
that is difficult to recover because it is greatly diluted.

5.3.1.4 Polyc:ondensation Reaction [i. 9, H 16.20, 4v--f5)

'Thennodynamically speaking, poIycondensation reactions are curbed in cat-
alytic cracking operating conditions (high temperature and low pressure).
However, although they are greatly inhibited. they are not deterred. They
result in the formation of polyaromatic compounds which are highly resistant
to cracking. and will gradually accumulate in the heavy liquid fractions and on
the catalyst in the form of coke.
Several reaction paths are possible. among them the following:
Polymerization of unsaturated hydrocarbon chains. followed by cycllza-
tion then dehydrogenation by acid hydrogen transfer or catalyzed by
metallic contaminants.
Alkylation of aromatics followed by cydization of the alkyl chain on the
first aromatic ring and then dehydrogenation of the new ring.
204 Cha/.Xer 5 CATALYTIC CRACKING

Condensation of the Dlels-Alder type lnvolvtng olefins and diolefins fOl-

lowed by dehydrogenation of the rings formed.

5.3.2 Reactivity of Hydrocarbon Families

[11, 12, 14, 16,20, 21,40,41, 49-55]
The reactivity of a hydrocarbon molecule and the type of changes it undergoes
in FCC conditions depend greatly on its structure. Figures 5.16 and 5.17 show
to what extent the various hydrocarbon families tend to produce gasoline by
cracking and coke {40].
Paraffins are not very reactive structures. especiaUy linear paraffins that
can be initially adsorbed only in the form of secondary carbocations.
Additionally, In the presence of unsaturated hydrocarbons that are much more
strongly adsorbed. such as aromatics, an adsorption competition will com-
mence which Is unfavorable to paraffins. It will result in a decrease in overall
paraffin reactivity. Paraffins mainly undergo !3-scission into olefins and paraf-
fins.
In contrast. olefins are much more reactive. They are converted by /3-scis-
sion into lighter oletins, but have a strong tendency to react by hydrogen
transfer, with the production of paraffins and molecules that are more unsatu-
rated. These unsaturated molecules result in aromatic compounds and espe-
cially coke by a sequence of polycondensation and hydrogen transfer reac-
tions.
It is very difficult to open a benzene ring by j3-scission.because of the high
resonance energy that stabilizes it. It is a little easier to open a polyaromatic
compound ring since the resonance energy per ring is lower than for benzene.
The most reactive aromatics compounds are by far the alkylaromatics. They
preferentially undergo selective l3-scission close to the aromatic ring (what is
termed a dealkylation reaction) when the alkyl chain is short and the carbon
in ex of the ring is highly substituted [55). When the chain is longer (more than
some 4 or 5 carbon atoms). scission can occur inside the ehain.It seems to be
especially favored in the ~ position as opposed to the aromatic ring when the
carbon in ex of the ring is not very substituted [56], leading to a benzyl carbo..
cation C6H s-CH;" A number of somewhat dated results indicate that the car-
bocation produced in this way might oscillate between two structures: the
benzyl carbocation and the tropylium ion which is a stable ionic aromatic ring
with 7 carbon atoms CiH7' [57-63). -"
Alkylarornatics can be involved in various other reactions:
isomerization by changing the relative positions of various alkyl chains
around the aromatic ring(s);
disproportionation and transalkylation when the alkyl chain is a methyl
or ethyl group;
sequences of side reactions: dehydrogenation and cyclizatton of an alkyl
chain with at least 3 or 4 carbon atoms on the aromatic ring. resulting in
the formation of polyaromatic compounds.
 o-~mr 5. CATALY7JC ~ 205

Polyrraphthenes
60 Gasoline
yield . /Monoaromatics

50
C'
~
t
'0
40
~
ell
.S
g 30
1lI
,/ 15OP,.araffins

-
C/l

~
."..

C\l
20
~111
0

10 _ Diaromatics

i 0
I
S <m .oc )
2 l
j 0 0.5 1.0 Severity = 100.WHSV
L--i-'I -----------------'-------~
Figure
; 5.16, Influence of the type of feed on the gasoline yield.

50
Aromatics With , _

!
Coke
y;eld
40 5cydes /

/4 cycles
j
~
"0
Q
's,
30

/
/ ! ... 3 cycles
~
0
o
20 / // t
/ ,," - 2cycJes
10
/."."" .
/ ,," .
~_~-:3.::.:: .
I
0.5 1.0

fbJre
5.1 -; Influence of the aromatic nature of the feed on the coke yield
 The reactivity of naphthenic rings increases with their degree of substitu-
tion, in other words with the possibility of forming tertiary carbocations on
the ring. The possibilities of evolution are varied:
isomerization of the ring with a change from 5 to 6 carbon atoms in the
ring or the reverse;
opening the ring: which is a difficult reaction.
changing the 6 carbon atom rings into aromatic rings by dehydrogena-
tion.
With an identical number of tertiary carbons on the ring, the reactivity of a
6 carbon atom ring is higher than that of a 5 carbon ring. With an identical
structure, unsaturated rings are more reactive than saturated ones and evolve
differently.. A saturated ring reacts partly by opening rings and successive
cracking of the chalri, whereas an unsaturated ring is changed preferentially
into an aromatic ring by dehydrogenation.
Alkyl chains coupled with naphthenic rings can undergo the same changes
as paraffins, provided they have a sufficient number of carbon atoms (;;. 6
or 7}
The 'rnaln reactivity sought in cracking is the one that results in gasoline
production. Gasoline selectivity varies considerably from one hydrocarbon
family to the other as shown in Figure 5.16 {40]. The best yields are achieved
with alkyl-monoaromatics that produce simple monoaromatics by dealkyla-
tion (toluene, xylenes and trimethylbenzenes particularly), and with poly-
naphthenes and especially dinaphthenes. Dinaphthenes undergo the opening
of one of the two rings quite readily, while the other is dehydrogenated into an
aromatic ring resulting in the formation of alkylmonoaromatics, and therefore
the same type of products as previously. Some of the one-ring alkylnaphthenes
are directly changed into alkyl-monoaromatics by dehydrogenation. This
explains why gasoline yields obtained from these structures are greater that
those {rom paraffins.
Polyaromatics are poor sources of gasoline. Meanwhile, as. shown in
Figure 5.17, they cause substantial coke production and the more rings cou-
pled, the more accentuated the tendency.

5.3.3 Reactivity of Industrial Feeds

A feed's quality can be defined as follows: the capacity to produce large
amounts of high added value liquids, i.e. mainly gasoline, and small quantities
of heavy residues and coke. The methods listed below can be used in an initial
assessment of the feed's quality potential:
analysis techniques of varying degrees of sophistication,
catalytic tests carried out in small laboratory facilities (micro activity
test" or MAT) or pilot plants.
 C/ulWS- CArALYT1C CRACKWS 207

5.3.3.1 Composition by Analysis

-Various analytical techniques of varying complexity can provide data on the
main characteristics of the feed, but can only roughly predict the real behav-
ior of the feed in the cracking unit (see Sectioo 5.3.3.2).
Elemental analysis gives the carbon, hydrogen, nitrogen. sulfur and
metallic contaminant content (Ni and V mainly).
Various simple standardized methods give general but valuable informa-
tion: Conrad son carbon, specific gravity. aniline point, etc.
Simulated distillation, which reaches an ultimate equivalent boiling tem-
perature of around 700C. provides the boiling point profile for the feed.
Mass spectrometry divides the hydrocarbons up into several families:
paraffins, naphthenes with one or more ceadensed rings, aromatics with
one or more condensed rings, naphthenoerornatics and sulfides (possi-
ble interference with aromatics).
Preparative liquid chromatography on silica (SAR technique) separates a
previously deasphaltenized hydrocarbon Jee{f into three fractions: satu-
rated (paraffins + naphthenes), aromatics (aU hydrocarbons containing
at least one aromatic ring) and resins.
NMR provides an overall idea of the percentage of paraffinic, naphthenic
and aromatic carbons and gives their primary, secondary, tertiary or qua-
ternary nature.

5.3.3.2 Reactivity [I, 3, 40J

The lower the molecular weight of a feed, i.e. generallyspeaking, the lower its
average boiling point, the harder it is to crack. In addition, a cut that is too
wide or improperly fractionated gives more gas-~d coke than a narrow cut.
The higher the aromatic and especially polyaromatic ring content. the lower
the feed's crackability. However.this feed will give a good gasoline yield if its
monoarornatic feature is strong. In contrast. it will give a lot of gas oil. heavy
residue and coke if its polyaromatic nature is very dominant. The Conradson
carbon residue value is also a valuable indication of the feed's tendency to pro-
ducecoke.
Naphtheni<:feeds are the most advantageous for gasoline production.
Paraffinic feeds are of variable quality depending on their degree of iso-
merization. They produce more gas and light gasoline and generally have a
slight tendency to produce coke. Predictably, gasoline production increases
when the paraffin content in the saturated fraction decreases while the naph-
thene content rises. Additionally, a high naphthenic content in the saturated
fraction is conducive to a good octane number since a large proportion of
naphthenes are converted into monoaromatics by hydrogen transfer.
After cracking, the feed sulfur that has not been transformed into H:!S is
mainly in the form of refractory thiophenic compounds in the liquid products.
The compounds have 1. 2. 3 or more coupled aromatic rings depending on the
product: gasoline. LCO. HCO or slurry. The sulfur in the feed does not cause
208 ~prer 5. CArAI.YT1C C::;;..CKING

any significant catalyst deactivation contrary to nitrogen which very severely

inhibits catalyst activity as soon as it is in excess of 1 000 ppm. Considerable
fractions of feed sulfur and nitrogen are incorporated in the coke laid down on
the catalyst and this can cause unwanted sulfur and nitrogen oxide emissions
in the regenerator.
Hydrogen treatment of the feed allows part of the polyaromatics to be con-
verted into naphthenoaromatics and polynaphthenes, thereby enhancing the
feed's tendency to produce gasoline and reducing its tendency to yield coke.
At the same time, it also helps substantially lower the sulfur, nitrogen and. if
relevant. metal and asphaltenic content in the feed. It can, however. cause a
slight drop in octane number in the resulting gasoline.

5.3.3.3 Combustion of Catalyst Coke in the Regenerator

a. Nature of Coke [1, 64-:66]
Very early on (before 1960). two types of coke were identified in the pores of .
cracking silica-alumina catalysts. One is the result of random stacking of lay-
ers of a graphitic nature (pseudographiUc or turbostratic coke). with no real
three-dimensional organization. The other is amorphous in nature and con-
sists of polynuclear aromatic molecules.
Today our understanding of cracking coke, particularly with respect to its
precise chemical nature, location and formation mechanisms, has not made
much progress. Even though these concepts are far from clear. all specialists
are in agreement at least on the polyaromatic nature of coke.
The amount of coke formed in the cracking catalyst zeolite can be consid-
erable, arguably up to 80% of the total coke in extreme cases. Obviously. this
zeolitic coke can only be made up of a limited number of condensed aromatic
rings, since it must necessarily fit in the limited space available in the struc-
ture's supercages, Pseudographltic coke can therefore only be located outside
the zeolite, l.e. on the matrix.
The ~~eran C/H atomic stoichiometry of deposited ~oke varies in a fairly
wide range between 1/0.5 and 1/1.2 approximately. This corresponds to hydro-
gen weight percentages in the coke of 4 and 9 respectively. The stoichiometry
value depends greatly on the type of feed processed, the operating conditions
and the catalyst. However. aUstoichiometry values must always be considered
with clrcumspectlon, since they can also reflect a malfunction of the cracking
plant: for instance, faulty catalyst stripping at the reactor outlet causes a
decrease in CjH. The variation in coke hydrogen content comes from the
nature and number of residual alkyl chains or naphthenic rings. mainly cou-
pled to aromatic rings. For example. the hydrogen content in the perylene
molecule (5 coupled aromatic rings, formula CZOH1i> is 4.76% wt, that of a
trimethyl perylene is already 6.12% wt.
b. Coke Combustion [1, 671"
Generally speaking, the combustion of a hydrocarbon residue produces car-
bon oxides and water and is highly exothermic. Little information is available
 ~5. CArAt-Y1lC CRACICJNG 209

in the literature on combustion kinetics of FCC catalyst coke. The reaction is

thought to be generally of the first order both with respect to carbon [1. 671
and oxygen [67]. with a rate expressed by the equation below:
E
r= k e- iT [C] [0 21

where[C) is the carbon concentration of the catalyst. [02] the oxygen partial
pressure. t the time. T the absolute temperature. E the activation energy, R the
ideal gas constant and k the rate constant.
In an actual refinery, the coke combustion process is probably more com-
plex than this simple equation would seen. if only for the following reasons:
Among the polyaromatic moleculesor parts of molecules making up the
coke, the most reactive to combustion are the richest in hydrogen. For
example. over 80% of the hydrogen in the coke has already reacted when
only 50% of the coke has been burned. Consequently. it is only at an
advanced combustion stage that the coke can reasonably be assumed to
be made up of pure carbon. The first order for carbon is therefore prob-
ably only approximate and should actually be higher than this.
It is hard to know whether the coke combustion rate is dictated by the
chemical reaction or by a physical mass transfer process. The factors
favorable to the first possibility are:
- thorough stirring of the fluidized bed that should lead to efficient
extragranular mass transfer and good uniformity of the temperature in
the bed;
- small grain size of FCC catalysts with sufficiently large pores to allow
better intragranular mass transfer.
The factors favorable to the second posslbility are:
- high regenerator temperatures (usually higher than 650C); .
- defects inherent to the regenerator or its operation: poor distribution
of air in the fluidized bed (rapid formation of large bubbles), bed zones
that are fluidized insufficiently or not at all.
Although the average regenerator temperature is easy to measure. the
real combustion temperature is not readily accessible because:
- the catalyst grains have widely different ages and therefore activity and
coke content. so coke combustion causes different amounts of heat to
be released from one grain to another;
- inside a grain the combustion front is raised to a temperature higher
than that of the rest of the grain.
Even though the equation above is approximate, it shows clearly that at a
given temperature, the target residual coke content in the catalyst after regen-
eration entails a certain residence time. After taking the catalyst circulation
rate into account, in terms of catalyst "inventory" in the regenerator. this
means a certain size for the regenerator. Temperature also has an impact on
regenerator sizing: an increment of 25~C would correspond to 40% less resi-
dence time required for regeneration [67}.
210 Chaore- 5. CATAl.Yl"fC CRACKING

5A The Catalyst
5.4.1 Historical Background [1, 2, 13,68-72}
Since the first Houdry fixed bed unit-in 1936, the cracking catalyst has consid-
erably evolved. Evolution has sometimes been fairly continuous, but it has
also been marked by important scientific and technical milestones.
Modifications in catalyst implementation (fixed bed to fluidized bed), the dis-
covery of new materials, or the development of new preparation techniques
have been at the root of these advances.
Among the main stages in this long evolution, the ones involving the FCC
catalyst exclusively should be pointed out in particular:
The first powdered catalyst was used in 1942 in the first FCC unit (Esso
refinery in BatonRouge): superfiltrol with a natural montmorillonite base
activated by acid and reduced to powder.
The lirst .catalyst in the form of microspheres was produced in 1946 by
spray drying: a stltca-alumtna. The better spherical shape achieved for
the grains of powder allows a great improvement in fluidization and a
reduction in fines lost by attrition.
1964 was a major turning point in FCC catalyst history with the first use
of a zeolite, faujasite (FAll). The gains in activity and selectivity are con-
siderable and have gone hand in hand with a gradual trend toward all
riser cracking in remodelling many FCC units. Here the zeolite is incor-
porated in a liquid suspension, or slurry, of the other catalyst compo-
nents before it is spray dried. The other components vary depending on
catalyst manufacturers and family: silica-alumina gel for the gel type, a
mixture of clay and a silica-alumina or alumina gel for the semi-synthetic
type.
The period from 1970 to the early eighties was marked by the develop.
ment of a series of 3 new manufacturing techniques that are still used
today: zeolite in-sill! crystallization (Engelhard), "silica sol" (Davison)
and "alumina sol" (Davison).
Some time in the mid-seventies, the first additives came into being. They
were designed to improve either the operation of the unit, e.g. the com-
bustion promotor, or catalyst performance, e.g. nickel passivation. The
following decade saw the development of vanadium traps and SO.r trans-
fer agents.
Up to the end of the eighties, the Y zeolite was substantially rare earth
exchanged to improve its stability and activity. The eighties marked the
beginning of a gradual decrease in rare earth content. This was due to the
race for higher octane numbers, the major objective of refining, and the
need to process heavier, and therefore more highly coking. feeds. USY
zeolite (ultrastable Y), used very early on in the sixties, then phased out
because of its high price, made a comeback and has gradually become
more widespread. It produces less coke and promotes the hydrogen
tran~fer reaction less, thereby achieving higher octane number gasolines.
 The eighties also experienced the trend to produce "tailor-made" catalysts ..
for refiners. Each FCCunit has its characteristics, constraints and often its pre-
cise production objectives. Only a "well fitting" c"atalystcan get the best out of
it. For instance in 1987, 7 manufacturers proposed 252 different catalysts on
the market, whereas there were 291 cracking units in operation worldwide.

5.4.2 Description of a Modern FCC Catalyst

first of all, a distinction should be made between the fresh FCC catalyst as it
is supplied by the manufacturer and the equilibrium catalyst in use in" the FCC
plant. Their catalytic properties and characteristics are different (fable 5.4).

5.4.2.1 Fresh Catalyst (l9, 70-73J

It is a complex composite acid solld consisting basically of the zeolite, which
is the main active agent, and the matrix. As ilJustrated in Figure 5.18, it is in the
form of a powder made up of mlcrospheres whose average diameter is approx-
imately 60 to 70 Jlm with a size distribution ranging from 20 to 100 um, The
powder is produced by spraying an aqueous solution (slurry) of a mixture of
the various solid catalyst components finely powdered.

Q. The Zeolite
The Yzeolite is the main zeolitic component in a cracking catalyst. It is a crys-
talline aluminosilicate whose faujasite structure is represented in Figure 5.19.
The structure is characterized by a three-dimensional lattice of identical
pores. with an opening approximately 8 Ain size, that is limited by a dodecago-
nal arrangement of oxygen atoms. The aluminosilicate framework carries neg-
alive charges located near alumina tetrahedrons [AlO..l-. When the zeolite has
been synthesized. the negative charges are compensated by sodium ions Na".
Most of these alkaline ions must be replaced by ammonium ions (that can be
broken down by calcination into H + and NHi) or rare earth ions RE 3 +. in order
to create the acidity required for catalysis. Each tetrahedron [Al0 4 J- of the
framework is therefore a potential acid site..Almost all of these sites are acces-
sible due to the structure's very dense network of .u1tra-micropores, that can
be entered by most of the molecules that are to be transformed (Fig. 5.19). The
Y zeolite can be incorporated in industrial catalysts in various forms: REHY;
REY, HUSY, REHUSY and DY, where H acts as a proton generated by the break-
down of ammonium ions (see Section 5.4.3.ld). Conventionally, the Y zeolite
content in the catalyst ranges from 10 to 50% by weight.

b. The Matrix [70-73)

The matrix includes the various grain components other than the zeolite. They
can vary widely and each one has a specific function:
The binder is either a silica or an alumina sol or a silica-alumina gel
before the spraying step. It provides cohesion for the catalyst micro--
spheres.
212 Ctitl()l8' 5. C,>,TAI,.Y7IC CRACKING

YZeofite
(Faujasite type Mesostructure
zeolite)

Pores
Filler

Binder

Macrospheroida/
catalyst particle
macrostructure

65 11m (average)

Figure
5.18 The FCCcatalyst.
 CtwJ1t1l5. CATALYTIC CRAcKrNG 213

Temary axis111

@
Sodalile cage Supercage (26 faces) Pathway of a molecule

IF~~~e I Faujasite structure (Y'zeoiite]: (The oxygen atoms and compensation cations
U are not shoum).

The diluent, kaolin.is designed to dilute the zeolite crystals in the micro-
spheres as inexpensively as possible. It is" generally inert, bUt special
treatment can provide it with some catalytic activity. It can also function
as a heat sink that protects the zeolite during regeneration. It also pro-
vides a macropore network that is useful in achieving proper diffusion of
reactants and products.
Various additives improving catalyst activity. alumina b~ng the main
one, can also be present. The alumina is usually introduced in the form
of discrete particJes of variable amounts of pseudoboehmite. It can go up
to 20% wt to boost the cracking activity of some catalysts that are
designed to process very heavy feeds.
c. Miscellaneous Additices [1, 70, i"l]
Various solid compounds can also be added to catalysts to improve their prop-
erties. They can be incorporated directly in the microspheres of the catalyst
when it is prepared. in which case they are dispersed in the matrix. They are
usually incorporated in microspheres different from those of the base catalyst.
The advantage of this solution is greater flexibility: the physical mixture of cat-
alyst and additive powders allows the proportion of additives to be varied as
 214 Cnaored. CAT';:..'!:,::; CRAC"f:~:;

needed. However. the drawback is that it dilutes the catalyst. and therefore the
catalytic activity. The more additive in the catalyst, the more pronounced the
tendency is.
Among the most common additives the following can be mentioned:
Combustion promoters: with a noble metal base (pd or Pt), they are used
in the form of independent microspheres to achieve 'partial or total com-
bustion of CO into CO2 in the regenerator when a few ppm of metal are
added into the total catalyst inventory in the unit
SOxtransfer agents: made of metallic oxides and basic in nature, e.g. alka-
line earths, they are usedto fix 50 2 in the form of sulfates on the catalyst
in the regenerator in the presence of small amounts of oxygen. The sul-
fates are then transformed in the riser and the stripper into H2S, which is
routed along with the cracking products to the fractionation-purification
section where it. Will be recovered. These additives are usually incorpo-
rated in microspheres that are independent of the catalyst.
. Metals traps: ~arious solids have been proposed to neutralize the detri-
mental effect of vanadium on the catalyst (see Section 5-4.2.2c). They can
be incorporated either in the catalyst microspheres or in independent
ones.
Octane promoters: the MFI zeolite incorporated in independent micro-
spheres significantly improves the octane number, mainly RON,at a con-
tent of less than 2% in the unit's total catalyst inventory. It works by pro-
moting the cracking of certain components (particUlarly linear or
single-branched paraffins and olefins) with a poor octane number.
thereby eliminating them from the gasoline at the e.xpense of a corre-
sponding drop in gasoline yield.

5.4.2.2 Equilibrium Catalyst

As soon as it enters the FCC unit, the fresh catalyst undergoes considerable
modifications due to contamination by the feed and because of the high tem-
perature (650 to 750C) and steam partial pressure conditions prevailing in the
regenerator. The result is a decline in performance, first of all rapid and then
gradual. If nothing is done. this irreversible degradation results in unaccept-
able catalytic performance after a few weeks or months have elapsed depend-
ing on operating conditions. A small fraction of the catalyst inventory circu-
lating in the plant is deliberately withdrawn every day and replaced with an
.equivalent weight of fresh catalyst in order to maintain constant activity over
time. The average catalyst with constant activity that circulates constantly in
the FCC plant is called an equilibrium catalyst. The modifications in the cata-
lyst basically have two causes: hydrothermal aging in the regenerator and
metallic contaminants present in the feed.
a. Hydrothermal Aging
Agingof the matrix is mainly seen in sintering of the elementary particles. lead-
ing to a reduction in the specific area. The situation is different for the zeolite.
 i
Complex and profound modiflcations take place in the zeolite structure' {69.
HJ. Generally speaking, the initial crystalline organization is maintained but
the following changes have been identified:
Gradual extraction of aluminum atoms from the aluminosiJicate frame-
work, leading to a decrease in the aluminum content and therefore a
reduction in the number of its potential acid sites.
Accumulation of aluminum species outside the framework. due to the
aluminum extraction mentioned above. The species are located either in
the structural micropores of the zeolite or on the outer surface of the zeo-
lite crystallites and are often called EFAL (extra-framework aluminum
species). a term that will be used later on in this chapter.
The NH.Y form (ammonium fonn of the Y zeolite obtained by ion exchange
of most of the initial sodium with ammonium ions) for example. undergoes
such modifications very readily. It is possible to control hydrothermal aging of
the Y zeolite partially during preparation of the new catalyst by manipulating
the parameters below, which willbe discussed more in detail later on:
residual sodium ion concentration;
introduction of rare earth ions in variable amounts, instead of ammonium
ions, to replace the initial sodium.

b. Metallic Contaminants {I, 15-781

The two main contaminants are the nickel and vanadium existing in FCC feeds
in the form of organometallic molecules in small concentrations that vary
depending on the feed: the sum or Ni + V is usually lower than 1 ppm in vac-
uum distillates, but can reach several ppm or even go up to 20 ppm in feeds
containing vacuum residue.
The contaminant molecules are rapidly brokeri'down in the riser when they
contact the catalyst. The two metals become fixed quantitatively on the
peripheral part of the catalyst microspheres. At high temperature and in the
presence of steam in the regenerator, vanadium migrates in the catalyst grain,
probably in the form of an oxohydroxide of y5+ and attacks the zeolite. deac-
tivating it via a process that is still today not totally understood (obstruction
of the pore network. destruction of the crystalline organization). Nickel has
only little or no mobility and remains located mainly inside a peripheral grain
layer.
Vanadium is the cause of a slight increment in molecular hydrogen forma-
tion in dry gases by dehydrogenation of certain hydrocarbons, It is mainly
responsible for the appreciable drop in the catalyst's cracking activity. Nickel
affects the catalyst's selectivity by substantially increasing the production of
. molecular hydrogen and coke.

c. Controlling Metallic Contamination

A large number of methods have been proposed. with the most well known
mentioned below.
c. Ultrastable Forms, or USY
Introducing a new catalyst containing an NH"Y zeGlite in an FCC regenerator
causes rapid, large-scale dealuminization of the zeotite framework. The steam
partial pressure is too low and the temperature too high for the silicon rein-
sertion process to occur ideally, so the equilibrhBD catalyst's performance is
not optimum. The manufacturer prefers to carry out this modification himself,
by including high temperature (;;;t: sO(tC) calcination of the zeolite in the pres-
ence of steam (or steaming) in his process flow scheme (Fig. 5.20). He stabi-
lizes the structure in conditions that help maintain excellent crystallinity, but
deliberately performs only part of the dealuminization. Removing approxi-
mately 50% of the aluminum and replacing it with silicon is sufficient to stabi-
lize the structure permanently. This treatment also provides another very
important advantage: it allows more thorough eJiIIIination of sodium if fol-
lowed by one or more ion exchange{s) with ammonium ions. For instance, a Y
zeolite containing 2 to 4% wt NazO after preliminaryexchanges can be brought
down to 0.2-0.3% wt NazO after steaming followed by exchanges. Such Yzeo-
lites are commonly called ultrastable or USY.
Just before 1990, even more sophisticated Y zeolites appeared on the mar-
ket. Uquid phase chemical treatments are reportedly able to remove a greater
or lesser amount of the EFAL produced by stabilization and even to keep the
residual EFAL in a considerable state of dispersion, distributed evenly to opti-
mize acidity. Such zeolites are often called DY(for dealuminated Y).
To prevent total dealuminlzatlon of the equilibrima USYzeolite, l.e. a total
loss of activity. a small amount of rare earths can beadded after stabilization.
This allows a good trade-off between sufficient acidity. and therefore sufficient
activity. and low hydrogen transfer.

d. Types of Y Zeolites in FCCCatalysts

Depending on the desired activity and selectivity, the various forms of Y zeo-
lite below can be present in FCe catalysts. . ,-
REV : A very active zeolite due to its high acid site density (high ues). It
promotes hydrogen transfer. and therefore coke production. and
gives low octane numbers and high gasoliDe yields.
HUSY : In the equilibrium catalyst. this zeolite has very low ues (:s;; 24.26A)
and exhibits a very low acid site density wIlich is not particularly
favorable to hydrogen transfer. It helps reduce coke production and
improves gasoline octane nmnber, but with slightly lower gasoline
yields.
REHY and REHUSY: Their properties are in between those of the first two
listed above. Their performance is closely related to their rare
earth content.
DY : Specific chemical treatment of the HUSY zeolite allows all or part of
the EFAL to be eliminated. The DY zeolite produced in this way is
reported to exhibit a slightly higher activity and a lesser tendency
to produce coke. as compared with the HUSY form.
 216 ChaO/llr 5 CATAl.YTIC CRACKING

Nickel
Some matrices are said to be able to neutralize the detrimental effect of nickel:
either by burying the metallic compound in the mass of
the rnatrtx
thereby making it inaccessible to reactants;
or because of their small surface area that is thought to promote sinter-
lng of nickel-based particles, thereby also decreasing their accessible
surface area.
Adding antimony- or bismuth-based compounds allows a significant if not
total reduction in the dehydrogenating and coking effects of nickel by forrninu
a less active metallic combination with it.

Vanadium
Incorporating various metallic oxides in the new catalyst micropsheres (or in
independent particles that exhibit no cracking properties as such) neutralizes
the effect of vanadium by trapping it in the form of non-volatile stable oxide
combinations. The most efficient oxides "are those of alkaline earth metals
MgO and CaO. those of rare earths REz03 and various mixed oxides such as
calcium, strontium or barium titanates.

':;.4.3 Design and Selection of an FCC Catalyst [19, 70, 711

Choosing the catalyst best adapted to a given situation necessitates a good
understanding of the nature and proportions of the various catalyst cornpo-
nents. Especially important are the various forms of the Y zeolite available and
the activity of the matrix.

5.4.3.1 The zeolite

.The zeolite is the major active agent in the catalyst and can be prepared in
forms that have Widely varying performance results by manipulating its ion
exchange property and its structural modifications. The residual sodium con-
tent is important: sodium neutralizes the Y zeolite's acidity and reduces it~
hydrothermal stability. It is therefore advantageous to eliminate sodium
totally, but difficult and costly. The sodium ions present initially in the Y zeo-
lite can be replaced partially by ion exchange with ammonium or rare earth
ions in an aqueous solution. Aseries of exchanges at ambient temperature can
not eliminate more than 75 or 80% of the initial sodium. In contrast, at around
IOOC this figure can easily reach over 95%after a sequence of several opera-
tions. The situation with rare earths is comparable,
A simple way of considerably reducing the sodium content with a limited
number of exchanges at ambient temperature is to proceed to intermediate
calcination between the 2 ion exchange steps. Most of the sodium ions then
migrate to easily accessible sites where they can be replaced by ion exchange.
Rare earth ions have a particularly great affmity for certain hard-to-get-to sites
where they can not be displaced by ammonium ions. .
 ChaplIN S. CATALYTIC CRACKING 217

a. Structural Modifications in the Zeolite

Above 500"C, aluminum atoms associated with protons are gradually
extracted from the aIuminosilicate framework. They are deposited in the pores
to lorm alumina and silica-alumina species (EFAL). In the presence of steam,
some silicon atoms become mobile (probably the ones from silica-alumina
debris) and are incorporated in the atomic vacancies left by the extracted alu-
minum atoms, thereby reinforcing the framework. This can be observed from
500"C on and speeds up when the temperature rises, to a limiting temperature
of approximately 8oo"e, when the total destruction of the framework becomes
the prevailing phenomenon.
Extraction of aluminum atoms and their replacement in the framework by
silicon atoms lead to a decrease in the number of acid sites (Fig. 5.20). It
should be pointed out that this process is much less pronounced for alumina
tetrahedrons neutralized by metallic, sodium or rare earth ions. It occurs
mainly tor the Y zeolite containing ions that can be broken down, such as
ammonium. This difference in behavior is at the origin of the rare earth
exchanged Y forms and the ones termed ultrastable, or USY, which enter into
cracking catalysts' composition.

500 < TOC -c 650

~-+.:zj>
Steam

NH4Y (2.5% wt Na:p) HV (2.5% wt Na20)

SiiAI.=. 3, UCS-'"24.65 A SiiAI -=- 5. UCS -=- 24.45 - 24.50 A

i Figure t
. I 5.20 I Stabilizing a zeolite by hydrothermal treatment.
L-J

b. REYand REHY
Due to the poor thermal stability of the NH4Y and especially the NH4X forms.
rare earth ions were introduced in the faujasite structure very early on, some
time in 1964.1t is now known that the essential function of these ions is to pro-
tect the zeolite's potential acidity by blocking dealuminization.
The richer the zeolite is in rare earths. the better it preserves its acid sites
in regenerator hydrothermal conditions. The equilibrium catalyst zeolite is
218 Chapter 5. CATALYl'lC CRACKING

usually characterized by a crystallographic parameter called unit cell size.

ues. The parameter, whose unit is the angstrom (10- 10 m), increases from 24.4
to 24.7 approximately with the framework aluminum content in new catalysts
and from 24.2 to 24.4 approximately in equilibrium zeolites. The high rare
earth content in the equilibrium zeolite allows numerous acid sites (i.e, numer-
ous aluminum atoms) to be preserved in the framework. It corresponds to
high DeS values (;;0. 24,35). This type of zeolites have strong activity, but also
the drawback of considerably favoring the bimolecular hydrogen transfer
reaction that increases coke production and lowers gasoline quality. The
poorer gasoline quality is largely related to the transformation of oleflns into
corresponding paraffins to a greater or lesser degree (Fig. 5.15). Paraffins are
more stable structures than oleflns and so are less likely to undergo consecu-
tive cracking themselves. The result is that lower gasoline quality usually goes
along with a slight improvement in gasoline yield.
As shown in Figure 5.21, the decrease in rare earth content means a reduc-
tion in the ues and therefore a decrease in'the equilibrium zeolite's acidity. As
a result, the catalyst manufacturer can "program" the acidity that the catalyst
will develop once it is in equilibrium conditions in the unit by introducing
more or less rare earths during preparation.
The beginning of the eighties was marked by a growing demand for cata-
lysts allowing better coke selectivity and higher gasoline octane numbers.
These properties require a substantial reduction in the hydrogen transfer ten-
dency, something that can only be achieved by using Y zeolites with a very low
UCS (~ 24.30) and little or no rare earths.

ucs (A)r-- ~----__.

24.40
I~";~:;t;;.'
. . High acid
&Ie density
HighHT
24.35 _ .......... _ _ ... - - - . ~ ,1~_ ..

24.30

24.2?

o 2 4 6 8 10 12 14 16
Rare earth content in the zeolite

rJgUrc
5.21 Influence of rare earth content on the zeolite's UCSparameter.
1fT: hydrogen transfer.
c. Ultrastable Forms, or USY
Introducing a new catalyst containing an NH..Y zeolite in an FeC regenerator
causes rapid, large-scale dealuminization of the zeolite framework. The steam
partial pressure is too low and the temperature too high for the silicon rein-
sertion process to occur ideally, so the equilibrilBD catalyst's performance is
not optimum. The manufacturer prefers to carry out this modification himself,
by including high temperature (~ SOO"C) calcination of the zeolite in the pres-
ence of steam (or steaming) in his process flow 5dreme (Fig. 5.20). He stabi-
lizes the structure in conditions that help maintain excellent crystallinity, but
deliberately performs only part of the dealuminization. Removing approxi-
mately 50% of the aluminum and replacing it with silicon is sufficient to stabi-
lize the structure permanently. This treatment also provides another very
important advantage: it allows more thorough elimination of sodium if fol-
lowed by one or more ion exchange(s) with ammonium ions. For instance, a Y
zeolite containing 2 to 4%wt Na20 after preliminary exchanges can be brought
down to 0.2-0.3% wt Na20 after steaming followed by exchanges. Such Yzeo-
lites are commonly called ultrastable or USY.
Just before 1990, even more sophisticated Y zeolites appeared on the mar-
ket. Uquid phase chemical treatments are reportedlyable to remove a greater
or lesser amount of the EFAL produced by stabilization and even to keep the
residual EFAL in a considerable state of dispersion, distributed evenly to opti-
mize acidity. Such zeolites are often called DY (for dealuminated Y).
To prevent total dealuminization of the equilibriWll USYzeolite, l.e, a total
loss of activity, a small amount of rare earths can be added after stabilization.
This allows a good trade-off between sulficient acidity. and therefore sufficient
activity. and low hydrogen transfer,

d. Types of Y Zeolites in FCCCatalysts

Depending on the desired activity and selectivity, the various forms of Y zeo-
lite below can be present in FCC catalysts. ..
ues). It
REV : A very active zeolite due to its high acid site density (high
promotes hydrogen transfer. and therefore coke production, and
gives low octane numbers and high gasoliDeyields.
HUSY: In the equilibrium catalyst. this zeolite has Yery low ues (~ 24.26 A)
and exhibits a very low acid site density wbich is not particularly
favorable to hydrogen transfer. It helps reduce coke production and
improves gasoline octane nmnber, but with slightly lower gasoline
yields.
REHY and REHUSY: Their properties are in between those of the first two
listed above. Their performance is closely related to their rare
earth content.
DY : Specific chemical treatment of the HUSY zeolite allows all or part of
the EFAL to be eliminated. The DY zeolite produced in this way is
reported to exhibit a slightly higher activity and a lesser tendency
to produce coke, as compared with the HUSY form.
220 Cilaoler 5- CATAUTIC CRAC--".:;

5.4.3.2 The Matrix

The function of the matrix, as illustrated in Figure 5.22 [70], is to pre-crack the
molecules that are too large to enter the zeolite's micropore network and sup-
ply it with the resulting molecular fragments. From this standpoint, an FCCcat-
alyst is somewhat similar to bifunctional catalysts.

~~
Pore A

~.
-<I
A.
S
C

Latgemolecule

PORE A NoliIlXe~ byIanJe moiIcules

PORE 8 Aa:essllIie; great CllI'IIriIdan to spedf.c surlaoe
Diameter: 2 to6 times 1IlIIt at. . _eC:HS
POREC AQ::essiblelillleconlritlWlnlDs;llICif'csW.lCe

- Figure
5.22 Function of the FCCcatalyst malrix.
Pre-cracking of large molecules that can not enter the miaopores of tile
zeolite. .
Supplying fragments of crocked large molecules to the zeolite.

In order to get the desired optimum performance, a certain balance must

be achieved in the equilibrium catalyst between the pre-cracking function of
the matrix and the acid characteristics of the zeolite. It is impossible to quan-
tify these parameters exactly, since the physicochemical characteristics of the
two components and their proportions in the equilibrium catalyst would have
to be known with precision. However, these characteristics vary from one FCC
unit to another according to the conditions prevailing in the regenerator. This
is why the easily accessible 21M ratio is generally referred to, l.e. the zeolite to
matrix surface area in the fresh catalyst.
Figure 5.23 [71] shows an example of variations in catalytic performance
versus the value of 21M at constant conversion. Particularly of note is that
increased matrix activity allows better overall conversion of the heaviest feed
fractions (pre-cracking effect). It also tends to lower the gasoline yield and give
a higher octane number, larger gas production, especially olefins, and more
coke.

5.4.3.3 Choice of Catalyst

The choice of a catalyst must take a number of factors into account: the nature
of the feed, the refiner's objective (minimum production of 350C+, maximum
 C/l;Ipret' 5. CATALYTiC CFIACKiNG 221

40,----------------.. . .
60
20

16~'
14 . ,
12 ---------

I
22

:7
I
J
"

~.MI
1~~~1---'---
o 1 2 3
I
4
Amorphous Z/M Zeolite
catalyst
".

!Figure i
. 5.23 I Effect of the Z/Jl ratio on selectiuity.
Yieldat constant concession.

liquid products or gasoline. better octane number, maximum olefins in the

gases. etc.), but also the technological limits of the FCC unit The best solution
can therefore vary widely from one case to another. and it might even be said
that each one is almost a special case.
To simplify, catalysts can be classified in five main domains shown
schematically (UCS of the zeolite versus Z/Jf) in Figure 5.2.1 [71J. The repre-
sentation does not include the various possible additives used to enhance per-
formance.
Two examples can be used to illustrate the choice of the best catalyst
possible.
222 C/JaDte5. CATAt me CRACKIN(3

LowUCS

Muirru11 CQnYIIfSian
Minirnlimc:oke
01350" Moderate~)'ield
Maximum C, c. C Moderate oc1anlI no.
A Mpimum octane no.

..-------.EE]
Goodconversion
Ma>cimum ga,oIine yield
Minimum QCtane no.
01350"
MinImum C] C,
Minimum C, + C,
B Muimum coke o ~~m conversion

High UCS Low ZJM

--L
Ratioof ZIM aetivilies HighZJM
- fncreasedmatrix aetMty
- Increased coke production
i-r---f- -- ----'

Figure
5.24 FCCcatalyst composition corresponding to specific utilizations.
'---

. Catalysts to Improve Gasoline Octane Number [71]

le first basic component is a USY zeolite with little or no rare earth content
) as to keep hydrogen transfer at a very low level. The matrix activity has
'br:: high (low 21M ratio) to favor olefinlclty and therefore gasoline octane
'_tmber.
T';"ile use of an MFI-based additive allows extra octane to be gained (+1 or 2
'0'-;:; RON, but only 0.3 to 0.8 points MON)at the expense of a slight loss in
asoline yield. This additive is mainly advantageous for the refiner who has an
.kylation unit. It enables him to offset his FCC gasoline loss by more very high
,!uality c.:<:ylate production, due to the surplus butenes and. to a lesser degree,
,[;mles to the isobutane resulting from the use of MFI.

l. ,!l:esiclualFeed Cracking Catalysts [62]

~''r,e strong tendency of these feeds to produce coke means that catalyst corn-
~L.1ents must be chosen to keep coke production within acceptable limits.
-\:irere are several possibilities depending on the FCC unit's constraints.

) If the unit is limited by the capacity of the regenerator air blower, the
choice should be oriented toward an HUSY or REHUSY zeolite and weak
matrix activity (high ZIM ratio) to minimize coke production. The draw-
back is that insufficient conversion of the heaviest fractions has to be
nccepted (350C+).
 ~ 5. CAT~ CRAOC/NG 223

Otherwise, the choice of an REHY or REHUSY zeolite that is richer in rare

earths than the first example and has stronger matrix activity (identical
or slightly lower 21Mratio) will give better results .
. Additionally, since residual feeds contain larger proportions of metallic
contaminants than conventional vacuum distillates, it can be highly beneficial
to add a vanadium trap to the catalyst and controlled amounts of antimony to
the feed.

5.5 Economics
Table 5.5 compares economic data for a conventional FCC processing a vac-
uum gas oil feed and a residue cracker RFCC (Conradson carbon 5 to 7% wt).

FCC RFCC
Capacity (t/year) 1300000 1300000
Battery limits investments (106 1999)
(equipment, erection excluding engineering) 89*' Il2*'
82** 103
Utilities (per ton of feed):
Electricity (kWh) 40.9*' 51.0*
64.5** 78.4**
Cooling water (m3) 28.3 29.1
Steam (t)
High pressure: 50 bar (production) -0.19 -aSS
Medium pressure: 20 bar (consumption)
. -, 0.26 0.33
Low pressure: 5 bar (production) - -0.04
*' Including all sections. even tertiary separation of catalyst fines and the waste heat
recovery turbine on the flue gases which drives the air compressor. Excluding pro-
pylene recovery and the DESOXIDE.l'\OX units on the flue gases.
** Without any waste heat recovery turbine. large machines being driven by electric
motor. thereby allowing the gross HP steam production to be shown.
~

I Table I
I 5.5 ! Economic data.

5.6 Conclusion
Fluid bed catalytic cracking is now a mature. economical and high technology
conversion process. It has evolved considerably in over 50 years. both from
the standpoint of the catalyst and the technology. The present refining trend
22/~ Chapler 5. CATALYTIC CRACKING

toward increasingly heavy crude supplies and a growing demand for better
quality motor fuels corroborates the gradual growth in FCC capacity. However.
it is also urging the development of the process into directions that are not
always compatible: .
increasing need to convert highly contaminated residual feeds;
economical production of feedstocks for reformulated motor fuels:
olefins from C3 to C;; for example [80).
So much so that the coming decades could see some sort of "specialty" FCC
units, but this would of necessity be at the expense of the process's present
flexibility. As for its operation, the FCC as an implement will continue to
progress at as steady a rate as in the past. Significant advances in catalysts can
be expected, but the most spectacular innovations will very probably be tech-
nological in nature.

References
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 Chapter 5. CATALYTIC CRAcKING 225

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21 Haensel V. (1951) Adu. CataLa, 179.
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:2 Meyerson S., Rylander P.N. (1957) J Chern. Phys. 27. 901-904.
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is Mignard S. (1988) Ph. D. Thesis Universite de Poltiers.
36 Magnoux P. (1988) Ph. D. Thesis Unlverslte de Poltiers.
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Amsterdam (the Netherlands), paper 9~ .
;)8 Catalagram (Davison), 73, 1985 et 75, 1987.
69 Scherzer J. (1984) The preparation and characterization of AIdeficient zeo-
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Magee J.S., Blazek J.1. (1976) Preparation and performance of zeolite crack-
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Monagraph 171, 11,615-79.
 C/vtJIer 5. CATALYTIC CRACKIIt6 227

74 Marcilly C. (1986) Petrole et Techniques 328, 12-18.

75 Donaldson R.E., Rice T., Murphy J.R. (1961) J.E.C 53 (9), 72.
76 Cimbalo RN., Foster R.L., WachtelSJ. (1972) a.G.J., May IS, 112-122.
77 Edison R.R., Siemssen J.O., Masologites G.P. (1976) o.G.1. Dec. 20, 55.
78 Agrawal B.B., Gulati l.B. (1972) Petroleumand Hydrocarbons 6 (4),193.
79 O'Connor P., Van Houtert F. (1986) Ketjen Catalysts Symp. '86, May 25-28,
Scheveningen (the Netherlands), paper F-8.
~O Man:iIly C. (1996) Petrole et Techniques 400. 4149.
 N
n-C; Ms M B" . B- C ~
B. -~---~---I Acid I--@
t
. n-C7
\M1 -, B
/ !
C f
!'>

/T~
Coke

' "'" , if
~
~

~
n-C- M" R' C- . c r-
b. 7 1~~.-~~-~-r-rAJ , Io)
J'
-I

I
n-C 7
J !
.!
]
~
f
:jJ
M B C C ~

n-C; M- B- c-
c. ,I Acid 1---1-1Acid I '@ ~

I
n-C 7
~M
\/ B
~c
. n-C 7 : n-heptane M~: single-branched Olefins CO: cracking olefins : metallic site
n-C;: n-heptene B=: double-branched olefins 8, C: paraffins ~:acidsile

Cok and cracking product (ormation mechanisms.

 ~ S. isoMERIZATION OF LIGHT PNWFtNS 237

6.1.5 Kinetics
The kinetics of the alkane isomerization reaction has been the subject of many
studies. Without going into detail, it can be said that: .
The acid monofunctional mecbanism is characterized by activation
energy values of approximately 40 to 50 kJ per mol, by an apparent order
versus hydrocarbons equal to 1 and by an apparent order versus hydro-
gen of zero [7].
The bifunctional mechanism is characterized by activation energy values
of approximately 105 to 135 kJ per mol, and a hydrogen order ranging
between 0 and -1 [8].
In addition, the selecttxtty achieved is different depending on the type of
mechanism. For instance for n-hexaee, when isomerization takes place by
means of an acid monofunctional mechanism, dimethyl-2,2-butane alone
appears as a secondary product, with 2,3-dimethylbutane and methylpentanes
as primary products. On the contrary, when isomerization occurs by means of
a bifunctional mechanism, methylpenlanes alone appear as primary reaction
products.

16.1.6 The Isomerbation Process

6.1.6.l The Feeds
Isomerization processes are relatively Oe."Cible as regards the feeds they can
accommodate. The CS/C6 feeds used come either from straight-run crude dis-
tillation or from catalytic reforming. In lhe second case, the reformate is sepa-
rated. into two fractions: the heavy one containing the C7+ molecules and the
light" one where all the benzene is concentrated. It is this light reformate that
can be sent after hydrogenation to the isomerization.unit either alone or mixed
with the straight-run CS/C6cut (Fig. 6.4)- '-.
Generally speaking, the feed distillation cut point is chosen at around
i0-80'C to avoid the presence of large amounts of benzene. cyclohexane and
hydrocarbons with more than 7 carbon atoms. The presence of these com-
pounds in an isomerization unit feed causes a decrease in yield or octane. This
is why the contents usually allowed in isomerization feeds are 2% wt for ben-
zene, 1 to 2%wt tor cyclohexane and less than 2%wt for C7+ hydrocarbons.
A typical isomerization feed. comprising approximately 50% wt Cs and
50% wt C6 is given in Table 6.3. Dependiog on the origin of the feeds, the es/es
ratio can vary.

6.1.6.2 Commercial Catalysts

Two isomerization catalyst suppliers are found on the market today:
Procatalyse proposes four types of different catalysts:
- IS632 developed by IFP: a zeoli tic catalyst made of platinum deposited
on mordenite;
 ~
~'l!
0>
c;
~
~
Straight-run
distillalion
cuts '1 Hydrolraaling I
<;t,

lsomerate i
i
~

I I_ Light ralormato

c, , I Heavy reformate
Catalytic cracking
Alkylate
cuts

FiJ::ure
6.4 I ROllJ scheme willi isomerization incorporated.
 Chapter 6- ISOMERIZATION OF lJGHT PARAFFINS 239

Components (%wt)

Isopentane 20.0
n-Pentane 29.0
Cyclopeotane 1.0
Dlmethyl-2.2-butane 0.3
2.J..Dimethylbutane 1.5
2-Methylpentane 11.0
J..Methylpentane 8.2
n-Hexane 19.5
!\'1ethylcyc:lOpentane
Cydohexane
.. 5.0
1.5
Benzene 2.0
C7+ 1.0

I Table
1 6.3 Composition ofa typical isomerization feed.
j
~

- IS 612 developed by IFP: a Pt on alumina catalyst which is chlorinated

in the isomerization unit;
- IS 6I2A and IS 614Adeveloped by IF?: Pt deposited on chlorinated alu-
mina, ready for use since chlorination is carried out previously off site.
VOP proposes two types of catalysts:
- 1-7: a zeolitic catalyst;
- 1-8: Pt on chlorinated alumina, a catalyst ready for use since chlorina-
tion is done off site beforehand.
The catalysts are in bead or extrudate form and usually contain between
0,2 and 0.4% wt platinum. whatever the support. The chlorine content of Pt on
alumina catalysts ranges from 5 to 12% wt.

6.1.6.3 Opuating ConditioDs and Performance

Since the two types of catalysts are intrinsically different. particularly with
respect to acidity, they are used in very different operating conditions.
Table 6.4 summarizes them and gives the RON of the product.
The Pt on chlorinated alumina catalyst can be implemented either in the
gaseous phase (H:!/HC > 0.5; P =20 bar), or in a rntxed phase (Hz/HC < 0.1;
P = 30 bar). In the second case. no recycle compressor is required on the
hydrogen. thereby resulting in better process economics. Compared with the
zeolltlc catalyst, the Pt on chlorinated alumina catalyst, working at lower tem-
perature. gives higher octane numbers by approximately 5 points. This is
240 Cl'tapter 6. ISOMffiJZATION c=~ 1-ii P':"RAFFI.'.$

mainly because it produces larger amounts of high-octane-number lsoi

such as isopentane and dimethyl-2,2-butane. Typical effluents produced by the
two types of catalysts are glven in Tables 6.5 and 6.6.

Pt on chlorinated alumina Pt on zeolite :

;

Temperature ("C) 120-180

Pressure (bar) 20-30
250-270
15-30
I
Space velocity (h -I) 1-2 1-2
r
H~/HC' (mol/mol) 0.1-2 2~
Product RON 83-84 78-80
,-r--
Table
6.4 Operating conditions and performance of Pt on chlorinated alumina and Pt on

- zeolite catalysts.

Components Feed (% wt) lsomerate (% wi)

e4 004 1.8
lsopentane 21.6 34.9
n-Pentane
Cyclopentane
- 26.5
1.4
.14.0
1.4
Dimethyl-2.Z-butane 0.9 13.4
2.3-Dimethylbutane 2.2 4.6
~-Methylpentane 13.1 13.7
3-Methylpentane 10.2 7.8
n~ 18.6 5.1
~fethylcyclopentane 2.8 0.6
Cyclohexane 0.4 1.4
Benzene 1.9 0
C.+ 0 0.3
sp.gr. d~5 0.652 0.646
RON 70 83
'--
Table
6..5 Typical performance results with a Pt on chlorinated alumina catalyst
'--
 C~
Compoaents
I Feed (%wt)

0.7
Isomerate (% wt)

1.8
Isopentane 24.1 40.0
n-Pentane 39.6 23.1
Cyclopentane 2.4 2.1
Dimethyl2.2-butane 1.3 6.6
2.3-Dimethylbutane 2.0 2.i
2-Methylpentane 13.1 11.0
3-Methylpentane 7.5 7.2
n.cs 7.8 4.9
MethyJcycl9pentane 0.9 0.6
Cyclohexane
-0.2 -
Benzene 0.4 -
C1+ - -
sp.gr. d~s 0.643 0.640
RON 73 81
..~
6.6 Typical performance results with a zeolitic catalyst
-

6.1.6.4 Simplified. Process now Schemes

Each type of catalyst has a corresponding specific process flow scheme
(Figs.6.5 and 6,6). With Pt on chlorinated alumina catalysts. the process needs
to use driers on the feed and the hydrogen, as "well ~as continuous' chlorine
injection to preserve the catalyst's chlorine content. The most commonly used
chlorinated compounds are carbon tetrachloride (CCIJ and perchlorethylene
(C2C1J, which is less toxic. A scrubber is also required to eliminate the
hydrochloric acid from the gases.
The process must include a compressor to recycle hydrogen when a
zeolitic catalyst is used. In the zeolitic process which gives lower performance
results than the Pt on chlorinated alumina process when operating on a once-
through basis. the unconverted n-paraffins and even lower-octane-number sin-
gle-branched isomers can be recycled to get muimum octane. Here the per-
formance differences between the two types of catalysts become less
pronounced. with the reaction becoming less sensitive to temperature as
shown in Figure 6.7.

6.1.6.5 Processes with Recycling

In order to recycle the unconverted n-paraffins and any single-branched lso-
rners, these compounds must be separated from double-branched isomers.
 N
110
N

Feed
I'"
iil

Chlorine
injection
Is
:;:!

~
r-
i:)
nouctO( ,
\"

~
~
~

Figure
6.5 I Simplified process flow scheme for isomerization on Pt/chlorinated Al:/o,,.
 Recycle hydrogen

To flare

Isomerization LPG
reactor

I
.f
PI

~
H2make up

m

~

-\ F.;.~"I
6.6 Process flow scheme for isomerization on zeolitic catalysts.
I
t
244 Cnapte- 8. ISO.'.rERiZATION OF (3-7" PARAFFINS

92
~ta Ion with n-paraffin recycle

E 90
~!
:2
'
g 88-
S
g
~ 86
g
.J;;
~
al
Q)
.84
lIJ

C
Cs paraffins 60%
82 Cs paraffins 30%
Cs cycles 10%

80 t--'------'-----'----"------J-..----'-""'------_
100 200 300
Temperature (0C)

Figure
6. i Thermodynamic equilibrium with and without recycling normal paraffins.

::: eparatlon can be carried out by distillation in large, energy-intensive columns

(depentanlzer; delsohexanlzer), or by adsorption on molecular sleves,

,:. Recycling with Distillation

Various recycle flow schemes can be proposed. Highoctane numbers of up to
91 can be achieved even with zeolitic catalysts thanks to complex process flow
schemes Involving several distillation columns. However, these octane results
will obviously be at the expense of process economics. The flow diagram giv-
ing the best RON/cost compromise is presented in Figure 6.8. It includes a
deisohexanizer and leads to an octane number of 88, whatever the catalyst
used. The richer the feed is in Cli the more advantageous this set up Is.

b. Recycling with Adsorption on Molecular Sieoes

VOP has proposed the TIP process (fatal Isomerization Process) for some
years now. It integrates a zeolitic catalyst Isomerization section and a molecu-
lar sieve n-/lsoparaffin separation section (Fig. 6.9). The n-parafflns adsorbed
on the sieve are desorbed by means of hot hydrogen. The TIP process oper-
ates in the vapor phase at relatively low pressures of approximately 15 to
 Fuelgas

Stabilization

H2 make up

n-C6 + Me-Cs recycle

Ptlzeolite: liON - 15 - 16
PtlA1fJ.J: liON - 16 17

IFigure
, 6.8 Processflowscheme with distillation recycling.
1l0N: difference in octane number bettceen the feed and the isomerate.

35 bar and at temperatures ranging between 200 and 340C. The process per-
formance results are presented in Table 6.7. Integrating the reaction and sepa-
ration sections, particularly from a thermal standpoint. means that the cata-
lyst used in the reaction section must only be the zeolitic one, since the
separation section works at 250C.
IFP has recently developed two molecular. sieve separation processes:
IPSORB and HEXORB< (Figs. 6.10 and 6.11).They areunique in that they inte-
grate a distillation and a molecular sieve adsorption section: a deisopentanizer
and molecular sieve desorption with isopentane for IPSORB':l, a deisohex-
anizer with methylpentanes desorption for HE.'\ORB B.
The aim of these process comblnations is to:
lower the n-paraffin content in the isomerate by adsorption on a molecu-
lar sieve;
raise the n-paraffin content in the feed by adding a separation column
(deisopentanizer for IPSORB and deisohexanizer for HEXORB) before the
reaction section.
Additionally. since the temperatures in the reaction and separation sec-
tions are independent. the two types of catalysts can be used in the reaction
section.
Table 6.8 gives the performance results expressed in RON with the two
types of catalysts and the two types of processes. using a feed whose RON is
equal to 68.
 ~
en
o
iif
'"
(;;
~
Feed Gas
~

fr,
r-
Isomerization LPG 1;\
J"
reactor -I
':E
Stabilization 'f
!J
~

Hz make up " 'I

] I Isomerate

FiGUre
6.9 I Simplified diagram of the TIP process (Total Isomerization Process).
 Chaplef6. ISOMERIZATION OF lJGHT PARAFFINS 247

Components feed (%wt) Effluent (% wt)

Butanes 3.2 1.6

Isopentane 22.6 51.8
n-Pentane 29.5 1.5
Cyclopentane 2.5 2.2
Dimethyl2.2-butane 0.5 9.1
2.3-Dimethylbutane 1.8 4.4
2-Methylpentane 12.3 15.5
3-Methylpenta11e 8.0 10.2
n-Hexane 13.7 < 0.1
Methylcyclopentane _ 3.9 2.4,
Cyclohexane 0.4 0.7
Benzene 1.5 0
C7+ 0.1 0.5
RON 72 89
MON 69 86

~
II
71Pprocess feed and effluent (% wt).

Chlorinated alumina ZeoUtic

Once-through 84 79
[PSORB~ 90 88
HEXORB 92 90

RONachieved with the IPSOR8~ and HYORBbprocesses.

6.1. 7 Economics
Ifthe composition of the gasoline pool in a typical refinery in the United States
and in Europe is considered, Tables 6.9 and 6.10 show that:
the isomerate and alkylate fractions in the gasoline pool are larger in the
U.S. than in Europe;
in both cases, these fractions are going to take on importance in the gaso-
line pool. at the expense of the reformate fraction. due to the decrease in
aromatics in reformulated gasolines.
248 C-.aoler6. ISOMERfZAnON OF us PARAFFINS

~
c0(1)
c'u;
g:ol------------,
~"5
IIlU
e.(I)

~~

c
.2 c
roE
~.2
.J:j0
<tl U
en

(;
i3
<IS
(I)
0:

Q)
,~
c
.!!!
c
(I)
e.
g
'ai
o

u_ "0
.. (I)
U~
-------------------

Isomerization Separation on
Stabilization Oeisohexanizer
reactor molecular sieve

Sleam

Hydrogen
i
PI

~
C&,Cli feed I rt:::1 ~
~
~

i
Bl:un:
f
~,

6.11 IIEXORU'!!l process. l\)

~
 250 ChatJlfK6 ISOMERIZAr/ONOF LtG":7 PARAFFINS

I Reformulated gasolines
I

Composition Conventional (% aromatics)

(% vol) gasoline
20% 10%

Butanes 5.5 3.5 2.0

[Isomerate 5.5 I 11.6 I 11.61
FCC gasoline 33.0 28.1 14.0
HCgasoline
Polymerization gasoline
1.9
1.0
I 3.5
1.4
15.8
6.6 I
Reformate 40.3 24.6 11.6
Ethers .3.4 10.8 10.8
Alkylate 9.4 16.5 27.6
Total
-..
.'.
--
100.0
--
100.0
--
100.0
'-- --:--
Table
6.9 Gasoline pool composition of a typical refinery (United States) (Source: Ensys
Energy, Systems Inc., Petroleum Economist (April /990)).
-

Composition
1980 1988 1995
(% vol)

Butane 6 6 6
Light gasoline 15 8 3
I isomerate 1 3 5 I
FCC gasoline 17 25 28
Relormate 60 52 49
MTBE - 2 3
Alkylate
-
1 - --
4
--
6 ~

Total 100 100 100

-Table
-
6.10 Average gasoline pool composition (Western Europe).
-

In 1998 isomerization processes accounted for a little more than 2%of the
refining capacity in the western world. This capacity, both planned and
.. installed, is very concentrated. It is located essentially in the United States and
in Western Europe (fable 6.11), i.e. in countries where unleaded gasoline is
replacing, or is due to replace; leaded gasoline.
As regards the catalyst market (see Chapter 3. Table 3.1), isomerization
only accounts for a 25 million share, whereas major processes such as FCC
represent nearly 40 times as much.
 ~ 6. ISOMERIZATION OF l.JGHr PARAFFfNS 251

United States. Western Europe Japan Other' Total

Installed capacity 15.1 11.8 0.75 5.9 3US

Number of units 49 37 3 22 111
Planned capacity 2.2 ' 2.5 - 4.6 9.3
Number of planned units 5 7 - 16 28
-:---
I Table
6.11 World Cs and Cs-Cs isomesizationcapacity (Mt/year).
'-----

A number of economic data 011 the isomerization process of 4/C6 cuts are
given in Table 6.12.

Direct
n.c.-Me<:, Total
recycle recycle

Capacity (light naphtha) (Mt/year) 200 200 200

I Battery limits investment (106 1999) 7 13 16
Isomerate - - -
Yield (tit of feed) 0.983 0.977 0.973
RON of product 80 85.5 90
MaN of product 78 84 89
Consumption per ton of feed
Hydrogen (t) 0.005 0.01 0.01.
MP steam (t) 0.14 -. 0.22 0.4
LP steam (t) - -- l.OS 2.06
Electricity (kWh) 20 34.2 77
Cooling water (m:!) 3.9 5.2 9.2
e..--- I
i Table I
6.12 I
ii- Isomerization of light gasoIiIIes. Economicdata. Western European conditions
'-----" in 1999.

6.2 Isomerization of n ..Butane

6.2.1 Aim
The main objective of isomerizing n-butane is to produce the isobutane as a
feed for aliphatic alkylation. or as a source of isobutene by dehydrogenation
to manufacture MTBE (Fig. 6.4).
252 Cnat;!t1f is ISOMERIZATIONOF LJ3~- P':':fAFFINS

6~2.2 Thermodynamics
Isobutane formation. like that of Cs/Cr, isoparafflns. is promoted at low tem-
peratures. The thermodynamic equilibrium is presented in Figure 6.12. As for
CS/C6 paraffin isomerization. the most efficient catalyst will therefore be one
able to work at the lowest possible temperature.

A-
1.0 L
0.9
lsobutane
0.8
c: 0-,7
.2
U 0.6
~.
G) 0.5
"0
:::i: 0.4

0.2
0.1
0
200 300 400 500
Temperature (0C)

Figure
6.12 Thermodynamic distribution of butanes in the vapor phase uersus temperature.

6.2.3 Catalysts
Since butane reactivity is lower than that of longer-chain paraffins, the catalyst
must exhibit much greater acidity. This is why zeolite-based catalysts can not
be used. Their acidity is so weak that they would have to work at overly high
temperature which thermodynamically reduces the formation of i:C 4 and pro-
motes cracking. The catalyst used today is therefore a Ptjchlorinated AJ 20 3 -

6.2.4 Reaction Mechanism

Two types of mechanisms are currently mentioned in the literature. In a very
acidic medium. the mechanism of n-butane isomerization is of the monomolec-
ular type. It proceeds by forming carbocatlons produced by hydride removal
from the paraffin. The carbocations then undergo an intramolecular rear-
rangement and are finally cut by j3-scission [9. 10].
 C/l;Ip/eI6. ISOMERIZATIONOF LIGHT PNVoFFINS 253

However. if the intramolecular rearrangement diagram for the butylcar-

benium ion described below is considered. it can. be seen that the
n-butane/isobutane transition requires passing via a highly unstable primary
carbocatlon that is very difficult to form. even on very acid catalysts.

This is why a bimolecular mechanism is quite often mentioned. It includes

transition through a C8 intermediate. produced by dlmerizatlon, and leads to
the production of'Isobutane, C1 to C3 cracking products and dlsproportiona-
tion products such as n-Csand i-e s. The mechanism has been demonstrated
starting with isobutane [11, 12]:

I-C 4 + X =:; (i-CJ X

(i-CJ X + (i-C4) X =:; (CJ X + X

i j (i-C~) X + (i-C~) X
(Cs)X + X
~ (Cs) X + (C3) X
(i-C4) X -'t i-C4 + X

with X: catalytic site.

In any case, the coexistence of the two types of mechanism can not be dis-
regarded.

6.2'; Kinetics
With a Pt on chlorinated alumina catalyst, the activation energy is approxi-
mately 35 kl/mol and the order with respect to n-butane.is close to one.

6.2.6 Process
The principal process on the market today, and ever since 1959. is UOP's
Butamer process. It uses a fixed bed catalyst with a Pt/chlorinated AIP3 base,
reference 1.4 (improved 1.8 catalyst). The IS 612 and IS GIZA catalysts from
Procatalyse are also suitable for this application.
The same as for C5/C6 isomerization with this type of catalyst, the feed
needs to be free of all pollutants. particularly water. This means driers have to
be installed on the feed. Continuous chlorine make up is also necessary to
preserve the chlorine content of the catalyst.
254 ChafJlef6. ISOMERIZATION OF LIGHT PARAFFINS

6.2.6.1 Process now Scheme, Operating Conditions,

and Performance

The process flow scheme is presented in Figure 6.13. A deisobutanizer is

designed to enrich the feed in n-butane and improve conversion. Two reactors
are utilized. The first one works at high temperature to promote the reaction
rate. The second one operates at low temperature, l.e. in a thermodynamically
more favorable range, to complete isobutane formation.
The operating conditions are as follows:
T = 18o-220C
P =15-20 bar
Space velocity == 2 h~l
~2/HC == 0.5 to 2.
In these conditions an i/Ci + n)C4 ratio is obtained corresponding to ther-
modynamic equilibrium and an isobutane selectivity of over 98% is achieved.
The n-butane isomerization process is very often coupled with an alkylation
unit to produce a high-octane alkylate.

6.2.6.2 Economics

Table 6.13 shows that most of the installed capacity is found in the United
States and in Western Europe, the same as for Cs-C6' It is in the United States
that demand is particularly sustained for producing MTBE. A large part of the
planned capacity is to be built in Saudi Arabia for export to the United States.

United States
Western Europe Japan Other Total
Canada

Installed capacity I
(Mt/year) 4.2 1.7 0.07 1.5 7.47
Number of units 20 5 1 6 32
Planned capacity 0 0.55 0 1.0 1.55
Planned units 0 1 0 4 5
L-~
Table
6.13 World butane isomerization capacity.
~

The investment for a unit processing 200,000 tfyear of feed is approxi-

mately 17.5 million.
 Hydrogen make up

Stabilization
Delsobutanizer column

nbulane feed
t chlorinatod
compound

f
!h

~
~
~ No'mai bulane n-C4

~
~Dfl" ~
Isobulane

I
l
l;il:t1 rC
(l,l' IJII/lII/Il!r I)m('e,~!l ((lOP), II)

8:
254 CMIJ/8r 6. ISOMERIZATION OF LiG."IT PARAFFINS

6.2.6.1 Process Flow Scheme~ Operating ConditioDs t

aDd Performance

The process flow scheme is presented in Figure 6.13. A deisobutanizer is

designed to enrich the feed in rr-butane and improve conversion. Two reactors
are utilized. The first one works at high temperature to promote the reaction
rate. The second one operates at low temperature, i.e. in a thermodynamically
more favorable range. to complete isobutane formation.
The operating conditions are as follows:
T = 180-220C
P =15-20 bar
Space velocity =2 h~l
~2/HC = 0.5 to 2.
In these conditions an i ICi + n)C4 ratio is obtained corresponding to ther-
modynamic equilibrium and an isobutane selectivity of over 98% is achieved.
The n-butane isomerization process is very often coupled with an alkylation
unit to produce a high-octane alkylate.

6.2.6.2 Economics

Table 6.13 shows that most of the installed capacity is found in the United
States and in Western Europe. the same as for Cs-CG' It is in the United States
that demand is particularly sustained for producing MTBE. A large part of the
planned capacity is to be built in Saudi Arabia for export to the United States .

United States
.
Western Europe Japan Other Total
Canada

Installed capacity I
(Mt/year) 4.2 1.7 0.07 1.5 7.47
Number of units 20 5 1 6 32
Planned capacity 0 0.55 0 1.0 1.55
Planned units 0 I 0 4 5
-,...-
Table
6.13 World butane isomerization capacity.
-

The investment for a unit processing 200,000 t/year of feed is approxi-

mately 17.5 million.
 Hydrogenmake up

Stabilization
Deisobutanizer column

n-butane feed
'" chlorlnatod
compound

f
P>

I
~ "",mal butane n-C. ~

dJ o rie
,
~
r-
~

J
Isobutane

l
l;iJ.:lIrl:
(1.1 J 11111w/lI:r 11nke.~s ("lIO").
m
256 C"$arer6. ISOMERlZAnONOF L :;-- PARAFFINS

References
1 Nenitzescu, Dragan (1932) Am. Chern. Ber., 66B, 1892.
2 BeUoum M., Travers Ch.. Bournonville J.P. (1991) Rev. de l1nst. Franc. du
Petrole 46. 1.
3 Roumegous A. (1978) Hydro-lsomertsatlon du n-heptane et du n-hexane
sur catalyseur platine-alumine hyperchloree (Etude de 1'). Thesis Doct-lng.
Universite Pierre et Marie Curie. i
4 Gianetto G. (1985) Ph. D. Thesis. Universite de Poltiers.
5 Guisnet M., Alvarez F., Gianetto G.. Perot G. (1987) Catalysis Today 1. 415.
6 Fouche V. (1989) Ph. D. Thesis. Universlte de Poitiers..
7 Garcia .I.J. (1974) Ph. D. Thesis, Universtte de Poltiers.
8 Chevalier F. (1979) Ph.. D. Thesis. Unlversite de Poitiers.
9 Magnotta V.L., Gates B.C. (1977) J Catal. 46, 266.
10 Funetes G.A.. Boegel J.V., Gates B.C. (1982) J Cacal. 78.436.
11 Bearez C., Guisnet M. (1983) React.Kinet. Catal. Lett. 22 [3. 4J. 405.
12 Bearez C. Guisnet M. (1985) Bull. Soc. Chim. Franc. 3, 346.
 -----7--
Aliphatic A1kyl~tio~

. Jean-Francais Joly

Aliphatic alkylation processes came in to being as a result of the boom in avi-

ation, and more particularly in military aviation at the beginning of the Second
World War. The development of more and more powerful airplane engines was
accompanied by the production of aviation fuels with increasingly high octane
ratings. As an offshoot, alkylate production plants were also built and com-
missioned.
A number of different isoparaffin (mainly isobutane) alkylation processes
.using oleflns were developed in the thirties. Aluminum chloride-based cat-
alytic systems were used to alkylate isobutane using ethylene, yielding access
to aItyIates rich in 2,2-dimethylhexane and 2.:Hlimethylhexane. These AlCI3-
based processes were rapidly displaced by more economical ones using con-
centrated liquid acids: HF and H~4' In the sixties, jet planes used kerosene
as fuel. thereby causing a large number of alkylation plants to be shut down.
However, from the fifties onward. new demand for high-octane-number gaso-
lines appeared subsequent to the production of automobile engines with ever
higher performance. As a result, alkylate production started off on a second
upswing.

/.1 Role of the Process in Gasoline Production

The groWing demand for higher quality gasoline has also brought new con-
straints on fuel lead content. The reduction in lead-based additives (octane
promoters) in gasoline began in the United States and Japan. and is now well
under way in Europe. This type of additive should end up being totally
excluded from fuels around the year 2000. Recently, the United States has
decided to prohibit lead entirely and. with the Clean Air Act. to limit the con-
centration in gasoline of certain other components considered to be toxic.
 258 Chapter 7. ALIPHATIC ALKY--:'~Ol.

Gasoline reformulation is therefore necessary and the requirements to be met

are essentially as follows:
total elimination of lead;
reduction in the benzene content: less than 1% vol;
reduction in the aromatics content: 25% vol maximum;
maximum olefin content: close to 10% vol;
oxygen content: greater than 2% wt;
vapor pressure: ranging from 0.46 to 0.56 bar.
In Europe, similar measures are being studied, but research and motor
octane numbers (RON, M01\') must be kept at high levels: RON/MON 95/85 for
.Eurosuper and 98/88 for Superplus. This will entail resortingmore and more to
compounds other than aromatics: highly-branched alkanes and oxygenated
compounds (ethers mainly, alcohols in some cases).
. Alkylates constitute a fuel base that meets all the criteria of reformulated
gasolines, as they consist only of highly-branched isoparaffins, and their aro-
matics and olefin content is very low (fable 7.1).

! RVP Aromatics Olefins

MaN I RON
(bar) (% vol) (% vol)

FCC gasoline 78-81 89-93 0.5 30 20

Reformate 87-92 I
j
96-105 0.37 70 0.7
Alkvlate 90-94 I 92-97 0.55 0.4 0.5
--=--
'- T:ible
I

7.1 Properties of the main motor fuel components,

-
In the United States, 11%vol of the gasoline pool consists of alkylates. The
alkylate content in European motor fuels has risen from 4% wt in 1988 to 6%
today.

7.2 Reaction Thermodynamics

Aliphatic alkylation consists in one mole of isobutane reacting with one of
olefin to form a mole of isoparaffin. When the olefin is a butene the reaction is
written as follows:
i-C..H10 + C"Hs ~ i-CsHlS
The reaction's exothermicity depends on the nature of the olefin
(Table 7.2). Because the alkylation reaction is exothermic and accompanied by
a reduction in the total number of molecules, it is therefore favored at low tern-
perature and high pressure.
 C1Iaprer 7. AUPHATIC ALKl'tATICW 259

Olefin M/(kJ/mol)

Propylene -815
Butene-l -89.4
Cis-butene-2 -82.5
Trans~butene-2 -78.4
Pentenes -74.9
r---
- Table
7.2 Influence of the type of olefin on the heat of
'--
reaction of isobutane olkylation.

7J A1kylate Compositions
The primary products of the isobutane alkylation reaction by olefins are given
in Table 7.3.

Olefins Primary products MON RON

Propylene 2,3-dimethylpentane 89 91
2,'klimethylpentane 84 83
Isobutene 2.2.4-trimethylpentane 100 100
Butene-I 2,3-dimethylhexane i9 71
2,4-dimethylhexane 70 65
Butene-2 2.2.3-trimethylpentane 99.9 109.6
2,2.4-trimethylpentane 100 100
2,3.4-trimethylpentane -96 103
-.
2,3,3-trimethylpentane 99 106
~
! Table i
i 7.3 Influence of the type ofolefin on the primary products From isobu-
tane Qlkylation.

Nota bene: The data in Table 7.3 refer only to Isobutane alkylation by olefins
with 3 or 4 carbon atoms per molecule. Isobutane alkylation by ethylene has
not been taken into account. The ethylene content of alkylation feeds is very
low - this olefin is a poison for HF and H~O~ catalysts. A specific Isobutane
alkylation process by ethylene using aluminum chloride as a catalyst has, how-
ever; been developed by Shell.
The real composition of alleylates is much more complex than suggested by
Table 7.3. They are complex mixtures consisting of paraffins with 5 to 12 and
more carbon atoms per molecule. Two representative compositions of indus-
trial alkylates produced from butene cuts are listed in Table 7.4. The C8 frac-
tions of these alkylates. the main reaction products. accounts for only 62 and
-;-f':. by volume.
260

AJkylation process
catalyzed by:
I

Compounds (% vol) H~04 I

HF
i

Propane 0.05 -
lsobutane 0.04 0.13
n-Buiane 0.92 4.87
Isop-ntane 8.76 5.10
n-Per.rane I! 0.23 0.01
2.2-0imethyJbutane - -
2,J.Dimethylbutane 5.36 2.38
2-Mf:th)'.lpentane 1.29 0.91
3-Methylpenta~e 0.64 0.4
-
I -0.17
n-Hexane
2,2-Dimethylpentane 0.25
2,4-DimethyJpentane 3.62 1.95
2.2.3--Trimethylbutane 0.01 -
3.J.Dimethylpentane 0.01 -1.31
2.3-Dimethylpentane 2.15
i
2-Methylhexane 0.22 0.24
3-Methylhexane 0.14 I 0.12
3-Ethylpentane 0.01 O,ol
n-Heptane - -
2,2,4-Trimethylpentane 24.20 38.02
2.2-Dlmethylhexane 0.04 -
2,4-Dimethylhe.~ne 2.89 4.19
2.5-Dimethylhexane 4.94 3.57
2,2,3-Trimethylpentane
3.1-Dimethylhe.,<ane
- -
1.53 1.35
-9.63
2.::.4-Trimethylpentane 13.15
2.:~Dimethylhe.xane 3.41 4.90
4Methylheptane - -
2Methylheptane 0.08 0.09
2,3.3-Trtrnethylpentane 11.47 8.14
3,4-Dimethylhexane 0.26 0.59
J.Methylheptane 0.23 3.20
2,2,5-Trtrnethylhexane 7.20 3.20
Heavy hydrocarbons 6.90 5.52
-~
. Table
7.4- Composition of industrial alkylates resulting from
~
isobutane alkylation by olefinic C4 cuts in the
presence of H.S04 and HF catalysts { 1J.
 Isobutane alkylation by butenes is a reaction that selectively produces cer-
tain isomers of the Cs cut (octanes). In aJkylates. 6 of the 18 possible Cg iso-
mers account for 90% of the cut. These main isomers are:
2,5-dimethylhexane, 2,4-dimethylhexane. 2,3-dimethylhexane,
2,2.4-trimethylpentane, 2,3,4-trimethylpentane and 2,3,3-trimethylpen
tane.
The most thermodynamically stable products are not a majority. At the
usual alkyfation temperatures. methylheptanes, 2,S-dimethylhexane and 2,2-
dimethylhexane should make up approximately 60% of the Cg cut. Sub-
stantially smaller amounts of these isomers are observed experimentally in
alkylates.
Testing has been done with HF as a catalyst in operating conditions
adjusted for one of two types of products: primary products (low temperature
and short contact time), or products at thermodynamic equilibrium (high tem-
peratures and long contact time). The results are summarized in Table 7.5.

lhermod)"uamie Composition
Operating mode For primary equilibrium at thermodynamic
products sought equlllbrium

TCC) -10 49 41
Contact time (min) 5 250 -
C8 cut (%)
224TMP 38.9 37 29.6
24DMH 4.5 33.9 56.8
234TMP 39.1 11.9 4.5
233TMP 14.2 8.~ 3.4
23DMH 3.3 8.9 -- 5.7
C:l/alkylate 80.4 35.7 -
! 214 TMP: 2.2.4-trimethylpentane: 23.; nIP: 2.3.4-trimethylpentane: 233ntP: 2.3.3-trimethylpen I
L~~tH: 2.4-dimethylhexane: ~3 D~IH: 2.3-dimethylhexane. I
Table I
. 7.5 I Isobutane alkylation by butene-2 (HF catalyst). Influence of operating condi-
tions on the composition of the ailly/ate Cs fraction [21

The 2.4-dimethylhexane content in the C8 cut increases significantly when

conditions favoring thermodynamic equilibrium are used. Isomer distribution
remains far from thermodynamic equilibrium. however. One of the reasons
why alkylate composition is far from thermodynarnlc equilibrium is that a
large proportion of compounds are the product of side reactions. In operating
conditions favoring octane isomers at thermodynamic equilibrium. the C8 cut
accounts for only 36% of the whole alkylate.
262 Chaot... 7. ALIPHATICALKYLATION

7.4 Catalysts
Isobutane alkylation by olefins can be carried out without catalyst in severe
conditions: temperature approximately SOO'C and pressures ranging from 200
to 400 bar. In the presence of acid catalysts. the reaction occurs at low tern-
perature (lower than 50C) and pressure (lower than 30 bar). Only two cata-
lysts are used industrially in alkylate production plants: liquid HF and H2SO.;
acids. The main physicochemical characteristics of these two acids are sum-
marized in Table 7.6.

HF H~4

Molecular weight 20.01 98.08

Boiling point rey- 19.4 290
Melting point COc) -82.8 10
sp.gr, d~5 0.99 1.84
Viscosity (mPa.s) 0.256 (OC) 33 (15C)
Hammett acidity (-Ho) 10.0 11.1
Solubility (% wt)
i-C4H\O in 100%acid (27C) 2.7 -
i-C4H\Oin 99.5%acid (l3C) - 0.1
HF In i.c.(Hlo (2T'C) 0.44 -
~3H8(27C)
I 0.90 -
..... Table
7.6 Main physicochemical characteristics of HF and HzSO.,
~
catalysts 13-6j.

The characteristics presented in Table 7.6 are valid for fresh acids, l.e. not
containing any dissolved organic species (polymers). The characteristics of
acids operating in alkylation units, or "equilibrium" acids, are not very well
known and can depend on the type of unit. For example, an "equilibrium ~ sul-
furic acid contains around 1.5 to 3% wt water and 7 to 8.5% wt organic matter
("red oils"). Isobutane's solubility in "equilibrium" acids is much greater than
its measured solubility in fresh ones: 0.4% wt for H~04 and greater than
3.6%wt for HF.

7.5 Reaction Mechanisms

The complete process by which isobutane reacts with an olefin is extremely
complex due to the large number or possible side reactions. The mechanism
of Isobutane alkylation by an olefin In the presence of HF and H~04 catalysts
 ~ T. At.!Pw;TiC AUO'l.A17O'I 263

is of the cationic type (acid catalysis) where the reaction intermediates are
carbocations. This set of reactions gives rise to two families of compounds: a
complex mixture of isoparaffins called "aE:;iate", and polymers soluble in the
adds called "red oils".

7j.l Alkylate Production Mechaaisms

7.s.U Main Reaction
The olefin, butene-lor butene-2 for example, is protonated by an add (HFor
HzSOJ to form a secondary carbocation. .
2.<:4 + H+X- ~ n..(4X- (X-: HSO~.or F-) (7.1)
i-cr + H+X- ~ n-C4'X- (7.2)
The n-C;X- species are in equilibrium with a mixture of butene-l and
butene-2 at thermodynamic equilibrium, where butene-2 is the most prevalent
by far:
'n-CtX- ~ 2-C4+H+X- (7.3)
n-C:X- can also react with isobutane, by means of a hydride (R-H) trans-
ler reaction to give rise to normal butane and a tertiobutyl cation:
Ii-C;X-+ f.C4 - H ~ iqX-+ n-C4- H (7.4)
This reaction is often called the initiation step. When a high i-C:tX - concen-
tration is reached, the butene-2 in equilibrium with n-C4X- (reaction 7.3) reacts
with the ;qx- carbocations togive 22~ TMPl:
2-C 4+'i-qX- -) 223 TMP+X- (7.5)
Equilibrium reaction 7.3 is therefore shifted to the jtght. If the rate"of reac-
tion 7.5 is much higher than that of reactions 7.1 and"7.2, then the olefin is
directly added onto the i-qX- cations without the nqX- intermediate. In this
case the nature of the i-egX- isomer produced depends on the nature of the
butene (223 TMP or 22 DMH~:
2-e4+ i-eSX- -) 223 ThfP+X- (7.6)
l-eZ+ i-C4X- -+ 23 t)MWX- (7.7)
When H~04 is the catalyst. most of the butene-l is isomerized into 2-C.
(reaction 7.3) before addition onto i-qX-. When HF is the catalyst, this tso-
merization is incomplete.
Desorption of TMP+X- and lh'\tH+X- generally follows skeletal isomerization
reactions by rearrangement of -H or -eH3 groups. The resulting Cs cut con-
tains the isomers: 224, 234, 233and 223 T~lP and 23, 24. 25, and 34 DMH.

1. 223 TMP: 2.2.3-trimethyJpentane.

2. 22 DMH:2.2-dimethylhexane.
264 Chaprer 7. AL./Pi,>iATlC Al.Kl"l..A"~"

Desorption takes place by a hydride (R-H) transfer reaction:

TMP+X- + i-e.t-H H ;qx- + TMP-H (7.8)
DMH+X- + i-e4- H H ;qx- + DMH-H (7.9)

The i-CtX- carbocations are therefore regenerated.

The mechanism described here is now widely accepted for isobutane alky-
lation by n-butanes. Alkylation by propylene, by isobutene and byamylenes is
more complex. since side reactions are at the origin of at least 30% of the com-
pounds present in the alkylates.

7j.1.2 Side lleactioDs

These are the reactions that cause the light Cs-C? and heavy C9-C 14 fractions
to be produced. The main_~nes are as follows.
Polyalkylation
TMJ>+X- + C. ~ ct2X- (7.10)
DMWX- + C4 ~ CilX- (7.11)
Ch X- + i-e4- H ~ iqX- + i.(.12- H (7.12)

Cracking
Chx-~qx-+q (7.13)
qx- + i-e4H ~ Cs-H + i-e 4X - (7.14)
q+WX-~qx- (7.15)
qx- + i-e4H ~ CiH + i-e4"X- (7.16)

Hydrogen transfer
(7.1i)

7.5.2 Red Oil Production Mechanisms

These are reactions that involve olefinic compounds where isobutane has
practically no function:
4q' + WX- ~ Ct6X- (7.18)

ct6 X- + q ~ n-C..- H + Ci6+X- (7.19)

Ci6+X- + q ~ n-C.-H + Ci6=+X- (720)
Consecutive hydrogen transfer reactions lead to the formation of highly
unsaturated polymers, which are soluble in the HF and HzS0.. catalysts and
cause catalyst deactivation. In the presence of H:!S04 acid, paraffin and olefin
oxidation reactions. also cause the production of red oils, water and S~.
 0..".. r: ALIPHArrc Auou1TCW 265

lsoparaffin oxidation
i-es + 4H~04 -+ i-ejH504 + 2H30+ + 2HS0:i + 502 .. (7.21)
Oxidation following butene oligomerization
4C.Hs + 2HzSO. -+ C16H 28 + 4HzO + + 2502 (7.22)
Butene oligomerization can develop either from butene provided by the
feed or from complexed butene in the form of n-C;X- (Eq. 7.1). Decomposition
followed by oligomerization of butene in the form of n-QX-lHS04 n~4) has
been studied with HzS04 as a catalyst in the absence of isobutane (fable 7.1).

T("q 20
I 20 10

C:4 in H~04 (% wt) 32 4.55 32

Cs-Cj (% wt) 9.2 13.6 12.7
TMPs (% wt) 33.3 7.7 37.2
DMHs(% wt) 18.9 7.9 13.0
c; (% wt) 38.6 I 70.8 37.2
. Product RON
Yield ex.
wt)
88.8
10
86.4
12
91.2
20
50 2 produced (% wt) 0.03 0.04 0.03
,-----'"1
i Table I
I 7.7 ! Products formed when butyl sulfate (HSOj n-G) decompose in the presence of
l--l sulfuric acid 17J.

Butyl sulfates decomposing in solution in sulfuric acid yield a poor quality

alkylate (RON =88). The low alkylate yield (less than 20%) bears witness to a
significant amount of red oil production. The presence of SOt reflects partial
oxidation of these oils by sulfuric acid.

7.5.3 Structure and Function of Red Oils

Red oils are highly unsaturated compounds that contain rings with 5 carbon
atoms and have an average of 10 to 20 carbon atoms per molecule. These poly-
mers can react with sulfuric acid to produce esters. The hydrogen/carbon
ratio is usually within the 1.52 to 1.75 range and may decrease if the polymers
are oxidized by H~04' Their function in alkylation has been the subject of a
great deal of discussion and publication. They can act as surfactants. For a
given stirring power, they help increase the acid/hydrocarbon interfacial area
per unit of volume. This effect is positive. since most of the alkylation reaction
takes place at the interface. They may also take part in the alkylatlon process,
and more particularly in hydride transfer reactions.
266 Ct/aprer 7, AUPHATIC ALKYlATJ:JN

7.6 Process Data

7.6.1 Feed Composition
Aliphatic alkylation units process olefinic feeds mainly resulting from the cat-
alytic cracking process (FCC). Feed composition varies depending on the refin-
ery. The refiner may have to process basically three types of olefinic feeds.
C4 Cuts
The typical composition of a C4 cut from FCC is given in Table 7.8.

Compound Boiling point eC) rA, wt) I

Cis. - ", -42.1 0.83-1.17

Isobutane -11.7 30.2-35.5
n-Butane -0.5 9.2-10.7
Butene-I -6.3 11.1-14.0
Isobutene -6.9 15.9-19.3
Trans-butene-2 +0.9 14.0-15.3
Cis-butene-2 +3.7 10.2-11.8
Butadlene-I.S -4.4 _ 0.25-0.30
-Table
-
7.8 Composition of olefinic C.,cuts coming from FCCand used as feed in alkylation
units.
-

In an increasing number of refineries. the olefinic C4 cut from FCC is used

as feed for etherification units (producing MTBE for example). The isobutene
etheriCication reaction using methanol provides a C4 cut that has a low
isobutene content (Table7.9).

Compound (%wt)

Cis 0.2
Isobutane 21.9
n-Butane 14.3
Butene-I 27.7
Isobutene 0.6
Trans- and cis-butene-2 34.2
Butadtene-I.S 0.5
Cs.olefins 0.6
,-""---
Table
7.9 Representative composition of an olefinic Cf cut coming from FCC and ,'laving
L...-.:....- been used in an ,,"ffBE production unit.
C3 + Col Cuts
A large number of HF alkylation units convert feeds .containing butenes and
propylene. A representative composition of such feeds is given in Table 7.10.

Compound (%wt)

Propylene 22.6
Propane 13.0
Butenes 31.9
Isobutane
n-Butane
...
21.2
10.0
..
Isopentane 1.3
-.--
Table
1.10 Composition of an olefinic C:rC4 cut coming from FCC and used as feed in an
HF alkylation unit
'----

C4 Cuts Containing C5
Reformulation may induce refiners to eliminate certain low-molecular-weight
compounds from motor fuels. particularly Cs oletins (amylenes). The com-
pounds then become available for use as alkylation feeds and allow a vapor
pressure gain in comparison with the initial oleflns (Table 1.11). A representa-
tive composition of a Cs cut from FCC,that can be used in alkylation after mix-
ing with the C" cut, is given in Table 7 . 1 2 . . .
In comparison with the C4 cut from FCC, the diolefin content of the C5 cut
is much higher: 1% wt instead of 0.3%.The amylene content in alkylation feeds
generally ranges between 5 and 15% wt.

Compound RVP (bar)

Pentene-I 1.34
Pentene-2 1.07
Methyl-2 butene-l 1.29
Methyl-l butene-2 1.00
Methyl-3butene-I 1.85
Cyclopentene 0.88
i-erq alkylate 0.25
'----.---------------------------'
: Table I
; i .11 Vapor pressure of C; olefins and of an alk) "late from the reaction of isobutane
:_--..f and an olefinic Cs cut ts;
 268 C~aDte' r. ALIPHATIC ALKYl.ATlC:J

Compound Boiling point eC) (%wt)

I
MethyJ-3 butene-l +20 1.37
Isopentane +28 44.86
Pentene-1 +30 4.66
Methyl-2 butene-l +31 8-'6
n-Pentane +36 6.92
Trans-pentene-2 +36 10.57
Cis-pentene-2 +37 II 5.72
Methyl-2 butene-z
Cyclopentene
Cyclopentane
+38
+44
+49
I 14.24
1.13
0.12
Methyl-2 butadiene-I,3 "
+34 0.20
Pentyne-l -. +40 0.09
Pentadlene-l.S +42 0.41
Cyclopentadiene +43 0.12
Methyl-3 butadiene-l,2 +41 0.13
........,
I Table I
! 7.12 I Composition of a typical c, cut from FCC[9}.

i.6.2 Feed Pretreatment

The principal effect of the impurities in alkylation unit feeds is increased cata-
lyst consumption. To a lesser extent, alkylate octane number also drops and
its end point rises. The influence of the type of impurities on sulfuric acid con-
sumption is shown in Table 7.13.

Acid consumption
Type of impurity
(kgJkg of if!.lpurity)

Water 10.6
Butadiene 13.4
Ethylene 30.6
Mercaptan (per kg of S) 17.6
Disulfide (per kg of S) 12.8
Methanol 26.8
Dimethylether ILl
MISE 17.3
-Table
-
l.13 Effect on acid consumption of the type of impurities in su~furic acid alkylation
unit feeds [1O}.
-
 OdD!fr 7. ALiPHATICALKYl.AflON 269

7.6.2.1 Effect of Diolefins

The diolefins in the C. cut cause a loss of sulfuric acid equal to around 10 times
their weight. Selective hydrogenation is of only little economic interest for sul-
. furic acid alkylation. However, it is more attractive for HFalkylation if it is car-
ried out in conditions where there are both hydrogenation of butadiene and
double bond shirt by posltton isomerization (butene-l to butene-2) simultane-
ously. It has been shown that the alkylate end point (C4 cut from FCC) is low-
ered from 200 to 175"C approximately. Additionally, there is also a very si,gnif-
lcant octane number gain: the RON goes from 93 to 96 and the MON from 91.5
to 93,5 [26].

7.6.2.2 Effect of Water

Generally speaking, H~04 alkylation unit feeds are not dried. Acid and caustic
treatment of the hydrocarbon phase before the fractionation section means
that an isobutane fraction saturated in water coming from the top of the main
fractionation column is recycled to the reactor. HFunit feeds are dried and the
residual water content is then very low (less than 20 ppm).

17.6.2.3 Effect of Oxygenated Compounds (A1c:ohol~, Ethers)

,
The presence of oxygenated compounds in alkylation feeds is the conse-
quence of ether production upstream of the alkylation unit. Their effect on
acid consumption is still inadequately understood.

7.6.3 Operating Conditions

Aliphatic alkylation processes are all operated in c~nditions such that "thefeed
oletins are completely converted. The operating parameters discussed below
influence only alkylate quality and catalyst consumption. There are three main
operating variables that allow the an...cylation unit to be optimized in terms of
product quality (octane number) and catalyst consumption for a given feed:
catalyst composition (water and red oil content);
reaction temperature;
isobutane/olefin molar ratio.
The stirring power in H~O.. units can also be considered as an operating
parameter. However, its effect on performance is not very well known (very lit-
tle literature available).

7.6.3.1 Catalyst Composition

The composition of the equilibrium catalyst in alkylation units is one of the
key parameters that governs alkylate quality. Sulfuric acid strength must be
kept close to 90?'; wt. so the refiner adds fresh acid containing 98-99.5?~ wt
continuously (or batch-wise). and draws off spent acid with a concentration of
about 90% wt (purge). To limit oxidation reactions that cause formation of part
of the red oils, the fresh acid must not contain any free 503'
The influence on alkylate quality of the water and red oil content of the
equilibrium sulfuric acid is known (Fig. 7.1). Optimum catalyst composition
corresponds to water content of approximately 1% wt and red oil content rang-
ing from 4 to 8% wt.

6
5

_.!j".....
~;,!. 4
'~'E 3
t;jl!!
-<::
til 0
()o 2

0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0

Red oils (%wt)

Figure
7.1 Influence of sulfuric acid composition on alkylare quality [21].

The water content of the HF catalyst is an important parameter. A low

value, l.e, 1% wt, is favorable for isobutane alkylation by an olefinic C3-C4 cut.
In contrast, overly high water content, i.e. higher than 1(\% wt, leads to iso-
propyl fluoride formation at the expense of alkylate production. The best alky-
late quality corresponds to water content of approximately 2.8% wt.

7.6.3.2 Reaction Temperature

The alkylation reaction is thermodynamically promoted at low temperature.
As a rule, the alkylate's RON increases by one point with each 11e drop in
reaction temperature. In practice, HzS04 alkylation units operate at tempera-
tures ranging from 0 to +lOe. Above + lOoe, oxidation reactions become too
prevalent, and it is impossible to operate at less than OC because the acid's
viscosity becomes very high. Trials have been carried out with a two-stage
operating protocol. In the first step, butyl sulfates are produced and then
transferred to a second reactor containing sulfuric acid and excess isobutane.
Controlled decomposition of the butyl sulfates then leads to alkylate produc-
tlon. The influence of reaction temperature on the RONis these particular con-
ditions is given in Table 7.14.
 TC"C) Yield 00 RON
-20 18& 100.6
-IS 201 99.4
0 175 96.0
10 127 92.6
_r----
Table
7.14 Effect of reaction temperature 011 Dikyfate yield and RON. Catalyst: H~O".
Yield: weight of alkyfate/weight of butene converted 17}.
'---

Hf units are quite different, since HF is not an oxidizer. The reaction tem-
perature here ranges between +10 and +4O"e. The effect of reaction tempera-
ture on the alkylate's RON is illustrated by Figure 7.2.

97

96

95

z
.
0
a::
\II
C
94

(3
93

92

91

90
15 20 25 30 35 40 45
Temperature (0C)
. ----,
- Fi~re ~--------------------------'
i.Z /IF alkylation. Influence of reaction temperature on RON. Feed: C~ cut
hom FCC [22].

7.~j.3 Isobutane/Olefin Ratio

Thts is the most important operating parameter. for it controls catalyst con-
scmpnon. reaction yield and alkylate quality. It is necessary to use a large
amount of excess isobutane with respect to the olefins to limit olefin polymer-
ization side reactions which form heavy compounds and red oils.
The tsobutane/olefin molar ratio governs the isobutane concentration in
the reactor. The influence of lsobutane concentration on the alkylate's motor
octane number (MON) when H2S04 is the catalyst is shown in Figure 7.3. A
higher isobutane concentration in the reactor brings about a significant
improvement in the motor octane number, while at the same time sulfuric acid
consumption decreases (Fig. 7.4).
As shown in Figures 7.5 and 7.6. the effect of the isobutanejolefin ratio is
similar for units using HF as a catalyst. They illustrate the influence of this
parameter on the motor and research octane numbers. as well as on catalyst
consumption for an olefinic C3-C4 feed. Alkylatlon units use tsobutane/oleiln
molar ratio valuesranging from 5 to 8 for H~04 and 10 to 15 for HF.

7.6.4 Sulfuric Acid Alkylation Processes

There are two major alkylation processes using sulfuric acid as the catalyst:
the Stratco and the Exxon/Kellogg. The two processes have the following
points in common:
a reaction zone where an emulsion of acid and hydrocarbons is formed
and the reaction occurs;
a settling zone for the two phases, acid and hydrocarbons, with the acid
recycled to the reactor and the hydrocarbons routed to the separation
zone;
an isobutane/n-butane/alkylate separation zone, with the isobutane recy-
eled to the reaction zone inlet.

'1.6.4.1 Stratco Process

This process is often called "effluent refrigeration process". A diagram of the
Strateo reactor is given in Figure 7.7.
The Stratco reactor allows contact time between the feed and the catalyst
to be kept to a minimum, thereby minimizingthe extent of the side reactions
that lead to formation of red oils. Avery high internal recycle rate of the emul-
sion permits proper dilution of the olefin in the reaction volume and control of
the emulsion temperature with an accuracy of 1~C. The reactor is horizontal,
and the two phases are stirred by a turbine. The reaction takes place almost
instantly when the two phases, acid and hydrocarbons. come into contact
while passing through the turbine blades. The heat of reaction is eliminated by
a tube bundle inside the reactor.
The Strateo reactor has a volume of approximately 34 m3 Its output is 0.39
to 0.44 m3 of alkylatejm 3 of reactor.h -1. The acidjhydrocarbon volume ratio is
slightly greater than 1. The pressure in the reactor is sufficient to keep the two
phases in the liquid state [27}. A detailed now chart of the Strateo sulfuric acid
alkylation process is given in Figure 7.8.,
 CIt6t*rT. ALIPHATIC AL.tunroN . 273

96

Isobutane concentration in the reactor (% vol)

i Figure
I 7.3 HzS04 alkyfotion. Influence of isobutane concenmuion in the retICtOr on the
alkylate's MON [2].

80
e
.Q
c.~
1:2
:J (II
70
~~
810
:20 60
u'"I:
ca
.g~
.2~ 50
"3
r.n
40

30 40 50 60 70 80
IsoC 4 concentration tn the reactor (% vol)

Figure
7.-+ H~O-/ alkylalion.lnfluence of isobutane concemnuion in the readOron sulfu-
ric acid consumption [23].
274 CnaDler 7. ALIPHATiC ALKYl.ATJC',

96

CD
.0
E
::I
c
(I) 94
c
<tl
U
0

92

0 20 40 60
IsobutaneloJelin ratio

Figure
7.5 HF alkylation, Effect of the isobutane/oletin molar ratio on alkylate motor and
research octane number (MON, ROA') [121.

2.5

1.5

0.5

o 4 B 12
Isobutanelolefin ratio

figure
"7.6 HF alkylation. Effect of the isobutanelofefin molar ratio on acid consumption
[12].
 ChapItr 7. ALIPHATICAooIAnoN 275

Acid
To settler

I Pressure relief

Figure
7.7 Alkylation reactor developed by Stratco (sulfuricacid alkylation) [2/ j.

The acid and hydrocarbons phases are separated in a settling drum located
above the reactor. The residence time in the settler is approximately 1 hour. All
of the acid circulates between the reactor and the settler. The bJdrocarbon
I phase rich in isobutane coming from the settler is expanded through a valve at
a pressure of approximately 0.6 bar. At this pressure part of the hydrocarbons
are vaporized. and the temperature of the liquid phase then drops to-7C. This
cold liquid hydrocarbon Is used as a coolant to eliminate the heat of reaction.
At the exit of the tube bundle that acts as an exchanger inside the reactor. the
hydrocarbons are sent to a flash drum. The vapor phase is compressed. cooled
and condensed. Propane is usually eliminated in this section of the unit. The
condensed liquid isobutane (containing a small proportion of al';yfate) is
directly recycled to the reactor inlet. After caustic washing or passing over
bauxite (elimination of sulfates), the llquld phase is sent to the isobutanejn-
butane/alkylate separation zone. The lsobutane is recycled to the reactor inlet.
Acid is drawn off from the unit, usually on a continuous basis. and fresh
acid is introduced so that the acid strength remains roughly constant. One or
more reactors and settlers can be used depending on the unit's capacity.

7.6.4.2 ExxonlKellolg Process (Cascade Autorefri,eration Process)

A simplified diagram of the reactor used by Exxon is given in Figure 1.9 and a
simplified flow scheme is shown in Figure 7.10.
The Exxon process uses an evaporator reactor in the form of a horizontal
vessel divided into several adjacent compartments equipped with agitators.
The heat of reaction is eliminated from the reactor by evaporation of an isobu-
tane stream brought directly into one end of the reactor. Sulfuric acid is let in
on the same end and moves by overflowing from one compartment to the next.
The feed-isobutane mixture is divided up into several aliquot portions that are
let in to each of the compartments at the same time. The last third of the reac-
tor usually contains one or two settling zones.
 !'I
lit
;llhlli\Ud _

"
~
t~

l
ri
t':
;0;

rs
~;
\!

Isobulane feed r "

Fresh acid ,I

fi\:urc
7.H I Diagram of the Stratco sulfuric acid rllllyialiofl process (2J).
 Flash vapors out

1
lsobutane
recycle
If
coolanl}~

FIgUre
: 7.9
I Diagram of the H:S01 alkylation reactor der:eloped by Exxon [Z].
-.-J

Feed

~_I"----'-;
Self-cooling system Propane
~-l

To treatment
and distillation

Isobutane recycle
L--- ---'
Figure
7.10 Simplified flow scheme of the "(.,,(OR alkylation process [2].
278 Chaar.,7. AI.IPHATIC ALK.YLATION

The temperature of the various stages is controlled by isobutane evapora-

tion. Since the olefin reaction rate is very fast, the gas phase contains no
olefms. The various stages work at pressures chosen so that the temperature
remains within the +2 to +12~C range. Since the isobutane content is the high-
est in the first stage, the pressure will also be the highest.(1.4-1.75 bar). The
pressure in the last stage is the lowest.(O.35-0.84 bar).
The residence time in the settling zone is some 30 to 50 minutes. Almost all
of the acid in the settling zone is recycled to the inletof the reactor's first stage.
The output of the Exxon/Kellogg reactor is from 0.15 to 0.18 m3 of alky-
late/m3 of reactor'h- 1, The acid/hydrocarbon volume ratio is slightly greater
than 1 [27J,
Compared with the Stratco process, the evaporator reactor provides two
advantages:
direct vaporization of tsobutane in the reactor makes exchanger tubes
. unnecessary; -
by avoiding fluid transportation and loss of fngortes, in-situ evaporation
of isobutane allows operation at lower reaction temperatures than with
the Strateo.
The evaporated isobutane from the reactor is compressed, cooled, con-
densed and the propane is eliminated at the top of the depropanizer. The
isobutane is recycled to the reactor inlet. The liquid hydrocarbon phase com-
ing from the settling zone is sent to an Isobutane/n-butane/alkylate separator
after treatment with potassium hydroxide.

7.6.4.3 H2.504 Alkylation Process Performance

The yield, alkylate composition and acid consumption with this type of cata-
lyst depend greatly on the composition of the olefinic feed and its impurity
content.
Q. Yield and Catalyst Consumption
Performance values are given in Table 7.15versus the type of olefinic feed pro-
cessed. Table 7.15shows the strong influence of feed type on sulfuric acid con-
sumption. Consumption can reach over 100 kg/t of q alkylate for feeds con-
taining propylene and/or a high amylene content
b. Alkylllte Composition and Quality
Table 7.16 gives detailed alkylate compositions according to the type of olefin.
With a sulfuric acid catalyst, the best alkylates are achieved with feeds hav-
ing a high n-butene content (fable 7.9).
A study of the alkylate Quality resulting from isobutane alkylation by
amylenes has recently been published. In particular, it appears that alkylate
quality and catalyst consumption depend heavily on amylene content
(Figs. 7.11 and 7.12). Additionally,catalyst consumption becomes excessive as
soon as the amylene content exceeds 20% wt.
 CNpter 7. AuPHATIC AL..Kl1.A1J(1rt 279

Type of feed Propylene Butenes Amylenes

Yield (vo! CS/vol olefin) 1.45-1.78 1.74 1.57

;..(;4 consumption (vol/vol olefins) 1.27-1.32 1.14 I
Catalyst consumption (kgft en 137-1il 51-102 102-171
MaN 88-90 92-94 88-90
RON 89-92 94-98 90-92

j~
Table
i 7.15 H:SO., alkylation: yield and acid consumption. Influence of the type of olefinic
l....--. feed 18J.

Type of olefin q n-C.i let I fCC i-C. 1-C s 2-C"5 M2BZ

Operating conditions

.
TeC) 9 10
1
10
I 10 10 9.5 10

i-CJolefins 8.6 7.2 II 7.8

! 8 1.3 7.5 8.2

H~O~ (%wt) 94.5 94.4 I 94.7 I 94.2 94.5 '94.6 94.4

Product composition (% wt)

C5 3 2.2
I 4
I 7.8 12.5 14.6 13

C6 3.8 2.6
! 3.9 l 5.8 1.5 1.4 5.8

C7 67.4 2.7 I 3.8 II s.s 1.5 1.3 3.6

TMPs 11.6 80 : 66 ! 54 32.1 II 22.3 45.6

DMHs I 1.9 i 8.1 10 8.5 I 3.7

I
2.7 12.7
I ! I I
C9 1.2 1 ~ 2.7 I 5.6 44 1 52.4
i

CIa... 11.1 3.4 9.6 I 12.7 4.4 5.3 19.3

I
I :
RON 89 1 97.8
I
: 94.6 193.2 91.3 I 91.1
i
91.2

MON 87.1 [ 93.9

I
;
:
91.5 ~ 90.3 88.4 I 88.1 88.8 It
I

Acid consumption (kgjt) 1171 ! 60 67 89 89 I 74 91

--
'-
I I I
Table
7.16 , Detailed composition of aikytates obtained /L'ith H.so. 1 as a catalyst. Influence
! of the type of olefin. M;?B::: methyl2 buJene.2. DIPs: trimeth~'[pentanes. DJIHs:
dimethylhexanes. I/O: isobutane/oletin molar ratio [7].
280 eNIDle' 7. ALIPHATIC ALKYLAfio,\

96r

:D a MON
.c
E
:::I
c:
ell
92
'" RON I
1;:
~
90
8 -......:..
88
~
86 I _J ! .
0 20 ttl )-
o 80 100
";' amylenes in the feed

Figure
7.11 H~04 alkylation. Intluon, ur
tllt'.II " .
motor (MOIV) and resf?mt" (/-\, l\,) 1/\ I. lit' content In the olefinic feed on the
, '" (,lilt' numbers [9J.

250

~ 200
~
c
.~
E
150

.i.>:
~ 100~-

soL
u
"0

o -
o 20
60 80 100
% amylenes in the leed

Rgun:
7.12 H:zS04 alkylation. I"tllh'/I'f' III /
sulfuric acid consu/II/ll/uI, t~'1 (". ,mn'lene content in the olefinic feed 011
 Oo.aOI6f'7. ALiPHATIC AumATlON 281

7.6.4.4 Sulfuric Acid Regeneration

H~04 alkylation processes produce large amounts of acid sludge (90% wt of

H2504). It is complex and costly to reprocess because the sulfuric acid can not
be separated physically from the red oils. It must therefore be destroyed, and
sulfuric acid is then made up from the 502 produced when HzS04 is reduced
by red oils. The simplified sulfuric acid reprocessing scheme is as follows:
the acid and organic oils are decomposed by air into 502, H20. CO2 and
N2:
502 is converted into 50 3;
50 3 is absorbed by water to be transformed into H~04 with a titer of over
.: 98.5% wt.

These operations are very often carried out outside the refinery.

7.6.5 HF AlkylatiOli Processes

, Two HF alkylation processes share the market: the Phillips and the VOP ver-
sion. HFand H~04 processes differ in that HF processes do not have mechan-
ical stirring systems such as turbines. The low viscosity-of HF and great solu-
bility of isobutane in the acid allow simpler technologies to be used: the
emulsion between the two phases is effected by injecting the hydrocarbon
feed into a continuous HF phase through nozzles at the bottom of a tubular
reactor. The resulting emulsion circulates from bottom to top in the reactor,
and separation is then done by settling, the same as for the HzS04 process.
Reaction temperatures ofapproximately 30 e allow water to be utilized to cool
D

the reactor. --

r.s.s.: Phillips Process

A simplified flow diagram of this alkylation process is given in Figure 7.13. The
mixture of fresh feed and recycled isobutane is injected into an HFacid circu-
lation loop. From the top of the reaction zone, the emulsion is introduced into
a settling zone. The residence time in the tubular reactor is 20 to 40 seconds.
Reactor output is from 4 to 7 m3 of alkylate/rrr' of reactor.h -I depending on the
acid/hydrocarbon volume ratio (between 1 and 4) [24]. The acid phase is recy-
cled to the reactor inlet after going through a water-cooled exchanger. A small
proportion of the HFacid is drawn off and sent to the regeneration zone (sep-
aration of HF from water + tars). The HF acid condensed at the top of the
regeneration column is recycled to the reactor-settler, The hydrocarbon phase
is routed to the main fractionation column. The propane withdrawn at the top
of the fractionation column contains HF. HF and propane are separated in a
stripper.
282 ChaPcer 7. ALIPHATIC AL.KYLATION

Main
f ract10fl3
t'1OIl..-- ----..HF stripper

Oebutanizer

i-C4 recycle
n-C4 to caustic
washing

Stabilized
alkylate
Dry
i$Obutane
<; to caustic
washing

Figure
7.13 Simplified diagram of the Phillips HF alkylation process {24].

7.6.5.2 UOP Process

A simplified diagram of this alkylation. process is given in Figure 7.14. In its
principle it is very similar to the Phillips process. The reactor is vertical and
acts as a heat exchanger. Nozzles allow the hydrocarbon phase to be dis-
persed in the acid, which is the continuous phase of the emulsion, the same as
in the Phillips process. The hydrocarbon feed is let in at different reactor
heights, and HF is let in at the bottom of the reactor. The heat of reaction is
eliminated by means of cooling water. Reactor output is approximately 2 m3
alkylate/rn'' of reactor.h -1 [24J. The acid and hydrocarbons are separated in a
settler. The hydrocarbon phase is fractionated and the isobutane is recycled
to the reactor inlet. An HF stripper is used to separate HF from the propane +
isobutane mixture coming off the top of the fractionation column. if the feed
contains C3 , propane and isobutane are separated in a depropanizer. The
propane is then alumina treated to remove any trace of fluorine. The alkylate
recovered at the bottom of the fractionation column is treated with potassium
hydroxide. Several reactors can be used depending on the unit's capadty, and
in this case they are in series.
 Chapter 7. AJ..IPHAT'IC AUOIA1ICW 2i3

I
depropanizer

~ ~
Alkylate

Olem
(butanes) I Butane
feed
KOH treatment

,~ Simplified diagram (butene feed) of the LOPHF alkylation process [25].

I

7.6.5.3 HF Process Performance

a. Alkylate Yield tuld Quality
The influence of the type of olefin on alkylate yield and quality in HF-catalyzed
processes is illustrated by Table 7.17. Since the catalyst is regenerated on site
by simple distillation. catalyst consumption corresponding to fluorine losses
in the tars is less than Ikg/t. It is unaffected by the type of olefin.

b. Alkylate Composition
Table 7.18 gives the detailed composition of alkylates obtained with various
oletins and HF as a catalyst.
284 Cft<lptfH 7. ALIPHATIC A(Kr..,.:- z-.

Type of feed
,
q i
i I-q 2-C.!
;.<:. Cj+C4 q
Yield (vol of CSlvol olefin) I 1.76 1.73 1.17 1.78 1.79 1.63
i-C4 consumption (vol/vol olefin) I 1.36 1.1 1.14 1.28 1.28 I
92 94.4 97.8 95.9 93.7 91.5
RON 1: 90
MON 91.6 94.6 93.4 90.8 90
..-----
......./: Table 1 - - - - - - - - - - - ' - - - - - ' ' - - - - - ' - - - - - ' - - - > - - - - ' - - - . . . . . . . . ;
7.17 Alkylate yield and motor (MON) and research (RON) octane number achieced
L- in HF processes [11 f.

AIkylale "j- Type of feed

composition
<"-' wt) ! q 2-C; I-C. Q+C4
CS 4.8 2.2 2.7 3.7
C6 II 3.9 1.8 1.7 2.9
C7 I 45.8 2.8 2.7 25.5
TMPs 30.5 81.2 65.6 54.2
DMHs 3.5 9.2 20.0 7.2
C9+ 11.5 2.8 7.3 6.5
RON 90.6 97+ 94 93
..... -
Table
7.18 Influence of the type of olefin on alky{ate composition with HF as a catalyst.
'----
TMPs: trimetbytpentanes, DMHs: dimethylhexanes [I2J.

Table 7.18 shows the poor quality of alkylates obtained by isobutane alky-
lation using butene-I. The high dimethylhexane content (compounds respon-
sible for the low research octane number) reflects incomplete isomerization of
butene-l to butene-2 before the alkylation step.

c. Spent Acid Regeneration

The HF acid purged from the unit, with a concentration of about 90% wt, is
regenerated continuously on the refinery site by distillation. For example, [28]
for an a1kylate production capacity equal to 58 000 t/year, the tar purge from
the bottom of the HF regeneration column is approximately 265 t/yearr The
corresponding HF consumption is 0.82 kg/t of alkylate. The regeneration col-
LImn treats 16 m3 of acid a day. .
 Chapfer 7. ALIPHATIC AurrtATION 285

7.7 Economics
A large number of studies comparing HF and H~04 processes are regularly
published. Comparison shows that neither of the two processes provides a
determining advantage. The criteria for choosing a process for a refinery are
as follows: .
composition of the available olefinic feed and, more particularly, its
propylene content;
cost of utilities;
price and availability of HF and H~04 acids;
geo~raphical location of the refinery: whether any sulfuric acid repro-
cessing plants are nearby. -
The processes can then be compared on the basis of the following points:
investment,
operating cost,
product quality,
operational safety.

7.7.1 Investments
There is no appreciable difference in investment for HF and H~04 units. In
1985, they amounted to $14.9 million (H~04) and $14.5 million (Hf) for a
capacity of 185 000 t/year [29J. These amounts are equivalent to around
20.10' 1999.

7.7.2 Operating Costs

a. Utilities
The cost of utilities tends to be in favor of H2S0 4 processes. A lot of HF units
use high lsobutane/olefin ratios. Here the cost of pressurized steam for sepa-
rating isobutane and alkylate is higher. Moreover, the power required to gen-
erate a large acid-hydrocarbon interfacial area in the reactor is much higher
for H~4 units, due to the difference in viscosity between HF and H~04' In
conclusion, there is no big difference in utility costs between HF and H~04
processes.

b. Catalysts and Chemicals

The catalyst cost is clearly in favor of HF units. even though HF acid is more
expensive than H~04' HF consumption is much lower than that of H~04'
because HF is regenerated on site. Catalyst cost for H2S0~ is estimated at 33%
of the operating costs compared with 5% for HE
286 Cnao,e'i ALIPH;.T/C ALKY"";:- :',

c. Alkylate Quality
The comparison must be made for the same feed composition. It is clear that
if feeds do not contain any isobutene (MTBE raffinate for example). the alky-
lates resulting from H2S0 4 catalysis have higher octane numbers.
d. Operational Safety
The safety criterion is important in choosing an alkylation technology. Both HF
and H2S0 4 acids are highly corrosive. At ambient temperature HF is a very
volatile gas (boiling point = 19.4QC), while sulfuric acid is a liquid with a low
vapor pressure (boiling point higher than 300'C). The refiner's choice is there-
fore dictated by a series of criteria, and among them those related to the cat-
alyst take on particular importance.

7.7.3 Installe~ Capacity

Table i19 gives an overvtewof the alkylation capacity worldwide (industrial-
ized countries) since 1982.
Since 1982, HFalkylation capacity has grown at the expense of units using
H2S04 processes (fable 7.20).
It should be noted, however, that the HE/H2S04 breakdown depends on the
country (Table 7.21). For example, in Japan there are no HF units.

United Stales
(l06 tjyear)
i Europe
(l0 s l/year)
Other....lrie.1
(l0 &tfyear)
Total
(10&l/year)

1982 37.5 ).6 4.9 46

1987 38.6 3.8 7.4 50.8
1990 43.8 6.9 8.1 58.8

r 1992 44.7 9.1 10.6 64.4

7.19 Alkylation capacity uioridioide since 1982.

L--

HF(%) H~04(%)

1982 48.7 51.3

1987 54.3 45.7
1992 58.7 41.3
1994 58.3 41.7
...---
'- Table
7.20 Alkylation capacity: percentage 01HEand
L..-----
H~S04 processes.
 N~ of HF units Number of H~.. units

United States 60 47
Canada 5 4
Europe 28 8
Rest of the world 34 33
Total 127 92
r----
- Table
7.21 Number of HF and H:S0-/ alkylation units in the world in 1994.
'--

An examination of planned new units and those under construction since

1995shows that the trend will undoubtedly change in the coming years. New
projects are essentially HzS04 units. The risks involved in HF processes are
undoubtedly the cause of this trend. H~04 projects are more popular by far:
14 out of a total of 23, and the Stratco process seems to be preferred to the
Exxon process: 14 Stratco and 1 Exxon.

7.8 Future Trends

A lot of research has been done both to decrease sulfuric acid consumption
and to develop different processes using- solid acid catalysts.

7.8.1 Two..S tep Process [7, 13}

In the first step of the process, n-butyl sulfates are formed from sulfuric acid
and iH>utenes in a stoichiometric ratio and at a temperature lower than OC. In
a second reactor, these esters react in the presence of free sulfuric acid and an
additional amount of isobutane to produce the alkylate. These two steps yield
good quality alkylates: more than 90% wt trimethylpentanes with RON values
as high as 98-100. The best alkylate quality is achieved when the temperature
in the second reactor ranges between -15 and -20'C.

7.8.2 Solid Add Catalysts

In order to replace liquid acids by a solid as alkylation reaction catalysts, sev-
eral solids have been studied in depth: exchanged zeolites, ion-e."'Cchange
resins (Amberlyst, Naiion), superadd solids (chlorinated alumina, sulfated zir-
conia). superacids adsorbed on solids (HF-SbFslAI203' BF:Jzeolites. oxides or
resins). Table 7.22 gives some of the published results with this type of solid
catalyst.
288 Cna:ml"7 ALIPHATICkKYLAT.':'.

Catalysts :\afion * resin Beta zeolite

TeC) 100 80 o
Molar i-C4/ 2-C4" 10 10 100
c.; conversion (%) 65-70 95 100
Product:
TMP/q (% wt) 62 30 80
Stability (h) 75 20 50

I'
'-i Table i - :- - - - - - - - - - - - - - ' - - - - - - - - ' - - - - - - -

.22/1nfluence of the type of solid acid catalyst in isobutane alkylation by butene-:

[14, 15, 16J.

The first two catalysts exhibit low stability and yield a small proportion of
trirnethylpentane due to a high reaction temperature. Only the zirconium cat-
alyst gives acceptable quality.
Among the solid catalysts promoted by strong acids, the most promising
from the standpoint of selecttvtty and stability are: silica impregnated with
CF3S0 3H or FS03H (Topsoe [17D, and alumina impregnated with BF3
(Catalytica [18)), silica impregnated with SbFs (CRL [19)). A number of com-
panies have developed specific processes with these catalysts.
Topsoe uses a fixed bed reactor containing a catalyst comprising silica
impregnated with CF;tS03H or FS03H. In 1993, CataJytica along with Conoeo
and Neste Oil operated a 1.1 m3/day pilot unit. In 1994, Chevron operated a
1.8 m3/day pilot unit using a slurry catalyst, consisting of SbFs on alumina, in
the reactor. IFP has developed new catalysts [20] including silica and an acid
phase composed of sulfuric acid and an additive (53, B03H, etc.).

References
Simmons M.e., Kelly T.R. (1991) Gas Chromatogr., Second lot. Symp.
Academic Press, New York.
2 Cupit C.R., Gwyn J.E., Jernigan E.e. (1962) Petro/chem. Eng. 33,47.
3 Weast RC, Astle M.J., Beyer W.H. (1986) Handbook of Chemistry and
Physics, 67th Edn, CRe Press Boca Raton, FL
4 Hyman H.H. Kilpatrick M., Katz 1J. (1957) J Am. Chern. Soc. 79, 3668.
5 Paul M.A., Long FA (1957) Chern. Rev. 57, 1.
6 Simons lH., Dredsner RD. (1944) J. Am. Chern. Soc. 66, 1070.
7 Albright L.F., Spalding M.A.. Nowinski J.A.. Ybarra R.M., Eckert RE. (1988)
Ind. Eng. Chern. Res. 27.381.
8 Jezak A. (1994) Hydrocarbon Processing 47, Feb.
 ChaplIN 7. ALiPHIfIICALK'J'tA1)ON 289.

9 Kranz K.E.. Mastem K.R.(1991) AC5 Symposium on AlkylatiDtJ,. Aromatization,

O/igomerisation and isomerisation of Short Chains Hydrocarbons over
Heterogeneous Catalysts, New York, August 25-30, 775.
10 NPRA, Q and A Conclusion (1992) Oil Gas I, April 27.
11 Lew L.E., Pfile M.E., Shoemaker L. W (1994) Fuel Reformulation, March.
April, p. 58.
12 Corm a A, Martinez A (1993) Catat, Reo-Sci Eng 35 (4), 483.
13 Albright LF.. (1977) ACS Symposiom Series 55, Chapter 8.
14 US Patent 4180695.
15 US Patent 3251902.
16 US Patent 4918041.
17 US Patent 5220095.
18 US Patent 5157 196.
19 US Patent 5157197.
20 EPA Patent 0539277. AI'
ZI Albright L.F. (1990) Oil GasI, Nov. 12, p. 79.
22 Jones EX (1958) Adv. Catal. 10, 165.
23 Wegg O. (1997) ACS Symposium S(~rie.<; 55,271.
24 Albright LF. (1966) Chern. Eng.. Sept. 12, p.205.
25 Hammershairnb H.V., Shah B.R. (1985) Hydrocarbon' Processing 64, 6,
Sept. I, 73-76.
26 Chaput G., Laurent J., Boltlaux J.P., Cosyns J., Sarrazin, P. (1992)
Hydrocarbon Processing. Sept., p. 51.
27 Albright LoF. (1966) Chem. Eng., August 15,p. 143.
28 US Patent 3 249 650 (1966). '.
29 Chapin L.E.. Liolos G.C., Robertson T.M. (1985) Hydrocarbon Processing.
Sept. 12, p. 67.
 ~ ~8"'---
L

~ -
.c"

,. --:

Philippe Travers

Gasoline production needs to be adapted to new unleaded motor fuel specifi-

cations. especially to meet octane demand. Refiners hue resorted not only to
conventional refining processes as discussed in previous chapters, but also a
whole new class of processes. These new processes im'olve etherification of
olefins by an alcohol (methanol, ethanol).
Two events have led to important modifications in motor fuel composition:
the decisions made by the United States in 1985 authorizing the addition of
oxygenated compounds to gasolines, and the regulations passed by the u.s.
government in 1990 under the name of Clean Air Act Amendment. A substan-
tial demand for oxygenated compounds has resulted. They make a significant
contribution to the octane number of the gasoline. pool and also replace oleflns
and aromatics whose content is limited because- ofatmospheric pollution.
In the United States, the mandatory oxygen content has been set at a min-
imum of 2.0-2.7% wt depending on the area ever since January I, 1995.
Expressed in terms of methyltertiobutylether (:\ITBE) content. this corre-
sponds to 11-15% voLin Europe the maximum allowable content is 2% wt oxy-
gen, i.e, 11%vol of MTBE.

8.1 Main Et~ers Used in Refining

Ethers (tertioalkylethers) are mainly produced by reacting a tertiary iso-olefin
on an aliphatic mono-alcohol. Today MTBEis the most important of the indus-
trially produced ethers. It is produced by reacting the isobutene in C4 cuts
with methanol in the presence of an Ion-exchange resin acid. catalyst.
TAME (tertioamylmethylether), produced by reacting the isopentenes
- also called lso-amylenes - in C5 cuts with methanol, has also become
increasingly successful. This is because of its low vapor pressure, but also and
292 Cnaprer 8 OLEFIN ETHERiFIG,;,';::;.

above all because it allows a decrease in the light olefin content1n gasolines.
Oleflns have very high photochemical reactivity and cause smog formation via
ozone. For these reasons, it is even superior to MTBE from the standpoint of
reformulated gasolines.
ETBE (ethyltertiobutylether), produced by reacting isobutene on ethanol.
is now recognized for its valuable contribution as a gasoline pool component:
a high octane number and a low vapor pressure. It offers all the advantages of
its homologue MTBE. By analogy, TAEE (tertioamylethylether) can be men-
tioned. It is produced by reacting isopentenes on ethanol.
Another potential source of oxygenated compounds is DIPE (diisopropy-
lether). It is produced by IrA (isopropyl alcohol) etherification by an ethylene
molecule in the presence of an ion-exchange resin acid catalyst. It exhibits
properties similar to those of MTBE and TAME with the disadvantage, however.
of readily becoming peroxided into unstable, even explosive, compounds.
Additionally, the Institut Francais du Petrole has just developed C7 ether
manufacture from dlmate, i.e. the gasoline produced by the Dimersol G pro-
cess (propylene dimerization process) (Chapter 9). Dimate contains more than
65% oleflns that can potentially undergo etherification, leading to the produc-
tion of a mixture of ethers: MEPEME (2-methyl-2-methoxypentane) and
DlMEBU (2,3-dimethyl-2-metho>..ybutane). They are the result of methanol
reacting respectively with 2~methylpentenes and 2,3-dimethylbutenes.

8.1.1 Properties of Ethers

The major advantage of oxygenated compounds (alcohols and ethers) is their
high octane number that helps compensate for the octane lost when leaded
gasolines were phased out (Fig. 8.1). Methanol, which is another compound
capable of providing the required oxygen, has the highest octane number in
this group of compounds. However, it has a number of disadvantages:
; a demixing tendency at low temperature requiring addition of a cosolvent
(heavy alcohol);
a corrosive effect requiring some equipment to be adapted:
~ the formation of azeotropes with light components in the motor fuel
causing the vapor pressure to rise considerably;
a self-ignition tendency.
In contrast, ethers (Table 8.1) offer a series of advantages:
) high octane numbers, sometimes in excess of 100 (MON) and 115 (RON);
OJ properties very close to those of the hydrocarbon components of the
gasoline pool;
') low vapor pressures (allowirrg more butane to be incorporated in the
gasoline pool);
) pollution control properties: 10 to l~ ethers in motor fuels cause a 10
to 15% drop in carbon monoxide and a 5 to 10% reduction in unburned
hydrocarbons in exhaust gases.
 ChaPter 8 OlEFiN ETHERtFIC.A1fON 293

MON t RON
120

Y Methanol (125135) 1
115 MTBE 1I
TAME I
110

-
- 105

Methanol 3.5 bar t

1001-'- r conventional

I
reforming
MTBE 1
TAME

95
C~ n1 Pyrolysis
gasoline 1
~
alkylation ,
!C
1 Cc. 1Ca1ven-_
I 3C4 I
alkylation 1 n-C..3..5bar I gasoline
FCC,
Ir
90 3-C..
I
tionaI
reforming 1 f
with

85
with
recycle
1 --~~- -
Pyrolysis isom.
I gasoline I -_ ........ --
.. .. -- -_ ... _-

80
'-H FCC
gasoline
r-! lsorn,
----_ ...--
direct
-. direct
!

I Lightgasoline
I 1 Ught g~soline I

l~!-----_--l MON:64
1 1
RON: 65

! F~.re I
~ Octane numberof gasolinepool components.

However. due to the presence of oxygen in their molecules, oxygenated

compounds have a lower heating value than motor fuels. This might cause
increased consumption: the higher the oxygen content. the more accentuated
the phenomenon is. This is the case fOT methanol. whose heating value is two
times lower than that of hydrocarbons.
 I ' 'I
i (PA
j

I i
Characteristics :Premium i !'timE ETBE TAME OlPE C~ ethers i Methanol i Ethanol i lBA
! I
Density (kg/m3) I 735-760 746 ! 750 1750 730 780 796 794 ! 792 789
Boiling I
point CC) 30-190 55.3 f ;"2.8 86.3 68.3 ll8 64.7 78.3 i 82.2 82.4
Blending vapor
pressure (bar) 0.7-0.8 0.55 ! 0.4 0.25 0.34 0.1 5.24 1.54 1.03 0.95
Heating value
I
t
LHV(kJ/1)
I
I 32020 1 26260 126 910 27375 i 127211: 15870 21285 25790r4130
Heat of i
vaporization
I
"1 ~
(kJ/kg) 289 337 , 321 310 310 1100 854
Oxygen content
C"..; wt) - 18.2 115.7 f 15.7 15.7 13.8 49.9 34.7 21.6 26.7

Clear blending
vaJueRON 95
118 .1 118 115 110 104 123-130 120 105 117
CleaT blending
valueMON 85 101 101 100 97 98 95 99 95 95
Sensitivity
(RON/MON) 10 17
i
17 15 - - 26 21 10 -
"-,---
Table
8.1 Properties ofoxygenated compounds.
'---

For all these reasons, refiners therefore tend to look to ethers rather than
alcohols.
MTBE's properties are listed in Table 8.2. Note that the blending octane
number is a function of the MTBE concentration, and of the composition and
octane number of the gasoline it is added to. Octane number response
decreases when the following increase:
the octane number of the base gasoline,
the ether content, and
the aromatic and olefin content in the base gasoline.
The octane number rises by approximately 2 to 5 points for MTBE concen-
trations of 10 to 15% in the gasoline.

8.1.2 Sources of Feedstocks

8.1.2.1 Sources of Hydrocarbons
Any mixture of hydrocarbons containing lso-oleflns can theoretically serve as
feedstock to produce ethers. However, isobutene from the C4 cut and
isopentenes from the Cs cut are generally used.
 C/laptM 8. OLEFiN ETHERtFlCATlON 295

Molecular mass ; 88.15

Density (kg,lm') 740.5
Boiling temperature at 760 mmHg ("C) 55.2
Vapor pressu.re at 30C (rnmHg) 313
Crystallization temperature ("C) -108.6
Ignition temperature (DIN) ("C) 460
Mass specific heat at 2S'C (kJ/kg' K) 2.13
Latent heat of vaporization at 25'C (kJ,kg) 341.5
Lower heating value of the liquid (kllkg) 35090
Standard formation enthalpy of the liquid CkJ/mol) -320.2
St~ndar4 fonnation enthalpy of the gas (kl/mol) -288.8
Specific heat 0( the-liquid Olmol K) - 188.1
Solubility:
MTBE in water at 20C (g/100Sof solution) 4.8
Water in MT8E at 20C (g/100g of solution) 1.5
Azeotropes at 760mmHg (% wt)
Water 4, MTBE96 ("C) 52.6
Methanol 14, MTBE86 ("C) 51.6
Hydrocarbons, MTBE DO azeotropes
:"-~I-- L.- _

8.2 Physical properties of MTB (methy{tertiobutylether).

Q. lsobutene

Isobutene is produced in naphtha steam cracking and in catalytic cracking. It

is found in the C4 cuts. whose composition differs significantly depending en
the process that they come from. The untreated C4 cut from steam crackzg
contains between 40 and 50%isobutene after butadiene extraction. The C4 cut
from catalytic cracking contains between 15 and 20% isobutene. The amount
can be higher if the catalytic cracking operation is adjusted (operating condi-
tions, catalyst) in order to maximizeolefin production (Table 52).
In 1990 approximately 75S of the isobutene in the world came from cat-
alytic cracking. mainly because the process was highly developed in the
United States. In Europe and Japan. 40%- of the isobutene is produced by naph-
tha steam cracking.
Most of the C4 cuts from catalytic cracking are used to produce gasolines
either by alkylation, as is done on a large scale in the United States. or by poly-
merization or alkylation in Europe.
Today the amount of isob~ene used for MTBE synthesis accounts for only
25?~ of the amount actually produced by refineries. Most of the steam cracking
isobutene is used for chemistry and for ~lTBE. In order to increase ~lTBE pro-
 296 Chapter 8 OLEFIN ETHERIFICAi:::m

ductlon, the isobutene in catalytic cracking cuts would have to be used before
the cuts are transformed into gasoline by alkylation.
Isomerization is also possible for the n-butenes (butene-I, trans- and cis-
butenes-2) in the C4 cuts from c-racking (skeletal isomerization process). These
butenes represent approximately 45 to 50% ",1 of the steam cracking C4 cuts
(after butadiene extraction) and 35 to 40% of the catalytic cracking cuts.
Isomerization offers the advantage of providing added value to a by-product of
MTBE units where n-butenes are not transformed. In this way. with the same
amount of C4 cut feed. 2 to 3 times as much MTBE can be produced.
Furthermore, additional amounts of isobutene can be produced by dehy-
drogenating the isobutane available in large quantities in associated gases of
natural gas. Dehydrogenation coupled with isomerization of n-but:ane has
already been used to produce MTBE. but this procedure is economically justi-
fied only for large production capacities.
Another source of isobutene is via the production of tertiary butyl alcohol.
a coproduct of propylene oxide synthesis. This process is limited by the
demand for propylene oxide, which does not have such intense expansion as
MTBE.
The characteristics of these different sources of isobutene are summarized
in Table 8.3.

Catalytic Steam Skeldal

cracking cracking" Dehydrogenation isomerization
(% wt) (%) (%wt) (%wt)

Isobutane 35 2 52 6
n-Butane II 5 1 44
Isobutene 15 45 48 17
Butene-l 13 28 _ 1 10
*
Butenes-2 26 -20 0 23

After butadiene extraction.

On a C~ cut from steam cracking (MTBE/skeletaJ isomerization integrated flow scheme).
.---
'-- Table
8.3
--
'----

b. Isopentenes
In the same way as for the C4 cut, isopentenes are produced in both naphtha
steam cracking and catalytic cracking. In both operations they are induded in
the Cs cuts. The n-pentenes in C5 cuts can be isomerized in the same way. The
.characteristics of C5 cuts are summarized in Table 8.4-,
 Catalytic Steam Skeletal
cracking aacking isomeriz.atlon..
(% wt) (%) (%Wi)

Isopentenes ... * 24 26 20
n-Pentenes 18 23 ,9
lsopentane 10 40 49
n-Pentane 17 7 17
Cyclopentene 20 2 3
Cyclopentane 10 1 2
Diolefins I I

After the first step of hydrogenation. ~

U On the catalytie cracking cut (one pass TAME/shletaJ Isomerization integrated now
scheme).
u* Among the isopentenes only methyl.2 butene-l and methyl-2butene-2 are reactive. They
account for over 95%of isopentenes.
..----
I Table
i 8.4 Cha.rrxten"stics of Cs cuts (% wt).
!
'----

8.1.2.2 Sources of Alcohols

Methanol is produced from natural gas by converting methane into synthesis
gas (COIHz) by steam reforming or partial oxidation, then by converting this
gas into methanol. " ,
Common commercial grade (grade M) methanol has the following charac-
teristics:
purity: 99.85% wt min;
water content: 0.1% wt max;
alkalinity: 20 ppm max (defined in NH3 equivalent).
Ethanol of agricultural origin. produced by fermentation of glucose. is sup-
plied in an anhydrous form with an added denaturant. The main characteris-
tics are as follows:
purity: 99.3% wt min;
water content: 0.3% wt max:
aldehyde content: 500 ppm mass max;
denaturant: 1.0% vol,
Ethanol is purified and dried by azeotropic distillation with cyclohexane as
a third solvent. Impurities (esters, aldehydes. alcohols) are a function of the
purification process. Ethanol is produced at a cost that is far from competitive
298 Chaprer8. OLeFIN ETHERIFICAT.D"

wtth that of motor fuels, so it needs to benefit from tax relief.Total tax exemp-
tion has been granted in France since 199~ (exempt from TIPP, the petroleum
product tax). '

3.1 J Integrated Etherification Process in a

Refinery Scheme
Etherification units can be readily integrated in processes that upgrade:
C4 and C5 fractions from catalytic cracking (Fig. 8.2) and from steam
cracking (Fig. 8.3);
gases associated with natural gas (Fig. 8.4).
Integrating etherification processes in the refinery scheme leads to two
types of production: high-octane compounds and raffinates whose qualities
are improved by removlngiso-olefins. Note that in a configuration combining
etherification and alkylation units, the MTBEunit is favorable to H~04 alkyla-
tion, since it eliminates isobutene, which yields low-octane alkylates.

8.2 Basic Data

8.2.1 Reaction Mechanism
Ethers are produced by adding alcohol to an iso-oleflnin the presence of an
ion-exchange resin. The MTBE synthesis reaction occurs according to the
reversible reaction below:

First step: Protonation of base species, with iso-olefin among them. This
forms- a tertiary carbocation, which is more stable than a secondary carboca-
tion, formed with n-cleflns:
(CH~2~C=CH2 + RS03H =:; (CH~2~C~-CH3' RSOj
CH30H + RS03H ~ CH3-O$-H2 RSO~

Second step: Rapid reaction of the tertiary carbocation, stabilized by the

acid group, with excess methanol:

(CHih-C'S-CH3. RSoi + CH30H :=; (CHi}J-C-o~-CH3. RSO~

I
H
(CHY3-C-Os-CH3. RSO~:; (CH3)3-C-0-(H3 + RS03H
I
H
 .. _-~.-~~_._-----_.

c,
0:/0 4 r
I h'
OIPE : C,
DIP!
MTBE

IsoC.

rco
CJ >

Alkylale

n0 4

.. I TAME
i
!l'

Oepentanlzer
i
H~\ITe
ttl Upgmding e,.,. c./ and Cs cuts from FCC.
C Il >

i
~
CD
300 Chap'IN 8 OLEFIN ETHERIFICATION

1-Butene

FG
Hydrogen

c
r
a
c
k

n Gasoline l....- Butadiene

9

Fuel oil

Figure
8.3 Upgradingthe C4 cut from steam cracking.

I------MTBE

Figure
8.1 Upgradinggases associated with natural gas.
 This mechanism shows the great selectivity of sulfonic resin for isobutene
conversion and its methoxylation compared with other side reactions (see
Section 8.4), A similar mechanism is involved in the production of diisopropy-
lether (DIPE), by propylene acting on isopropanol. The operation includes two
steps {4]:
Hydration of propylene with water to give isopropyl alcohol (lPA) as per
the reversible reaction below:
CH3-CH=CH2 + H20::; CH3-CHOH-CH3
Etherification of isopropyl alcohol (lPA) with propylene to give diiso-
propylether:
CH3-CHOH-CH3 + CH3-CH=CH;::; CH3-CH(CHiJ-O-CH(CH:J2
The two are reversible reactions. Low temperature is favorable to IPAand
DlPE production.

8.2.2 Reaction Kinetics and Thermodynamics

Etherification is an exothermic reversible reaction (~H = -37 kl/mol), pro-
moted by excess methanol. The kinetic equation [1] is of the simplified
Langmuir type to the extent that isobutene is considered to be virtually not
adsorbed on the resin, since methanol (MeOH) is more adsorbed than MTBE.
The isobutene conversion rate is written (in llter-h rl-kg "):

[f.C~] [MeOH] _!: [MTBE]

V= k!:!. . Ke
. V [MeOH] + & [MTBE]
with:
M mass of catalyst in kg
V volume of feed in liters
k constant of MTBE formation rate (liter-h -I. kg-I)
Keequilibrium constant defined on the basis of concentrations at equilib-
rium
& ratio of adsorption coefficients for MTBE and methanol
According to this equation. MTBE synthesis at low conversion follows a
oorder versus methanol and a I order versus isobutene.

8.2.3 Catalysts
The etherification reaction is catalyzed by an ion-exchange resin of the macro-
crosslinked sulfonic type (copolymer of polystyrene and divinylbenzene). The
resin's particular feature is that its volume increases and its crosslinked struc-
turecomes apart in contact with water or methanol at temperatures of approx-
imately 100 to 110C (mechanical strength limit of the resin).
302 Chapter 8. OLEFIN ETHI:f'lIFJCAiJON

Its main physical and chemical properties are:

shape: bead
size: 0.35 to 1.2 mm
. pore diameter: 250 A
specific surface area: 45 m2/g
pore volume: 0.3 cm 3/g
water retention: 50 to 54%
density: 770 gil
acid site concentration: 1.8 rneq/rnl (4.9 meq/g)
The leading manufacturers of this type of resin are:
Rhorn and Hass (Arnberlyst 15 and 35)
e. Dow Chemical (Dowex M31)

Bayer (K261 I)
Purolite (CTl75)

8.2.4 Side Reactions

Etherification reactions are very selective for production of ethers (MTBE.
TAME, ETBE). In MTBE synthesis. selectivity (isobutene conversion into
MTBE) is higher than 99%. The main side reactions are:
production of TBA (tert-butyl alcohol) by isobutene reacting with the
water present in the feed (resulting from saturation of the C.. feed after
washing):
(CH3)z-C=CH2 + H20:; (CH3)3-C-OH

production of dimers (dlisobutylene) by isobutylene reacting with itself:

(CH;}z-C=CHz + (CH3)z-C-CH2 ==:
(CH:V2-CH-CH=CH-CH-(CH:02

production of MSBE (methylsecondarybutylether) by n-butenes reacting

with methanol:
CH3-CH2-CH=CHz + CH30H :; CH3- CHz- CHCH3-OCH3

.;) production of DME (dimethylether) by methanol reacting with itself:

CH30 H + CH30 H =; CH3- O- CH3 + H20

production of codimers by isobutylene reacting with n-butenes:

(CH:V2-C=CHz + CH3-CH2-CH=CHz :;. .
(CH:vz-CH-CH=CH-CH2- CH2-CH3
 ,
These reversible reactions are promoted at high temperature. Note that the
by-products recovered in the MTBE product (TBA. MSBE, 'dimers and
codimers) have properties comparable to those of ether (high octane num-
ber). The more volatile DME is recovered in the C. raffinate. The by-products
of TAME and ETBE synthesis are similar to those of MTBE synthesis. The by-
products of DIPE synthesis come from propylene dimerization and trimeriza-
tion reactions leading to production of low-octane polymers, which addition-
ally deactivate the catalyst. Water minimizes these reactions:
CH3-CH=CHz + CH3-CH=CH2 --+ CH3-CHz-CH-=CH-CHz-CH3
C6" 12 + C3H 6 ~ C9H 18
The'lPA dehydration reaction is also undesirable, since 2 molecules of IPA
are required to produce DIPE:
2(CH3-CHOH-CHi) ~ DlPE + H20

8.3 Process Data

8.3.1 Feed Treatment
Because of the acid and anionic nature of the resin, any feed impurities
- basic and cationic impurities, but also peroxides and dloleflns - will poi-
son the resin and shorten its lifetime. Basic impurities are the result of feed
c..
production processes (acetonitrile and propionitrile respectively for and C5
cuts from catalytic cracking). They .also come from treatment processes
upstream from etherification units (caustic from sweetening processes fQl'cat-
alytic cracking cuts, acetonitrile, dimethylformamide and N-methylpyrrolidine,
solvents in butadiene extraction processes forsteam cracking cUts). The
nitrites react in the presence of the acid catalyst to produce ammonia or ter-
tiary arnines which neutralize the catalyst's acid function. Strong bases have
the same effect on add groups. Impurities also come from the alcohols used:
ammonia in the methanol, esters and aldehydes in theethanol. for C. and C5
feeds, the most usual method of removing these basic impurities is washing
with water. Treatment on molecular sieves is also used. Guard beds containing
resins are used to remove impurities from alcohols,
Peroxides affect the resin's skeleton by destroying aromatic groups,
thereby causing a reduction in active sites and therefore a decrease in cat-
alytic activity, Peroxides are minimized by preventing contact between hydro-
carbons and air during intermediate storage.
Cations such as the sodium ion act on acid sites to replace hydrogen ions
and make the site inactive. Iron in the presence of oxygencatalyzes peroxide
formation.
Diolefins are detrimental only at high concentrations (e.g. an untreated C4
feed from steam cracking). They lead to the formation of gums that foul the
catalyst and shorten its lifetime.This effect is particularly perceptible with the
304 ClI8Drer8, OLEFIN ETHER/FICA':"'::;';

C5 cut, ev.en for low diolefin concentrations (isoprene, pentadiene and

cyclopentadlene). Diolefins also cause TAME to have a particular smell and
color because they combine with the sulfur present in the feed.
Water will have a reversible passivation effect at concentrations higher
than 1 000 ppm.
Note that the resin's activity can be partially restored by increasing the
operating temperature.

8.3.2 Raffinate Treatment

An appropriate C4 and Cs raffinate purification treatment - elimination of
diolefins and oxygenated compounds - is necessary to meet the specifica-
tions required by the upgrading processes downstream from etherification,
Typical specifications for these raffinates are as follows:
methanol: 50 to 100 ppm
DME: 300 to 500 ppm
water: 400 to 500 ppm (saturation)
ether: IOta 20 ppm
Water washing, stripping column, improved fractionation and molecular
sieve absorption are the standard types of treatment used to lower the level of
these oxygenated impurities, or even eliminate them. The concentrations
required for alkylation units are 50 ppm, whereas they are lower than 1 ppm
for n-butane isomerization (see the configuration with isobutane dehydro-
genation, Fig. 8.3). Removal of diolefins from the raffinates by hydrogenation
allows lower acid consumption in alkylation units.

8.3.3 Operating Conditions

The characteristics of etherification reactions can be summed up as follows:
liquid phase, exothermic, reversible reactions. Choosing operating conditions
is a trade-off between the need for high reaction rate, good selectivity and
almost total conversion..
As a result, the main operating conditions for the MTBE process are as fol-
lows:
, methanol/isobutene molar ratio: 1.1 to 1.2;
temperature: 50 to 90"C in the main reaction section and 40 to 60Cin the
finishing reaction section;
, pressure between 7 and 20 bar;
space velocity: 4 to 6 h- l .
The operating conditions for other etherification processes are similar,
even though the equilibria are less favorable. This will lead to lower perter-
.rnance values despite the decrease in space velocity.
S.3.4 Process Flow Schemes
8.3.4.1 MTBE Procets
The process flow schemes are of 2 types depending on the desired result when
treating the C. cut:
Conventional scheme to produce motor fuels, achieving approximately
96 to 97% isobutene conversion.
Scheme with reactive distillation to upgrade the Cc raffinate for produc-
tion of high purity butene-I by eliminating isobuteoe. Conversion targets
are very high, up to 99.9%. When this scheme is applied to MTBE pro-
duc!ion for fuels, it achieves maximum isobutene conversion.

a. The conventional flow scheme (Fig. 8.5) comprises 4 sections:

washing.
reaction,
MTBE fractionation,
methanol recovery.
The washing section eliminates basic impurities from the C. feed. Washing
is performed with condensates or demineralized water circulated counter-cur-
rently in a column. The reaction section includes a main reactor where most
of the etherification reaction takes place (some 90%).followed by a finishing
reactor operating at lower temperature. The ~ITBE is fractionated in an
azeotropic distillation column. The C4 raffinate (unreaeted isobutene and non-
reactive components) and the methanol entrained byazeotropy (low-boiling
point azeotropes with the C whose methanol content increases with.pres-
sure) are recovered after condensation at the top of the column. Meanwhile,
the MTBE is withdrawn as a bottom product. The methanol recovery section
includes 2 columns. The first is for washing with water circulated counter-cur-
rently to extract the methanol from the Col raffinate. It is followed by a
water/methanol fractionating column, from which the water is recycled to the
washing column and the methanol to the reaction section. .

b. In the flow scheme with reactive distillation (Fig. 8.6), the finishing
reactor and the azeotropic distillation column are replaced by a column sys-
tern with a reaction section integrated in the upper part. The produced MTBE
is separated and at the same time the isobutene is converted. It is an applica-
tion of the Le Chatellier principle. which states that in a reversible reaction,
eliminating one of the components moves the equilibrium toward formation of
that same component (here MTBE is the product that is eliminated continu-
ously by distillation). The system includes several catalytic zones, and allows
maximum conversion to be achieved. It also permits integral recovery of the
heat of reaction and therefore minimizes energy consumption. The reactive
distillation process is being applied increasingly when the process is adjusted
to yield motor fuel.
 Co)
o0)

~
Waler washing Main Finishing Siabiflzer Water washing MeOH/H 20 ~
~
column reactor reactor column column

C 4 rallinate
~
11'1
~~
:!j

~
(:)
;00

C4 cui

Weier
Methanol

MTSE
Recycled methanol

IFf':~ M'/7U:'I'lYJn.~.~. COIll'c'/Ifi'lfIlIl flc)/II.~dll''''{'.

 . ..
---~ _,-~-----~-- .~"_~, ~r___ i

Waler washing Main Reaclive Waler washing MaOH/H20

column reactor distillation column column column

C 4 raHlnalO

nL _.
lood
WUler
Mothanol
i
po

I Recycled methanol
MTBE
~

".;illll t ll

j H.6 IFP'sMTBE process. Flow scheme with catalytic distillation (lFP process).
I
 Co)
g
Main reaction Finishing R
section reaction section t
~
<II
Water washing Stabilizer Water washing MeOH/H20
column column column ~
~
Cs raffinate
+ ~
TAME ~
~
:'i
\1

c, feed

Water
Methanol

Recycled methanol I TAME

IFP's TAME process. /lig" conversion (90-.95%). Optioll 3.

8.3.4.2 TAME Process
The TAME and MTBE processes are similar, with the important difference that
the C5 cut is already incorporated in the gasoline pool, contrary to the C. cut.
The C5 cut, light gasoline (lBP GOGC) from the wide-range gasoline cut. exhibits
the following characteristics as compared with (4:
A higher dlolefln content (isoprene, pentadiene and cyclopentadiene)
that will require installation of a selective hydrogenation unit upstream
from the TAME unit, the aim being to improve the quality and quantity of
TAME produced.
A less favorable equilibrium resulting in lower conversion.
The process flow scheme will depend on required Cs 'converslon, financial
constraints and the ultimate use of the Cs cut. It can be built gradually. step by
step in the following way:
A base flow scheme (option 1) corresponding to 75% lsoamylene eonver-
sion with production of a (5 + TAME mixture sent as is to the gasoline
pool. It consists of:
- a washing section designed to eliminate basic impurities from the (5
feed, similar to the one in the MTBE process,
- a reaction section with 2 reactors.
- a methanol recovery section with 2 columns: a ~ater washing column
to extract methanol from the (5 ralfinate, followed by a water/methanol
fractionating column, that can even be shared with an MTBEunit when
the two units are located on the same site.
Addition of a fractionating column (option 2) to the previous scheme
between the reaction and methanol recovery sections allows pure TAME
and a C5 raffinate to be produced. .
Addition of a finishing reactor on this raffinate between the fractionating
column and the methanol recovery section (option 3) allows overall con-
version to be boosted to over 90%with production of pure TAME and a
C5 + TAME mixture (Fig. 8.I).
Use of a reactive distillation column replacing the fractionating column
and the finishing reactor results in conversion higher than 90%, with pro-
duction of pure TAME and a Cs raffinate. However, this flow scheme is
less flexible to operate than the previous one. .
The 4 options are summarized as indicated in Table 8.5.
Note that C5 cuts contain more contaminants than the C4 cuts, and so cause
more rapid catalyst deactivation. .

5.3.4.3 ETBE Process

ETBE and MTSEtechnology are very similar.The same plant without any mod-
ification can be used interchangeably to produce MTBE or ETBE. tsobutene
310 Chapter 8. OLEFIN ETHERlFlCAnON

Oa>tlons 1 2 3 4
I i
lsoamylene conversion (%) 75 zs 1 92 92
I I
Production of pure TAME
I -no yes
I
I
yes
I yes
;
Production of a Cs cut"
I no yes I no yes

'" That does not contain any ether and can be sent to an alkylationor skeletal isomerization
unit.

IT~I, i
,-r-:-:-:-l
8.5

conversion is approximately 92% with a conventional scheme and around 95?v

with a reactive distillation reaction. The major differences between the 2 pro-
cesses are:
a less favorable equilibrium and a lower ethanolfisobutene ratio (more
limited ethanol/hydrocarbon azeotrope), resulting in a lower conversion:
a higher water concentration recycled with the ethanol (water/ethanol
azeotrope), resulting in a higher production of TBA (tert-butyl alcohol)
- a reaction by-product;
a higher level of ethanol Impurities, resulting in a shorter catalyst lifetime.
Fractionating columns can be added to purify the ETBE product.

8.3.4.4 DIPE Process

Because of the large amounts of propylene (more than isobutene . and
isoamylenes) producedin refineries, diisopropylether and isopropyl aicohoJ
can significantly raise oxygenated compound production.
The UOP process (Fig. 8.8) features 4 sections [4]: Iractlonatlon, reaction.
DlPE/IPA/water fractionation and washing. The first fractionating section
(depropanlzer) concentrates the feed from the reaction section in propylene
by separating it from the propane contained in the C3 feed. The reaction sec-
tion includes 2 reactors respectively for IPAand DIPE synthesis. The DlPEsyn-
thesis reactor is a fixed bed type operating at lower temperatures than the IP.-\
reactor due to the low water concentration. The second fractionating section
comprises an initial IPA/water separation column. with the water recycled to
the IPA synthesis reactor. The second column separates DlPE from unreacted
propylene which is sent back to the depropanlzer, The DlPE and IPA from the
top of the first column areseparated in thethird column, with the IPA ....i th-
drawn from the bottom being sent back as feed to the OWE synthesis reactor.
The DIPE recovered as liquid distillate from this IPA/DlPE splitter is purified in
a washing section.
;.

euedoJd _ - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -,

r-------------------.,o----t---- J918M

UOI18:>!J!Jnd
'tdl

'-- .L- -'_ peel t:)

sere
JOleJedes uuiruee JOI::leeJ JOI:leOJ
3dlO l'tdl' :>!dOJIOeZV 3dlQ Vdl J9ZlUedoJdeo
 ..
Co)

Main reaclion Fractionating Hydro-Isomerization Water washing MeOH I H20 ~

1i
seclion column and elherillcalion column column !'l>
reactors
Ce rallinale ~
~
+ ;:
elhers rn
~
~l.

Etherified
Dimale! I Recycled methanol , dimale
feed

IFP's DlMATOL process.

8.3.4.5 Dimatol Process
The process flow scheme (Fig. 8.9) is similar to the conventional type MTBE
scheme, with the addition of a finishing section including a hydroisomeriza-
non and an etherification reactor between the fractionating column and the
methanol recovery secuoa, In the reaction section the 2-methyl pentenes and
2.3-dimethyl butenes undergo etherification. Isomerization. of 4-methyl
pentenes to 2-methyl pentenes and their etherification in the finishing section
yields an overall conversion of over 80%.
Note that, contrary to the other feeds for etherification units. the dimate is
contaminant-free. As a result. a feed washing system is not necessary and the
catalyst lifetime is longer. In actual fact. practically the same amount of oxy-
genated compounds can be produced by the Dimersol (see Chapter 9) and
Dimatol together as by MTBE or TfME. .
A I 600000 t/year catalytic cracking unit can supply the following amounts
of ethers of various types (2]:
MTBE on C4 feed 52000 t/year
TAME on C5 feed 56 000 t/year
C7 ethers on dimate feed 42 000 t/year

S3.5 Reactor Design

S.3.5.1 Main Reactor
~(TBE synthesis is an exothermic reversible reaction. As such, 2 reactors are
required to achieve high conversions: a main one working at between 50 and
90:C and a finishing reactor operating at a lower temperature. some 50C. It is
important to eliminate heat in the first reactor in order to minimize side reac-
tions and extend the catalysfs lifetime. The difference between the various
processes resides partly in the design of the main reactor.
SNAM Progetti has chosen a tubular reactor to remove heat with an exter-
nal fluid. Huels/UOP and ARCO use multi-stage fixed bed reactors with heat
eliminated by circulating the liquid phase in an outside exchanger, CDTECH I
operates a reactor that works at the bubble point of the CJMeOH/MTBE mix-
ture. with the heat of reaction eliminated by vaporization. In the IFP process,
the reactor is of the expanded bed type. It operates in the liquid phase. with a
rising current and liquid recirculation so as to eliminate the heat of reaction
and control the slight expansion of the catalytic bed. Catalyst expansion agi-
tates the resin bed. thereby allowing optimum mass and heat transfer and pre-
venting hot spots inside the resin. The system provides excellent flexibillty
with respect to isobutene concentration and feed flow rate.

1. Joint venture between CRt (Chemical Research Ucensing) and Lummus.

314 Chapler 8 OLEFIN ETHRIF/CAilo.',

8.3.5.2 Finishing llcactor

Two types of reactor can be used: a fixed bed reactor, or a reactive distillation
column. The way the resin is placed in the column differs according to licen-
sors. CDTECH has proposed a system of bales containing the catalyst placed
in layers in several beds; HuelsjUOP a system of structured trays containing a
catalyst patented by Koch; and IFP a system, called Catacol, using "doublets",
Le, superposing a bed of catalyst in bulk in a reactor with distillation trays
above it.
In contrast, TAME synthesis kinetics, as compared to MTBE and ETBE, is
slower and the approach to equilibrium more limited, The use of an expanded
bed reactor can not be considered, so fixed beds are utilized.

8.3.6 Product Yield and Quality

Commercial grades of ethers are summarized in Table 8.6, except for TAME,
which currently does not have any specifications.

Compounds MTBE ElBE*

!
Ether purity (% wt) 98.5 max 91Smin !
Hydrocarbons. (% wt) 0.1 max (CJ - I
Other oxygenated products (% \\1) 1.5 max 9 max including 8 ethanol]
* Specificatlon published by decree in France's "Journal Offlcie)" (March 28, 1!I96).
,-r--
Table
I
8.6 Commercial ether specifications.
'---

8.4 Economics [5}

MTBE prices regularly follow the same trend as those of premium gasoline. An
upward trend was experienced between 1985 and 1990, when the ratio of
MTBE/premium gasoline prices went from 1.2 to 1.4, due to strong world
demand at the time. Since then, the upswing has slowed down, mainly because
of the collapse of crude and methanol trading prices, but also because huge
MTBE production capacities have been commissioned. However, thanks to
future prospects, the coming years should bring a continuation of the growing
MTBE/premium gasoline ratio,
Methanol prices undergo much more pronounced and irregular fluctua-
tions, mainly due to surges in production and demand. The normal price of
methanol is usually situated at 0.6 times the price of premium gasoline.
 Chaptllflt. OLEFIN THERIFrCAnoN 315

The C4 cut is mostly used as LPG and as a gasoline component. The drop in
LPGdemand, the regulations on gasoline vapor pressure, the increased refin-
ing operation severity and the growing production of natural gas are such that
supply is expected to exceed. demand. The normal price of the C4 cut is cur-
rently 0.8 times the price of premium gasoline.
As an indication, in 1995 the average price of premium gasoline was approx-
imately $25O/t, compared with $300/t for MTBE.

8.4.1 Production Capacity

MT8E is 'currently the chemical product with the highest growth rate in the
world. Production has gone up by over 15% per year since the early eighties.
Production capacity topped 1'9 million tons in 1994 and could hit 30 to
35 Mt/year in the year 2000. Figure 8.10 situates the variations in world MTBE
production from different types of feeds. World MTBEproduction and planned
MTBE units are indicated in Table 8.7.
Although MTBE production has experienced a high growth rate, oxy-
genated compounds today account for only approximately 3.5% of the world
gasoline pool.

24

20

16
m
QJ

~
c:
.9 12
<II
c:
~
s 8

O"'::~-'----_.L-----"'=-..l.- _ _.L-_---'
76 80 84 88 92 96

Figure:
I
. 8.10 I' JrrB. World capacity according to isobutene soun:es (3j.
Soarce:IFP/Strategy and Corporate Planning Diuision.
316 Chapter 8. O..F IN ETHfRIFJc;,-::;'.

,
Capacity 1995
I Planned units

SC , FCC TBA
I
C. Total % I SC/FCC~ TBA I Col i
i
United States 790 3960 2810 4170 11 730157.4 2940 430 7470
Canada - -, ,- 530
530 2.6 - - 1400
South America 200 45 - 500 745 3.6 675 - 1 100
Western Europe 1300 9S0 1070 -
3350 16.4 580 - 1 180
Middle East 45 lUu - 2400 2545 12.4 520 - 1900
Eastern Europe 305 ! - - - 305 1.5 - - 1900
Africa
Southeast Asia
-1
625 1 320,
- -
320
-j
300
-I 0
1245j 6.11
i 50
690
-
-
600
290
1

Total 3265 5405: 3 880 7900 20450 100 5455 j 430 15840
Total" 20450 21725
-~
Table
8.7 MrBE- World capacity 00.1 t/year) [3/.
'--- SC:C4 cut from steam cracking FCC: Col cut from FCC
TBA: isobutene from tert-buty! alcohol
C-/: C4 cut from natural gas

8.4.2 Process Licensors

This simple process requiring no specific catalyst is proposed by many licen-
sors and is also operated internally by refining companies. The main licensors
are ARea, BP, CDTECH, EDELEANU. Huels/UOP, IFP, and SNAM Progettl.
Technology differences are basically in the main reaction sections and the fin-
ishing reactor sections.
For DlPE. several licensors, RWE-DEA/UOP, Mobil and Nippon Oil, dijler in
the catalysts they use.

8.4) Investments
8.4.3,1 MTBE Process
The type of feed has a great impact on investments. For example, the C4 cut
from catalytic cracking contains much less isobutene that the cut from steam
cracking. As a result, 100000 tons of steam crackingC4, or 300 000 tons of cat-
alytic cracking C4, are required to produce approximately 70 000 tons of MTSE.
Tables 8.8. 8.9, 8.10 and 8.11 give investments 2 for the MTBE, TAME, DIPE
and D1MATOL processes, along with material balances and utilities consump-
tion. .

2. USCulf Coast, including the catalyst. engineering and tia:nsing fees.

 Origin Catalytic Steam sc,
of feed cracking cracking dehydrogenation

~lty of unit (t/year) 70000 70000 70000*

feed:
Col cut (t/year) 302700 100 900 96600
Methanol (t/year) 25500 25400 25400
Prodm:ts:
( .. rafftnate (t/year) 258200 56300 . 52000
MTBE (t/year) 10000 70000 .. 70000
Battery limits
investments (lQ6 1999) 8.0 5.0 4.0
, Illitial catalyst
I inventory (lQJ 1999) 80 40 55
Consumption
per ton of MTBE:
15
.
Electricity (kWh) 5 5
Steam (t) 125 0.3 0.2
Coolingwater (m3) 55 20 15
Catalyst (lOO 1999) 0.6 0.4 0.4
In this flowscheme, capacity is generally(rom 300 000 to SOD 000t/year or even 700 000 t/year.
-
~Tabk
I
: 8.8 Economic data./FP's MTBEprocess.

-
I Type of process Option 2* Option 3*
I
I Capacity of unit (tjyear) 100000 100000
Feed:
Cs cut (t/year) 275300 193 700
I Methanol (t/year) 31400 22000
I
Products: -
i
Cs raifinaterrAME (t/year) 306700 128 700
Pure TAME - I
87000
Battery limits I
I investments (lOli 1999) 8.6 7.4
, Initial catalyst
: inventory (loJ 1999) 250 I, 210
I Consumption per ton of TAME:
~ 1edricity (k\Vh) IS 2
Steam (t) 0.1 0.6
Cooling water (ml) 20 35
Catalyst (Ill' 1999/year) 0.16 0.14

Set! Section 8.3.4.2.

---,
T3bIe :
8-9 ! Economic data. IFP'sTAJIEprocess.
_~I
318 ChapCII'B. OLEFIN ETHERIRCA7:0,v

Capacity of unit (t/year) 110000

:
Feed: i
C3 cut (t!year) 160.000
Reaction water (t/year) 42000
Products:
Propane (t/year) 68800
Hydrocarbon purge (t/year) 3500
Water purge (t/year) j 24600
I
D1PE (t/year) 106800 :

Battery limits investments (I()6 ) i 20

I
Consumption per ton of DIPE:
Electricity (kWh) 0.1
LP steam (t) 0.3
MP steam (t) 1.3
,-r---
Table
8.10 UOP's DlPEprocess.
'-----

Capacity of unit (in Cj ether) (t/year) 51000

Feed:
C3 cut Ct/year) 137100
Methanol (t/year) 14100
Products:
LPG-C 3 Ct/year) 38550
C7 ethers (t/year) 51050
Gas..oline (t/year) 61600
Battery limits investments (10' 1999) 14
Utilities consumption ( 1999/t of feed) 5
Catalyst consumption ( 1999/t of feed) 7
....
.---
Table
8.11 Economic data. IFP's DIMATOLprocess.
'---

References
Gicquel A (1981) Activation d'une resine sulfonique par un acide de Lewis.
Application ala synthese du Methyl Tertio Butyl Ether (MTBEJ, Ph. D.Thesis.
2 Nocca J.L., Forestlere A.. Cosyns J. (1994) Setting the Pace with IFP for the
21st Century, IFP's New Technologies for Reformulated Gasoline, June 1994.
3 Torc~ B. (1994) S~lUation actuelledes composes c.ygenes : productlonj
cons'ommation, Petrofeet techniques, Jan-Feb 1995,No. 393, p. 48.
4 ~cg~erT"L", HammershaimbH.U., Marinangeli R., Keessom W. H., Bozzano
R" "0 ~1993) Production of IPA and DJPE from Propyle.e Usinglon-Exchange
esu, Catalyst. AIChE Houston,Texas, 21,23 March.
5 T~~C"-t B. (1997) Valorisation du butadiene et des coupes c..."
l/aauatit
c rm"que, April 1997 p. 3.
 Oligomerization' !
[.:.. -i~-';:~ -: . '. ~ .~

_ Pierre Leprince

In competition with alkylation, addition reactions of olefins with other olefins

have been at the origin of processes designed to produce high-octane gaso-
Jines. Following a boom period during and after the Second World War,
oligomerization units were gradually closed down, especially in the United
States, to make way for alkylation units which were better suited to the race
for high octane numbers between 1960 and 1980. .
Today oligomerization units have made a come back in refining in two main
areas:
upgrading Cz and C3 cuts from catalytic cracking, whose ethylene and
propylene are converted into olefinic gasoline;
producing high-quality middle distillates from light oJefi,ns.
Note that this evolution is due to significant scientific progress that led to
the development of highly effective catalytic systems: e.g. organometallic cat-
alysts active in the liquid phase, solid zeolite-based catalysts.

9.1 Background Information

Olefin oligomerization reactions are exothermic and endotroplc (reduction in
the number of molecules). As a result, conversion is promoted by low tern-
perature and high pressure.
Table 9.1 gives average values of reaction exothermicity for various olefins.
322 Cl1aor~ 9 OLIGOMERIZATION

Reaction M1iH
(kJ/lDolofproducij

2 C3H6 -+ C6H 12 (hexenes) 84.2

3 C3H 6 -+ ~HlS (nonenes) 158.5
4 C3H s -+ Cl2H 24 (dodecenes) 252.8
2 C4Hs -+ CSH16 (octenes) 84.2
3 C4H s -+ C12H 24 (dod ecenes) 168.5

i~
; 9.1
~
Exothermicitv of otisomerizatic-: reactions.
. ~

A number of catalytic systems can activate the olefin oligomerization reac-

tion:.
phosphoric acid deposited on a solid support (quartz, kieselguhr);
amorphous or crystallized (zeolites) silico-amines;
transition metals (nickel and titanium) which act in the homogeneous
phase.
Table 9.2 gives the main characteristics of these different catalytic routes.

Catalyst
PO",H,.SiOZ"Al:t0,
zeolites
Ii Organic nickel salt
I

Reaction temperature lO~200bC 50-60C

Selectivity Low in dimers Very high in dimers

Relative reactivity Ci < Cj < C; < iso-C:j C;; > Cj > n-q:> iso-C;

Side~ reactions Cracking Heavy oligomers

Skeletal is omertzatton !
Catalyst poisons Basic compounds. H2O, \
Polar compounds,
dic1efins diolefins
.....r - -
Table
i I
9.2
L....-

9.1.1 Acid Catalysis

The reaction takes place via a carbocation formed by the reaction of the olefin
with the catalytic acid. For propylene. t.~e mechanism is as follows:
 Olefin reactivity rises with the molecular weight. Consequently, by means
of a sequence ot consecutive reactions a mixture of dlrners, trimers and
tetramers is obtained. Their end point is approximately 215C in propylene
oligomerization and 230C in butene oligomerization.
The activity of this type of catalyst is hindered by the presence of basic
compounds (caustic, ammonia, ethanolamine from the feed H~ removal unit).
It is also disturbed by the presence of butadiene which must be eliminated
when the butene feed comes from steam cracking. .

9.1.2 Catalysis by Transitien Metals

Olefin oligomerization can be accomplished in the homogeneous phase by
complex catalysts containing titanium and nickel or cobalt salts. This method
is widely used in petrochemistry to produce alpha-olefins from ethylene or
butenes (Alphabutol, Dimersol X processes). In refining, this type of process
has found an application in order to reduce the C3 cut propylene content and
produce of a high-octane oleflnlc Cs gasoline, mainly in the United States. It ls
also implemented in converting ethylene from catalytic cracking C2 cuts into
gasoline (Dirnersol E process).
In this type of reaction, olefin reactivity decreases with molecular weight. '
It will therefore be easy to get good dimer selectivity (Cli for propylene).
The reaction intermediate is the result of the monomer coupling on the
metal or being inserted on the metal hydride. Below is a simplified diagram for
propylene.
324 ChaOlef 9 OI..lGQ.\!RIZATION

First insertioo Secood iDRrtiOD Primary Isomers

products

C
I .... hexenes-S
Ni-C-C-C-C-C -+ hexenes
1and 2
Ni-C-C-C _+_C_=_C_-_C_ / C

\:,\i-C-J-C-c-c -; methyl2 methyl-:?-

pentene 1 -; pent;ne 2

C C
I I -; meth)'1-4 .... methyl-2-
Ni-C-C-C
C J pentenes pentene 2

Ni-C-C
I
.0=<:-\
- .
II
Ni-C-C-C-C
1and 2

-; dimethyl-2,3 -; dimethyI-2.~
butene 1 butene2

In this type of catalysis, dioleflns (butadiene) are reaction poisons, the

same as in acid catalysis. Added to this, there is an inhibiting effect of polar
compounds (alcohols, ketones, arnlnes, etc.).

9.2 Industrial Processes

Alkylation processes, designed to upgrade olefins to isoparaffins which are
highly prized for the gasoline pool, have been stiff competition for oligomer-
ization. Oligomerization processes have developed only to fit specific situa-
tions such as: surplus amounts of light olefins, quantitative need for gasoline.
kerosene and diesel oil.

9.2.1 Catpoly Process (UOP)

This process can transform propylene, butene or a mixture of both. It uses a
phosphoric acid catalyst laid down on a solid support of the kieselguhr type.
The process (Fig. 9.1) involves a reactor where the catalyst is divided up into
several beds. Cold propane is introduced between them to adjust the temper-
ature which rises because of the reaction exothermicity (fable 9.1). After elim-
ination of the entrained acid, the product is sent to a stabilization column
which removes the excess C3{C4
The process works under the following conditions:
Space velocity: 0.5 to 1 m3{h per m3 of catalyst
Temperature: 180-200C
Pressure: 30-40 bar
 Reactor Stabilization

LPG

Water
injection

Acid
trap

i
i
L Figure
9.1 Catpoly process diagram (COP)
I

Under these conditions. conversion to gasoline ranges from 90 to 95%. A

certain degree of hydration should be maintained in order to keep catalyst
activity constant, so 50 to 150ppm water is necessary in the feed.
Additionally, the catalyst bed temperature should also be carefully con-
trolled. Temperature control is even more difficult as catalyst activity is vari-
able over time. At the end of the run the non-regenerable catalyst is unloaded
and replaced by a fresh load.
Table 9.3 shows the properties of the resulting essentially olefmic gaso-
line.
 326 Chaoter 9. OLIGOMERIZATION

Feed CJC~ C3
I

~
Product characteristics:
sp.gr. d"f 0.730 . 0.730
Distillation:
IBP CC) 35 I 50
EP ("C) 215 I, 215
RON 92 94
MaN 80 82

I~~3k I Characteristics afalig<>meri=atian gasoline (Catpoly process}

9.2.i Polynapbta Process (IF~)

This process is designed to convert C3, C4 and Cs oletins into a gasoline cut. It
uses a slllco-alurnina catalyst in a fixed bed reactor. After preheating. the feed
is sent to two in-series reactors separated by a heat exchanger that eliminates
the heat of reaction. The product undergoes separation: stabilization of the
gasoline and gasoline/gas oil separation (Fig. 9.2).
The process works under the following conditions:
Temperature: ISO-200C
Pressure: 30-50 bar
Space velocity: 0.3 to 0.5 m3/h per 01 3 of catalyst
Under these conditions conversion reaches 95-98%.
The catalyst gradually loses its activity due to gums deposited on its sur-
face. It can readily be regenerated by oxidation of the gums with a mixture of
air and steam. The product is made up of a gasoline/gas oil cut whose main
characteristics are given in Table 9.4.

Products Gasoline Gas oil

sp.gr. dIG 0.740 0.810

ASTM distillation:
IBP (0C) 40 150
EP C'C) 200 350
RON
.... r - - -
95 -
Table
9.,. Product characteristics (Polynaphta process).
'----
 '8-
- - - - -..... 0
<II
<!J

- - - - - - _..... ~
328 C/la/Jter9. OLIGOMERIZATION

9.2.3 Dimersol Pro~ess (IFP)

This process implements a soluble catalyst consisting of an organic nickel salt.
It involves a liquid phase reactor whose temperature is adjusted by external
circulation of the liquid phase cooled in a heat exchanger, The catalyst is
injected continuously in the reactor. The catalyst is eliminated from the prod-
uct by ammonia injection and caustic washing, and the product is then frac-
tionated (Fig. 9.3).

LPG

Reactor

Gasoline

Catalysts Fresh Spent

csusnc caustic

: Figure i
U Dimersol process !lOU) diagram (lFP).

The process works under the following conditions:

Temperature: 40-50C
Pressure: 10-30 bar
Residence time: 1-5 h
Under these conditions, conversion of 80 to 89%is achieved. The unit's out-
put can be kept constant whatever the feed flow rate by means of controlled
catalyst injection. However, since the catalyst is eliminated by aqueous basic
solutions, specific treatment is required for discharged effluents.
 Chapter 9. OttGo~ 329

The resulting oleflllic gasoline has the following characteristics (fable 9.5):

Feed c,
Product characteristics:
sp.gr. if 0.700
ASTM distillation:
IBP COC) 60
EP (0C) 210
RON 96
MON ~ 82
~r--
Table
9.5 Gasoline characteristics (Dimersol process).
'--

9.2.4 MOOD Process

(Mobil Olefin to Gasoline and Distillate)
This process uses a zeolitic catalyst to oligomerize light"oleflns to lso-olefins
with a higher molecular weight. The catalyst, ZSM5, is a crystallized silico-alu-
mina whose pores have a diameter of 5.5 A. This fact gives it particular selec-
tivity to produce olefins with a low methyl and ethyl group substitution ratio.
The process generally involves four fIXed bed adiabatic reactors, three in the
reaction phase and the fourth being regenerated, The three reactors are
placed in series with intermediate heat exchangers .designed to absorb the
heat of reaction. The reactor effluent is fractionated to produce a distillate cut
and a gasoline cut which is recycled when maximum distillate production is
desired. The distillate cut is generally sent to hydrotreating to saturate its
olefinic bonds, thereby providing a high Quality product (kerosene or diesel
oil).
The process works under the following conditions:
aC
T~rature: IS0-200
Pressure: 7-12 bar
Space velocity: 1 to 2 m3; h per m3 of catalyst
It can use light olefins as feed. from ethylene to butenes, but also olefinic
cuts with an end point of 2OO'C (Table 9.6).
By appropriate recychng, either maximum gasoline or maximum distillate
production can be obtained from an olefinic C:JC~ cut (fable 9.7).
The products are essentially olefinic. The heavy cut must be hydrogenated
in order to enter the diesel oil pool. Typical product properties are given in
Table 9.8.
 t;,N'Pt.,r 9. O!..IGOMcRIZATION
330

:- f~d I Ci i CiJC;j ! C;/C;

r-; :C
I
-I .l
(;~('X,wt)
(% wt) I
.
I 3
I 2
4
I
2
C ',. gasoline (% wt)
J(~"C distillate (% \\It)
I 57 .
39!
27
67
28
69

-~'T"~
'J.fl I Yields (JfOGD process).
I

-.. Max. gasoline Max. distillate

Type of operation

l":I- I eX, wt) 4.5 2

C~ ( , wt) 5.0 21
l\- ISC gasoline (X wt) -
-84
12
1lI~ :- distillate (% wt)
l':,- ISDC gasoline (% wt) 84.0 -
~(l~ :- distillate (% wt) 6.5 -
l;"S line/distillate ratio 12.0 0.14
- i
'1'.11'
'J. Yields (MOGD process).

Distillate cut I
Gasoline cut -.
Untreated After bydrotreating

;p.~r. di'U 0.73 0.79 0.78

l'l'N 92 - -
:\'\'N 79 - -
l't<t;tlle number - 33 52
~ullur (~..; wt) "'0 < 0.002 < 0.002

U~,irog(11 consumption: approximately 110 m3/t.

------,
- rl;.t~!
. . .).~ I Product properties (MOOD process).
 Chapwf. ~ n c w 331

9.3 Economics
, 9.J.l Process Licensors
Phosphoric acid process: UOP (Catpoly). Huls and Chevron.
SiJico-aiumina process: fFP (polynaphta) and Mobil (MOGD),Badger. UOP
(Hexall).
Homogeneous phase process (nickel): IFP (Dimersol).

9.3.2 Investments. Operating Costs

Table 9.9 gives typical values for the Dimersol and Catpoly processes in their
refining appltcattonsr

Dimersol Acid catalysis

Capacity:
Feed (t/year) 100000 100000"
Product (gasoline) (t/year) 75000 75000
Battery limits investments (106 1999) 4.2 5.1
Utilities (per ton of feed):
Electricity (kWh) 10.8 12.0',
HP steam (t) 0.14 0.85
Cooling water (m3) 28.5 30
Catalyst/chemicals ( 1999) 7.9 -
75% Ci. 74% C.
'----
: Table I ". -
9.9 j Economrc data.

References
1 Tabak SA. Krambeck F.J. (1985) Hydrocarbon Processing 64, 9. 72.
2 Chauvin Y, Andrews Y.,Gaillard J., Juguin B., Leonard J., Derrien M. (1987)
AlChE, Spring Natl. Meeting, Houston, 3/29-4/2/37, Preprint N 700 15 P.
3 Nierlich F. (1992) HydrocarbonProcessing 71, 2, 45.
4 Chauvin Y., Gaillard J., Leonard J., Bonnifay P. (1992) Hydrocarbon
Processing 61, 5. 110.
5 Ward DJ.. Frame R.. Friedlander R.H., Imai T. (1985) Hydrocarbon
Processing 64, S. 81.
 -~10'~l
----.. _._'"-~:--..,..-_ ....:..-;. : '.:-:1
.... \. i - .<:-~-..:.~-;~~;~ --:-i ..::~~;~.~ ::....:. :. ,: ...i
Hydr~c~~~king .:,-1

Alain Billon
Pierre-Henri Bigeard

In technical literature the term hydrocracking is used non-restrictively for the

conversion of both vacuum distillates and of residues. In the present chapter
the hydrocracking process exclusively involves the conversion of heavy feeds
free of asphaltenes and of high metals concentration.
The forerunner of hydrocracking is the Bergius process, brought on stream
in Germany in 1927 to hydrogenate distillates derived from coal. The present-
day version is a catalytic cracking process that converts heavy hydrocarbons
into higher added value. lower molecular weight compounds under hydrogen
pressure. The first modern hydrocracking unit was commissioned in 1959 by
the Standard Oil Company of California (throughput: 50 000 t/yea.r) in the
United States. '-
Table 10.1 illustrates the wide range of applications for hydrocracking, and
shows the variety of feeds that can be used and the assortment of products
that can be obtained.

Feeds Products

Naphtha Propane butane

Kerosene Naphtha
Gas oil Naphtha> jet fuel
Vacuum distillate Naphtha. jet fuel, diesel oil, lube oil base
Deasphalted residue stocks. steam cracking, and catalytic
cracking feed
Ught or heavy gas oils from converston Naphtha and/or middle distillates
processes: coking.FCC. VB. etc.
- Table i
to. I i Hydrocrackillg applications.
 334 Chapter 10. HYDROCRACKIN$

The process allows middle distillates to be converted into naphtha and

liquified petroleum gases. However.it is mainly used to convert vacuum distil-
lates coming directly from crude oil or from some other conversion processes
(visbreaking. coking, catalytic cracking. residue conversion). and even deas-
phalted residues. The products are gasolines, jet fuel and diesel oil, depending
on geographical and seasonal market requirements. It can also be used in the
preparation of steam cracking feed and/or Jube oil base stocks with good vis-
cosimetric properties. These lube oil base stocks are the starting point in the
production of multigrade engine oils and special oils (turbine, hydraulic and
transformer oiJs).ln some countries. hydrocracking can be associated with cat-
alytic cracking for optimum production of middle distillates and gasoline.

10.1 .Function of ~he Process

Depending on the objectives chosen with respect to product quality and
degree of conversion, two types of process can be distinguished: mild hydroc-
racking and conventional hydrocracking. Their main characteristics are pre.
sented in Table 10.2. Mildhydrocracking is an improved hydrotreating process
giving relatively low conversion (between 20 and 40%wt) and operating at low
pressure (approximately SO-SO bar total pressure). Conventional hydrocrack-
ing is a process that allows high conversion (70-100% wt) of heavy distillates
at high pressure (lOG-ZOO bar total pressure). The two processes are similar
when the reactions that occur during them are considered, but the much lower
hydrogen pressure in mild hydrocracking results in differences in performance
and product distribution. In the mild process, the amount of distillates pro-
duced is small (20-40% wt), since the hydrotreated residue accounts for most
of the effluent. The conventional process allows significant distillate produc-
tion that can amount to 80-90% wt.
Hydrocracking, like catalytic cracking, is used to convert heavy cuts but
under very different conditions. Catalytic cracking requires high temperatures
(over 500C), low pressures and does not use hydrogen. This leads to very
rapid catalyst deactivation: continuous catalyst regeneration is therefore nee-
essary. Hydrocracking works at relatively low temperatures (350 to 430 Cl
under high hydrogen partial pressure (60 to 150 bar). This limits carbon
deposit on the catalyst and consequently allows a fixed bed technology to be
used with cycle runs from approximately one to three years. ".
Analysis of the diagram in Fig. 10.1 will give a better understanding of the
function of hydrocracking. It shows the mean value of the hydrogen to carbon
atomic ratio, Hie. versus the number of carbon atoms per molecule of the var-
ious petroleum fractions. The limits of the diagram are the curves obtained for
paraffins and aromatics. The naphtha cut can have a wide Hie ratio range to
meet specifications which depend on the type of process it comes from. In
contrast, middle distillates must have a highly saturated structure, l.e. a very
high hydrogen content, to meet market quality requirements (smoke point for
.Jet fuel, cetane number for the diesel oil cut). In order to have good vtscosl-
 0.."., 1a. 1-Irr:JRocRAcKJ 335

Conftlltional hydrocraddng Mild Ilfdrocracking

Feeds Vac\Ull distillate Vacuum distillate

Gas oil' from a conversion Gas oil from a conversion pro-
process cess
Deaspbalted residue Deasphalted residue

Products Propane. butane

Naphtha
Keroseee, dieseloil Kerosene. diesel oil (2Q.40% wt)
Lubeoil base stocks
Catalytic cracking feed Catalytic Clilddng reed (60 to
. 80% wt)
.
Operating conditions:
Pressure(bar) 100-200 so-so
Temperature CC) 350-430 3ID-44O
Hz/reed (mJ/ml) 800-2000 a-.soo
Spacevelocity(h -I) 0.2-2 9.2-2
Reactortype f"1Xed bed F'lxed bed
Hydrogen consumption
(%wt offeed) 1.4-4 9.5-1
Conversion (% wt) iO-lOO 2D-4O
Product quality ,Good Fair ",

L.-r----
Table
10.2 Main characteristics of hydrocracking.
'----

metric characteristics (high viscosity index) a lube oil base stock must be
mainly composed of iso-paraffmic and naphtheno-paraffinic structures. A
steam cracking feed must also exhibit a highly pronounced paraffinicstructure
in order to avoid too rapid coking of cracking furnaces and quench heat
exchangers. The conversion of the vacuum distillate fraction into middle dis-
tillates therefore requires not only a reduction in the number of carbon atoms
but also an increase in the H/C ratio. Heavy feeds can be converted by thermal
or catalytic processes. Thermal processes can accomplish a carbon-carbon
split, but they do not allow an increase in the H/C ratio in the converted prod-
ucts. The main characteristics of the three principal conversion processes are
presented in Table 10.3 and the important parameter that differentiates them
is the hydrogen partial pressure.
Figure 10.2 iJlustrates how the three processes are situated on the graph
showing H/C ratio versus number of carbon atoms per molecule. The catalytic
cracking unit produces a significant amount of good quality gasoline, but mid-
dle distillate characteristics are far from meeting the requirements on hydro-

.-,
336 CNpl(If 10. HYDROCRACKING

4 C,

o 380 QC
e

/i
/,'
..
,,
:~gas~
-----.
,*1<'
",11'
,,
.
/

A~.... ./
Numberof CiIfbon atoms/molecule

10

Figure
10.1 Hie ratio of the oon'ous petroleum cuts.

gen content. The mild hydrocracking process produces a significant amount of

desulfurized vacuum distillate cut with a hydrogen content that Is slightly
higher than that of the initial feed and relatively smaD amounts of moderate
quality middle distillates (cetane number approximately 38-42). Conventional
hydrocracking yields products with a more favorable Hie ratio. In addition. it
is the only process that can achieve complete conversion of heavy feeds with-
out forming any non-upgradable by products.
 Hydrogen
Reactor Middle
partial ~eeof Naphtha
pressure type COIlTersion quality dbWlates
(bar) quality

Conventional
hydrocracking 8(}...150 FIXedbed High Fair GoOd
Mild
hydrocracklng 40-70 Fixed bed Fair Fair Fair
Catalytic
cracking 0 fluidized bed High Good Low
l-~
Table
10.3 Characteristics of conoenion processes.
'---

150'C 25O"C ! High-pressure

~/,",_;ng effluent
0
!
~ .: . - Paraffins -SSO'C"-
2 -- ... _-.---_.- ......
6 .'

If Mild hydrocracking eff~u:.n~ ~ ,

IArabian light
Vacuum gas oil
...
.:/
w....... - ~ .. - ... .. . ,,'

=em:~~

Numberof carbon atoms/molecule

L..:-- 10 20 30 ---'

I FJ.gUfe
i 10.2 Comparison of catalytic concersion processes: FCC, mild and concentionat
hydrocracking.
 338 CtJaptef 10 HYDROCRACKING

10.2 Background Information [1-9]

10.2.1 Typical Composition of Hydrocracking: Feeds
The most frequently used feed is a distillate from vacuum distillation. Certain
characteristics (Table 10.4) are particularly important. For example the pres-
ence of asphaltenes and metals in large amounts causes very rapid degrada-
tion in performances by irreversibly poisoning the catalytic system.
Industrially, the asphaltenes content is limited to 200 wppm and metals con-
tent to 5 wppm in order to get a satisfactory catalyst cycle.

Sulfur(% wt) 0.1-5

Nitrogen (wppm) 200-3000
Paraffins and naphthenes ~% wt) 30-60
Aromatics (% wt) 30-70
Polar compounds: resins (% wt) 1-15
Asphaltenes (wppm) 20-1000
Metals (wppm) 0-10

Typical composition of a straight run vacuum distillate..

10.2.2 Reaction Families

Transformation of a petroleum distillate into naphtha, kerosene and diesel oil
occurs according to complex reaction patterns that can be grouped into two
main reaction families:
2 hydrotreating reactions (hydrodesulfurization, denitrogenation, aromat-
ics hydrogenation);
hydrocracking reactions as such (splitting C-C bonds) or C-C rear-
rangement reactions (hydroisomerization).

10.2.2.1 Hydrotreating Reactions

These reactions are described in detail in Chapter 16. In hydrocracking, feed
desulfurization is practically complete, due to the high H2 pressure and the
operating temperature level. It is even possible to produce a naphtha cut that
can directly be fed into the catalytic reforming unit without pretreating, l.e,
with a sulfur content lower than 1 wppm.
The denitrogenation reaction is very important for this process due the to
lJDpactof nitrogenated compounds on the acid sites of the hydrocracking cat-
,,~ even at low concentrations. For hydrocracking catalysts whose support
 i
is highly acid (zeolite typecatalysts). the nitrogen content must be controlled
before the teed contacts the catalyst in order to optimize the overall operation
of the catalytic system. .
lhe aromatics hydrogenation reaction is a prerequisite for cracking cyclic
hydrocarbons. In fact it is not possible to crack an aromatic compound under
hydmcracking conditions. On the cOntrary, the naphthenes resulting from the
hydrogenation of aromatic rings can be converted under these conditions.

10.22.2 Hydrocracking and HydroisomematioD Reactions

Hydrocracking allows a reduction in the average molecular weight of the feed.
Dependingon the position of the reacting C-C bond, there can be three main _.
types of reactions:
1.Simple hydrocracking reactions: a C-C bond i~ a chain is cracked:
R-CHz-CHz-R' + Hz -+ R-CH3 + R'- CH3
2. Hydrodealkylation: a C-C bondadjacent to a ring is cracked:

o-
~ I CHz- R 0I
+H 2 -+ ~ +R-CH3

3_ Ringopening reactions: a C-C bond in a ring is cracked:

O+H, . . C,H..

The hydroisomerization reaction improves the quality of some cuts: clear

octane number of light gasoline, cold behavior characteristics of gas oil and
lube aUs. The reaction takes place via a series of equilibrium reactions: .

R//'~::; R~::;~~::; R~

r.::,:~ :-,:--drocracking process conditions. with operating temperature

lc....<;:>:::a.~ ~O'C. the hydrocracking mechanism is essentially of the carboca-
t,=-n ::?:- :::sthe typical example of a bifunctional kind of reaction, l.e, lnvolv-
:::~ z,::. :.~'= catalyst's hydrodehydrogenating function and its add function.
:::-.e ~"'-:~:' accepted mechanism indudes the formation of an intermediate
:UY.r.-~~ :....ilow ed by splitting of the carbocation after rearrangement. The
:-~..:.:.: ..! ;'Sj-x':on products that are highly branched due to the strong ten-
C.~::=-f::' :::= more stable tertiary carbocatlons, The paraffin hydrocracking
::-::-::-~ :-.i:.S been the subject of a significant amount of research. It con-
 340 Chapter 10. HYDROCRACKJNG

: sists of a series of elementary steps involving acid sites d?d hydrogenating-

dehydrogenating sites provided by a metal or a metallic sulfide. The function
ofeach site in the reaction process is clearly identified: the first ones isomer-
ize or crack the olefinic reaction intermediates produced by the second ones.
The mechanism (Fig. 10.3) can be summarized as follows:
Step (1): dehydrogenation of paraffins (n-p) to n-oleflns (n-< on metallic
sites.
Step (Irn): migration of gaseous phase n-olefins from the metallic sites to
acid sites.
Step (2): adsorption of n-olefins on the acid sites in the form of linear car-
bocattons (protonanon step).
Step (3): lsojrertzation of carbocations on the acid sites.

n-p i-p
I

(1 m) A A (4m)
n-o: ::: ::: n-o i-o ::::::: i-o
M M

(2) (4)

(3)

~ Cracked products
L 'Figure
10.3 Bifunctional hydrocracking mechanism.
Ootted line: step when reaction intermediates are transferred between the acid func-
tion and the hydrogenating function.
Unbroken line: chemical step.
A; add site i-p: iso-paraffin n-C": n-catlon
M: metallic site rr-o:n-<llelin j.C+: iso-calion
n-p: n-paraffin i-<l: iso-olefin
The numbers between parentheses Indicate the nature of the steps (set!
Section 10.2.2.2).
 C1fi/I(JItIf to. HYDROCRACKING 341

Step (4): desorption of isomerized carbocaUons ill the form of iso-olefins

with the loss of a proton (deprotonation step).
Step (4m): migration of lso-olefms (i-.o) to metallic sites.
Step (5): cracking of carbocations giving a paraffm and an olefin.
Step (6): hydrogenation of the oletins formed ("JSO) on the metallic sites
to paraffins.
In these bifunctional catalytic reactions, the characteristics of strong acid
sites and hydrogenating sites govern the rates and selectivities of the opera-
tion. Their balance determines the activity, stability and selectivity of cata-
lysts.

10.2.3 Reaction Thermodynamics

Hydrotreating, aromatics hydrogenation and cracking reactions are all
exothermic. The approximate values for heat of reaction are indicated in
Table 10.5.

Ayerage heat of reaction

Reaction type
at '*rC (kJ/mol)
Aromatics hydrogenation

~
~ +3Hz -+ -210

Paraffins hydrocracldng
RH + Hz -+ R'H + R'"H '0
-46 to -58 .'

Naphthenes hydrocracking

~ + H2 -+ R'H -42 to -50

Aromatics hydrodeaJkylation

~ +Hz -+ RH+(" -42 to-46

L--:
Tabl~ i
10.::> I Heat of reaction {;alUI/S.

----J

Accordingly, controlling the rise in temperature is very important when cal-

culating an adiabatic hydrocracking reactor. Overly high increases in temper-
ature promote excessive coking of the catalyst and therefore rapid deactiva-
tion. On the hydrotreating catalyst. due to the reactions that take place on it.
 342 Chaprer 10 HYDROCRACK/N(i

exothermicity is at the maximum and so a minimum number of quenches are

necessary. On the hydrocracking catalyst, exothermicity is lower for a hydro-
cracking catalyst, but runaway temperatures are a rea} risk"as since the hydro-
cracking catalyst used exhibits a high acid function. Temperature control is
obtained by gaseous quenches in the reactors, and catalyst bed repartitions in
these reactors are decisive to keep the unit operating smoothly while optimiz-
ing the catalyst cycle run.

10.2.4 Kinetic Data [10-18J

The available kinetic data are mainly relevant to hydrocracking of normal
paraffins as studied by a great many authors with platinum base catalysts
deposited on zeolites. N-paraffin conversion is the result of two principal reac-
tions: hydro isomerization and hydrocracking. At low severity (low conver-
sion), hydro isomerization predominates. while at higher severity (higher con-
version) cracking begins to occur. .
Normal paraffins are difficult to crack as they lead to the formation of pri-
mary and low stability carbonium ions. They are first isomerized to branched
paraffins and then crack giving lighter products. An increase in the number of
carbons makes the molecule more reactive and favors cracking rather than
isomerization.

10.2.5 Catalysts
There are two possible approaches to achieve hydrocracking. In the first, all
the reactions can be carried out on a single catalyst. This solution was espe-
cially used for the first process developments and led to the use of catalysts
with an amorphous slllca-alumlna carrier. The second approach consists in
using a more complex catalytic system where a hydrotreating catalyst is asso-
ciated with a hydrocracking catalyst~The hydrotreating catalyst is chosen for
its performance in denitrogenation and aromatics hydrogenation reactions.
The hydrocracking catalyst is bifunctional: it must crack the heavy
. molecules (acid function) and hydrogenate the unsaturated compounds
formed during the reaction or present in the feed (hydrogenating function).
The balance between these two functions is used to manage catalyst formula-
tion to adjust catalyst activity and selectivity.
On a catalyst with a large number of hydrogenating sites as compared to
acid sites, the olefins formed will have a high probability of undergoing only
one cracking reaction before they find another hydrogenating site. This type
of catalyst is proposed when the objective is to minimize secondary or tertiary
cracking, l.e. to maximize the production of middle distillates. In contrast, if
the number of acid sites is much larger than that of hydrogenating sites, the
oleflns will be very likely to undergo a series of cracking reactions before they
find another hydrogenating site. This type of catalyst is selected to maximize
the production of gasoline.
 Chil!r:IW 10. HYOROCRACXIHG 343

10.2.5.1 Hydro~Debydrogenating Fan~tion

The hydrogenating function has three roles to play. The first Is to carry out the
hydro-dehydrogenation reactions in the bifunctional mechanism (Fig-,10.3).
The second is to protect the catalyst's acid sites to prevent too rapid coking
of the catalyst, i.e. to hydrogenate the heavy polyaromatic compounds. The
third is to continue the hydrotreating reactions (elimination of residual nitro-
gen compounds and hydrogenation of aromatics).
The two major types of hydro-dehydrogenating catalysts are noble metals
and mixed sulfides on carriers. The most widely used noble metal is palladium
at concentrations of approximately 0.5% wt. It is generally used in association
with a zeolite-base acid function. The palladium is incorporated in the zeolite
framework by ion exchange. Typical preparation of a Pd/zeolite catalyst is as
follows:
synthesis and modification of the zeolite, extrusion with a binder and cal-
cination;
ion exchange with a palladium salt and calcination.
The catalyst is implemented by hydrogen treatment in order to disperse
the metallic phase in the zeolite framework. This type of catalyst is used when
the objective is to maximize gasoline production. Noble metals allow very high
hydrogenating activity if it is not subjected to high hydrogen sulfide partial
pressure. In addition, these catalysts are unable to promote hydrotreating
reactions (HOS + HDN) and so they must be used in association with a specific
hydrotreating catalyst in two separate steps.
For the other cases an association of mixed sulfides of group VIII and group
VI metals is used. This is very thlo-reslstent. The associations of nickel with
molybdenum or tungsten are the most active for hydrogenation reactions; so
hydrocracking catalysts are formulated from NiMo or NiW phases. The metals
are introduced by co-mixing with the zeolite or the stlic3-aIuminafollowed by
extrusion and calcination. Lastly, sulfiding is n-ecessary to activate the catalyst
whose metallic phase is active in the form of sulfides. The atomic ratio (group
VIII metal/(group VIII metal + group VI metal)) is usually approximately 0.25.
The weight per cent of metals in the catalyst is approximately 10 to 30% (in the
form of oxides).

to.2.5.2 Add Function

The acid function of hydrocracking catalysts is provided by a refractory oxide
of the amorphous or crystallized (zeolite) silica-alumina type. It can also be
supplied by an alumina whose acidity can be enhanced by adding halogenated
compounds, particularly fluorine.The acid strength of each of these systems
varies and can be illustrated by the desorption curve of ammonia adsorbed on
the sites versus temperature (Fig. 10.4). Zeolites provide the greatest acidity in
the hydrocracking temperature range (350-440C). Zeolites, which are more
resistent to poisoning by ammonia because they are more active than amor-
phous silica-alumina. can be used in the one-stage hydrocracking process.
344 C1Iaprer 10, HYDROCRACKIN(>

100 200 300- 400 500 600 700 800

Temperature (0C)

Figure
10.4 Thermodesorption of ammonia on an acid solid.

A Y zeolite is mainly used in catalysts selected for maximum naphtha produc-

tion, which requires considerable acid strength. Its faujasite type structure is
shown in Figure 10.5. The Y zeolite is also Widely used in catalytic cracking. It
is synthesized in the sodium form with the following composition:
Na[(AIOi), (SiOV2.s]H20
The replacement of sodium ions by protons gives it very great acidity. The
coexistence of three properties: tridimensional pore framework with large-size
pores, good acidity and good thermal stability, explains the advantages of this
zeolite as a catalyst base in the hydrocracking process.
The characteristics of a zeolite can be adjusted by modification treatments.
Optimum acid properties can be achieved by ion exchange of initial alkaline
cations and dealuminization. The acid site concentration of a zeolite can there-
fore be adjusted (Fig. 10.6). An increase in the thermal stability of low initial
Si/AI ratio solids is possible by suitable dealuminization of the framework.
During a catalyst's lifetime it will have to withstand high temperatures, partic-
ularly during regeneration, so the thermal stability of a zeolite Is an important
parameter. In addition, dealumtnization creates a secondary pore network.
which promotes the diffusion of reactants and products (Fig. 10.7)
Table 10.6 presents the different hydrocracking catalysts' available accord-
ing to the selected product objective (naphtha, kerosene, diesel oil or lube oil)
and the process type (one or two steps).
 ~ter 10. HyDROCRACK/NG 345

Ternary axis 111

Sadalitecage Supercage(26 laces) Path of a molecule

Structure of Y taujasite.

500< roc <650

~
Sleam

NH,Y (2.5% wt Na20) HY (2.5% wt Na20)

SilAI:. 3. UCS:. 24.65 SUAl :. 5, UCS:. 24.45 24.50

I
L
F~l
U16) Adjusting the acid site conceturation of Q zeolite.
 ModifiedY zeolite

t
Pore
volume
Pore diameter (A) -

5 50 100 500
Pore diameter (A}

Figure
10.7 Porosity of a modified zeolite and of a conventional zeolite.

l I
Hydro- Hydro- Hydro-
'genatlnglgenating genating
Acid Acid Acid 1
Appll- function function function
Process function function function
cation type
type Si0v'AJ1O, Doped
Pd NiMo NiW Y zeolite
amorphous alumina

Max.
naphtha
One
step

Max.
naphth~
Two
steps
I -
Max.
kerosene

Max.
One
step

Two
!
kerosene steps

Max. One
diesel oil step

Max. Two

diesel oil steps

Max.
One

lube
oils
.----
step

'- Tahl~
10.6 Type of catalysts used in hydrocracking.
The size of the dots is proportional to the frequency of use.
'----
10.2.6 Effects of Feed Impurities and Components
Hydrogen sulfide, nitrogen compounds and aromatic molecules are com-
pounds that come into play during the reactions. Their effects on a hydroc-
racking catalyst, whether on the acid or the hydrogenating (unction, must be
taken into account These effects are complex and will be summarized in this
section.

10.2.6.1 Effect of Hydrogen Sulfide

Studies on model molecules (n-heptane) show a negative effect of hydrogen

sulfide. However, in the presence of nitrogen compounds, hydrogen sulfide
partial pressure has no effect on the cracking reaction if it remains limited to
under 5 bar.

10.2.6.2 Effect of Nitrogen Compounds

Two types of molecules should be distinguished: ammonia coming from the

denitrogenation reaction and residual organic nitrogen compounds. The
increase of the ammonia partial pressure results in a decrease in activity
which can be offset by raising the temperature. This effect can be explained by
a drop in acid function strength caused by ammonia adsorption on the acid
sites. The inhibition is reversible, as the adsorption-desorption equilibrium is
rapidly established. This can be observed in an industrial unit when the water
injection pump, located at the reactor exit and designed to eliminate the
ammonia that has been formed, does not work for some time. Under these con-
ditions the ammonia partial pressure rises and conversion declines. When the
pump is started up again, the ammonia accumulated in the recycle gas is ellm-
inated and conversion returns quickly to its former value. .
The concentration of nitrogen compounds remaining after the hydrotreat-
ing step can range from 1 to 100ppm at the cracking catalyst inlet. The nitre.
gen contained in these structures is in the form of heterocyclic nitrogen com-
pounds. With the increase of their concentration at the cracking catalyst inlet,
a decrease in conversion is observed that can be offset by raising the temper-
ature. However, contrary to the effect of ammonia, this effect is only slightly
reversible since desorption is slow for these compounds. .

10.2.6.3 Effect of Aromatics (polynuclear-Aromatics: PNA)

Polyaromatic compounds have substantial inhibiting and poisoning effects. In

once-through operation. PNA present in smaIl amounts in the feed are found in
the residue fraction. In contrast. in liquid recycle operation, the effect of accu-
mulation is very severe. These slightly soluble compounds are readily
deposited on cold spots and cause heat exchanger plugging. During a run it
therefore becomes difficult to keep the HPseparator temperature low enough.
thereby causing a drop in recycle hydrogen purity. which in tum causes a
348 C!W'ter fa HYDROCRACKING

decrease in reactor hydrogen partial pressure. Furthermore, due to their great

stability and adsorption, PNA deactivate the catalyst. In actual practice a
residue bleed of approximately 3 to 10%\\1 of the fresh feed is required to keep
the PNAcontent constant in the residue.

10.3 Process Data

10.3.1 Typical Flow Schemes
Depending on the charactistics of the feed processed, the type of products
desired and catalysts performances, several process flow schemes can be pro-
posed. Whatever the type of process, two sections can always be distin-
guished:. .
-a high pressure section with:
- one or several furnaces designed to heat the feed and the hydrogen,
- one or several reactors,
- a gas-liquid separator,
- a recycle gas compressor;
a low pressure section to fractionate the reaction products.
There are two main flow schemes for the hydrocracking process:
a one stage process working once through or with liquid recycle for total
conversion;
a two stage process with intermediate separation of products.

10.3.1.1 One.Stage Flow Scheme (Fig. 10.8)

The one-stage flow scheme is used to aChiE;:ve partial or complete (recycling
the unconverted fraction) conversion of the feed. In this process configura-
tion, the feed is first hydrotreated, then aJl of the effluents, including gases. are
let in on the hydrocracking catalyst. The catalyst mainly carries out the con-
version reactions and the continuation of the hydrogenation reactions. This
set up therefore includes the hydrotreating and hydrocracking reactions in a
single stage. The hydrocracking catalyst works under high H~ and NH3 partial
pressure. Conversion ranging from 50 to over 90% wt can be achieved with rel-
atively moderate operating conditions on a once-through basis. The residue,
which has been deeply hydrorefined, can be used in a mixture to enhance a
catalytic cracking feed. Unmixed, it can be fed into a steam cracking unit or
serve as a high viscosity index lube oil base stocks. This is the simplest flow
scheme and also corresponds to the lowest investment.
When the flow scheme includes liquid recycle, the feed is totally converted
by recycling the unconverted residue from the bottom of the distillation col-
umn to the cracking reactor. A slight bleed is used on the residue to prevent
heavy polyaromatic compound (PNA) accumulation, as this would be detri-
 ReaClor
Stripper Dlslillatlon Gas 10 amine unit
No.1
LPG

Gasoline
Furnace

Kerosene

~ 0- Diesel oil

~-~Lr .~~,~ ,
J

Feed

-. ~
I
I
Residue

H,O,age. I p
:r
8
I~
Fil:llfC
IO.K I OlJe-swge bydrocracking.
~
CO
350 Ch801er 10. HYDROCRACXING

mental to catalytic activity and cause rapid deactivation (see Section 10.2.6.3).
The common conversion per pass values can vary from 50 to 85%. Compared
to the once-through system, more middle distillates are produced. By adapting
the cut point between the residue and the preceding cut, the yield in a partie-
ular cut can be maximized. giving gasoline, kerosene or gas oil preferentially.
Meanwhile, investments. which are related to the unit's hydraulic capacity
(fresh feed + recycle), are also higher. For large capacities of fresh feed (i.e.
above 2.0-2.3 million t/year approximately), mechanical and hydraulic limits
may make the use of a single reactor train impossible. A two-stage solution will
then be contemplated.

10.3.1.2 Two-Stage Flow Scheme (Fig. 1O.9)

In this configuration, the first stage is operated like the once-through one-stage
set up (see Section 1O.3.1.1).. The unconverted fraction is sent to a second
hydrocracking stage. The hydrocracking catalyst in this second stage works
under very low H~ and NH3 partial pressures and this allows it to work under
much easier conditions. The use of catalysts with a noble metal base hydro-
genating function can therefore be considered. Common conversion values are
50% in the first stage and 50-70% per pass in the second stage with residue
recycle. This set up is the most advantageous approach when the feed con-
tains more than 2 500 ppm of nitrogen. It maximizes the middle distillates
yield, but at the expense of higher investments. However, when the fresh feed
capacity is such that a unit can operate with one single train in the two-stage
scheme, but that two trains are required in the one-stage scheme, then the
two-stage flow scheme becomes particularly attractive.
The flow scheme used in mild hydrocracking is that of a conventional
hydrotreating unit working in a single stage.

10.3.2 Operating Conditions

The main operating conditions of the hydrocracking process are adjusted
depending on the following objectives:
degree of conversion to be achieved;
minimum evolution in selectivity for the desired product;
product quality (aromatics content for middle distillates);
minimum catalyst cycle to be considered.
The following parameters are available for use:
o hydrogen partial pressure;
catalyst temperature;
hourly space velocity of the feed;
~ hydrogen recycle ratio.
 R.aclot R,.clot Reactor
No.1 No.2 No.3
Stripper Distillation Gas to amIne unit

1 LPG

~8J
A
.. Gasoline

.Kerosene
..--.

DleaeloU

Feod .

W f
Hyd,"90~ 8
is
1

Fillurc
10.9 I 7ivo-stage IIyc/rocracking.
I
...en
(,.)
 352 CnSDler 10. HYDF/OCRACKING

"
,. 10.3.2.1 Hydrogen Partial Pressure
The usual hydrogen partial pressure for the hydrocracking process is approx-
imately 100 to 150 bar. The need to work at high pressures is justified by the
thermodynamic constraints of hydrogenating the aromatic molecules present
in heavy feeds before they can be cracked. If the hydrogen partial pressure is
too low, the high nitrogen and polyaromatic compound concentration will
cause the cracking catalyst to be poisoned, and therefore rapidly deactivated.
As a result, it will become impossible to obtain products meeting commercial
quality specifications.
The following example clearly shows the influence of hydrotreating a vac-
uum distillate on the subsequent hydrocracking operation. This effect is illus-
trated when three different feeds are hydrocracked with a commercial hydro-
cracking catalyst (NiMojzeolite) (fable 10.7) at the same total pressure. The
first feed is a straight run vacuum distillate which has undergone no pretreat-
ment. The second one is the unconverted residue from hydrotreating the first
feed at a total pressure of 70 bar and the third has been hydrotreated at twice
this pressure (140 bar). The three feeds have a similar distillation range. but
differ Widely in their sulfur, nitrogen and aromatics concentrations.

feed 1 feed 2 feed 3

Unconverted Unconverted
Origin of Vacuum
fraction fraction i
after after
feed distillate
hydrotreatiDg hydrotreating
at 70 bar at 140 bar

sp.gr. d~5 0.906 0.864 0.844

Sulfur (% wt) 2.43 0.02 0.004
Nitrogen (ppm) 650
.. 10 1 .
Aromatics (X wt) 47 31 9.6
_.-- i
Table
10.7 Characteristics of typical feeds.
'--

The three feeds were hydrocracked at the same total pressure (120 bar).
The sulfur and nitrogen contents were adjusted so that the concentration in
sulfur and nitrogen products was the same for the three tests. The conversion
achieved versus the temperature and the middle distillate selectivity is pre-
sented in Figure 10.10.These results confirm the importance of'feed quality for
conversion during hydrocracking. For 70% conversion, a temperature of 365'C
I' .
is required for the feed hydrotreated at 140 bar, 381C for the feed
 ~ 10. HYOROCRACKlNG 353

hydrotreated at 70 bar and 397Cfor the untreated feed. As for the middle dis-
tillate selectivity, there is no significant effect due to the feed quality. Such a
wide difference in performance can be explained because the higher the nitro-
gen and aromatics compound content, the larger the proportion of zeolitic cat-
alyst acid sites poisoned. The neutralized acid sites must be offset by raising
the temperature significantly: 16 to 32C.

Feed 1 HOT 140 bar

.. Feed 2 HOT 70 bar
Feed 3 no HOT

90 90

"i j
t ~
80
iii ~~
s 80
~o
cl)

~
0
U U

70 70

60 60

50 55 60 65 70 75 80 360 370 380 390 400 410

Middle distillate seie.ctivity Temperature
(%wt) ("C)

~-"l--'- - - - - - - - - - - - - - - - - - - - - - - - - - - - '

:~~i Influence of on initiol hydrotreating stage on onestage hyclrocracking.

~ Hydrocracking conditions: HYC 642 (zeolitic) catalyst; pressure: 120 bar.

The impact of hydrogen partial pressure in the first stage can also be seen
in the quality of the resulting products (Table 10.8). The aromatics level is sig-
nificantly higher in the converted products from the lower pressure
hydrotreating operation and this confirms the importance of this stage for
final hydrocracking performances.
 354 ChaOlef 10. H"DROC~t?!'r.~

Operating coodJtions
I Feed 2*
i Feed 3*
;

Temperature CC) 375 375

Total pressure (bar) 120 120
380C- conversion (% wt) 60 80
Kerosene
Smoke point (mm) 22 35
Monoaromatics ('J& wt) 12.1 3 i
I

Dtarornattcs (% wt) I 0.6 0.2

Triaromatics (% wt) 0 j 0
Gasoil
sp.gr, d~5 0.831 0.825 j

Aniline point CC) 86 95

Monoaromatics (% wt) 11 0.4
Diaromatics (% wt) 1.3 0.3
Triaromatics (% wt) 0.2 0
Residue
Monoaromatics (% wt) 3.8 0.87
Dlarornatlcs ('Jf. wt) 0.5 0.2 I
Trtarornatics (% wt) 0.5 0.2
.. Forfeed characteristics see Table10.6. !

,-""---
Table
10.8 Characteristics of products obtained by hydrocracking.
~

10.3.2.2 -Reaction Temperature

Likehydrotreating units, hydrocracking units are operated at constant perfor-
mance or more exactly at constant conversion. The selected temperature
range depends on catalyst activity. The approximate values are as follows.
expressed in average temperatures at the beginning and end of the run:
DC
Amorphous catalyst: 401J-440
Zeolitlc catalyst for middle distillates: 380-420C
Zeolitic catalyst for naphtha: 36o-390 DC

According to the temperature range, it is difficult to maintain product qual-

ity all throughout the run, as cracking reactions are limited by a rise in tern-
perature which is thermodynamically unfavorable to aromatics hydrogena-
tion. Consequently, the degradation in product quality will be much more
noticeable for an amorphous catalyst than for a zeolitic catalyst. It is also dif
ficult to maintain the target product selectivity, a larger production of gas is
. generally observed.
 0IiPIIlr '0 HYDROCRACXING 355

IOJ.2.3 ~eed Hourly Space Velocity

For this process, the hourly space velocity range is as follows: 0.3-2 rrr- 01
feed/m3 of catalyst per hour depending on the type of feed and catalyst.

10.3.2.4 Hydrogen Recyc:1e Ratio

Hydrogen has several functions, with the main ones bein~:

to maintain enough hydrogen partial pressure to pr"v"nt too rapid coke

deposit on the catalyst;
to control the thermal gradient in the reactor;
to keep the gas and liquid properly distributed in thE: reactor;
to lower the ammonia partial pressure on the hydro~racking catalyst.
As such. the hydrogen recycle ratio has a beneficj;J/ action on catalyst
activity.. In hydrocracking, hydrogen recycle expressed in mJ of hydrogen
per mJ of feed is approximately 800 to 1 800.

10.3.3 Product Yields and Quality

Several cases will be discussed:
maximum naphtha from vacuum distillate;
maximum distillate from vacuum distillate;
maximum distillate along with lube oil production.

10.3.3.1 Maximum Naphtha from Vacuum Disti1lare

Gasoline production can be maximized from vacuum dj:~lillate using a one-
stage total conversion process. The feed characteristics, j'j':lds achieved and
product properties (light gasoline and heavy naphtha) <ire presented in
Table 10.9for a typical case.

10J.3.2 Maximum Middle Distillate from Vacuum Disrillate

In the (ollowing tables we have summarized the main t:':tmical data corre-
sponding to four different cases in order to point out tho:: respective advan-
tages:
Case A: one stage, once through, 90% conversion.
Case B: one stage with liquid recycle for total con':<::";jrm (70% conver-
sion per pass).
Case C: two stages with total conversion. The sele-....: rj conversion per
pass is only 50% at each stage in order to rnaximiz middle distillate
selectivity.
Case D: two stages with 85% overall conversion. ('/.'I<:rsion, which is
50% in the first stage. has been raised to 70% in ~:-.': ;.econd stage to
reduce investment costs for the unit.
356 Ch/Aplef10 HYDROCRACKING

Feed:
sp.gr, d~5 0.927
Sulfur (% wt) 2.42
Nitrogen (ppm) 1300
Viscosity at lOOC(mm 2/s) 8.5
ASTM 2887 distillation COC)
5% 330
50% 449
95% 546
Yields (% wt of feed):
H~+NH3 2.8
Ct -C 4 3.6
CoC ,-
H.S
Light gasoline 24.7
Heavy naphtha 60.9
Total 103.8
Chemical Hz consumption
(% wt of feed) 3.8
Product properties:
Light gasoline
sp.gr. d~5 0.658
ASTM D86 CC)
IBP 33
50% 54
EP 82
- PIN/A (% vol) 86/12/2
RON 84
Heavy naphtha
sp.gr. d~s 0.760
...
ASTM 086 CC)
IBP 94
50% 140
EP 193
P/NjA (% vol) 43/46/11

""-~
RON

Table
61
I
10.9 Hydrocracking of vacuum distillate. Characteristics of feed, yields and product
~
quality.

In all these cases the fresh feed capacity of the unit is 1 500 000 t/year and
the feed is a vacuum distillate from a Middle Eastern crude (Table 10.10).
 ~ TO HyoRfXRA.CKJNG 357

Feed: Vacuum distillate

sp.gr.d'l 0.932
Sulfur (X wt) 2.95
N1trots (ppm) 840
Vlstosity at l00'C (mmZ/s) 11.1
ASnI 02887 distillation ("C)
5% 405
~ 485
95% 565
Operating condltions: Case A CaseB Case C CaseD
Reactor pressure (bar) 155 ISS 155 155
Cataly5t volume (mJ) 360 431) 370 350
Duration of run (year) 3 3 3 3
Recycle compressor
now Ate (m3/h) 280000 ~ 280000 470000 410000
Feed throughput (l/year) 1500000 1500 000 1500000 1500000
Capadly of first stage (tIre-) 1500000 - 1500000 1500000
Capadly of second stage (t/yNr)
DisUllltion capacity (t/year)
-
1500000
-
2150000
1500000
3000000
750000
2250000
Con~ per pass (%)
15t-. 80 70 50 50
2nd stage - - 50 70
Yields (% wt of feed):
H~+~ 3.24 3.24 3.24 3.24
Cl-C~ 0.40 0.-) 0.30 0.25
CJ-C, 3.00 2.50 2.21 1.55
Light psoIine 9.00 8.00 7.50 4.50
Heavy naphtha n.oo 12.00 . 9.50 7.50
Keroseue 38.50 39.00 33.70 30.00
G.lS oil 27.41 34.41 46.05 38.81
Residue 10.00 3.00 0.00 18.50
Total 102.55 102.55 102.50 102.35
Hydrogen aKlSumption
(% WI of feed) 2.55 2.55 2.50 2.35
Product pmpertles:
Ught g;uo(ine
sp.gr.d'f 0.655 0.665
'- -. 0.666 0.670
RON 80 80 80 79
Heavy IUphtha
sp.gr.dl/ 0.743 0.7-15 0.741 0.741
P/Nf,\(% vol) 40.:56/4 40i54/4 39/56/5 38;55/1
Keroseae
Smote point (mm) > 25 > 25 >25 >25
Flash point ('C) > 40 >40 :>4(} >40
sp.gr.fIIl 0.800 a.79B 0.802 0.803
Crystallization point <-60 <-60 <-60 < -60
Gas oil
Pour paint ("C) -12 -12 -12 -12
Cet_number 62 62 59 59
AromaPcs (% wt) < 10 < 10 < 10 < 10
Sulfur (ppm) < 20 < 20 <20 < 20
sp.gr.d't 0.826 0.828 0.837 0.832
Residue (pmge) i

sp.gr: rJ'f 0.830 0.832 -

-
0.835

I
Viscosity at loo'C (mm:/s)
Vl afteF dewaxing
5.0
125-130
5.3
120-125 I -
I
5.5
-
- ---
I
Table!
10.10 Hydrocracking of vacuum distillate (maximum middle distillate operation).
Characteristics of feed. yields and product quality.
 The different operating modes have been compared on the basis of th!-
same fresh feed capacity of 1 500 000 t/year, at the same pressure of 155 bar
and a catalyst cycle of 3 years. The different flow schemes all exhibit high mid-
dle distillate selectivity and low gas yield. Note that middle distillate selectiv-
ity and yield rise gradually from the one-stage-once-through mode to the one-
stage with recycle then to the two-stage mode.
With 85-90% conversion, kerosene + gas oil selectivity reaches 80% wt in
two stages compared to 71%wt in one-stage. once through.
With total conversion. kerosene + gas oil selectivity goes up to 78% \\1 in
two stages compared to 74% wt in one stage with recycle.
Hydrogen consumption remains relatively constant whatever the case con-
sidered:
2.64-2.75% wt <?f the feed with partial conversion; ,
.- 2.83-2.90% wt with total conversion.
The products from a hydrocracklng uni~ are of excellent quality:
The very naphthenic heavy naphtha is an ideal feed for catalytic reform-
ing where it will give high hydrogen yields.
The kerosene is produced at international specifications.
Gas oil properties meet the most severe specifications, in particular
those governing aromatics content (Northern Europe or United States l.
Furthermore, this base with its very low sulfur content and high cetane
number can be mixed with low quality gas oil cuts to make them mar-
ketable.

10.3.3.3 Maximum Distillate Associated with Lube Oil

Production from Deasphalted Oil
Because of the reactions involved, the low viscosity index compounds, Le, pol-
y~romatics and polynaphthenics, ~re turned Into high viscosity index com-
pounds. i.e, mononaphthenes, aIkylated monoaromatics and long-chained
isoparaffins. Hydrocracking also allows production of high viscosity index
lube oil stocks. Their viscosity is low, especially at high conversion, when the
starting point is vacuum distillate. However, heavy bright stock type oils can
be produced by using heavy asphaltene-free feeds -such as propane deas-
phalted oils. In this example, three degrees of severity are presented with con-
version ranging from 41 to 82% wt (fable 10.11). For light gasoline, heavy naph-
tha, kerosene and the gas oil cut, product quality is similar to the qua/il)'
achieved with a vacuum distillate.
Note that even at high conversion it is possible to produce a lube oil base
stock with a high viscosity (Table 10.12). The variation in viscosity index and
in viscosity at lODGe versus the position on the oil is presented in Figure 10.1 J.
Different types of lube oils can be obtained by vacuum distillation of the lube
oil base stock. In the present case, two base stocks were selected (300 N with
a viscosity index between 115 and 122 and a bright stock whose viscosity at
,IOOGe is 32 mm 2js (centlstokes) and viscosity index is 106-109).
360 C/",apter 10. HYOROCRACKING

40
-- --- ....... ......
------~ ..
130

---- ----- .............

-":::.,
120

110
30
100

20 -(

10

V 100eC (mm2s-l ) VI (02270)

of dewaxed residue a L..-..---i-----+-----!------I of dewaxed residue
a 25 50 75 100
Position on total oil (% wt)

Figure
10.11 Variation in VI and viscosity: deasphalted oil (Middle East).

10.3.4 Hydrogen Consumption

Hydrogen consumption is an important factor in hydrocracklng for it is con-
siderable; as a result installing a hydrocracking unit often entails building a
hydrogen production unit. Consumption can vary from 1.5 to 4% wt of the feed
depending on the type of feed, the hydrogen partial pressure in the unit and
the severity of the operation. Consumption can be broken down according to
the main reactions that take place on the catalyst, i.e. hydrodesulfurization.
denitrogenatlon, aromatics hydrogenation and hydrocracking. Table 10.13
gives a typical example of hydrogen consumption distribution in hydrocra!=k.
ing a vacuum distillate in a one-stage, total conversion process with two elit
ferent hydrogen partial pressures. Most of the hydrogen is consumed in aro-
matics hydrogenation and in cracking.
 Case 1 Case 2 Case3

Lube 011 base stock after

residue dewaxJng:
Yield (% wt of the feed) ,45.5 30.8 135
sp.gr. d~S 0.866 0.860 0.855
Viscosity at looC (mm 2/s) 13.8 12.1 11.5
Viscosity Index 112 116 117
Pour point rC) -18 -18 -1&

300 N lube oil by vacuum distillation

of lube oil base stock:
Yield (% wt of the feed) 24.0 18.5 8.8
sp.gr. d~5 0.865 0.860 0.856
Viscosity at looC (mm 2/s) 9.0 8.8 8.5
Vlscositj; index lJ5 120 122
Pour point ee) -18 -18 -18
Noak volatility (% wt) <9 <.9 <9

150BS lube oil by vacuum distillation

of lube oil base stock:
Yield (% wt of the feed) 16.0 92 3.5
sp.gr, d~s 0.878 0.875 0.872
Viscosity at looC (mm 2/s) 32 32 32
Viscosity index 106 .107 109
Pour point CC) -18 -18 -18

-r;:bi~r
110.12/ Production of lube oils from hydrorefined lube oil base stocks.

-
Reaction Hydrotreating j Hydrocracking
Tolal
type
I
I
eatalyst
i
catalyst

Desu_otI 0.27 0 0..27

Hydrogen
Denitmgenation 0.03 0 om
partial pressure: Aromatics
hydrogenationI
l 1.10 0.30 UO
140 bar
Hydrocracking 0.22 0.38 0.60
Total 1.62 0.68 2..30
Desulfurization 0.27 0 021
Denitrogenation 0.03 0 0.D3
Hydrogen
partial pressure: Aromatics I 0.43 0.47 Q.9
hydrogenation;
iO bar
Hydrocracking I 0.25 0.3S 0.6
Total i 0.98 0.82 UJO
,----'
i i
Table I
10.13 I Hydrogen consumption (?~ ur of the feed).
I
360 Cr.aPIBr 10. HYDROCRACKING

40

30
-- --.. ........
-----":::...
---- .
----- .....
~~-
130

120

110

100

20

10

V 100C (mm2s-') VI (D2270)

of dewaxed residue 0 '------f----+---+-----' of dewaxed residue
o 25 50 75 100
Position on total oil (% wt)

Figure
10.11 Variation in V[ and viscosity: deasphalted oil (Middle East).

10.3.4 Hydrogen Consumption

Hydrogen consumption is an important factor in hydrocracking for it is con-
siderable; as a result installing a hydrocracking unit often entails building a
hydrogen production unit. Consumption can vary from 1.5 to 4% wt of the reed
depending on the type of feed, the hydrogen partial pressure in the unit and
the severity of the operation. Consumption can be broken down according 10
the main reactions that take place on the catalyst, i.e, hydrodesulfurization.
denitrogenation, aromatics hydrogenation and hydrocracking. Table 10.13
gives a typical example of hydrogen consumption distribution in hydrocra.!=k-
ing a vacuum distillate in a one-stage, total conversion process with two dif-
ferent hydrogen partial pressures. Most of the hydrogen is consumed in aro-
matics hydrogenation and in cracking.
 Case 1 Case 2 Caa3

Lube oil base stock after

residue dewaxing:
Yield (% wi of the feed) :45.5 30.8 13.5
sp.gr, d~s 0.866 0.860 0.855
Viscosity at lO()~C (mm 2/s) 13.8 12.7 115
Viscosity index 112 116 117
Pour point CC) -18 -18 -18

300 N lube oil by vacuum distillation

of lube oil base stock:
Yield (% wt of the feed) 24.0 18.5 8.8
sp.gr. d~5 0.865 0.860 0.856
Viscosity at lOOC (mm 2js) 9.0 8.8 8.5
Vlscositj; index IJ5 120 122
Pour point CC) -18 -18 -18
Noak volatility (% wt) <9 <.9 <9

150 BS lube oil by vacuum distillation

of lube oil base stock:
Yield (% wt of the feed) 16.0 92 3.5
sp.gr. d~5 0.878 0.875 0.872
Viscosity at l00C (mm 2/s) 32 32 32
Viscosity index 106 107 109
Pour point CC) -18 -18 -18
""'-'-
; Table

E Production of lube oils from hydrorefined lube oil base stocks.

Reaction Hydrotreating Hydroeracking

type catalyst
I catalyst TGIal

Desulfunzanon
Oenitrogenation
II
0.2i
0.03
0
0
0.27
om
Hydrogen
partial pressure: Aromatics 1.10 0.30 1-4:0
hydrogenation
140 bar
Hydrocracking 0.22 0.38 0.60
Total 1.62 0.68 2.30
Desulfurization 0.27 0 021
Denitrogenation 0.03 0 G.03
Hydrogen
partial pressure: Aromatics I 0.43 0.47 D.9
hydrogenation;
iO bar
Hydrocracking ! 0.25
i
O.3S 0.6
Total i 0.98 0.82 1.80
,----r i i I
Table I
10.13 I Hydrogen consumption (?f, u:t of the feed).

--'
364 ~pter 10. HYDROCRACKING

6 Martens l.A., Jacobs P.A. (1990) Evidence for branching of long-char

n-alkanes via prolonated cycloalkanes larger than cyclopropane. 1. Cal
124, 357-366.
7 Olah G.A. (1972) The general concept and structure of carbocalions based
on differentiation of lrivalent (II classical-) carbenium ions from three cen-
ter bound penta- or tetracoordinated (<< nonclasslcal-) carbonium ions.
The role of carbocations in electrophilic reactions. 1 Am. Soc. 94:3.
February 9, 808-820.
8 Vynckier E., Froment G.F. (1991) Modeling of the kinetics of complex pro-
cesses based upon elementary steps. Kinetic and Thermodynamic Lumping
of Multicomponent Mixtures (Astarita G., Sandler S.l. eds.) Elsevier Selene..
Publishers B.V., Amsterdam, 131-161.
9 Weitkamp J. The influence of chain length in hydrocracking and hydroiso-
mertzatlon of n-alkanes. Hydrocracking and hydrotreating (John Ward.
Shai A. Qader eds.) A.CS. Symposium Series 20, 1-27.
10 Weitkamp J. The influence of chain length in hydrocracking and hydraiso-
merization of n-alkanes. Hydrocracking and hydrotreating (John Ward.
Shai A. Qader eds.) A.Cs. Symposium Series 20, 1-27.
11 Martens J.A., Parton R, Uytterhoeven L., Jacobs P.A. (1991) Selective CO[1-
version of decane into branched isomers. A comparison of platinum/ZS:\I
22, platinum/ZSM-5 and platinumjUSY zeolite catalysts. Applied Cataiysi
Elsevier Science Publishers B.V., Amsterdam, 76, 95-116.
12 Froment G.F. (1987) Kinetics of the hydroisomerization and hydrocrackink
of paraffins on a platinum containing bifunctional V-Zeolite. Catalysis
Today 1. Elsevier Science Publishers B.V., Amsterdam, 455-473.
13 Giannetto G.E., Perot G.R., Guisnet M.R. (1986) Hydroisomerization and
hydrocracking of a-alkanes. 1. Ideal hydroisomerization PtHY catalysts.
Ind. Eng. Chern. Prod. Res. DeC). 25, 481-490.
14 Baltanas M.A., Vansina H., Froment G.F. (1983) Hydrolsomerlzatton and
hydrocracking. 5.'Kinetic analysis of rate data for n-octane. Ind. Eng. Prod.
Res. DeC). 22,531-539.
15 Vansina H., Baltanas M.A., Froment G.F. (1983) Hydroisomerization ami
hydrocracking. 4. Product distribution from n-octane and 2.2.1-
trimethylpentane. Ind. Eng. Prod. Res. Dev. 22,526-531.
16 Steijns M., Froment G.F., Uytterhoeven L., Jacobs P.A.. Weitkamp J. (1981)
Hydroisomerization and hydrocracking. 2. Product distributions from
n-decane and n-dodecane. Ind. Eng. Chern. Prod. Res. Dev. 20, 654-660.
17 Steijns M., Froment a.F. (1981) Hydroisomerizatlon and hydrocracking. 3.
Kinetic analysis of rate data for n-decane and n-dodecane. Ind. Eng. Chern.
Prod. Res. Deu. 20, 66Q..668.
18 Luzarraga M.G., Voorhies A. Jr. (1973) Hydroisomerization and hydroc-
racking of cyclohexane in the presence of a palladium-hydrogen-faujasite-
catalyst. Ind. Eng. Chern. Prod. Res. Dev. 12,3,194-198.
19 Rhodes A.K. (1994) World crude capacity, conversion capability inch
upward. Oil Gas 1 93, 5, 45-48. 50-56.
 1

1
~: ~~~<' ~ ~~:: ;~~'~~4:~: ~'~~~~,;~~;~4
of ReSid1;1es
.. . - --t .

Visbreaking 1

~~,.~.,,':lq~' ;, ....: ~&J -,l'4*~.,.~,.>-.;o_...i J

1

Pierre Leprince 1

1
The thermal decomposn iou of hydrocarbons was discovered accidentally in
1861 in a little rettnery In NI~W Jersey when a batch distillation unit was left 1

unattended for a while. The increase ill temperature in the distillation drum was 1
such that the heavy n~l>ilhlt' broke down into a light gasoline fraction. Later on
arnund 1910 hatch thermal n;wking processes were d~veloped. They work~d 1
at around 401fT under a pressure 01 ;j to 7 bar in 48-hour runs. In 1925 conttn-
uous processes worldn}t at \ill In 5~);''C carne into being. They were designed 1

to boost the distillate yh'l<l (gasnlinl~. lamp oil and diesel oil) on the crude. 1
Today catalytic cra('kil\~ .ulll hydrocracklng processes have replace.d .the
equivalent thermal processes. However, these operations are still use? In t~e 1
Iorm 01 mild cracking 10 I\p~radc rt~sitlul~:;. The aim is to lower the VISCOSity
of heavy residues to ll1akl~ them usable as heavy' fuel oils (see Vol. ~, 1

Se~..tion 10.3.2) complylll~ with connnercial specifications. The process IS 1

termed visbreaklng audit I~ applicdl 0:
almosplwrit' rcsidw':., I" }~\'lllla:\IIlHllll ;.:asotine and diesel oUwhile com-
1

plying willi r(':~i(IIl.11 "1IIIIH sl.thility and viscosity specifications; 1

vacuum residues, to reduce Viscosity to a level such that they can be used
as industrial Iuel oils. sumetlmes afh~r adding a light diluent (gas oil). .. 1

1
1\ .\ Background Information
1
\ t.i.t Feed Composition
1
Itt-simplified terms, it rl~~hl\le Is a colh)ldal system composed of a dispersed
phase: micelles COlllilillll1lo{ lwavy aromatl malthenes and asphaltenes. and a 1
continuous phase: tlw olhN 11l;\ltlwn(~s. Asphaltenes are comple.x molecules
with a molecular wc~l~ht o!lIvl'r \ nOll :lwl il dominant aromatic feature, con- 1

I
366 Cra:::~' 1~. VSSRCAKING 0" RESIDUES

tainlng allphatlc chains, heteroatoms (5, N, 0) and heavy metals (Ni. \".
Malthenes have a lower molecular weight than asphaltenes, They consist 0;
paraffinic, naphthenic and aromatic molecules and also contain heteroatoms
and heavy metals. but to a Jesser extent than asphaltenes.

11.1.2 Cracking Reactions

In vis breaking, the malthene phase is cracked into smaller molecules while the
amount of asphaltenes increases by aromatic condensation and cyclization.
The cracking reactions and their mechanism are well understood for light
hydrocarbons and petroleum distillates (stearn cracking process to product'
ethylene, propylene, butadiene, benzene. etc.). The effect of temperature on
the components of heavy fuel oils is less well understood. but the Iollowin;
reactions can be identified:
Splitting of a C...:....C.bond in aliphatic chains in paraffins (formation of
olefins}and in alkylarornatlcs (dealkylation). This is the primary reaction.
Oligomerization and cyclization to naphthenes of the olefinic compounds
resulting from the primary reaction.
Condensation of the cyclic molecules to polyaromatics.
Added to these are reactions Involving the asphaltene heteroatoms (sulfur
and oxygen):
formation of HzS, thiophenes, mercaptans;
formation of phenol.

11.1.3 Reaction Kinetics and Mechanism

Most of the products obtained are the result of chain reactions by radicals.
From a kinetic standpoint, the reaction rate can be represented by a 1st order
expression:
v= dx = k (1-'~) exp (_~) or kit = In _1_
& RT I-x
where x is the weight fraction of the converted feed.
The activation energy (E) varies according to the nature and composition
of the feed (fable 11.1).
Asphaltene and coke formation reactions have an activation energy of 250
to 380 kl/mol, They become significant with the reaction temperature rises.

11.2 Process Data

11.2.1 Operating Variables
In.an industrial unit several operating variables can be used to modify or
adjust the performance.


Feed E(kJ/moI)

Long residue 315

Short residue 230
Deasphalted residue 150
..... ..-----
Table
11.1 Visbreaking activationenergy.
'---

11.2.1.1 Furnace Exit Temperature

This temperature is taken as a criterion even though the reactions occur in an
increasing temperature range in the furnace tubes. It is between 430 and 490C
depending on the feed processed and the type of unit, since the unit can in fact
include a soaking drum where the reaction continues after the furnace. The
furnace exit temperature is chosen depending on the desired conversion: an
increase of 6 to 7Ccauses conversion to rise by 1%. However,conversion has
an upper limit dictated by precipitation of asphaltenes in the visbroken
residue.

11.2.1.2 Feed now Rate

By increasing feed flow rate. residence time is shortened. but at the same time
the flow conditions in the furnace tubes and in the soaking drum are modified.
A 3e rise in the furnace exit temperature is enough to offset a 10% increase in
the feed flow rate with the same conversion.

11.2.1.3 Pressure
In units without a soaking drum, a pressure of a few bar is enough to keep the
feed from,vaporizing. In units with a soaking drum. the pressure is chosen so
that the desired products are vaporized and quickly leave the "reactionzone,
while the heavy products soak in the liquid phase. Five to eight bars is used
for short residues and 10 to 12 bar for long residues.

11.2.1.4 Product Recycle

This method is not used in visbreaking, because the very heavy products to be
recycled tend to form coke. thereby disturbing furnace operation.

11.2.1.5 Steam Injection in the Furnace Tubes

Steam is injected to improve heat transfer in the furnace tubes. It brings about
a drop in conversion which must be offset by raising the temperature.
368 Chapl t t. V/SBREAKING OF RESIDUES

11.2.2 Product Properties and Yields

Four products result from the visbreaking process: a gaseous fraction (eil. a
gasoline (Cs-165C), a gas oil (165-350C) and a residue (3S0C+). The yields
and properties of these products depend on the type of feed (Table 11.2) and
on the conversion achieved by an appropriate choice of operating conditions
(fable 11.3).

One stage without Two stages* with

Type of operation
~
recycle or soaking I
I
recycle without soaking
'"
Type of feed # Short residue Long residue
sp.gr, d~5 1.010 0.978 I
Vso
Yields (% wt):
42.0 34.6
I
C1-C4 1.9 3.6 I
i
I
Gasoline C5-165'C 4.1 7.8 1
Gas oil 165-350C 11.7 25.8
Residue 350'C+ 82.3 62.8
Conversion (%) 6.0 11.4
l

-~
.. Visbreaking and thermal cracking of vacuum distillate.

Table
I
11.2 Typical yields.
'----

Products Yield/conversion

c-.. 0.32
Gasoline 0.68
Gas oil 2.30
H~ 0.01 of feed sulfur %.. I
.. Mean value that depends on the type of su((ur In the feed.
..... ...----
Table
J
11.3 Yields versus conversion.
'---
11.2.2.1 ConTC1'Sion
Conversion is defined. by the sum of gases (H2S, C4) and gasoline produced,
divided by the inlet feed of the unit. The value is set by taking three parame-
ters into account:
feed type and properties;
unit characteristics (furnace with or without soaking drum);
desired products.
These parameters are not independent. The unit must be operated for a
given feed so that the products are obtained in optimum conditions (little coke
[ormation in the furnace, minimum duration of maintenance shutdowns, sta-
bility of thevisbroken residue, etc.). In actual practice in vfsbreaking units, the
conversion that depends on feed origin (fable 11.4) varies between 6 and 7%.
When the objective is to maximize gas oil production, it can vary from 10
to 12%.

I
Usual conversion (% wt)
Type of crude
versus feed
!
Arabian heavy 6.0
[ran heavy . '6.5
Kuwait 7.0
Nigeria 7.0
Brent 7.0
Sarin (paraffinic) 4.0
Souedieh (asphaltenic) 5.5
- i Table I
i 11.4 i Usual conversion in ui:sbn!aking.

11.2.2.2 Product Quality

The gaseous fraction (C4> contains inert gases (CO, C010 NV. the H~ from
feed transformation and C1 to C4 hydrocarbons (fable 11.5). The sulfur con-
tent is from 2 to 5 times that of the feed. The HzS must be eliminated by amine
treatment (Chapter 17) before the fraction is used in the form of LPGor as fuel
gas. The hydrocarbon fraction contains equal parts of unsaturated com-
pounds (ethylene. propylene. butenes) and their saturated hornologues.
The gasoline (Cr 165:C) is a low quality motor fuel: low octane number, high
olefin content (.... 45%), high suJfur content (0.2 to 0.5% wt of feed sulfur), and
presence of nitrogen compounds. It also contains diolefins (maleic anhydride
370 Chapter II. VISSREAKING OF RESiDUES

Conversion (% wt of the feed)

, 7.0 7.0 12
i

Feed:
sp.gr, d~5 1.014 0.986 0.966
Conradson carbon 16 14 12
Sulfur (% wt) 4.0 3.0 3.0
Vso 42.0 34.6 - !
,
Gas composition (% wt):
CI-C4 I - - -
H2 I 0.3 - -
C1
I
16.5 - -
C2 28.5 - -
C3 27.5 - -
. C. .. 27.2 - -
Product properties: -.
Gasoline (Cs-16SC)
sp.gr. d~s 0.748 0.743 0.745
RON- 62 60 62
MON 59 58 60
Sulfur (% wt) l.0 0.8 0.8
Gas oil (165-350C)
sp.gr, d~s 0.960 ,0.930 0.910
Residue (350C+)
sp.gr, d~s 1.05 1.02 1.01
Conradson carbon 20 19 21 1
I
I
Sulfur (% wt) 4.2 3.1 3.1
i
Vso 40.5 39.7 - j
.... r - -
Table
11.5 Product characteristics.
'---

index w 10). It needs to be hydrotreated before the fraction can be used as

feed for catalytic reforming.
The gas oil (l65-350C) has a low cetane number (~ 50) and contains up to
2 to 3% wt sulfur (0.4 to 0.8 times the content in the feed). Its ASTM color
varies rapidly with air oxidation. It has a high olefin content (bromine number
close to 25). It can be used as a diluent to lower heavy fuel oil viscosity when
its sulfur content is not too high. Otherwise it has to be routed to the
hydrotreating unit which improves its cetane number. stability and color. It
can then be used as a component of the gas oil pool.
The residue (350C+) is an improved viscosity fuel oil in comparison with the
feed. However, a certain amount of fluxing gas oil needs to be added if it is to
 CItapW I t. VISBR~ OF RESIDUES 371

meet commercial standards. Since it is necessary to know the mixing law

between the fuel oil.and the fluxing agent. a mixing index V has been defined
with the following formula:

V, =A(t) + 33,5 "log log (y, + 0\85)

where:
t is the measurement temperature
A Is a constant that depends on the temperature (A so = 19.2;A 100 = 26.4)
y, is the viscosity at temperature t (rnml-s)
The factor V, is additive in weight and is used to calculate the viscosity of
. the "fueloil-gas ollmixture. This gives the amount of fluxing gas oil required to
get a fuel oil complying wTth commercial specifications. The main quality of
this type of fuel oil must be its stability, because the asphaltenes it contains
remain in suspension. The fluxing gas oil must therefore have a high aromat-
ics content (LCD, aromatics extracts), since aromatics have a strong asphal-
tene dispersing capacity. Its sulfur content is similar to that of the feed, how-
ever.

11.3 Implementing the Visbreaking Process

11.3.1 Process now Schem.es
After preheating, the feed is raised to cracking temperature in a pipe still. At
the exit of the pipe still the reactions are interrupted by injection of a cold gas
oil or residue quench. The hydrocarbon mixture passes through a cyclone sep-
arator and then undergoes fractionation into C.i, gasoline and gas oil (part of
which is used for quenching) and residue (Fig. n.l).)n some cases" the pipe
still effluent is sent to a soaking drum that lengthens reaction time (Fig. 11.2)
and allows the pipe still to operate at a temperature approximately 30C lower.
Lastly, if the aim is to produce maximum gas oil, visbreaking can be com-
bined with a thermal cracking unit using the heavy distillate from the frac-
tionation tower as a feed (Fig. 11.3).
Figure 11.4 shows the flow scheme of a visbreaking unit with the pipe stilI
and its soaking drum. The effluent is then sent to an atmospheric distillation
column which provides a gaseous fraction (H2' Ct. Cz), an LPG cut. a naphtha
that is subsequently fractionated into light gasoline and heavy naphtha, a gas
oil and an atmospheric distillate. The residue is routed to a vacuum column
which supplies a distiUate and a visbroken residue. The distillate, mixed with
the atmospheric distillate. is sent to catalytic cracking, while the vis broken
residue is mixed with gas oil which acts as a fluxing agent to adjust its viscos-
ity. The flow scheme of the unit. typical with 135 tjh of feed. shows the yields
in various products and the most common operating conditions (temperature
and pressure) for the furnace, the soaking drum and the atmospheric distilla-
tion.
 372 Chapter 11. V;S3REAKING OF RS:::_=$

Fl3diooation

Cyclone , - - - - - Gas
separator + gasoline

Gas oil
{16S-350'Cj

} Residue
'-----..,-------
Figure
11.1 Simplified flow diagram of a visbreaking unit.

Soaking
reactor Fractionation
c;
Gasoline

Gas oil

Feed Preheating Fumace

L..- _ .} Residue

Simplified flow diagram of a visbreaking unit with $OOking drum.

 Chapter 11. V'SBREAK/NG OF RESIDUES 373

Fractionation Cracking
fumace

~--- C; gasoline

Cyclone 1 - - - _ Gas oil

separator
Preheating VlSbreaking
pipestiU

1-- } Residue

; Figure
11.3 Row scheme showing combined uisbreaking and thermal cracking.

11.3.2 Specific Equipment

11.3.2.1 Furnace
The function of the furnace is to raise the feed to the reaction tern perature and
keep it there long enough to accomplish the desired conversion (Fig. 11.5).
Different types of furnaces can be used:
where heat is transferred:
- by convection alone,
- or by radiation alone,
- or by a combination of both;
some may have several in-series radiation cells,
may include vertical or horizontal tubes,
and may be fired by gas or fuel oil.
However. they must meet certain requirements in order to function
properly:
The average heat flow must be 22 to 30 kWjm2, and in no case should the
heat flow exceed 60 to 70 kW/m~ locally. Above this, coke deposit would
 w
j;;!
o Pressure (bar)
LPG
Gas

~
o Temperature (0C) b
~
<=) Flow rates (Vh)
Light
gasoline
i
~
Heavy
naphtha
'"~
~
ITl
~
Gas oil to m
desullurizalion

Atmospheric
column
Vacuum Dislillnto
column to FCC

Atmospheric
residue
395 Fluxed vlsbroken
vacuum residue
(refinery fuel)
 a..",., tt. VlsBREAKm OF RESIDUES 375

Feed Steam

Fractionation
or soaking
"------, drum

Radiant
zone

Stack
250C

./ / ,1"

F~!
11.5 ' Figure] ].5 Typical cisbreaking conditions:
_'__i - Furnace inlet: 305-325T (15 to 40 bar).
- Furnace ail: without soaking: 480-500C (2 to 10 bar)
with soaking: 440-460C (S to IS bar).

accelerate and become detrimental to proper furnace operation

(mcreased pressure drop I, increased tube skin temperature l).
The tubes must be able to resist 650C. Steel alloys (9 Cr-O.5 Mo) are gen-
erally selected.

1. For a tube 100 mm in diameter, a 3 mm layer of coke increases the pressure drop
by 35~.
2. I nun of coke increases the skin temperature by 20 to -I0'c.
376 Chapter 11 VIS3F1EAKING OF R:slous

The steam or condensate injection devices must be installed in the zone

where hydrocarbon vaporization is slight in order to increase the turbu-
lence of the flow. thereby reducing coke deposits. Steam injection ratios
of some 0.5% of the feed are common.
Decoking equipment is indispensable. It has an injection device for an
air/steam mixture that allows furnaces to be decoked at around 550'C.

11.3.2.2 Soaking Dl"Um

Located just downstream from the furnace. this drum is designed to lengthen
the feed residence time so that' the furnace can operate at a lower temperature
(Table 11.6). Approximately 40 to 60% of the cracking occurs in the drum.
Since these reactions are endothermic, the exit temperature is lower by 10 to
ZOC than the inlet temperature.

Furnace exit
temperature eC)
Residence time
(min)
1
!

410 32 With soaking

440 g With soaking
455 4 With soaking
470 2 Without soaking
500 0.5 Without soaking I

-~ I
Table
11.6 Temperature-residence time relationship for a conversion of 6% (weight).
'---

The soaking drum is a reactor with flow from bottom to top, a volume of
around 15 mJ/l OOOt/day of feed and a height-to-diameter ratio of 5 to 8. These
dimensions correspond to a residence time of 15 to 20 min. The soaking reac-
tor provides the following advantages:
A 15% reduction in fuel oil consumption, due to the furnace exit temper-
ature which is lower by 20 to 3O"C.
Longer running time between two decoking operations, because the coke
deposit rate in the furnace is three to four times slower than in conven-
tional units.
Better selectivity due to the difference in activation energy between the
production of light molecules (250 kJ/mol) and of heavier molecules
(230 klIma!). As a result, gas oil components contribute less to gas and
gasoline production with a soaking drum and the conversion of heavy
.fractions is higher.
 ~ ft. V/SBREAKIl'G OF RESIOUES 3n

A reduction in furnace and heat exchanger costs - despite the cost of

the chamber itself, overall investments are 10 to 15% lower.
A recent development in soaking drums is to equip them with perforated
trays. The trays are designed to even out the residence times of the different
portions of the feed, thereby favoring high conversions.

11.3.2.3 Cyclone Separators

The function of this equipment is to separate the reaction products into a
gaseous and a liquid phase without lowering the temperature. The flash
occurs in the upper part of the separator, whose tangential inle,tprovides good
gas/liquid separation. The liquid trickles down the walls' and comes together
in the lower part. Some of the liquid is cooled by exchange with the unit's feed
and used as a quench in the lower compartment (Fig. 11.6).

Reaction
products

Fractiona1ing
col..m
Coke
trap -==~;:::f:::LII . .

Gas oil
:-. - Quench ----11---'

Stripping
steam:..-.--.............

Residue

Coke trap

Figure.
11.6 Diagram of a cyclone separator.
378 C/latlt6r r 1 VIS8REAI<ING OF RESJ!)UE.S

11.3.2.4 Heat Exchangers

The thermal cracking residue has a strong tendency to foul the heatexchang-
ers in which it circulates. Heat exchangers therefore need to be equipped with
by-passes so that they can be cleaned without shutting. down the unit.
Additionally, pieces of coke that might plug exchanger tubes must be retrieved
by coke traps and filters incorporated at the pump inlet.

11.3.2.5 Coke Traps and Filters

Coke traps are installed at the bottom of vessels operating at high tempera-
ture. They hold back pieces of coke larger than a few centimeters. Filters are
of the basket type installed upstream from the pumps and can be cleaned \\;t11-
out stopping operation.

113.3 Environment

Process water from the top of the fractionating column contains H2S, mercap-
tans. phenols and thiophenols. organic acids and hydrocarbons. It must be
stripped to eliminate the H~. The phenols remaining in solution are eliminated
by biological treatment, During decoking operations, the furnace effluent ls
cooled and water is added to it to collect the fine particles of coke that it WH
tains. The water recovered from the furnace must be filtered. settled am!
treated.
The coke recovered (several tons) during maintenance shutdowns is a dry
product that is incinerated.

1104 Efonomics
The bask thermal cracking patents are public property. The enhanced process
patents and know-how are held mainly by Shell. IF?, KeUog, Lummus. UOP and
Forster Wheeler,
The battery limits investments indicated in Table 11.7 include the furnace
section, the soaking drum and the fractionation section. They do not include
water or coke treatment units.
Energy consumption is approximately 1.5 to 2% of the feed for a visbreak-
Ing unit without soaking. When soaking is included in the process, energycon-
sumption is lower by 10%. When residue visbreaking is followed by crackingof
the distillate, energy consumption reaches 2.5 to 5%of the feed depending on
the degree of thermal recovery,
Table 11.8gives the distribution by geographical zone of world visbreClkio~
capacity, which amounts to 154.7 Mt/year. Note that nearly 44%of this capaC-
ity is installed in non-OECD Europe.
 C/IapW '1. VrSSREAKING OF ResiDuEs 379

Capacity (Mt/year) 1.3

Battery limits investments (106 :~) 29
Utilities (per ton of feed):
Fuel oil (10 6 k.J) 0.42-0.50
Electricity (kW) 3.1
Steam produced (t) O.l1~.I4
Cooling water (m:!) 0-0..6

~ Economic data.
L

Africa 5.1
Asia 17.1
CIS 7.1
Australasia 2.6
OECDEurope 67.8
Non-OECD Europe 6.6
Middle East 15.9
North America 8.0
South America 23.9
Total 154.7
I
.....,;-
j Table

E World uisbreaking capacity (1996) (M! of teed/year).

References
1 Schuster R. (1995) La tiuista di combustibli 49, 2, 45.
2 Castellanos J., Cano J.L.. Briones V.M., Del Rosa! R. (1992) Retiista del
lnstituto Mexicano del Petroleo XXIV, 3, 68.
3 Haples R. Petroleum refinery process economics. Penwell Books. Penwell
Publishing Co., Tulsa.
 Roger Swindell

The thermal conversion of heavy oil fractions has been developed using two
different technologies:
The first. delayed coking, consists in the thermal decomposition of hydro--
carbons in an empty drum where the coke produced in the reaction is
deposited. At the same time. the light hydrocarbons exit the drum and
are routed to a treatment plant. The process is today considered open art.
several companies (Foster Wheeler, Conoco and Lummus in particular)
have the know-how required to build and operate this type of process.
In the second. the hydrocarbons are decomposed in a fluidized bed of
coke particles. part of which is withdrawn continuously. The most recent
version of this type of process. called Flexicoking, was developed by
Exxon Research and Engineering Co. - ..

12.1 Delayed Coking

Delayed coking is the most widely used technology in the refining industry. In
the United States where it is very widespread. the main objective is to convert
heavy residues into light products. with the coke being used as fuel.In Europe
and in the CIS member countries, the objective is to produce a specific grade
of coke used to manufacture anodes for the aluminum industry. Delayed cok-
ing is a highly flexible process that can be adapted to a variety of feed types
and produce different grades of coke depending on market needs...

12.1.1 Feed Types

Delayed coking units generally process heavy residues such as:
vacuum residue.
catalytic cracking decant oil or slurry.
382 ~ 12. COKING

visbreaker residue or thermal cracking tar.

asphalt or lube oil extracts.
Product yields and quality depend on four characteristics: the carbon
residue. the sulfur content, the metals content and the TBP cut point.

12.1.1.1 Carbon Residue

There are two methods of determining this characteristic: the Conradson and
the Ramsbottom methods. The Conradson method is more frequently used. so
reference will always be made here to this value. l.e. the CCR (see Vol. 1.
Section 5.1.7.2.d). The higher the CCR, the higher the coke yield at given oper-
ating conditions. Since the usual objective is to maximize the distillate yield,
l.e. to minimize coke production. the higher the CCR, the more difficult it is to
reach this objective. In thepast CCR values were normally lower than 10%
weight in the atmospheric residues used as feed. Today, however, with the use
of heavier residues frequently from heavier crudes. CCR values often in excess
of 20 or even 30% weight can be found.:

12.1.1.2 Sulfur Content

The sulfur in the residue tends to become concentrated in the coke and in the
heavy distillate. In the same way as for the CCR, the changes in type and ori-
gin of feeds have resulted in an increase in their sulfur content. Consequently,
the sulfur content in coke is tending to increase.

12.1.1.3 Metals Content

Metals, mainly nickel and vanadium, also tend to be higher in feeds and wind
up almost exclusively in the coke. A metals content of over 1 000 ppm weight
is frequent in coking unit feeds.

12.1.1.4 TBP Cut Point

The TBP cut point for a typical vacuum residue is approximately 550C, but it
can vary depending on the origin of the crude and the operation of the refin-
ery vacuum distillation unit. The TBPcut point is related to the CCR, to the sul-
fur and to the metals content. As such, it influences coking product yields and
quality.

11.1.2 Background Information

12.1.2.1 Chemical Reactions
The exact mechanism of coking reactions is relatively complex and this makes
it rather difficult to give a precise description of the reactions and changes tak-
ing place in the reactor. Two principal mechanisms can be identified which
coexist for most of the feeds processed and there are three separate and suc-
cessive stages in the reactions that occur.
The first mechanism involves dealkylation-precipitatlon reactions of high
molecular weight asphaltenes and resins. The second mechanism consists of
polyaromatic condensation reactions. The three identifiable stages in the pro-
cess are:
1. Partial vaporization and preliminary cracking while the temperature is
rising through the furnace to reactor temperature.
2. Cracking of the vapor phase as it passes through the coke drum.
3. Successive cracking and polymerization of the liquid phase retained in
the reactor until it is converted into coke-
These reactions are all endothermic ~nd cause a drop in temperatureof
around sooe in the reactor (coke drum).

12.1.2.2 Operating Conditions

Three operating variables determine product yields and quality: the tempera-
ture, pressure and recycle ratio of the heavy fraction in the reactor effluent.

a. Temperature
The coking temperature (48~50Soe furnace outlet temperature) has a direct
impact on the volatile combustible matter (VCM) of the coke produced. At
higher temperatures, a larger proportion of the feed is vaporized at the reac-
tor inlet. thereby causing less coke to be formed. It can therefore be stated that
the coke yield decreases as temperature increases,.at constant recycle ratio
and pressure. However, at overly high temperatures, the coke produced will be
very hard and difficult to remove by hydraulic cutting systems. At too Iowa
temperature, soft coke with a high VCM is produced.

b. Pressure
Atconstant temperature and recycle ratio, an increase in pressure keeps more
of the hydrocarbons in the liquid phase in the coke drum, thereby increasing
the coke and gas yields. When the main aim of the coking unit is to improve
refinery conversion, the coke yield must be kept to a minimum and the distil-
late yield maximized. In this case, the lowest possible operating pressures
must obviously be sought. The effect of pressure on yields is shown in
Table 12.1 for two different operating pressures.

c. Recycle Ratio
The recycle ratio has the same effect as pressure on product distribution: the
higher the ratio, the higher the coke and gas yields. The recycle ratio controls
the end point of the heavy distillate. The higher the ratio, the more heavy
product there is recycled to the coking reactor where it is converted into coke
and gases. When the aim is to maxtmtze the liquid product yield, the recycle
 384 ChlDrM 12. COKING

Coking pressure (bar) I 1.0 3.0

I I
Gases + C4 (% wt) 9.1 9,9
Cs-19S"C naphtha (% wt) 12.5 lS.0
195"C''' distillate (% wt) 51.2 44.9
Coke (% wt) 27.2 30.2
:.--
Table
12.1 Yields at constant recycle ratio.

ratio is lowered, the same as for pressure. This type of operation is the most
common today, to such an extent that there are units working with a recycle
ratio in the neighborhood of
5% and units are even being contemplated with
no recycle at all. However, the heavy distillate quality is inversely proportional
to its yield as shown in Table 12.2.

Pressure (bar) 1.1 1.0

"I
Recycle ratio (%) i 15 5
Yield (% wt) 25,7 35.2
Distillate properties:
sp.gr, d~o 0.936 0.957
CCR(%wt) 0.35 0.8
,--"'-----
Table
12.2 Heavy distillate yield and quality.
'---

12.13 Products
12.1.3.1 Gas
The gas produced Includesfuel gas used in the coking unit or sent to the refin-
ery fuel gas network after desulfurization by amine washing. Another fraction
made up of C3-C. can, after desulfurization (amine washing and Merox mer-
. captan elimination), be used as feed for an alkylation or polymerization unit
due to its highly olefinic nature (Chapter 7).

12.1.3.2 Naphtha
AIter chemical elimination of mercaptans or hydrotreating. the light naphtha
is sent to the gasoline pool. After hydrotreating, the heavy naphtha becomes
 ChaDw12. COK1NG 385

a catalytic reforming feed or is routed directly to the gasoline pool to take

advantage of its high olefin content.

12.1.3.3 Distillates
The light distillate (light coker gas oil) requires hydrotreating in order to sta-
bilize its color before it is sent to the refinery gas oil pool. The heavy distillate
(heavy coker gas oil) is often used as feed for the FCC, mixed with straight-run
vacuum distillate. It can also be sent as feed to a hydrocracker to boost the
gasoline, kerosene and gas oil yield from crude.

12.1.3.4 Coke
Several types of coke can be produced.
a. Coke for Anodes
This coke is called sponge coke because of its characteristic spongy appear-
ance. However, not all cokes of this type are necessarily of anode grade. To
meet the specifications governing anode coke, the metals content must be low
(lower than 200 to 250 ppm weight), and the same is true for the sulfur content
(generally less than 2 to 2.5% weight). These two characteristics are directly
related to the quality of the feed. and so the original crudes must be low in sul-
fur and metals. However, this type of feed is often paraffinic and tends to pro-
duce low-density coke.
Anode grade coke must be calcined before being used. This often takes
place in the refinery. A short discussion of calcination is found in
Section 12.1.6. The most important characteristic of this type of coke is its den--
sity after calcination, measured by the VBD (vibrated bulk density). Green
coke, l.e. before calcination, is characterized bv its VCM and its hardness.
These two properties have a direct influence o~ the VBD of calcined coke.
Hardness is normally expressed by the HGI coefficient (Hardgrove grindability
index). Typical characteristics of an anode coke are given in Table 12.3.

Green coke Calcined coke

I
VCM (% wt (dry)) 8-10 0.3
Sulfur (% wt) < 2.5- < 2.5
Ash (% wt) <0.2 <0.2
Ni + V (ppm) < 200 <200
HGI 80
VBD (kgfm3.) > 780
Real density (g,Icm3) > 2.06
Table,
12.3 T.vpical specifications for anode gradecoke.
386 cn.prer12. COK'NG

The choice of feed for a unit designed to produce anode coke is crucial,
since the properties of the feed determine the characteristics of the coke pro-
duced. Feeds are usually residues from atmospheric or vacuum distillation, or
the heavy distillate from an FCC (decant oil). An anode coke unit is character-
ized as a rule by recycle ratios of over 35% and operating pressures of 2 to
4 bar, required in particular to obtain the desired density. Higher temperatures
also improve the HGI and VCM. and yield calcined coke with a better VBOo

b. Needle Coke
Needle coke is of a higher quality, produced by coking special aromatic tars
such as decant oil from FCC, thermal cracking tar, steam cracking residue and
coal tar. Needle coke is used to manufacture graphite electrodes for electric
arc steel mills. It must undergo calcination and other treatment before it
attains its final characteristics. .
Its crystalline structure is ln the form of small needles that give it not only
its name but also its electric conductivity. High density and a particle size dis-
tribution exhibiting low fines content, as well as a low coefficient of thermal
expansion (CTE), are important properties in obtaining a high quality calcined
coke. Typical specifications for this type of coke are given in Table 12.4

Green coke Calcined coke

VCM (% wt (dry)) 5-7

Sulfur (% wt) <0.5 < 0.5
Ash (% wt) < 0.1 < 0.1
Real density (g/cm:l) - 2.10-2.14
CTE (lO-7rC) - 2.5
Resistivity (ohm-em x 10-6) - 125

-~
Particle size 1mm (% max)
. 25

12.4 Typical specifications of needle coke.

-

Feed for a needle coke unit must have a low sulfur and ash content. The
maximum values generallyaUowable are 0.5% weight and 0.1% weight respec-
tively. Since the tars that serve as feed for this type of unit are often derived
from distillates, these maximum values do not cause any major difficulties.
They do seriously limit the choice of potential feeds, however. Feeds must
have a high aromatics content which is where the coke obtains its crystalline
structure.
Operating conditions for needle coke units include pressures of over" bar
and recycle ratios of between 60 and 100% in order to maximize the yield of
this high value product. High temperatures are also used to reduce the VCM
 ChiIpW 12. COKING 367

In
and the HGI. Because of the difference operating conditions, needle coke
units differ from ~e coke units. Higher temperatures and pressures yield
harder coke and lower fines production.
c. Fuel Coke
Heating coke is by far the most commonly produced grade of coke worldwide.
It is only a by-product of delayed coking operations. used as a tool for con-
verting heavy residues into distillates. This type of unit is designed to provide
operational f1exibiUty in order to process a wide range of residues. The empha-
sis is on processing increasingly heavy residues. longer operating lifetimes
and totally safe, economical operation with due regard for environmental reg-
ulations.
This grade of coke generally" has a high sulfur and '~etals content"
(Table 12.5).PhysicaDy, it looks like something between sponge coke and shot
coke. Shot coke consists of ball bearing-like spheres of coke ranging from 0.5
to 1.5em in diameter:. The spheres do not exist in a free state in the coke bed,
but are bound in an amorphous mass. Shot coke usually has a low HGI and
high sulfur, and is most generally used as fuel in cement kilns and thermal
power plants.
Fuel coke units are characterized by very low operating pressure and recy-
cle ratio. They often have numerous large coke drums up to 8.5 meters in
diameter.

12.1.4 Typical Product Yields and Characteristics [1. 4J

Table 12.6 shows typical yields from various feeds (crude distillation
residues). with specific gravities of 0.950 to 1.050and CCRs of 5 to 22%wt. All
yields listed correspond to identical recycle ratios.and operating pressures.

12.1.5 Description of the Delayed Coking Process [5]

12.1.5.1 Coking and Product Separation Section
This section comprises three main parts:
The furnace: preheats the feed and the recycle to reaction temperature
and provides the heat of reaction for the endothermic reactions of ther-
mal cracking.
The coke drums: normally installed in pairs, where the cracking reactions
occur and the coke produced accumulates.
The fractionating column: separates the cokingproducts exittng the cok-
ing drum in the vapor phase.
A simplified diagram of a typical unit is shown in Figure 12.1. The heavy
residue feed is preheated in the furnace to a temperature between 485 and
505~C in a very short time so as to minimize coking inside furnace tubes. The
388 C!I6pfef 12. COXING

two-phase effluent leaving the furnace is sent to one of the two coking reac-
tors. The vapor phase separates directly from the liquid phase, which under-
goes continuous cracking causing it to be converted into coke and a gaseous
product. The vapor phase exiting the coking reactor is routed to the main frac-
tionator where the condensable products are separated and heat recovered by
circulating reflux. The non-condensable products leave the top of the column
and are sent via a compressor to an LPG recovery section. The naphtha recov-
ered at the top of the main fractionator is also sent to the LPG section for sta-
bilization.

VCM (% wt) max. 2

Moisture (%,wt) 8-12
HGI 35-70
Sulfur (% wt) 3-7.0
. . . ...--r--------....:.....--------~
Tjlble
12.5 Typical specifications of fuel coke.

I A B C D
I
Feed:
Cut point ("C) 485 485 540 540
sp.gr, d"f' 0.980 0.952 1.044 1.012
CCR(% wt) 5.2 11.1 22.0 15.6
Sulfur (% wt) 0.6 0.5 5.3 3.4
Metals (Ni + V) (ppm) 50 44 910 90
Yields:
C4- (% wt) 6.2 7.4 10.5 9.2
Naphtha Cs-195 GC (% wt) 18.5 20.4 21.4 17.4
sp.gr, d"f' 0.754 0.730 0.759 0.745
Sulfur (% wt) 0.1 0.2 0.9 0.5
Gasoil 195 wt)
DC+(%
65.3 54.5 33.0 48.5
sp.gr.d'f 0.919 0.850 0.930 0.902
Coke (% wt) 10.0 17.7 35.1 24.9
Sulfur(% wt) 1.1 0.8 6.4 5.1
Metals (N[ + V) (% ppm) 500 249 2592 361
,-'---
Table
-
12.6 Yields at constant recycle ratio. Feed characteristics. Product yields and
'----
characteristics.
 Overhead gas

Fraclionaling
column
Cooling water Culling water Naphtha
pump pump
loblowdown

Light distillate
stripper

IE
u m
giii
~II
Coking
furnace

~._~
..
~":ao-e-- feed pump

Freah ,d
Fuel
i
iii

FiKU(L!
i
12.1 I Coking unit flow scheme. (.0)

m
 The vapor phase entering the bottom of the column encounters a heavy
dlstillate reflux that desuperheats it and condenses out the recycle which
moves downward to the bottom of the tower. The recycle is then mixed with
the fresh feed coming from the preheat train before the two are sent together
to the furnace. The washed vapors then go to the rectifying zone in the column
where light and heavy distillate sidestreams are drawn off by means of circu-
lating refluxes.

12.1.5.2 Rcovery Section (Coker Blowdown)

:r.;<; ~'::':tir)fl is designed to recover the hydrocarbons contained in the vapors
zr',,:n stearn purging and cooling the coke bed. Its function is to minimize efflu-
ent discharges during normal operation of the unit. The system employed is
shown in Figure 12.2. It includes a drum, a condenser, an overhead drum, a
cooler and the pump; 'assoclated with these items. The vent is usually con-
nected to the refinery flare network. The system ensures complete recovery of
all hydrocarbons sent to the section. . .

Condenser

'/take up

Non-condensables
Blowdown to flare
drum
Slowdown
overhead drum

Colo't,drum Recove-::::
'1ap()l~
Oil

Concensed
water
COndensates

Recove~:-d
Steam heavy c;]

BJowdown system.
 C/QpW IZ. CoKING 391

The gas oil circulating in the blowdown (generally coker distillate) aDows
condensation and recovery of the heaviest hydrocarbons in the feed vapor,
whereas the light fractions rise to the top where most of them are condensed
in the overhead condenser and recovered in the blowdown overhead drum.
Here the aqueous and hydrocarbon phases are separated, with the water
phase recycled as make up cutting water after steam stripping to remove pol-
lutants (H~ in particular).

12.1.5.3 Coking Cycle

A pair of coke drums is generally used in seml-conttnuous operation. While
one of them is in the reaction stage, the other undergoes stearn purging. cool-
ing and coke removal by cutting with a high pressure stream of water. These
operations are normally carried out in a 24-hour cycle as indicated in
Figure 12.3.

Hours

Key

[J Coking

~ Steamstripping

B Cooling

@] Draining

[] Opening

rsJ Oecoking

0 Closing and testing

~ Preheating

! Figure .
I 12.3 Operating cycle.
!_-
392 ~ 12. COKING

The decokmg operation takes place as described below:

1. Steam-out
When the coking reactor is full of coke, it is purged with steam to remove
the residual oil. The steam-hydrocarbon mixture is first routed to the fraction-
ator and then to the blowdown where the hydrocarbons are separated and
recovered.
2. Cooling
The coke bed is then cooled by injecting water in the bottom of the reactor
to reach an average temperature of below 90"C. Here again, the steam mixed
with any hydrocarbons is sent to the blowdown section.

3. Draining
At the end of the cooling stage, the coke drum is full of water which is
drained .out and reused "durin.s the foilowing cycle.
4. Opening
It is now possible to proceed to open the reactor by dismantling the bot-
tom and top flanges. This is done manually or more frequently seml-automatl-
cally, but can be entirely automated.
5. Decoking
Hydraulic cutting is the most common method of removing the coke from
the drum. High pressure jets of water are used to cut through the coke and
remove it from the drum in layers. The mixture of coke and water coming out
of the bottom is sent to the coke separation and handling section so as to
recover the water for reuse after removing most of the coke and fines..
6. Closing and testing
Alter the. coke has been removed, the bottom and top flanges can be
mounted back on the drum and tightness is checked by pressurizing with
steam.
7. Preheating
The overhead vapors from the coke drum in the coking phase are used to
heat the empty reactor by condensation using the cold wall effect. The recov-
ered condensate is routed to the blowdown to separate the water from the
hydrocarbons.
8. C~klng
Once the empty drum has been preheated. it is put back on stream by
switching the feed from the furnace and the full drum undergoes the same
decoking operation.

12.1.5.4 Coke Separation and Handline

During the hydraulic decoking operation, considerable amounts of coke and
water exit through the bottom of the coke dru~. Before the coke is dispatched
 Cha;Jlw '2. CoKJNG 393

from the refinery, it must be separated from this cutting water. Furthermore.
coke fines need to be removed from the water before it can be reused during
the following cycle.
Two of the most common separation techniques are the coke pit (rig. 12.4)
and the coke pad. The coke-water mixture is sent to a coke pit or to a large pad
of concrete that is inclined to allow the water to run off more easily. The water
separates out by flowingthrough the pile of accumulated coke and runs into a
settling canal where the fines decant. In the pit system. after the pile of coke
has been allowed to dry for several hours. it still contains around 10% mois-
ture. It is then loaded directly into rail cars by crane. or crushed and screened
and sent by conveyor to storage silos. This system is particularly well suited
to large capacity units producing fuel grade coke. especially when it contains
shot coke. .

Coking
/ structure
I and drum

=========~r===rT~m

I
L-,
Coke pit

rtgure r - - - - - - - - - - - - - - - - - - - - - - -.. . .
12.4
_ _I
i Coke pit.

Among the improvements designed to protect the environment are totally

enclosed separation techniques to prevent steam emissions from the pile of
coke which can remain hot in some places. Two examples of these techniques
currently in operation are shown in Figures 12.5(gravity separation) and 12.6
(slurry system).
 O
(,,)
Drum in
operaUon !
~
1- From coking
L . . - - furnace l
iil
.~ Tuvent
~
Sell/lng
Watermake up '"
~
hoppers

~ Recyclod water
~~.
lor cooling
.. .1Ilt! Clillilln

Sludge
~ .. lecirculallon

Gravity separution system.

 From' Vent
furnace

Drum being Orum In Water

decoked operation makeup

~MI l~~
ffi~ ffi~

Recycled
water
-c-~-

L L\
51OOge + water

4 ~

Canal
( ) Cok. CO," 0-,:' "'0< :;:/
Slurry pump
Draining pit T Conveyor belt
i
N

Fil:urc:
i
Co)

12.6 I Coke slurry separation system. m

396 Chapler 12. COKING

In the gravity system, the coke along with the cutting water from the coke
drum first goes to a grinder located directly at the drum exit. After crushing,
the coke-water mixture flows by gravity to settling hoppers where it accumu-
lates and the water settles out before it is drained off. After draining, the coke
is unloaded onto a conveyor belt that is also enclosed, and routed to the stor-
age hoppers, some other means of dispatching or a calciner. In the slurry sys-
tem, the coke and water mixture goes through the same grinder, but after-
wards runs into a ditch and to a slurry pump. It is pumped to the top of one of
the settling hoppers, where the coke and water settle out and are then treated,
the same as in the gravity system.
In the two systems described above, the bottom of the coke drum as well
as all the equipment are entirely enclosed, thereby preventing the clouds of
escaping steam so characteristic of a coking unit in the decoking phase. Dur!ng
decoking operations. any steam emissions at the top of the coke drum are elim-
inated by spraying with cold water or by using a wash column with an induced
draft blower. The top and bottom flange unheading and reheading operations
are automated and remote controlled in order to minimizerisks for personnel.

12.1.6 Coke Calcination

In calcination of petroleum coke from a delayed coking unit. the green coke is
subjected to very high temperatures (1 200to 1500C)for 90 min or more after
it has been crushed. The aim is to remove the volatile compounds (VCM) from
the green coke. This improves its physical characteristics, such as thermal
conductivity and real density.
There are two calcination methods: a rotary cylindrical furnace and a
rotary hearth.

12.1.6.1 Cylindric,!ll Furnace

These are the oldest calciners, which resemble the ones employed in cement
factories. They include a rotary furnace with the green coke inlet in the upper
part. As it passes through the furnace. the coke is subjected to increasingly
higher temperatures until it exits from the bottom where it Is cooled before
dispatching.

12.1.6.2 Rotary Hearth

The rotary hearth calciner was first implemented in the coking industry some
25 years ago. It is a circular platform that rotates and where the green coke
introduced peripherally is slowly moved to the center. There it undergoes high
temperature soaking which confers the desired properties.
Ever since the two types of calciners were first used. improvements in their
design and operation have mainly been aimed at energy efficiency. The volatile
combustible matter (YCM) in the green coke fed into the furnace supplies
most of the fuel consumed in the unit
 Chapw 12, CoKING 397

12.1.7 Economic Considerations

12.1.7.1 World Mackel
In 1992, annual world production of green coke (non-calcined coke) was
approximately 30 million tons. Seventy-five per cent of this total was produced
in the United States ana only 8% in Europe. The success of the process in the
United States, as a means of upgrading the bottom of the barrel, is due to its
efficiency in removing carbon from heavy residues with a relatively modest
investment. An added advantage of the process is that it affords a neat and
effective way of getting rid of some of the petroleum wastes found in refinery
tanks as well as' the oil recovered from API separators, for example.
Better added value for the coke still remains a critical element in the choice
of this process. Thriving production and less and less acceptable quality have
significantly influenced the market value of coke. For example, a typical 1982
lf.S, value of $50 a ton fell to $5 or $6 a ton in 1992. The same year, the U.S.
exported some 15 million tons of coke to Europe.
Fuel coke has a heating value of approximately 32 600 to 33 400 kJ/kg, but
it is not necessarily a fuel that is easy to burn for the following reasons:
Its low volatility and high carbon to hydrogen ratio (greater than 20)
means it has a slow combustion rate. This can however be corrected by
using it mixed with a fuel having a higher volatility.
Its high sulfur content requires potential SO:! emissions to be monitored.
Its high nitrogen content and high ignition temperature require NO,r to be
monitored.
Its high metals content can lead to problems of fouling and corrosion in
boilers.. .
Its hardness can cause problems with grindingand transportation equip-
ment. "
The major fuel coke market is the cement industry in Europe, the United
States and Japan where the 50 2 released is absorbed in the cement. Today
only a small amount of coke is consumed in thermal power plants in the United
States, but with the advent of the new generation of fluidized bed boilers, the
market can be expected to develop. An even more recent and promising devel-
opment is the gasification of petroleum coke to co-produce electricity, hydro-
gen and steam for the refinery. This technology has already proved its value
and the synergy between refining operations and electricity production is
bound to be exploited in the future.

1~.1.7.2 Process Ecoaamic:s

a. Utilities Consumption
Since a delayed coking unit runs on a semi-continuous basis, utilities con-
sumed continuously need to be added to intermittent consumptions during
decoking operations. The continuous consumption items are listed below
(Table 12.7) expressed per 1 000 m3j h of fresh feed.
398 CnaoIet' 12 COKING

Continuous consumption:
'Feed capacity (m3jh) 1000
Fuel (kJ1h)
Electric power (kW)
,81.5x 106
2250
I
I
Exported steam (kg/h) 11500
Boiler feed water (m3jh) 12.7
Cooling water (m 3/h) 15 to 90
Make up process water (m3/hjper t/day of coke) 150 to 220
Intermittent consumption:
fuel (kW for 5 h/day) up to 2 000 i
Steam (t{h for 1 h/day) up to 10
Air (std. m3jh for 5 h~day) up to 1 350
,-r-----;-
Table
12.7 Utilities consumption in coking.
'---

b. Chemicals
A delayed coking unit requires approximately 2 m3/year of anti-foaming agent
and 8 m3/year of dernulslfylng agent.
c. Number of Operators
For a conventional unit with two coke drums working on a 24-hour cycle, it is
common practice to have 4 operators for the unit itself and 3 additional oper-
ators for the decoking crew.
d. Investment
In the economic conditions prevailing in Europe at the end of 1999, the approx-
imate investment for a unit processing 2 500 tjday of fresh feed (conventional
vacuum residue) was 50 million. This figure does not include any LPGrecov-
ery or gasoline stabilization sections.

12.2 Fluid Coking: Flexicoking

Flexlcoklng is a continuous process developed and licensed by Exxon. It
includes thermal cracking in a bed of fluidized coke and gasification of the
coke produced. It is a highly flexible process that can be applied to a wide vari-
ety of feeds. It can process almost all liquid fractions, including atmospheric
and vacuum residues of any origin, even those rich in contaminants (metals,
sulfur, nitrogen, etc.),
The process allows virtually total conversion (99%) of the feed into
gaseous and liquid products. The remaining 1% is a solid bottom discharge
 O'Japter 12. CoKiNG 399

which contains over 99% of the metals present in the feed. The naphtha and
distillate produced are processed in the refinery's catalytic cracking and
hydrotreating units. as well as in the desulfurizatlon units which can"recover
95% of the sulfur present in the feed.
In the F1exicoJdog process, approximately 97% of the initial coke is con-
verted into gas with a low heating value (about 4 200 to 5 000 kJ/std m3).The
gas is termed low BTUgas and is burned in furnaces or thermal power plants
in the refinery or in neighboring facilities. The solid bottom discharge from the
unit can serve as feedstock for a metals recovery unit.

12.2.1 Feed Types

The process can accommodate the same feeds as delayed coking. By defini-
tion, it is insensitive to metal contaminants. since there is no production of
coke. where they would concentrate. making it unsuitable for industrial use.

12.2.2 Background Information [3J

12.2.2.1 Chemical Reactions
The coking and cracking reactions that occur in the fluidized bed are similar
to the ones that take place in the delayed coking reactor. Standard oxidation
reactions occur in the gasifier in the presence of air and steam (Chapter 14):
In the oxidation zone of the ftuidized bed:
1
c +2 Oz~ co ~'Z98 '" -110.8 kl/rnol (1)

1
CO +2" o, ~C02 AH m'" -283.5 kJ/mot (2)

In the reduction zone:

C + H20 ~ 2CO JlI'29g = 172.7 kl/rnol (3)
C + H20 =:; CO+ H2 AHi9s = 131.2 kl/mol (4)
H20 + CO =:; CO2 + Hz Jlf"298 =-41.12 kl/mol (5)
Reactions 1 and 2 are very rapid and take place both on the surface of the
coke and in the gaseous phase. Reactions 3 and 4 are much slower and deter-
mine the overall gasifkation reaction rate. Reaction 5 occurs exclusively in the
gaseous phase and is an equilibrium reaction under the gasification condi-
tions.

12.2.2.2 Operadnc Conditions

Fluid coking operates at pressures and temperatures similar to those used in
delayed coking (510"C. atmospheric pressure). In the gasification reactor the
temperature reaches 870"e.
 400 ~ 12 COXING

12.2.2.3 Products
F1exicoking yields the same type of gaseous and liquid hydrocarbon products
as delayed coking with one exception. Instead of coke. the unit produces a low
BTUgas whose characteristics are given in Table 12.8along with those of other
industrial fuel gases. The low BTU gas (LEG) has a heating value of around
4 200 to 5 000 kJ/std m3 and contains from 45 to 55%nitrogen. Its characteris-
tics are very similar to those of blast furnace gas. Once the gas has been puri-
fied by amine treatment and solid particles have been removed, it becomes a
safe and reliable fuel,

BIasi furnace Refinery fuel

Origin Flexicoking
-. 'c
ps gas

Composition (mol %):

CO 18.6 23.3 -
H2 21.0 3.2 -
C\ toC.. 0.8 0.1 100
CO2
I 10.4 11.5 -
N2 45.6 53.7 -
H2O 3.5 8.2 -
Molecular weight 23.7 28.2 18.9
Heating value (kJ!std m3) 4765 3100 39080 .
.... r - - - -
Table
12.8 Characteristics of different fuel gases.
'---

12.2.3 Typical Yields

For a feed whose characteristlcs are presented in Table 12.9, Table 12.10 lists
estimated yields before gasification and Table 12.11 gives product quality.
Figure 12.7 gives an example of a Flexicoklng unit material balance. It also
indicates the possible uses for products.

12.2.4 Process Description [2]

A simplified diagram of a Flexrcoklng unit is presented in Figure 12.8. The unit
consists of a fluidized bed reactor, a product washing column at the top of the
reactor, a furnace where the coke circulating from the reactor is preheated by
the gas and coke from gasification, a gasification reactor, a cooling system for
the furnace overhead gas and a recovery system ,for fines.
 C1wIptw,2. COKIIlG 401

Origin of crude Arabian heayY

TBP cut point CC) 565
sp.gr.d"f 1.048
Sulfur (% wt) 6.0
Nitrogen (% wt) 0.3
Conradson carbon (% wt) 27.7
Nickel (ppm) 64
Vanadium (ppm) 205
<--
Table
12.9 Characteristics of (J typical feed.

- -
Yields % lt1 on feed % vol on feed
Sulfur. oxygen and nitrogen compounds 1.55
H~ 1.19
COS 0.00
CSH 0.05
C~H 0.04
NHJ 0.02
CO 0:.15
CO2 0.10
C3 8.32
H2 0.14
CH. 2.58
q 0.60
C2 2.24
C3 ".
1.13
C3 1.63
C4 I 2.62 4.60
C""
4 I 0.05 0.08
C; 1.39 2.39
i.e. 0.19 0.35
n-C4 I 0.99 i.rs
Liquids 53.28 62.12
Cr220C 14.76 20.36
220-345C 10.15 11.90
345-52SeC 28.31 29..86
Coke"
I 3-t.13
Total 1 100 66.72
* Normally 97.3% of the coke is gasified.
<---I
Table,
'. 12.10 I
I
Yields (before gasification).
402 Chap/er 12 ColaN(>

Cut("q <::,-220 220-345 345-525

I
sp.gr. d~ 0.758 0.899 0.996
Sulfur (% wt) 1.07 3.84 5.98
Nitrogen (% wt) 0.005 0.017 0.29
eCR (% wt) - - 4.74
Nickel (ppm) - - 0.87
Vanadium (ppm) - - - 2.80
Hie ratio (wt) 0.159 0.135 0.12
Pour point CC) -, - -23 28
Bromine-number (g/100 g)" "" 109 58 32
Cetane number - 30.8 -
Vlscostty (mm 2/s at 37.SC) 0.6' 3.2 36.5
(mm 2/s at 99C) 0.4 1.1 12.6
PONA (% vol):
Paraffins 21.4 14.6
Olefins 54.9 26.1
Naphthenes 5.1 2.5
Aromatics 18.6 56.8

LBG (after treatment)

Composition (mol %):
CO 18.64
CO2 10.45
H2 20.99
N2 45.61
CH. 0.80
. HzS -
COS om
H2O 3.50
Total 100.00

Heating value (kJ/std m:l) 4765

.---
'- Tllble
12.11 Product quality.
'----
 CNptM 12. COQIG 403

Sulfur In products
Yield
on feed(t) 8"e After UIe
(%wl) treatment treatment
(%wt) (%wt)
Ovemeadgas
12 6 .0 (3) Fuel gas
(c4- ) (48 400 kJlm; LPGIIICOYIlIY
AlkyIIIion
~~

Feed

Residue565OC+
I
CCR 21.4"'-wt Nap/'llha
15 0.8 <0.01 (2) Fuel
S 3.4"'-wt s
U
/C,22O"C) GasQin&pool
P8llOCtlemical
G)
V 387ppm Ol feedstDck
c:
.2
Nt 135 ppm
~
a:
Oistilla18
46 3.0 < 0.3(2)5 LS lueleil
(220-52S'C) COtIYeISion unit
Petrochemic:aI
leeclsb:k

LBO 26.2 ~0(4) Fuel

based on (NO.-O)
contained (5 020 kJlm3)
ClIfbOn

0.8 <2.0 Fuel

5.2 Vllnadium Metals nlCOvery

I
1

L Figure i
12.7 I F7ericoking unit materialbalance.
i (I) T)pical yields for a leed from a .lliddle Eo:st crude.
(2) r:,pical value after h}Y1rotreating. Can (:Q7y according to end use.
(3) Aber .UEA treatment and mercaptan extmdion lor C1 and C4 curs.
(4) The sulfur content depends on regulations go~-eming off gases after combustiotL
 ~

. 2
I
low Btu gas
Tertiary
cyclones I 10 treatment

f
!\i

~
~
Washing
To Iracllonator - - - ,
I ~
I
Venluri YCOlumn
Fines
Slurry

Gasification

Steam

AirIan

Furnace

Figure
I Z.8 I Simplified diagram of'he Flexicoking process.
 C1l8I>/.,2. CoKING 405

The residue feed preheated to approximately 250-350"C enters the reactor

where it is thermally cracked to give a product containing gas. naphtha. distil-
lates and coke that is laid down on particles of fluidized coke. The overall heat
of vaporization and the heat of reaction required by the residue are provided
by a stream of hot coke coming from the furnace. The cracked products are
cooled and washed in the washing column and can be recycled to the coking
reactor if need be. The light fractions rise to the top of the column and then go
to a fractionator where they are separated into gas, naphtha and distillates tor
further treatment in the refinery.
The coke from the coking reactor is sent to the furnace where it is heated
by the coke and gas from the gasifier. Part of the circulating coke is routed
from the furnace to gasification. where it is converted into Hz, CO, Nz CO2,
H20, ~ and a small amount of COS in the presence of air and steam at high
temperatures (800 to 1 OOOC).
The gas produced by gasification along with the particles of entrained coke
are sent back to the furnace. There they are cooled. by contacting the coke from
the reactor. thereby supplying part of the heat required in the reactor. A coke
stream. sent from gasification to the furnace, provides the rest of the heat.
The coke oven gas leaving this reaction section is used in a waste heat
boiler to generate steam before going through cydones and a washing unit.
including a venturi and a washing column. to recover coke fines. The gas
minus its solids is sent to the treatment section for HzS removal.

12.2.5 Uses for Low Btu Gas

The gas with its HzS and solids removed is a clean fuel that can replace natu-
ral gas and other fuels consumed in a refinery. The Flexsorb process by Exxon
Research and Engineering Company was specially *signed for HzSremoval. It
reduces the HzS content in the gas to Jess than 10 ppm. Aiter purification. the
gas can be used as fuel in several ways.
In specifically designed furnaces it is possible to get very high efficiency
for an investment similar to that for a conventionally fired furnace.
fa specifically designed boilers with or without electricity generation by
turbogenerators, that can consume large amounts of gas with very high effi-
ciency. In comparison to a conventional boiler, an added investment of around
10 to 15%will be required in this case. Approximately 10 to 20% conventional
fuel is generally allowed for to guarantee the safety and reliability of the instal-
lation. U a condensing cycle is used, efficiency is slightly lower (25%J.than for
a couventionaI power plant (30-35%).
In gas turbines, although there has been no industrial experience as yet.
this use remains an interesting application for the future. However. the gas has
to be compressed from O. i to 17 bar In order to achieve efficiencies similar to
conventional fuel gas (28%compared to 32%).
By modifying existing furnaces. Here a slight drop in efficiency is to be
expected and the use of an additional fuel is required. The cost of revamping
406 Chaplet 12. COKING

a conventional furnace can range from 2 to 3 million for a duty in the-range

of 170 to 315 x 106 kJ/h.
By revmnping existing boilers. The same considerations must be taken
into account as for a specially designed boiler and the cost is approximately
the same as for revamping an existing furnace.
Other uses are less conventional but just as valid:
feed for a hydrogen production unit (steam reforming);
fuel for a hot oil circuit, a naphtha reforming unit, a waste heat boiler.
rebollers, for superheating steam or preheating FCC feed.
In some situations, Flexicoking gas can be used in neighboring installations,
such as Iuel-Ilred power plants and steel mills.
As an illustration, consider a refinery with a Flexicoking unit having a
design capacity of 5 000 Velay. AU of the gas produced by gasification can be
consumed as follows: .
in new boilers, vacuum distillation, naphtha reforming and stearn reform-
ing furnaces, and in a steam superheater;
by transforming an existing atmospheric distillation furnace, existing
boilers and some existing reboilers.

12.2.6 Use of Purge Coke

This coke comes from three different sources in the unit:
bottom discharge from the fluidized coke bed;
fines coming from the cyclones;
moist fines coming from the washing column.
It is fairly low in sulfur but high in metals, especially in the fines. The dry
product is a relatively good quality fuel. The moist fines can also be used as
fuel or the metal they contain can be recovered in conventional facilities.

12.2.7 Economic Information

12.2.7.1 Installed Capacity
World installed capacity is 7.7 million tons/year, 2.9 million tons of which is
processed in Exxon refineries. Table 12.12 gives the breakdown by company.

12.2.7.2 Economics
For a unit with 3 800 t/day capacity, battery limits investment amounts to
83 million (1999). The utilities consumption for the unit is shown in
Table 12.13. Running time between maintenance shutdowns is 21 months on
the average. Some units have been able to operate non-stop for 2 years, and
one for even more than 1 000 days. A maintenance shutdown lasts 45 days.
 -
Feed
Company Country capacity ComlllitsioDed
(Mtfyear)

ToaOil Japan 1.05 September, 1976

Lagoven Venezuela 2.60 November. 1982
Shell Oil I USA (California) 1.10 March. 1983
Esso Ndherlands 1.60 August. 1986
Exxon USA (fexas) 1.30 September. 1986
Total 7.70
.....--
..... Table
12.12 World f1ericoking capacity.
"'-

Nominal feed capacity (tId) 3800

Steam consumption (I/d):
High pressure steam 186
low pressure steam 95
Superheated steam 13.5
Steam production (tnt):
High pressure steam 127
Low pressure steam 29
Boiler feed water (or/h) 113
Cooling water (m3/h) 1960
Power (kWh/h) 493
...----- "

~ Table
12.13 Utilities cOlf$lll'flption.
"---

Referentes
1 Elliott 10. (1990) Latest Coker Designs increase Liquid Yields. Reduce
Emissions. Oil Gas1.. Nov. 8.
2 Allan D.E., Metvailer w.J., Wiechert S. King R.C. (1981) Advances in Fluid
and Flexlcoking Technology. Chemical Engineering Progress 77, 12.
3 Allan D.E., Blaser D.E.. Lambert M.M. (1982) Flexicoking of Residue with
Synthesis Gas Production. 1982 NPRA Meeting, San Antonio, Texas.
4 Janssen H.R., Leaman G.L Improved coking design can up liquid yields. Oil
Gas J. June 25 1984.
5 Debiase R., Elliot lD., Hartnett T.E. Delayed coking process update. 188th
meeting Am. Chern. Soc. St Louis. April 1984.
 -.-=1,~a-~:--';~~~J
... ~. '" . :...... <1
';. - -.-- .. : ,.: . ;-'.j
Resiclue Hydroconver~ion

Frederic Morel
Jean-Pierre Perles

The first industrial units for catalytic hydroconversion of residues date back
to 1965.At the time the objective was to produce desulfurized heavy fuel oils.
Then in addition to fuel oil desulfurization, it evolved into maximum conver-
sion to distillates - mainlygas oil- at the expense of residual fuel oil. Today
some forty residue hydroconversion units are in operation, but this only
amounts to 5%of world conversion capacity. The steadily shrinking heavy fuel
oil market and the mandatory reduction in heavy fuel oil sulfur content are
favorable to this type of process. The trend is bound to become more accen-
tuated with the arrival on the market of heavy and extra heavy crude oils. As
a result, the processes have good potential for development despite their
operating costs, which sliD remain very high.
The typical objectives for refiners are as follows (Fig. 13.1):
Produce desuliurized fuel oils (LSFO).l First adopted mainly by Japan and
the United States. the reduction in fuel oil sulfur content has now spread
to most developed countries. European specifications on emissions from
heavy fuel oil combustion range between 400 and 1 iOO mg of 50 2 per
std m3 of stack gases depending on the rated output of the boiler. This
corresponds to a fueloil sulfur content from 0.25 to 1% wt for combus-
tion units without any stack gas treatment (Fig. 13.2).
Pretreat a conversion unitfeed: catalytic cracking (FCC) of residues or cok-
ing. A feed that has a Hie ratio increased by hydroconversion, a low
Conradson carbon. and a low nitrogen and metals content, gives much
higher FCC gasoline yields. Meanwhile it also minimizescoke production

1. LSFO: low sulfur fuel oil.

 Makeup Recycle hydrogen
Gas
:1ydrogen

Sulfur

/- ..... Gasoline
Atm. Res. 1-- Gas oil
Vac. Res. ________ )- Vacuum distillate

Atm. Res. or
' - - - - - - - -.. vac. Res.

H~+NH3
~----- to claus unit

Water to biological
~-------_.. treatment

i
~ Figure
13.1 Simplified flow diagram of residue hydroconoersion.

2000

S: l%wt
E I

~ 1500 I

-- I
I

~
I
I
I

g 1000 I
I
E I
::l I
E I
'x I

~ 500 : I S: O.25%wt
T-----~---1-------
I I

II
I

100 300 500 700

Heating power output (MW)

Figure
13.2 Maximum SO? emissions for new boilers.
(Source: Eurcpean Directioe- lOCE No. L 336/9 of December 7, 1988).
 and catalyst deactivation. Additionally, deep FCC feed desulfurization
yields gasollnes that do not require any further desulfurization and
reduces SO~ emissions at the regenerator exit.
Produce maximum distiUates, mainly gasoils. AIl residue hydroconversion
processes allow the residue to be partially converted into light fractions
to a greater or lesser degree. The result is a reduction in the amount of
unconverted residue (usable as LSFO, as feed for a secondary conversion
unit or even for a gasification unit) and better flexibility, allowing refiner-
ies to process a diversified crude oil supply. A subsequent hydrotreating
stage is often necessary to adjust the characteristics of the distillates
produced.

13.1 Integration in a Refinery

Typical feeds for residue hydroconversion processes are atmospheric and vac-
uum residues. These residues are sometimes processed mixed with diluents,
such as LCQ2, HCQ3 or aromatic extracts. In addition to reducing the viscos-
ity of very viscous vacuum residues, dlluents also partially inhibit asphaJtene
precipitation and coke formation due to their highly aromatic structure. Both
these phenomena are detrimental to catalyst stability and unit operability.
The residue components that limit hydroconversion performance are
mainlyasphaltenes (or heptane insoluble compounds, made up of pericon-
densed naphtheno-aromatic rings connected by alkyl chains or sulfur bridges
(Fig. 13.3)) and Ni and V metals. Metals concentrations are particularly high in
residues from extra heavy erodes (fable 13.1).

13.2 General Introduction to Residue

HydroconversioD Processes
The various processes use a variety of reactor configurations (fixed. moving,
ebullating or entrained beds) each with its own catalytic system. In all
instances. operating conditions are severe because residual oil fractions areso
resistant to treatment.
Space velocity (h- I) 0.1-0.5
Hz pressure (bar) 100-170
H2 recycle (std m3jmS) 600-1600
Temperature COC) 340-450

2. LCO: light cycle oil (see Chapter 5).

3. HCO: hea v-y cycle oil (see Chapter 5).
 Figure
13.3 AsphaJtene structure [6].

Type of-crude Conventioual Heavy

Type of residue Almas. Vacuum Vacuum Atmos.

Original crude Arabian Kirkuk SaCaniya Cold Lake

Yield/crude (% wt) 48.0 18.7 34.0 13.8

sp.gr, d~s 0.988 1.021 1.035 1.024
Viscosity at lOOe(mm 2/s) 95 880 3900 1095
Sulfur (% wt) 3.95 5.14 5.28 5.05
Conradson carbon (% wt) 13.8 18.2 23.0 18.3
C7 asphaltenes (% wt) 5.7 7.5 U.S 10.5
NI + V (ppm) 104 189 203 325
'"-~
Table
13.1 Characteristics of four petroleum residues.

-
 Chapter J3- RESIDUE HYOROCONvERsIoN 413

Residue hydroconversion reactions are mainly of two types: hydrogenoly~

sis (elimination of contaminants from the feed: sulfur, nitrogen and metals:
Ni + Y, etc.) and residue conversion to light fractions: gases. gasoline. gas oil
and vacuum distillate. Typical performance is as follows:
Hydrodesulfurization (%) HOS 80-95
Hydrodemetallization (%) HOM 80-99
Hydrodenitrogenation (%) HON 20-60
Conradson carbon reduction (%) HDCC 50-80
Asphaltene reduction (%) HDAC 7 50-90
Vacuum residue conversion (%) CONY 30-90
Choosing the type of process, its catalytic system and operating conditions
allows one or more of these operations to be promoted.

133 Background Information

133.1 Chemical Reactions

Residue hydroconversion reactions are both thermal and catalytic in nature.
with a close relationship between the two types of reaction, which are some-
times called thermocatalytic (Fig. 13.4). Schematically speaking, contaminant
elimination reactions o-ms, HOM, etc.) are largely catalytic. The mechanism
includes the following: reactants are diffused in the catalyst grains. they are
adsorbed and react with hydrogen on the catalytic surface. and finally prod-
uets are diffused away from the grains. Cracking and condensation reactions
are mainly thermal. They proceed according to a (ree radical mechanism and
operate in the reaction volume left by the inter- and intra-grain voids of the
catalyst.
The catalytic reactions mentioned above are generally exoltll:rmic,
whereas thermal cracking reactions are endothermic. Overall, residue hydro-
conversion processes are exothermic. The heat of reaction is an estimated
34-42 kJ per mole of hydrogen consumed.

13.3.1.1 Hydrodesu1furbatioD (HDS)

Desulfurization is a major aim of residue hydroconversion processes.
Desulfurization ratios vary from 80 to 95% depending on the type of' feed and
on process efficiency. The product sulfur content is not only in the uncon-
verted residue. but also in the resulting distillates. Note that target sulfur spec-
ifications for heavy fuel oils are less than 1%.for diesel oils less than 0.J5% wt
and for gasolines less than 0.005% wt. Furthermore, if the residue is used as
feed for an FCCunit. a low sulfur FCCfeed (for example 0.3% wt) directly yields
low sulfur gasolines 100 ppm wt).
414 Chapter 13. RESIDUEHyOROC:;;. :?SION

A. Hydrodesulfurizalion of dibenzoll1ioptA!ne

~+~
Y~'YJ~

oyo ~ [l\AP] --!L 0-0 + H,s

Transient
intermediate

B. Hydrodesul!untation of .~ulfides
A R

~Hu-S-CH2--o~ ~+~C--O +H~

C. Hydrodemetanization of porphyrins

R R

R
~R

R A

R R

1 H2 (+ H2S)

Ni,sy

D. Hydrodenitrogenation of quinoline

OQ -~ 09~otH, C 3Hr

t1 H
I
2
NH, <, ~ c,H'J y H,
or +NH:,

co'"
H, H
~
C9 H
LC(NH,
Thmpo~~
~
H2 " , r- C
V
3H 7

+~
intermediate
 I
_1_ E. - . "_ro2_of poIyarom_
: /HR2 2- gR,
R, R,

F.Hydrogen transfer "

- Catalytic hydrogenation
of potyarornatics
oo~ 00
_ _I
. Homogeneous phase
hydrogen transfer
to the ~ radical r-!-----"
00 +4R 00 +4RH

G. Secondaty thermal aacking of aliphatic chains

H. Thennal condensation01 polyaromatic radicals

0Ql01 ~ - COke

060 ooY6
Fi~
13.4 Hydroconrerzion reactions,
416 C.,-13. RESIDUE HYDROw"ONVeRSKJN

The sulfur compounds present in petroleum residues are of two types: sul-
fide and thiophenic. Sulfides are partly found in the asphaltenes in the form" of
condensed naphtheno-aromatic rings connected by sulfur "bridges"
(Fig. 13.3). Although they can be decomposed catalytically, sulfide type com-
pounds (Fig. 13.48) can also be dissociated thermally due to the low energy of
the C-S bond (320 kJ/moJ). This is observed in purely thermal processes
such as vis breaking and coking. Thiophenic compounds are decomposed only
catalytically. Catalytic action gives rise to parallel reactions with or without an
intermediate hydrogenation step, followed by hydrogenolysls of the C-S
bond (Fig. 13.4A).

133.1.2 HydrodcmctallbatioD (HDM)

It is necessary to eliminate the metals contained in residues fora number of
reasons. First of all, desulfurization catalysts can withstand only a low metals
content, so a prior demetallization step is critical. Second. when the
hydrotreated residue is used as LSFO, residual metals cause vanadium corro-
sion in furnaces and promote dust formation in combustion off gases (often
limited to 50 mg of dust per std m3 of off gases). Finally, when the residue is
used as feed for an FCCunit, the amount of metals in particular determines cat-
alyst deactivation, and therefore its consumption in the uniL The various
residue hydroconversion processes result in a very thorough elimination of
metals (from 80 to 99%).
The metals in petroleum residues are in the form of soluble organometallic
complexes. The most common are of the porphyrin type, with a Ni or V atom
bonded to nitrogen atoms with four heterocyclic structures. Metals are also
present in other, poorly defined, non-porphyrin structures but which would be
more reactive than porphyrins. All these metallic compounds are present in
the resin and asphaltene fractions of vacuum residues. Note also the presence
of Fe, Ca and Na in organic form in some residues from particular crudes.
The hydrodemetalJization reaction is thermocatalytlc, Demetalllzatlon is
promoted by partial decomposition of the asphaltenes which contain most of
the metals. An intermediate hydrogenation step is crucial for porphyrins
(Fig. 13.4C) and results in more complete demetallization. The reaction prod-
ucts are metallic sulfides of the NiSor V3S4 type. Vanadium-base structures are
more reactive than those with a nickel base. The sulfides are deposited in the
catalyst pores, covering its surface gradually with one or more layers. The sul-
fides themselves have a catalytic effect for HOM reactions. In addition to the
effect of covering the catalyst surface. the metal deposits also gradually plug
up its pores and make it less accessible to reactants. In this way metal
deposits. along with coke, work to deactivate catalysts.

13.3.}'} Hydrodcnitrogcnation (HDN)

Residue denitrogenation is a desirable reaction that is, however, very difficult
to accomplish. Denitrogenation ratios commonly vary from 20 to 60%.
European regulations specify maximum NOx emissions of less than
 ar.pw 13. RESaE HYOROCONVERSKJN 417

450 mg/std m3 of combustion off gases. To meet this requirement. heavy fuel
oils must have a low nitrogen content, often ranging between 02 and 0.4% wt
(see Vol. 1, Chapter 5). When residue FCC feeds are pRpa.red. a low nitrogen
content is also sought 0.2% wt). as acid cracking ~ysts,~_ inhibited by
nitrogen.
Nitrogen is present in residues in two principal forms: non-basic hetero-
cyclic structures (pyrrole family) and basic heterocydic ones (pyridine fam-
ily). Pyridines are naturally less reactive than pyrroles. but have a stronger
tendency to become adsorbed on the catalyst. thereby inhibiting its activity.
Denitrogenation reactions are catalytic in nature. Contrary to the desulfur-
ization of thiophenIc compounds, denitrogenation always includes a prior aro-
matics ring hydrogenation step followed by hydrogenolysis of the C-N bond
(Flg. 13.4D).The hydrogenation step is limiting in the HDNreaction.

13.3.1.4 Hydrogenation of Aromatics IUncs anti

Hetcrocydic Compounds
These hydrogenation reactions restdt in a higher HIt ratio in the product
(improved quality) and a 50 to 80% decrease in the C~son carbon (advan-
tageous for a residue FCC unit feed. whose maximum Conradson carbon con-
tent must be in the range of 6 to 10%wt).
Hydrogenations are intermediate steps that make heterocyclic compounds
stabilized by resonance more reactive. Hydrogenation is indispensable as an
initial reaction step for HOM and HDN reactions and pfomotes HDSand decy-
clization reactions {Figs. 13.4C. D and E). Polyaromatic compounds are more
reactive than monoaromatics whose resonance energy per carbon atom is
higher.
Furthermore, hydrogenation reactions also affect the saturation of oleftns
and the capture of free radicals fonned by thermal aaddng. They thus help
limit secondary cracking and radical polycondensatiaD reactions. A hydro-
genation deficit can not prevent polycondensation of heavy radicals to coke.
which causes catalyst deactivation, coke formation and greater pressure
losses in the reactors.
Hydrogenation reactions can be coupled with a mechanism called "hydro-
gen transfer", which consists in catalytic hydrogenation ofpolyaromatic com-
pounds to naphthenoaromatics. The naphthenoaromatics then transfer hydro-
gen to free radicals in the voids of the catalytic bed before being catalytically
rehydrogenated once again (Fig. 13.4f). This concept of hydrogen transfer is
the basis for the "donor solvent" type of process family (see Section 13.4).

13.3.1.5 Cracking and CondeDsati~Reactions

Residue cracking reactions are essential in that they yield light, high added
value products: gases. but mainly gasolines. gas oils and vacuum distillates.
\ acuum residue conversion is highly variable depending on the type of pro-
cess and can go up to 90~{'.
 418 :::-.a,:,re<' 73_ R=sJou; HYDROCONVE!~SJON

Part of the conversion into light fractions is the result of hydrogenation and
. hydrogenolysls reactions. These reactions yield products whose molecular
weight is only slightly modified. but whose boiling temperature is substantially
lower. For example. dibenzothiophene boils at 332C. whereas the biphenyl
resulting from its hydrogenation boils at only 256"C. Another proportion of the
conversion into light fractions comes from splitting C-C bonds by catalytic
hydrocracking. "
Most of the residue conversion into light fractions is the result of thermal
cracking at high temperature. however. Thermal cracking reactions occur in
the voids of the catalytic bed and proceed according to a free radical chain
mechanism. The mechanism leads to the formation of light fractions by sec-
ondary cracking of the radicals produced (Fig. 13.4G). Additionally, it also
results in the formation of polyaromatic coke precursors by condensation of
heavy radicals (Fig. 13.4H). The heavy radicals can in tum be .captured by the
activated hydrogen on the catalyst, thereby reducing their tendency to con-
dense and consequently form coke.
Thermal cracking reactions cause splitting of C-C bonds in compounds
with sufficiently labile bonds and a weak tendency to become adsorbed on the
catalyst surface. Aliphatic C-C bonds and. to a lesser extent. naphthenic ring
C-C bonds are mainly involved. Monoaromatic ring C-C bonds are stabi-
lized by resonance and are therefore less apt to be thermally cracked. The
same is true of polyaromatics, resins and asphaltenes, which are additionally
strongly adsorbed on catalysts. .
There is a complementary relationship between catalytic hydrogenation
reactions and thermal cracking and condensation reactions. Catalytic hydro-
. genation of aromatic rings into their naphthenic homologues destabilizes
C-:-C bonds through loss of resonance. This makes them easier to decompose
thermally.
The activation energy of thermal cracking (> 160kl/rnol) and condensation
reactions is higher than that of hydrogenation reactions (around 100 kl/mo'),
which are also thermodynamically limited. At bigfi operating temperature. an
imbalance may therefore occur between the two-types-of reaction. This leads
to coke formation. causing a deactivating effect on the "catalyst and pressure
losses in the reactors.

13.3.: Catalysts {l]

Most residue hydroconversion processes (Iixed, moving and ebullating beds)
use supported pelletized catalysts. The active phase is dispersed on a sup-
port, generally consisting of alumina or silica with a large surface area.
Entrained bed. or slurry. processes employ what is called dispersed catalysts.
They are in the form of fine particles injected with the feed. or formed in situ
in the reactor from a soluble catalytic precursor. Whlle the size of supported
catalysts can range from less than 1 mm to approximately 2 to 3 mm, dispersed
catalyst size is in the neighborhood of a few JlIIl.
133.2.1 Supported Catalyst.
The catalytic system is more and more frequentlya combination of two cata--
Iyst families placed in series in the reactors. Each one has specific and com-
1>lementaryfunctions.
The first family consists of one or more HOM catalysts. They are essentially
designed to accomplish deep demetallization of the feed in order to protect
the HDS catalysts downstream. They can operate at high temperature. thereby
also promoting thermal cracking reactions. They are often preceded by a
guard bed with no catalytic activity, that acts as a filterfor the feed in fbed bed
processes. The second family is made up of one or more HDS catalysts placed
after the HOM catalysts. They are designed to refine the products thoroughly
(HDS, HD~. HDCC~. Table 13.2 presents the general characteristics of the cat-
alytic s y s t e m . ' .

Type Guard HOM fIIlIi

material eataIysts caf.IItsIs
HOM HIlS
Main func:tioDS Trap TrapNi+ V HDa:
partlcles HDAC, tfDII(
CONY
Shape BeadHings Beads-exlrudates ~

Grain diameter (nun) 3-10 0.8-3 0.8-1.6

Surface area (m 2,'g) < 1 ~180 150-250
Total pore volume (cm 3/g) < 0.25 0.7-1.2 0.4-8.8
Average pore diameter CA) lOS-l()6 2~1000 8O-D
Active phase - NiMo-Mo NiMo-CoMo
%of total catalyst volume <5 3~jO 3O-iU
~
I Table
0.2 Example of characteristics of supported catalysts for residue hydrocOlll:tl!nion.

The catalysts are most generally in the form of extrudates - cylinder or

multilobe - or beads. Spherical particles flow more readily and are better
suited to moving bed reactors. Small grain size improves performance by
reducing diffusional limitations, but in exchange it is also conducive to
increased pressure drop. Catalysts are small in size to facilitate fluidization of
ebullatlng beds. so they require very good mechanical strength.

-l, HDCC: hydrogenation of Conradson carbon promoters.

_420 Cr.aorer 13. RESIDUE HYDROCOr.tVERSION

a. Guard Material
A major problem in operating residue hydroconversion units is the occurrence
of pressure drop in the first reactor. Pressure drop is partly the result of the
solid particles present in the feed being deposited on the first layers of cata-
lyst. The particles can be of a variety of origins: organic or inorganic iron.
sodium chloride, coke from furnace tubes or the reactor. 5 sediments, thermal
degradation products from storage tanks, solids formed by reactions with
additives present in the feed or catalyst fines from upstream units. They have
large diameters, ranging up to over 100 um, and can neither enter nor react
inside the catalyst grains. They are laid down on the outer surface of the cata-
lyst or between catalyst grains. As a result, they tend to fill the inter-grain
voids (increasing pressure drop) and bond the catalyst grains together (mak-
ing It difficult to unload the catalyst). Periodically "skimming" the catalytic
beds is a solution. but it means shutting down the unit.
Specific guard material can be effective in trapping these large particles in
fixed bed reactors. It has no active surface (fable 13.2), but does have very
large diameter pores, up to over 100 urn, It filters out the large particles that
become deposited in its ultralarge pores. A small bed of this type of material
placed upstream from fixed bed reactors can reduce pressure drop in the reac-
tors. protect the catalysts downstream and thus lengthen catalytic system run-
ning time.
The high selectivity of this type of material for iron in comparison with a
conventional HOM catalyst is illustrated by the following retention capacity
values:

HDM catalysts Guard material

V (%wt) 11.7 3.9
Fe (% wt) 0.1 2.0
I
,

b. HD.UCatalysts
HDhl catalysts' main function is to eliminate most of the Ni and V metals con-
tained in the feed. Consequently, they must be sufficiently active toward HOM
reactions and also have enough retention capacity to guarantee satisfactory
run durations. They also take part in HDS reactions, but to a lesser degree
(Fig. 13.5).
A key characteristic of the HOM catalyst is its pore distribution. A typlca
zone of HDMand HDS catalyst pore distribution is illustrated in Figure 13.6.

5. The coke comes from polymerization of olefins or from free radicals present In the feed:
or formed in situ.
 CIwJrw 13. !1Es;Dt/EHYcRocONVeiSJOH 421

t
100 :-

l
E
.g
~
::::E
c
J:

25 50 75 100 :

.__ "OS .... r:o wi) I

I Figure:
i 13.5 HDM/HDSselectiGiq tJI cota(vsts.
Feed:Jliddle Easrenr atmosphericresidue.
(The cun;es are at"librium conduions.)

s' _ I
11.00 ~ _ t I

0.80 i MiCl'OlloroSlly\ Macroporosrty i

j ~ 0.60
1, 00-
~ 0.40
:s
0.20
(3
o 10' 100 1 000 10000 100000
Porediameter (A)
- .. - -

Figure
13.6 Catalyst pare distribution.
422 ~ 13 RESIDUEHYDROCONVERSION

First of all. the total pore volume must be large enough to be able to trap a
large amount of Ni and V sulfides. Retention. capacity can go up to 1009('.
expressed in weight of Ni + V in relation to the weight of fresh catalyst. Second.
the developed surface area in the mesopore volume (pore diameter (41)
between 100 and 500 A) must be as large as possible. Figure 13.7 shows the
impact of the average pore diameter of several monomodaJ catalysts. Whereas
catalysts with micropores (<I> < '100 A) promote HOS reactions, those with
meso pores are conducive to HOM reactions and to asphaltene decomposition.
Lastly, a certain proportion of macropores (~ > 500 A) is also necessary.
Macropores make it easier for large molecules containing the metals from the
feed- resins and mainly asphaltenes - to enter the mesopores located inside
the catalyst grains. Ready access promotes a uniform deposit of metals in the
grain and therefore permits high retention capacity (Fig. 13.8).

1.5

.::-
:;E
~ 1.0
(I)
,~

~
a:
0.5

' - - - - - ' - - - - - " - - - -........... --~

o 100 200 300 1300
Average pol1! diameter (A~

L--
Figure - - - - - - - - - - - - - - - - - - - - - - - - - -
i 13.i Effect of average pore diameter on catalytic activity [ I/.

The catalyst's intrinsic activity comes from its active phase (often Nl-Mo in
sulfide form) deposited on the support. Its activity must not be too strong as
it would cause metals to be laid down preferentially on the peripheral part of
the catalyst grain. This would in turn lead to surface plugging and therefore to
lower metals retention. However. its activity must be suflicient, since good
hydrogenation slows down coke deposit on the catalyst. In short, the choice
of intrinsic catalytic activity is a trade-off between metals retention capacity
and hydrogenating activity.
 0.8 0.4 02 0 02 0.4 0.6
00sIanl;a lrllall1e eentBr Qf fie paI1il:;le (mm)

"~~'" ',,,, "'" ""

-. -.
B
-,-,
-,
" ',- -,"'~ \" -, ~

llLl
I

.....
I
I I

Poisoning
,
I
II
~~H~~' c ~" 8~ "C
I
__ .. __ ... ~_ ... _ ... __ ..

G.6 0.4 0.2 0 0.2 0.4 0.6

~ Inlrn lhe';""" dille panide (rMI)

Figure
r---"1
,i-. ----1

13.81 Effect of pore diameter OIIlIletals deposition {4. 51.

l.---J A microporous catalyst. B. macroporous eutDly$t

HOM catalyst deactivation Is the result of both Ni + V metals and coke being
laid down on the catalyst. In fixed beds, deactivation is offset by gradually rais-
ing the temperature. During the catalytic run, metals are regularly deposited
on the catalyst. gradually covering its surface aod plugging its pores. In con-
trast, coke is laid down very quietly on the catalyst by adsorption of the most
polar compounds. and then reaches a phase plateau related to the thermal
level (fig. 13.9). Then it undergoes gradual grapbitization and covers more
active sites. Coke deactivation is predominant in high temperature operation.
It is minimized by using a support whose surface is the least acid possible and
adsorbs the basic compounds in the feed'~- among which resins and
asphaltenes - only slightly. A catalyst manufactured on the basis of such a
support can operate at a higher temperature than an HDS catalyst. In addition
to its 00:\1 and asphaltene decomposition functions, it also allows high con-
version to light fractions.
424 CrA:lter 13. RESIDUE HrDROCONVERS/iJN

25 ~

20
I
I

i
~ 15

~
t! 10 I
:

5 t

OIC-----''-----'"-----'----
o 0.2 0.4 0.6
Catalyst age

Figure
13.9 Deposit of carbon and metals versus catalyst age (fresh. non sulfided,
dry catalyst) {5J,
'---

c. HDS Catalysts
HDS catalysts are the second family of catalysts commonly employed
in residue hydroconverslon processes. In addition to HDS reactions. they
must also promote deep refining reactions: hydrogenation. HDN and HDCC.
They also take part in HOM reactions, but to a lesser degree (Fig. 13.5). They
are placed downstream from the HOM catalyst(s) and therefore receive a
mostly demetallized feed and do not need a high metals retention capacity
(Ni + V < 20% wt).
Their supports have a very different pore texture from that of HDM cata-
lysts, with a large proportion of mlcropores and a few mesopores (Fig. 13.6).
Their surface area is large and easily accessible to the light fractions in the
feed. though less so to the heavy ones. The active phase is generally a Co-Mo
base to promote HDS reactions. or a Ni-Mo base which is more effective for
hydrogenation. HDN and HDCC reactions. HDS catalysts are often operated at
lower temperatures than HOM catalysts, i.e. under conditions that are ther-
modynamically more conducive to hydrogenation reactions.
d. Catalytic System Optimization
The catalytic system is made up of one or more HOM catalysts followed by one
or more HDS catalysts. The aim is to achieve a performance level as constant
as possible over a specified run duration. The choice and volume of each of
these catalysts depend on the unit's configuration (type and volume of reac-
tors. hydrogen pressure), the feed characteristics and the required perfor-
mance.
The principal feed characteristic is the amount of asphaltenes and metals.
The asphaltene content determines the reactivity in relation to the various
 hydrocreating reactions and therefore largely determines the catalyst volume
and necessary pressure (Fig. 13.10) for a given objective. The metal content
dictates the volume of HOM catalysts required. The proportion of HOM cata-
lysts can vary between 30 and 70% (fable 13.2). Figure 13.1! illustrates the
changing HD"I and HOS ratios versus advancement in the flxed bed reactors
with HD~t and HDS catalysts.

100 . . . - - - - - - - - - - - - - - - - . . . . . ,
f I
:::-90 I ! I I I i
~
t I i'Bl i I i
80
!

5 70 I l 'r-...... I .. i
~
~60
I I -i---:-
, ~~
r--. l ~
850 12J.
I .... :---~ !1 ~i I t I i
~40
J:
! ! p 1.-ro+--:-L I r:
-g30 ....
I i , i
III
::E 20 I I
~

a
:I: 10 I I I i ;
~

,
I I
i
I I I ;

o 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Aspnalteneeontent \.~ wt)

Fq:08e :
13.10! Effect offeed asphaltene content on HDS and HD.lf {S}.
t

e. Trwztment ofSpent Catalysts

Spent catalysts used in residue hydroconversion contain not only coke but
espedally metals (mainly nickeJ and vanadium. in the form oi sulfides) origi-
nally from the petroleum residue. Metals can account for up to 100% of the
weight of new catalyst. In the near future. these spent catalysts wiU no longer
be permitted in Jandfills and retreatment will become mandatory.
Once catalysts have been unloaded from reactors they can not feasibly be
regenerated. Although it is easy to eliminate the sulfur and coke deposited on
the caralyst by combustion. the selective elimination of nickel and vanadium
deposits is much more difficult to accomplish. However. this type of regen era-
tlon process is now being developed. Another approach is the destructive
treatment of spent catalysts followed by selecttve.recovery of the metals they
contain. After coke combustion. they can be destroyed by high temperature
alkaline treatment. The solid is then leached. The resulting solid residue
mainJy contains metals such as AI. Co. Ni, etc. which are in tum separated out
by pyremetallurgtcal techniques. The resulting solution mostly comprises Mo.
V. W.etc. salts, which can be recovered selectively.
 426 ChaartN 13 RESiDUEHYDROCONVERSJON

j 98
~ 97 HOS catalysts
:E
HOM catalysts ,
0
:t 96
en0
:r:

90

80

70
60
SO

2345678
Residence time (h)

Figure ,
13.11! Variations in HDM and HDS fo~ a vacuum residue veTSIlS advancement in the
reactors.

13.3.2.2 Dispersed Catalysts

Dispersed catalysts are made up of fine particles injected as is or formed in
situ in the reactor from a catalytic precursor. Thepartides are in suspension
in the reactor and are entrained with the effluents exiting the reactor.
There are two catalyst families:
The first is composed of low price. low catalytic activity particles used in
high concentrations (0.5 to 5% in relation to the feed). They are for exam-
pie natural clays, charcoal impregnated with iron sulfate or other metals.
or finely ground spent HDT catalysts.
The second category includes catalytic precursors implemented in small
concentrations (around 100 ppm). They are organic or inorganic metallic
.c ompounds often with a molybdenum base: for example molybdenum
naphthenate. By in situ thermal breakdown, the precursors are turned
into molybdenum sulfide aggregates or particles associated with a hydro-
carbon matrix. The particles are about a micron in diameter and are
evenly dispersed in the feed. They can have large surface areas
 (> 100 m~lg). but are. however. less active than supported catalysts.
especially in lIDS and hydrogenation reactions.
One of the major advaotagesof dispersed catalysts is that they can be
employed at high temperature. mainly due to the dispersion and movement of
the particles which consequently run little risk of agglomeration and pressure
drop. The high temperature causes a high degree of thermal cracking and con-
vers ion to light fractions, but also a considerable amount of polycondensation.
This is where the catalyst fulfills its main function as a pclycondensatlon reac-
tion inhibitor by capturing the heavy radicals that are formed. Figure 13.12
shows the great reduction in coke formation with increasing catalyst concen-
trations.
The spent catalyst is fodnd in the non-converted residue. It is difficult to
separate out and purify and so is seldom recycled.

13.3.3 Kinetics and Operatinc Conditions:

Conversion to Light Fractions,
Metals, Sulfur, and Nitrogen Elimjnarion
The complex composition of petroleum residues and of the hydroconversion
products makes a detailed kinetic analysis difficult. even more so since ther-
mal and catalytic reactions are closely coupled. A global approach to the
behavior of each reaction family is. however, possible.
Thermal cracking reactions have a high apparent activation energy
(> 160 kl/mo!). The low conversion at 320C is virtually total at a temperature
100C higher (Fig. 13.13). This is why these reactions are more significant in
processes working at high temperature (ebullating and entrained beds). The
higher the molecular weight of the various residue components. the more
crackable they are and their crackability decreases going from paraffins to
oleflns, naphthenes and aromatics. Pressure has only a slight effect on thermal
cracking reactions.
The reactions of polynuclear aromatics polymerization and condensation
that are associated with thermal cracking make themselves felt considerably
above 410'C. As a result. products are unstable and catalyst coking is faster
and more severe. The higher the feed asphaltenes content. the stronger this
tendency is. A high hydrogen pressure win therefore be necessary to hydro-
genate the many radicals created when.feeds are rich in asphaltenes and
thereby prevent polycondeosation.
HD~I and HDS catalytic reactions follow kinetics of an apparent order of
between 1 and 2 in relation to the compounds under consideration. Apparent
activation energies are related to diffusional limitations in the catalyst grains.
Their aooroximate value is 100 kJ/mo!. The HDS reaction is considered to be
irrever;ible. The respective reaction rates of HOM and HDS reactions depend
on the nature of the catalyst. The rate of elimination is faster for vanadium
than for nickel.
:\.;r:e~ically. the effect of hydrogen pressure on catalytic reactions is slight.
but :~em1odynarnically it is more significant. Hydrogen pressure promotes
 I ,i
j ; ,'I
:>l! I:,
;- tO~:i

8 -' II
~Ii~
:'-::;.'- -o-----D----------------i:;J
I __..:.-_-'-_--1_ _1--
o'- -'-_--:-'-::------:-'-----::-':-_--'
o 0.1 0.2 0.3 0.4 C.5

; Figure
! 13.12 .
I
i ffectofMo on coke production Oleo injected in naphthenate form).
'---

100 r-----------------:
80
182-343"C

371 427 482

Fuetor temperature ('C)

I,,13.13
Fagure I'

Lariation in product distribution u:i:,'; reaction temperature.

I i
 awu. 13. REsiwE HrDRot::otwsRso 429

reactions of aromatics hydrogenation, of denitrogenatioo (equilibrium reac-

tions under industrial operating conditions) and of free radical stabilization.
The last reaction limits free radical condensation, thereby resulting in reduced
Conradsoo carbon. better product stability, less catalyst coking and conse-
quently a longer catalyst run.

13.4 Technologies and Process Data [1]

The processes differ essentially in the configuration and number of reactors
they use. Reactors may be of the fixed. moving, ebulJatiDg or entrained bed
type (Fig. 13.14). Moving and ebullating bed reactors have an on-line system
for fresh catalyst make up at the top of the reactor and another for spent cat-
alyst withdrawal at the bottom.
Hydrovisbreaking processes and those of the "donor solvent" type are also
worthy of Dote. Donor solvent processes include a soaking reactor under
hydrogen pressure where the free radical reactions occur with hydrogen trans- .
fer between a hydrogenated distillate and the residue that is due to be con-
verted. In another reactor, the distillate is rehydrogenated catalytically and
then partially recycled to the soaking zone. This type of process was devel-
oped for coal hydroliquefaction, but does oat appear to have had much suc-
cess with petroleum residues.

13.4.1 FiXed Bed Processes

Fixed bed processes are by far the most common: 34 units of this type were
operating in late 1993, Le, 80%of aUresidue hydroconversion units. The major
licensors are Chevron, Exxon, IfP (Hyvahl) and UOP/Unocal.
The reaction section has several in-series fixed bed reactors (Fig. 13.15). In
each reactor the reactants and products circulate from top to bottom by trick-
ling. The fluid approaches piston flow as closely as possible. as it is the most
favorable for the advancement of all reactions. Catalyst volumes are very large
due to the low space velocities and high Dow rates. (For example over 1 000
m3 of cataJyst divided up among several reactors is required for a capacity of
1.5 Mt/year of vacuum residue.) Reactors have the largest diameters possible
(up to 5 m) in order to limit pressure drop. As a result, fluid linear velocities
are slow in the reactors (0.2 to 0.5 cm/s) and fluids need a highly efficient sys-
tem of distribution in the reactors. Poor distribution can create non-irrigated
zones which are quickly plugged up and in tum result in increased pressure
drop.
-Since all of the reactions are exothermic, the temperature profile rises from
top to bottom of the reactor. Temperatures are controlled by gas injections
located on flow lines between reactors or between two beds of catalyst. Several
strategies ior managing reactor temperatures are possible: the mean tempera-
ture variation between the various reactors can rise. remain unchanged or fall
(Fig. 13.16) depending on process and catalyst characteristics.
 20j

I~
15~1.
11
j
~
t
I
'\
j,
~10~:I

8 11\
51i~
i \,
I ;",---o----o----------------..a
I I
0'----'-----'--........----''------'---------"''---__
o 0.1 0.2 0.3 0.4 C.5 0.6 0.7 0.8 G.9 1
%MoIIeed

Figure --------------------------J
iI 13.12 . t Effect olMo on coke production (Me. injeaed in naphthenate famt).
I

100 r------------~

80

182-343=C

:t .\
[ 343-538"C ,
20! .. . :

or--~
315 427 482
Fsaetor temperature (OC)

I FIgUre I:-- - - - - - - - - - - - - - - - - - - - - - - - - - - -
/13.13 I lanation in product distribvlion u:i:h reaction temperature.
! :
 E +30
_ +20
OJ
::J
a1 +10
I
Qj Base h'-----------......,.---~-=---==---___,
I

~ +10 I
I
~ +20 ,
I

HDM+conversion _ ' ....., - - - - HDS

o 20 40 60 80 100
Residence time (0/1

Figure
. 13.16 "Falling" temperature profile of the Hyoah! process.

Temperature variations during a run normally hit a maximum of 42G-430C.

Overly high temperatures cause pressure drop, catalyst deactivation by cok-
ing and instability of the product fuel oil. Fuel oil stability can be assessed by
"several methods (SHFT, Martin Bailey P-value, Asvahl flocculation rate,
NF07-063 sediments, ASTM tests 01661, D2781, 02740, etc.). For instance the
Asvahl flocculation rate detects residue precipitation when the residue is
diluted with a mixture of solvent and antisolvent (xylene and iso-octane) in
variable proportions. The stability constraints limit the degree of conversion
to light fractions (Fig. 13.17). The same limits apply to all the other residue
~ydroconversion processes: moving, ebullating or entrained beds.
Run duration is often shortened by the occurrence of pressure drop sub-
sequent to impurities (coke, iron, sodium, sediments, etc.) being laid down in
the catalytic beds, more particularly at the top. These deposits can also cause
poor fluid distribution and create non-irrigated zones which will get plugged
up and thereby increase pressure drop. The solutions to the problem are deep
desalting of the initial crude (the residue should have-a Na content < 5 ppm
for example) and filtering of the feed for the unit (present-day filters allow par-
ticle removal to less than 25 11m). A further possibility is to place a guard mate-
rial at the top of the reactors. Provided these precautions are observed. fixed
bed process operability is good.
 Sediment content (ppm)

8 800

Q) 6 600
"
c:
.Q
i
:i 4 400
0
0
0
u:
2 200

0
20 40 60 80
Conversionof 550C-+- (% wt)

Figure
13.17 Residue stability versos conversion. Hyvahl process.
Base case: Kuwait vacuum residue.
Sediments content: AFNOR NF 07463.
Flocculation rate: Asoahl method (xylene equivalent).

Fixed bed processes are well suited to treating feeds that contain less than
100-120 ppm of Ni + V metals and runs can last one year:' Set ups with swing
reactors that can be switched on stream during operation of the unit allow
feeds with a higher metals content to be treated. There are at least two swing
reactors followed by one or more conventional reactors (Fig. 13.15). When the
catalyst in one of the swing reactors is deactivated, the reactor is temporarily
isolated from the others. The spent catalyst is unloaded and replaced by fresh
catalyst, and then the reactor is placed back on stream. During this operation,
the unit continues working with the other reactors. The swing reactors are
loaded with HDM catalysts that provide good protection for the other reactors
. loaded with HDM and/or HDS catalysts. A fixed bed process with swingreac-
tors combines the advantages of good operability typical of the fixed bed pro-
cess with the possibility of treating feeds containing up to 400 ppm of metals
for a year.
Table )3.3 shows examples of Hyvahl process performance with atmo-
spheric and vacuum residues of various origins under different severity con-
ditions (e.g. the Kuwait vacuum residue with two different severities).
With the maximum conversion option, conversion of the 550C + residue,
which depends on feed composition and objectives, can go up to 60-70%. With
the HDS option, residue conversion is significantly lower. The HDS option max-
imizes the amount of feed for a residue FCC unit.
434 C!la;:)tBl' 13. RS1DUE HYDROCONVERSION

Type of crude Conventional Heavy

Typeof residue
Original crude II AtmOSPIL
ARbian
Vacuum
Kuwait
I Vacuum
Kuwait
I Vacuum
Safaniya
Vacuum
Cold Lake
Typeof operation CO:\'V ! HDS COW I CONY I CONV

Feed analysis:
Yield on crude~ wt) 48.0 34.0 73.8
22.5 'j',1 22.5
sp.gr.d~ 0.988 1.031 1.031 1.035 1.024
VIScosity at lOO'C (mm2/s) 95 4.010 4.010 3,900 1.095
Sulfur (%\\1) 3.95 5,51 5.5] 5.28 5.05
Nitrogen (% 'it1) 0.29 0.36 0.36 0.46 0.65
Conradson carbon
(%wt) 13.8 21.8 21.8 23.0 18.3
C, asphaItenes (%wt) 5.7 9.0 9.0 11.5 10.5
Ni+ V (ppm) 104 169 ]69 203 325
Mid-nm yjtlds (% \\1):
H~+NHl 3.9 5.3 5.4 5.3 5.1
Ct-C. 2.1 0.9 2.2 2.6 3.2
Gasoline 3.5 1.0 2.2 4.6 5.2
Cas oil 21.5 9.5 19.5 19.7 27.5
Vacuum distillate 40.8 10.5 29.5 32.8 37.0
Vacuum residue 29.7 64.6 43.2 37.1 24.0
": coosumplion:
%wt in relation to feed
HOS ratia("";)
HD~1 ratio (~~)
1.5
94
98
1.8
88
94
Ilr ;:
98
2.1
90
93
2.0
90
95
HDCC ratio (?,) SO 64 &l 70 70
HDAG raUo C'.;) 96 92 89 is 85 I
550'C- converslon 63 3S 56 57 66 i
Cbaracteristiaof hvd.r'l>
treated atmosphericresidues:
Yield'fetd(% \\1) 70.5 85.1 72.7 69.9 61.0
Yieldtcrude 00 wt) 33.8 19.1 16.3 23.9 45.0
sp.gr, diS 0.934 0.963 0.965 0.970 0.958
Sullur~ 'it1) i 0.30 0.75 0.80 0.10 0.80
Conradson carbon (% \\1) 4.0 8.8 10.3 10.0 8.9
C7 asphaltenes(%\\1) 0.3 O.i 1.3 5.3 2.5
Ni+ V (ppm) 2.0 11 4 20 24
!
Table!
13.3 Examples of fIXed bed hydroconoersion process performance.
_1_-
 Chapter 13. RESlaE H ~ 435'

In all cases, HOS ratios are some 90% and HOM ratios are over 90%.
Chemical hydrogen consumption ranges from 1.5 to 2% wt in relation to the
feed. The hydrotreated residues are properly desulfurized and stable and can
be used as an LSFO base stock or as feed for a residue FCC unit.

13'-+.2 MoviD: Bed Processes

Moving bed processes were developed to treat feeds with a high metals con-
tent. There were only two industrial units of this type in 1993.The reactants
(feed and H2 recycle) can circulate downward in moving bed reactors (Shell's
co-current Hycon process, Fig. 13.18) or upward (Chevron's OCR, Fig. 13.19.
and IFP's Hyvahl-Mcount7r<urrent processes).

Makeup
gas

HOM reactors HYCONfixed c:::::>

bed reactors L
Tofractionation

, Figure"
j 13.1sl Hycon processflow scheme [9].

The reaction section includes one or more moving bed reactors followed
by one or more fixed bed reactors. The moving bed reactors are loaded with
HDM catalysts while the fixed bed reactors contain HDM and HDS catalysts.
Temperatures are controlledby inter- or intra-reactor quenches.
An on-line device allows semi-continuous renewal of the catalyst in the
moving bed reactors. Part of the spent catalyst is withdrawn periodically from
the- bottom of the reactor and is then replaced by fresh catalyst at the top.
Special equipment and procedures are used to transfer the catalyst under high
pressure and temperature. During withdrawal and make up operations, the
catalyst circulates by gravity in
piston flow inside the reactor. Outside the
withdrawal/make up periods. the catalyst is normally stationary in the reac-
tors. In a counter-current moving bed process, the upward fluid flow may
cause the catalyst to expand slightly. Catalysts are generally spherical in shape
so that they will flow more readily..

OCR HDS HDS

movingbe<l fixed bed fixed bed
I

~
Fresh
catalyst

Spent
catalyst

Feed Products to
+ hydrogen separation

CJ
,~:I OCR process reaction section no;

All the spent catalyst withdrawn from the bottom of the reactor is rich in
Ni + V metals. In fixed bed reactors, it is only the upper part of the bed that is
saturated in metals. As a result. for a given catalyst. the moving bed process
consumes less catalyst than the fixed bed: This is especially true for the
counter-current moving bed process. where the fresh feed (i.e. richer in met-
als) encounters the spent catalyst in the bottom of the reactor. The catalyst's
metals retention is higher and so consumption is lower.
The feed must be desalted and filtered the same as for fixed bed processes.
However, it is not possible to use a guard material at the top of a moving bed
reactor.
Moving beds encounter some problems of catalyst attrition. The catalyst
moving in the reactor is subjected to considerable mechanical forces. even
more accentuated as the catalyst expands slightly. This is particularly true for
the counter-current moving bed where the upward flowtng feed tends to flu-
idize the catalyst. For proper operation of moving bed reactors, cataiysts
must be able to resist attrition and have good activity and metals retention
capacity.
 The main advaotage of moving bed processes is that they can treat feeds
with a high metals content for long run durations. Product quality and yields
are similar to those of fixed bed processes under the same operating condi-
tions (Table 13.5). Operability is more difficult because of catalyst with-
drawal/rnake up operations and catalyst tines entrained into downstream fixed
bed reactors.

13.';.: Ebullating Bed Processes

Ebullating bed processes were initially designed for deep conversion of
residues into light products. Then they were applied to treat residues with par-
ticularly high proportions of metals and other impurities. such as tar sand
fines. Six industrial units of this type were operating worldwide in 1993(li-Oil
and LC-Fining processes).
The reaction section includes one or more ebullating bed reactors laid out
in-series (Figs. 13.20a and b). Contrary to moving bed processes, there are no
fixed bed reactors downstream. Vacuum residue conversion can be very high.
as much as 80%.
The fluids circulate upward in the reactor and keep the catalyst in suspen-
sion. A recirculatiug pump for the reaction liquid in the reactor accelerates the
liquid's rising velocity. The catalyst is in the ebuUating state and thoroughly
mixed. :\fosinteriog occurs among catalyst grains and. the pressure drop is low.
However, catalyst expansion lessens the effective useot the reaction volume
(the volume of the expanded bed is 30 to 50% larger than the bed at a st.~d
still). Additionally. catalyst ebullition causes a certain degree of attritlon, The
fines produced tend to plug up downstream equipment and are eventually
found in the non-converted residue.
Because the fluids recirculate vigorously, their flow in the reactor is highly
agitated. in contrast to the piston flow of fixed or moving bed processes. The '
result is a slight stage effect and therefore a less effective use of the reaction
volume. which is partially offset by the presence of several in-series reactors.
Fluid reclrculatton leads to an isothermal temperature profile in the reactors.
Temperatures are controlled by inter-reactor quenches.
The same as for moving beds. ebullatlng beds use an on-line seml-conttnu-
ous catalyst renewal system. Catalysts are often in the form of small extru-
dates (diameter < 1 mrn), which are easier to Ouidize without any pressure
drop problems. however. Contrary to the moving bed where all the catalyst
withdrawn is saturated in metals. the catalyst withdrawn from the bottom of
ebullatlng bed reactors consists of a mixture of particles of varying age.
Catalyst use and consumption are. as a result. more pronounced.. '
The likelihood of catalyst grains becoming agglomerated and plugging up
the reactor is slight.' The temperature profile is isothermal. so the process .
operates at higher average temperatures than fixed and moving beds.
Conversion to light fractions is higher (up to 80% wt). Reaction volumes are
smaller than for fuced or moving bed processes. High temperatures lead to
rapid and severe catalyst coking.
438 C/lapref 13. RESIOI.!E HYDROCONVEFlS.'ON

Catalyst l ..
addition

~
1GaS~i~~
separator

C':JGas
r---, Gas
~andljquid
E:=J Catalyst
~ 1 t----l-o--. Distributing plate

Hydrogen
/
and feed

Recycle
loop .'
Figure
13.203 H-Dil process r///.

Ebullating bed operability is more difficult than fixed bed because catalyst
renewal oper~tions are carried out at high pressure and temperature, and
because dUril)g them downstream equipment can become obstructed.
Catalyst c~nsumption is high and product quality is lower than for prod-
ucts from fixed or moving bed processes. In particular. at high conversion the
stability of nO~-eonverted residue is borderline for use as a base stock for com.
mercial heavy. fuel oil. Another prime use of the residue is to gasify it in order
to produce h}lrdrogen.
 ,
-1._-------- - - - - -
--1---'~--'-' -- ----,-------

.- ------, ~
CUlnly:il I(
l\;!purUtl
uddllion
... I ~

r------'...
c- Recyclo
H 2 make up compressor
---~

- ... Fualona {J

H;,: furnace
Fracllonation
Naphlha
Iw
Gas 011

Vacuum
Residue
leed -
Q- ~ Catalyst
Vacuum Oisllllata
10 FCC f
Feed
furnace I.
withdrawal

I ~ r
Vacuum Residue recycle HSV
i
l
F;~".
13.20b Jo7()//~ scheme of /I.(}j{ process with two reactors.
Q

L,
 ~
Atmospheric and Vacuum

t
distillation Distillates To refinery

Recycle gas i:>

.r-I.
&
Crude _.- -- ~I~ ~ . ~

f-
III
:x:

Addilive - - ~reul~-:I ~
~
~-----~V\I~ I 10- Gas
I Naphtha

Hydrogon .... - - - _ _ _. 10- Korosene

~ MhlllllllllnlHlnln

.~_~ Vacuum WIS nil

I __ .. HydrogoJ1l1lod
roskluo

Hllllrc
t3.21 I vee /'t"OC(!S.<; flow.<;clteme.
 13.4.4 Entrained Bat Processes
Even more so than ebuUatiog bed processes. slurry or entrained bed pro-
cesses are designed to operate with residues having a high proportion of imp~
nnes, or even those containing wastes such as spent solvents and used plas-
tic and tires. These processes are in the demonstration stage today: Veba's
vee. Petrocanada's Canmet and Exxon's Mlcrocat.
The reaction section (F"tg. 13.21) includes one or more in-series reactors
where the feed. the recycle gas and the dispersed catalyst circulate in an
upward stream. The linear velocities of the gas and the liquid must be high
enough to entrain the catalyst and keep it from accumulating in the reactor.
A process layout up t~ is often proposed comprises a fixed bed reactor
associated with a slurry reactor. The fixed bed reactor is designed to refine
the light fraction produced by conversion in the slurry reactor (Fig. 13.21).
The general operating conditions are similar to those for ebuUating bed
processes: high reaction temperatures and pressures, and residence times
shorter than those for fixed or moving bed processes. Pressure losses are low
and temperature profiles are isothermal in the reactor. Conversion to light
products is very high (up to 90% wt).
However. slurry process operability is difficult. High reaction tempet'Mures
mean that coke is formed and agglomerated with the catalyst. The catalyst
tends to accumulate in the reactor, which can in turn plug up the unit or
equipment downstream.

13.4.5 Advantages aM Drawbacks of the

Four Types of Process.
Product Yields and Characteristics
Differences in process performance involve the ability to treat feeds that
are more or less rich in impurities as well as the yields and quality of the
products (Table 13.4).
Table 13.5 gives examples of product yields and quality from the different
processes applied to a heavy Safaniya vacuum residue. The resulting products
may need further hydrotreating steps to adjust their quality, especially in the
case of ebullating and entrained bed processes.
When operating a fixed or moving bed "type of process. wide-range gasoline
is produced in small amounts (1 to 5% wt). Its naphtha fraction has a low
octane number (around 60) and can serve as a catalytic reforming feed pr0-
vided it undergoes pretreatment. The gas oil yield is higher (10-25% wt). Its
sulfur content is often lower than 0.1% wt. Its cetane number hits a high of
42-45 and a further severe bydrotreatirig step is required to unprove it. The
same holds true for its aromatics content (40 to 50% wt). The vacuum d~
late is produced in significant amounts (20 to 35% wt). It is properly desulfur-
ized.-(S = 0.25-0.5% wt). In contrast it has a high nitrogen content that is not
favorable to using it as an FCC or hydrocracking feed.
442 C1lIIpIfK 13. RESIDUE ~

_.
Type of process I
Fixed bed Moving bed Ebullating bed I EntrniDed bed r.

Number of units (1993) 34 2 6 Demonstration

Maximum Ni + V content
in feed (ppm wt) 120-400* 500-700 :>700 >700
Tolerance for impurities Low Low Average High
Max. conversion of
550"C" (% wt) 60-70 60-70 80 90
I
1 Distillate quality Good Good Good Poor
Fuel oil stability Yes Yes, Borderline No
Unit operability Good Difficult I Difficult I Difficult

* SWing reactor.
-Table
-
13.4 Comparison of the different processes.

~ T(C)

2 3 4 5 6 7

:V
J!
,

Safaniya Vac. Res. feed (1)

Vac. Res. prodUCed by HVB process (2}
by fixed bed process (3)(4)
by ebuUating bed crocess 151(6)
by SlUrry process 17)

25 50 75 100
Cumulative yield (% wt)

Hydroconcersion of a vacuum residue: variation in product distillation curves

according to the type of hydrotreoting process.
 Figure 13..22 shows the wide differences in the distillation curves for a
Safaniya vacuum residue effluent according to the hydroconversion process
applied to it: bydro\isbreaking (HYB), low and high severity fixed bed catalytic
hydroconversiao. low and high severity ebullating bed hydroconversion and
slurry hydrocom-ersion. -

Type of proas Flxed/moving bed EbuUating bed . Entrained bed

Gasoline: I I

Yield/feed r-; \1<1) 1-5 3-10 10-15

sp.gr. dl i 0,T20--{).74O 0.il0-0.r20 0.T20
Sulfur (% >4)
Nitrogen (ppm)
.' < 0.01
< 30
0,01-0.2
<50
0.06
200
PIN/A (% vel) 65/25/10 - -
Gas oil:
Yield/feed (S \111)
sp.gr. dIS
10-25
0,850-0.875 I 20-35
0.840-0.860
4(}.45
0.866
Sulfur (%wt) <0.05 <0.1 0.7
Nitrogen (ppm)
Cetane nUl8ber I <500
42-46
< I 000
42-46
1800
40
Aromatics ~ wt) 40-50 - 40-50
Viscosity al:50'( (mm~/s) 2.5 - 3.5
Cloud poiat CC) -15 - . -9
Vacuum distillate:
Yield/feed (% \1<1) 20-35 35-45 20-25
sp.gr, d15 0.925-4).935 0.930--0.940 I 1.0lO
Sulfur (% ld) 0.2-0.5 0.4-0.8 2.2
Nitrogen (ppm) < 2000 < 2500 4300
Viscosity aI: ItlO'C (mm2/s) 8-12 8-12 7
Conradsoaearbcn (% wt) I <0.5 <1
I
<2
Vacuum residae:
Yield/feed r:. . .
1) 35-60 2G-l0
I ~20
sp.gr. dP 0.980-1.010 1.010-1.050 I I 1.160
Viscosity lit loo'C (mm~/s) 150-1200 1000-2000 60000
Sulfur (% 1rt) 0.5-1.0 1-2 2.7
Nitrogen (ppm) < 4000 < 5000 11000
Conradsoo carbon (% wt) 15-20 20-30 4i
Ni+VCPsm) 10-40 50-100 ,I 90
Shell P...aIue stability - 104-2.0 1 1.1-1.4 ! 1.0 - - .
'-c--
I
j
I Table
f 13.5 E:m1aple of product yields and quality for the different processes
L...........-- (ke/: Sataniya vacuum residue).
 444 Ct..;Jltlt 13. RESIDUEHYDROCONVERSION

13.4.6 Associating the Hydrotreating Process with

. Deasphalting and Hydrogen Production [3]
An attractive residue conversion set up associates a heavy solvent deasphalt-
ing unit (DAS) with a fixed bed residue hydroconversion unit. Together they
can be used to process increasingly heavy residues and get very high conver-
sion and purification performance. Depending on the case, deasphalting can
be located upstream (called the "indirect" process) or downstream from
hydroconversion (the "direct" process). In both cases the product asphalt can
be utilized as a fuel, or preferably upgraded with partial oxidation (pOX) to
produce hydrogen. The deasphalted oil (DAO) is upgraded in an FCCor hydro-
cracking unit after a preliminary hydrotreating step if need be.
The following examples implement the Hyvahl fixed bed hydroconversion
process with HOM and/or HDS catalysts depending on the case. Figures 13.23
. to 13.25 and Table 13.6 show the overall performance of a variety of process
combinations on a very heavy Safaniya vacuum residue (2 Mt/year):
Simple residue hydroconversion (HOM+ HDS)does not produce a fuel oil
with a very low sulfur content (S = 0.75%wt). Its Conradson carbon is too
high (10% wt) for it to be used in a residue FCCunit.
The association of hydroconversion (HDM + HDS) and SOA (direct pro-
cess, Fig. 13.23) yields a fuel oil with 0.5% wt sulfur that can be sent to a
residue FCC unit due to its low Conradson carbon (5.5% wt) -.The amount
of asphalt produced is small and the resulting hydrogen production can
be absorbed by the refinery, although it does not cover all the refinery's
needs.
The association of DAS + HOT of the DAO (indirect process, Fig. 13.24)
produces a fuel oil with a very low sulfur content (S = 0.2% wt) or an
excellent feed for FCC (Conradson carbon = 2.5?~ wt). However. the
amount of asphalt is very large: 0.813 Mt/year as compared to 0.215 with
the direct process. Partial oxidation yields hydrogen in excess of refinery
demand. .f

Another combination is the result of a compromise between the two pre-

viously mentioned: a simple HDM step upstream from deasphalting and
HDT of the DAO (semi-direct process, Fig. 13.25). This associatlon of
HDM + SDA + HOT of the DAD allows the amount of asphalt to be opti-
mized (0.450 Mt/year). Gasification of the asphalt yields the hydrogen
required to meet refinery needs. The 3iSC+ effluent is of a quality simi-
lar to that of the indirect process. Implementing the HOM step alone
requires reaction volumes some four times smaller than for direct hydro-
conversion. thereby reducing investments considerably.
 Gas

Atmospheric
residue

4.78 MVy
Vac.
Dis.
~_.~. ~~~l.I~~~~~~_~._... _._ _._ :.~
Gasoline Gas oil

Vac. Dis.
:
I

y
_ _ ~

~ . J'- " J
I.IDC'---~Gasolillo
~ ._~-~ Kerosene
Gas oil

2.21 MVy

Hydrogon
0.048 MVan
Hydroconversion

OIVar.":.J .
Vac. Res.
1 Asphalt
0.770
=
LS fuel oil (8 0.5% wi)
1.483 MtJy i
~

if?
!,
0.986 MVy 0215 MVy ,..'.

Hl:lIrc
13.23 \ IIp/:racfillg residues by noc. I'RnS, S[M atu! POx.
1l1l.S/! stock- Arabian heavy crude (8 Mt/year).
I
~.
 I

Gas i
~

Vacuum Residua 2.57 Ml/y

I

fli'
~
I :
Almospheric 1 Gasoline
1 HOC Ilj
residue Hydrogen
:1

I
Vac. I Kerosene + gas oil
4.78 Ml/y I Dis. 0.082 Ml/y I

Gasoline
+ gas oil

I
UAU t l81ueloil

~Ga~ma
(8 = 0.2% Wi
1.40 Mlly
1.191 MVy FCC LCO
2.21 Ml/y
HCO

..
' ~rogonO".3MIIy
Asphalt

~
0.813 Ml/y
l

Figure
13.241 Upgrading residues bynoc. SIJA, IlDT. FCC: and POx.
Base stock AmMon heany crude (8 Mt/yem).
 VUCUUITI gas oil

. .....
2.57 Mlly
' .__ .,
----_.- ---...
._.,...
G HOC
. "" GlIsolino
.. Korosono. gus oil

HydrOlJCn

r--
Atmospll(J(/c 0.082 Mlly
rosiduo 1.494

rE~ l
Vacuum Distillate
4.70"MiIv-""' 6~~: - .~~~ol 011
Ga.:I~~~... 0.44' MU;~,?
MVy
1.270MVy
(8 .. 0.2%wl)

L u MVy
, _.L!_ _--"
Hydrogon
D.024 MVy

"'[~~HOM
2.21 MVy 9
SOA ~
':2'~ogen , !Ii
I ' i;>
0.0310 MVy
0.450 ;:Q
Vacuum Rosidue 1'503
p MtY ("
:/
Hydrogon .. ~
:t
0.085 Mt/y
~
g
t)

l\.. -.
".
"'l:lI r .:
IU~
I
111)f/I'(/(IiI"I1lt'/rtll~$ by IIDC, ImAt. SDA. IlLn; and POX
! I
1J1l.~e stock: Arubiun JW(IIIY cnule (8 Mt/year). ~
../
448 Chapter 13. RcS:OUE HrDROCONVERSION

(HDM I DAS
HDM
Processes
Vacuum
Safaniya
(HDrtf
+HDS)
+HDS)
+SDA
I +HDT
+SDA
+HDT
+ POX
I + POX
+ POX

Process ! Direct Direct I! Indirect Semi-dtrect

i
sp.gr. d~s I 1.052 0.965 0.947 iI 0.928 0.925
I
Viscosity at 1oo'C (mm 2/s) 55000 75 59 50 35
Sulfur (% wt)
~

6.0 0.75 0.5

I 0.2
I 0.2
Nitrogen (ppm wt)
Conradson carbon (% wt)
5 000
27.7
3200
10
2500
5.5
Ii
1300
?~
_.a I 1200
2.5
C7 asphaltenes (% wt) 13.4 4.2 <0.05 <0.05 < 0.05
Ni + V (ppm wt) 270 25 2 <1 <:1
I
u
---l
I~:I Characteristics of 37SC+effluenJ$ according to various combinations;

13.5 Economics
The table below shows typical investment items and operating costs for the
four combinations presented above. The data correspond to processing
2 Mt/year of Safaniya vacuum residue. Investments increase with process corn-
plexity, but operating costs decrease from 29 to 24 per ton.

Processes
+ SOA + POX. 'I- POX
I
(HDM 'I- H.DS)! (HOM + HDS) SDA + HDTI HOM + SOA
,+ HOT + POX

Process Direct I Direct !

i
Indirect I Semi-direct
Investments (106 E 1999) I I
in battery limits:
HDM + (HDS)
I

213
I
! 213
r

-
!
I 134
SDA I - i 33 62 46
I
HDTDAO I - - 55 I
46 I
POX ! - i i
81 , ~O3 ! 134

I
Total 213 327 320 t 360
i
I
Operating costs I

(10& 1999/year): i
Investments + utilities
i
34 I 52 50 57
Catalyst 4
I 4 1 3
j
Hydrogen 20 ! - - -13
Total (106 Elan) 58
I 56 ; 51 47
(e/t)
1
29 Ii 20 26 24
~r I
I Table I
! 13.7 I Investmentsand operating rosa.
References
Le Page IF.. Chatlla S.G.. Davidson M. (1990) Raffinage et conversion des
produits lourds du petrole: Editions Technip. Paris.
2 Gray M.R. (1994) "Lpgrading Petroleum Residues-and"Hear.-'Y Oils. ~larcel
Dekker.
3 Billon A.. Mornsson E., Morel F.. Peries J.P. (1994) Les precedes IF? Hyvahl
et Solvahl de conversion de resldus. Rev. Insf. Franc. du Petrole 49. 5.
4 Van ZigiU langhout W.C. (1980) Oil Gas J. i8 (48), 120-126.
5 Dautzenberg F.:-'l.. de Deken J.C. (1985) ACS prepr. Div. PeL Chern. 30 (1). 8.
6 Le Page J.F., ChatHa 5., Davison M. (1992) Resid and HeaLy Oil Processing.
Editions Technip, Paris.v -
-7 Beaton Wi, Bertolacini RJ. (1991) Resid hydroprocessing at Amoco. Catal.
Rev. Sc. Eng. 33 (3 and 4).281-317.
8 Kressmann S. Morel F.,Harle V., Kasztelan S. (1997) Catalysis Today (to be
publishing).
9 Scheffer B.,Rohscklager K.W., de Boks F.e. (1997) The Shell residue hydro-
conversion process. Development and achievement. ACS" meeting San
Francisco. April 13-1t, 347-350.
10 Reynolds B.E., Bachtel R.W., Vagi K. (1992) Chevron's onstream Catalyst
replacement (OCR). NPRA meeting New Orleans.
11 Colyar JJ.. Wisdom L.I. (1997) The H-Oil Process: .i worldwide leader in
vacuum residue hydroprocessing. NDRA meeting. San Antonio.
 14
Hydrogen Production

Gerard Bourbonneux

The importance of hydrogen in refining is due to the requirements of catalytic

processes which are being increasingly used to purify or convert petrolewn
fractions. Part of the required hydrogen is a by-product of catalytic reforming.
However. even when hydrogen is carefully recovered from hydrogen purges.
it often needs to be produced in specific units. The hydrogen. balance of a
refinery is directly related to the feeds processed and the product quality
required. Any change, either in the characteristics of crudes available on the
market or in product specifications, will ha\l'e an impact on the hydrogen
balance.

14.1 Hydrogen in the Refinery {l]

1-+.1.1 Requirements
The reflning processes that consume hydrogen are:
hydrodesulfurization,
hydrogenation processes.
distillate hydrocracking,
heavy residue hydroconversion.
In ail these instances. hydrogen consumption is the result of chemical reac-
tion plus losses in purges and amounts dissolved in the products.
Hydrodesulfurization is widely used in refineries to treat a number of very
diverse cuts. from naphtha to gas oil and vacuum distillate cuts. The hydrogen
required by these units is supplied by the gas produced in catalytic reforming
452 Cf"oP/er 14. HYDROGEN PRooucTION

units containing 70 to 90~6 volume hydrogen. Typical consumption figures are

as follows:
Ught distillates: 0.6 kgJt,
jet fuels: 1 kg/t.
atmospheric gas oils: 3.5 kg/t,
cracked gas oils: 5 to 10 kg/t,
vacuum distillates: 5 to 10 kg!t,
deasphalted oil: 10 kg/to
Chemical consumption could be higher Ifthe aim is deeper desulfurization
or a more complete hydrogenation of olefins and polyaromatics.

Hydrogenation of the most common cuts includes:

hydrogenation of light and middle distillates from thermal conversion
units (vis breaking. coking);
selective hydrogenation of steam cracked gasolines, converting diolefins
and mono-olefins to paraffins;
isomerization of light distillates;
hydrofinishing of lubricants;
hydrogenation of various streams (cuts rich in benzene. benzene con-
verted to cyclohexane, benzene produced ex toluene. heavy steam crack-
ing feeds).
Typical hydrogen consumptions are:
light and middle distillates: 10 to 15 legit,
steam cracked gasoline: 5 to 8 kg/t,
isomerization of gasoline with:
- end point 80C: 0.6 to 1 kg/to
- end point 110'C: 3 to 4 kg/to
Hydrocracking and hydroconversion of heavy residues. Hydrocracking of
vacuum distillates or deasphalted residues operated at 100 to 200 bar con-
sumes from 25 to 35 kg1t of hydrogen. Consumption is reduced to 20 to 30 kg/t
with deep conversion at 200 bar. Residue hydroconversion consumes from 15
to 25 kg/t depending on the degree of conversion selected. These very high
pressure units need hydrogen at over 99% volume purity in order to meet over-
all economic concerns.

14.1.2 Sources
There are three sources of hydrogen:
refining operations for which hydrogen production !s not the main objec-
tive (catalytic reforming, purges from hydrotreating units. etc.):
specific production units (steam reforming. partial oxidation):
 supplies from outside the refinery (petrochemical and fertilizer plants)
that may be gathered together ill a network.
a. Catalytic Reforming
.-\5 discussed in Chapter 4, hydrogen is produced by dehydrogenation of naph-
thenic hydrocarbons into aromatic hydrocarbons as well as by hydrodecy-
dization of paraffins. Hydrogen production depends on a number of factors:
feed characteristics (cut, PONAanalysis):
type of catalyst and operating conditions selected (pressure, tempera-
ture) to achieve a specified octane number:
type of process (discontinuous. continuous or semi-eontinuous regener-
ation).
Hydrogen produ~ti.OO4I'angesJrom 15 k!y'tof i~d for the oldest units work-
ing in a discontinuous ~ode at high pressure;:.o 25 to 35 kgft for cont~ous

b. Parges from Units

..
"" ..
regeneration units working at pressun:s.of 3 to 10 bar.
-
.

Catalytic and thermal cracking processes provide small amounts of hydrogen

(0.5 kg/t of feed) diluted in gases rich in olefins (IS to 20% vol). Here. hydro-
gen recovery "is generally not economic. At most, these effluents are mixed
with methane and serve as fee<} for partial oxidation units (see Section 14.3.2).
Purges from gas oil hydrodesulfurization and distillate hytlrocracking tmits are
rare (the makeup hydrogen is increasingly pure) and flow rates are generally
too low. Only purges from units performing deeper residue conversion can be
recovered. The purges are purified either by membrane permeation or by PSA
(see Section 14.2.5).

14.13 Hydrogen Balance

Catalytic reforming is today the largest source of hydrogen for the refiner.
Revamping these units for operation at lower ;.ressure and with continuous
catalytic regeneration' generally allows hydrogen self-sufficiency in refineries
without hydroconversion. However. in the long term the limits placed on ben-
zenebd aromatics content in motor fuels WiH reduce catalytic reforming
throughputs, and therefore hydrogen production.
The balance sheets presented in Table It I emphasize the impact on
hydrogen availability of the type of crude processed. the refining flow scheme,
and the product breakdown andspedflcations.
The first two columns show the production of a typical 8 Mt/year refinery
.supplied with 34;API crude before and after the new sulfur specific~ationS carne
into effect on diesel oil in 1996. Column 3 shows the effect of heavier crude
supply (60?6 Arabian Ughtj40% Safaniya). Columns 4 and 5 show balance
sheets with a residue hydrodesulfurization unit incorporated with high or low
pressure catalytic reforming. Refineries with codng and hydrocracking (with a
net hydrogen deficit) are represented in columns 6 and 7.
 - ._--~
_.-.........-._- ...'-'--_.-"-"_.-- ;--- .,I.
Ihnner)' 1993 Ill' nlll'I')'
_ . .. _-- 111'11\')'
crude witII
Rl,nlll'l')'
vacuum resldue IIU5 wllh
KI'(hll'I')'
willi
~l.'

1.3 standards 96 standard. .upply ruklJl' hydnwl'!wklll'

Column number
_._.~,-"._----

I
~----~---
2
----~~-~--

3 4 5
- 6 7
(I
~
Reforming tiP Reforming LP ~
~:
PrudlKflulI (MI >: ::I
I..P(; n.2:l 0.27 o.n o.a 0.3 0.3 1J.3 ~
)'elrodwlJIkal (I'\'(/slo\"l;s tt:J3 o.:m -3.20 0.9 0,9 0,9 0,2 <'1
.:
(,1
"I
(ii\sulln('~ I.litl 1.61 1.7 1.7 1.7 1.:1:1 ~
K('rl>SI~IIC 115 11.5
1.8(i
(JAil O.4:i OA3 0.43 O,tlli s ~
,\,
],
1',
DIesel oils I.S(i 2.94 2.l}(i 2.DO 2.05 z.so ~
'" ~J

Domestlc healinJ,! 011 1.15 1.15 - 1.4:l 1.5 1.5 1.3 ~ ~ tl

l lcnvy Iiu-l uils
Very low sulfur luel oil
i.is
(J.lD
1.2!1
11.111
-0.25 -
(J.'\
-
U.S
-
0.1 l.ltl.~ ~
t~ ~
>8
.- (,
r'
8-
Low sulfur fuel 011 (UO n.20 -- - -
-
-- a.
~~ .;~4J
High sulfur fuel 011 O.!15 0.99 '-- 7 tIl

Lube 011 hase stocks

11ItuIIlCIIs
(J.17
11.:11
0.17
11.31
0.17
- 0.27
-
(1.29
-
11.29
1I.23t~
O.. 25-tj ~
~!.
,~

Coke - - - - -;. 11.25 -

---iOil]
--:4' 07-
I
Hydrogen pro(j~ction (kt) '~-l:t8-'- ~:s-. '--riL5-~

including: reforming 13:R

13.9
13.9
67.4
ISA
23.8
7.0 /5.9 /9..5 24.0 .~ ~
7.
hydrogen unlt - - 52.0 /6.8 7.,9
. - 76.0 0-
1iY;I;:;;gcll CO~l;;;;I~Ii(;;1 (1.1) ---11~4--- ~:5---- -2iR~-
--,._-~.-

~--iil.5- ~ 'jorU,'--
;,u:/udillg: I illS "-
1 /1.4 JJ.i 11.7
2:UI
11.7 1fJ.I to
resklue I IllS
vllrloll~ pretrenuuonts
-lIy<ir;;~;;n:lvi\ii;l);illiy-(ki ) ----
-
-!1.8--~
_.
-
-
--iff--
-------_ ... -
.~---_._
2.'J.:f
. 2(i.5
..
- _-_._ _._.. -
-
12./ /2./
... -_._-- .. -
_~

.-------_
..--
-~_.,-
-
.').4
~~-,

- .... ...... _----

-
.. ....--. __ !J(J.(J'

I ---. ----------------------
--~~. . " ~ .. ,,-- ... --
-~- ... ~_ .. .. _-~--_.-.-

~Uh III'W dle!lel oil SIIIdlknllolls. V;"'1lI1111 residue lIDS + hydrocrnc kill". flO'X. Amhlan I.lllhl/111'X, Salalllyli.
Table
I.. ~ _. "(I'flinrl R MII)'('(r,- refirwry Atuuta! balance sheet.
 C::.JOUIT 14.' ~ PROOt/CT:CN 455

Hydrogen production by specific units becomes a necessity for refineries

processing mainly heavy crudes (column 3), and for those with residue desul-
furization or hydrocracking units. There are two major hydrogen producing
technologies:
steam reforming of light hydrocarbons,
partial oxidation of heavy residues.
There are additionally processes that allow the hydrogen present in refin-
ery streams to be recovered: mainly Pressure SWing Adsorption cPSA) and
membrane permeation. Cryogenics is also used, but is usually of interest
only if the recovery of other (hydrocarbon) components is economically
attractive.
"

14.2 Hydrogen Production by Steam Reforming [2]

Hydrogen can be produced by catalytic steam reforming of light feeds accord-
ing to two flow schemes which differ in the final purification step (methanation
or selective adsorption).
For methanation, the process line up includes:
production of synthesis gas by steam reforming,
conversion of carbon monoxide into hydrogen and carbon dioxide in two
stages by steam,
carbon dioxide removal.
methanation of the residual CO.
Hydrogen purity ranges between 95 and 98% volume depending on the -
technologies used and the feed nitrogen content (e.g. natural gas reforming).
Hydrogen recovery from the produced synthesis gas is approximately 98%.
For selective adsorption (PSA). the production sequence includes:
production of synthesis gas by steam reforming,
conversion of carbon monoxide in one stage,
selective adsorption (PSA).
Here hydrogen purity is over 99.9% vol irrespective of the feed. Hydrogen
recovery ranges from 80 to 90%vol depending on the complexity of the PSA
unit.

14.2.1 Production of Synthesis Gas

Steam reforming consists in converting light hydrocarbon feeds into synthesis
gas (a mixture of H2, CO, CO2 CH~ and H20 ) by reaction with steam over a
nickel catalyst.
456 ChaDtfK 14. HYDROGeN PRoOUCTION -

14.::.l.f Reaction Thermodynamics

The main equilibrium reactions are:
CH4 + H20 =; CO + 3H z Mf"298 =206.0 kJjmol (1)
CO + H20 :::; CO2 +. Hz 6lrZ98 =-41 kl/mol (2)
For hydrocarbons higher than methane, the overall reaction becomes:
CnH2n+Z+nH20 =:: nCO+(2n+ I)H z (3)
This reaction is preceded by a primary methanation reaction:
n-l 3n+l n-l
CnH 2n+ %+ -2- H20::; -4-' CH4 + -4- CO2

This exothermic reaction is practically complete between 400 and 600C.

The process continues with reactions 1 and 2. and as both are equilibrium
reactions, the composition of the reformed gas is dependent on operating con-
ditions (pressure, temperature) and on the amount of steam used,
The methane conversion reaction is further from equilibrium than the car-
bon monoxide to hydrogen conversion reaction. which is relatively insensitive
to pressure, and so is very dose to equilibrium.
The coking reaction:
2CO =:; CO2 + C Mli9s =- 172,2kl/mo]
which is favored by a decrease in temperature and an increase in pressure is
prevented by injecting excess steam with respect to stoichiometry so as to
favor reactions 1 and 2.

14.2.1.2 Steam Reforming Feeds

Light hydrocarbons (natural gas, refinery gas. LPG and naphtha up to an end
point of 200 to 220"C) are likely candidates for steam reforming feeds.
Natural gas is the ideal feedstock. Usually. an appropriate amount of gaso-
line has to be extracted from it (maximum C3-'7 content is a few % \\1) so that
it can be treated on a conventional steam reforming catalyst. The purity of the
hydrogen produced by the methanation process may be significantly lower
only if there is a high nitrogen content in the feed.
Naphthas were often used in the past. but presuppose:
a system to pretreat the feed in order to limit coking in the preheating
tubes;
perfectly controlled desulfurization to achieve a sulfur content of
0.5 ppm wt;
a specific catalyst to promote destruction of the coke produced by crack-
ing the feed.
The aromatics and naphthenes must be limited to approximately 30% wt,
and a high olefin content requires special precautions in the desulfurization
reactor to limit and/or remove the heat of reaction produced by hydrogenat-
lng the oleflns.
 Liquefied petroleum gases are a commonly used feed that generally cause
less severe problems than natural gas or naphtha. i.e. nitrogen free and no ten-
dency to coke. LPG has specific risks:
chloride J content should be limited to 0.5 ppm, and
propylene/butene content, which may be high and cause the same ther-
mal effects as naphtha olefins.
Refinery off gases can be added to the selected feedstock under certain
conditions.

H.2.1.3 Catalysts and Conditions of Use

A nickel catalyst deposited pn an alumina support is the most frequently used.
The catalyst is placed in tubes that are generally heated by radiation in a fur-.
nace, and works under relatively severe conditions:
furnace outlet temperature: 820 to 880C,
furnace inlet temperature: 540 to 580C.
furnace outlet pressure: 20 to 25 bar,
steam/carbon (molar ratio): 2.5 to 5.
The composition at equilibrium. which depends on the pressure, the tem-
perature and the steam/carbon ratio, can be obtained from the curves in
Figures 14.1, 14.2and 14.3; established for pressures ot I, 5, 10,15.20.25,30,
35. and 40 bar.
Given the catalyst's behavior under real conditions of use, a temperature a
few degrees higher than the operating temperature should be taken into con-
sideration in order to determine the concentrations of the different products
at equilibrium.
The nickel catalyst is either precipitated or impregnated on an alumina
base when the feed is natural gas, and on a silica/alumina mixture for naphtha
reforming.
Developments in catalysts involve formulation and shape to increase activ-
ity, as well as mechanical strength to decrease pressure drop and tube skin
temperature. particularly in the zone where heat flux is at a maximum. Several
types of catalysts can be used, especially when the feed gas contains heavy
hydrocarbons.
The steam reforming catalyst is sensitive to certain poisons, with the main
ones being:
sulfur compounds, which require deep desulfurization of the feed; the
effect is. however, reversible and less significant at high temperature;
.halogenated compounds. which come from the chlorine present in water
and in certain natural gases:
. arsenic, the effect of which is permanent.

1. Introduced by water wash.

458 C1IBoler 14. HYOROGENPRooucrION

102 9

(j)
ctl
OJ
2:- 5
~
I
o
0:>
tfl

3r--.....lr----1-------~_.:__-----_i

2r---+----------;--~---~

2 3 4 5 6 7
H20 I C (molarratio)

i Figure
, 14.1 Methane refonning at 800C (from a BASF paper). Residual methane IJe13US
'--- steam/carbon molar ratio for pressures from 1 to -10 bar:
 100

50
4tI
30 I
~=<2.666i
20 C I
I
"0 I
>
#.
10 I

5 I
4'
i
3

.:..+bi~~~::r::!~ ; 50
~~~~:;i;'3F""'''-------:-.J,------!'----J,----!~~-~-l40

~~"----l--------!--J,---l---~~'--;l,--+---,.I. 30

0.2 ~.-+-----+---+--\-+-----,\---~l___I20

0.05 -""-----7''---t+---,~~.....----_'_:_---f__--''''''''''''--...-: 5
0.04 4
0_03 13

0_02 ---r---,4#~f---'----:--_\_-l----!..--i 2

0.01 _.L-...t......~I.LL~_ _- - ' : __ _----:>l__ ___l..__i

500 600 700 800 900 1000

i'-: Figuu - - - - - - - - - - - - - - - - - - - - - - - - -
! 142 Composition at equilibrium for pure methane cersus temperature:
H;:OIC:: J.666: each canoe corresponds to a pressure hom 1 to -10 bar (From
BASF)-
GO.fume of gas at outlet)
'/ (colume expansion)
.
=( volume of gas at inlet
_
 100
I I

50
!
~ i
40
30 ~~ I
I~~ ~>~ I
HZO=4

'0
>
rfl
20

10
I~CH. "'i"" ~'~, ~
'c.. ~
~ I
c i !
i I
I
I
\ '\'" ,,~~'\
I
I
I
i
5
4 \ \ \ -. -. \"-" !
3 1\ f\ \ \\\ \ ,\'\ I
2 I \ \ \ \\\\i\\ I
lEV
d--
\ \ r\ \\\1\\\
\\ \ \ \\ I
I
T' \

,-
\ 100
\ \, \ \ '\ \ '. \ \'

0.5 ~
~ ;;0-----:::::::;;
\ i\ ,\H \\ \\\
2
50
~~
..........-~
\ \ \ \ \ \. \
40
0.4

0.3
,~
I \ \ \ \ " \J I30 I
0.2 1\ \ \ \ \1 20
>--
\ \ \ \

I i~ -= ~ \J
- l,
A- CO\ I
0.1 10
Il'~ :;....
)~
I

CO~ \: i:
\ ;

0.05 I I j
/ / ///hY \ .\ i
0.04
j 0.03
! i/ / ///$1 \ i :
: I
0.02
V // / I I \ !
!
2 j

v~r
I

0.01
500 600 700
I
800
1\ 900
. i
\
1000
I I-
IFigure 1

i 14.3 : Composition at equilibrium for pure methane versus temperature: HP/C =4;
',--'_ . each curve corresponds to a pressure from } [040 bar (From BASFi.
 Organic sulfur is transformed into hydrogen sulfide at 350/400~C in the
presence of cobalt and molybdenum-based catalysts. The hydrogen sulfide is
in tum adsorbed on zinc oxide in a section included in the unit. Hydrogen is
recycled at the inlet to this catalytic section.
If the feed sulfur content becomes too high, a regenerative washing system
needs to be installed to replace the solid bed which is rapidly limited in
adsorption capacity.

I~.:.1.~ Types of Reaction Furnaces

The reactors used are made up of a set of tubes heated by radiation in fur-
naces which can be broken ~own into four types (Fig. 14.4):
Top fired furnaces: placed on each side of rows of modular' tubes (KTI,
Lummus. Uhde). The small number 0{ burners allow large production
capacities to be achieved (600 to 1 000 tubes) in a compact assembly. The
radiation efficiency is high and temperature control is difficult as a result.
Bottom fired furnaces: today relatively seldom used. they can burn liq-
uid fuels. They have some drawbacks: low thermal efficiency, high tube
skin temperatures. especially when low residual methane content is
desired.
Side fired furnaces with one or two rows of tubes placed in a staggered
arrangement. Radiant horizontal burners are placed between two refrac-
tory walls on either side of the tube in 5 or 6 rows (KTI. Topsoe). The heat
can be perfectly well distributed should there be any modification in
capacity. The flue gas exit from the top of the furnace simplifies waste
heat recovery. The large number of burners and complexity of fuel oil and
air distribution limit their capacity (100 to 150 tubes).
Terrace wall furnaces with 2 or 3 banks of burners allow heating to be
adapted to different rates (Foster Wheeler).

H.2.U Heat Transmission in Furnaces

In all types of furnaces the combustion chamber works under negative pres-
sure and requires a draft fan. Furnaces comprise a radiation zone (thermal effi-
ciency 45 to 55~~) and a convection zone where heat is recovered from the flue
gases.

d. Radiation Zone

The tubes used are made from centrifugally cast alloy steel. with internal diam-
eters ranging from 80 to 130 mm, thicknesses from 10 to 20 mm depending 00
the metallurgy and lengths of 10 to 15 meters. They must Withstand buckling
at high temperature and are mechanically designed for high pressures and
temperatures while also enabling excellent beat transmission. The type of tube
support is of prime importance in furnace design. Dilatation of several cen-
timeters requires serni-flexlble connections between the tubes and the inlet
and outlet headers/manifolds with counterweights or suspension springs.
 462 Chaplet 14. HYDROGEN PRO=::-:::TION

Toplired Bottom Side Terrace

fired fired waH

--: Figure I
i 14.4 I Types 01steam reforming furnaces.

The heat flux inside them ranges from 64 to 75 kJ/s/m:! with tube skin tem-
peratures between 900 and 1 OOOGC (Fig. 14.5). Great care is needed when fill-
ing the tubes with cold catalyst in order to reduce pressure drop differences
to less than 5%, the operating pressure drop being 4 to 5 bar.

I
;
I:.
~:;~-~
/t.'~,: /~\ M1
fJ I1' : ~. .'
f..J ". II .'
I '; iI 1

I!
:1
:i
il
I 400 BOO , 200 1 600
Temperature ('C)
I
I

- ~:: I Top fired tumaces. Temperature ,..,nte

 The most common steels used for tubes are HK40 (2SCr-20 Ni) or manau-
rite 36X (25 Cr-35 Ni) while outlet manifolds are made of Incoloy 800 for small
capacities:

intennediate capacities up to 180 000 Nm 3/h include an internal refrac-

tory:
the synthesis gas then feeds waste heat boilers equipped with fire tubes
to produce medium pressure steam. and pre-heat boiler feed water tubes
where the required steam generation pressure exceeds 60 to 80 bar.

b. Concection Zone
This zone comprises the various tube bundles designed to recover the heat of
flue gases extracted by the fans. The off gases preheat the feed and after that
the feed mixed with steam to 500 to 600C, which is lower than cracking
temperature. The flue gases are cooled while generating and then superheat-
ing medium pressure steam (25 to 40 bar). They may even generate high pres-
sure steam. Then they are discharged into the atmosphere at between 150 and .
200C, and in this case furnace efficiency is in excess of 90%. Stack gas
temperatures as low as 100 to 130C can also be achieved by heat exchange
either ",ith combustion air or with demineralized water if the fuel used is
sulfur free.
The choice between generating more steam or preheating air (for which
the investment required is usually higher) depends on the economics of
exporting steam.,

14.2.1.6 Flow Scheme. Performance

Figure 14.6 shows synthesis gas production by natural gas steam reforming.
Typical compositions of synthesis gas exiting a steam reforming unit are pre-
sented in Table 14.2. Several different feedstocks are shown.

Feedstock Methane : Natural gas j LPG Naphtha

i Composition (% vol); I
i CH~ 3.06 ! 2.91 2.39 2.12
CO
CO2
12.16
9.66
12.62
lOAD
I 13.62
12.73
ltIi
14.19
H2 75.12 73.98 ! 71.86 69.52
N~ 0.09
~foiir ratio
H20/CO ...H2 0.36 0.38 0.46 0.51
L....;~-

I Tahit .
, 14.2 Gas composition after steam retorming.
-- Pressure: 24 bar. Temperature: 850C H:PIC =4.
464 c.~(er 14. HYDROGEN PRooucr:c.v

~~-~ ' ..
l ._._._._._. ._.~

I
T

I
 The influence of the feed can be seen in Figure 14.7 which shows:
the H2 + CO yield (std m3/GJ of feed):
the percentage of residual methane:
the CO + CO2 yield (std m3;GJ of feed);
versus the HP/C ratio.

14.2.2 Carbon Monoxide to Hydrogen Conversion

The conversion reaction is in equilibrium as shown below:
CO + H20 ::!i; CO2 + Hz Mf;s =-41 kl/moi,
Although it is promoted at low temperature by the presence of steam, a
temperature of 25O-C is required even with a H?O/C ratio of 3 in order to shift
. the reaction totally over to the right. At low H20 /C ratios, side reactions lead
to hydrocarbons or to oxygenated compounds.
Conversion technology is different depending on the hydrogen production
flow scheme, particularly the last purification step,

l4.2.2.1 Purificadoa by MethaDation

This final purification step, which uses part of the hydrogen produced, allows
very deep CO conversion (0,3 to 0.8% residual CO) and so justifies imple-
menting two catalytic conversion stages with intermediate cooling.
The first stage at high temperature. (300 to 560C) is activated by cata-
lysts with an iron oxide (80 to 95% wt) and chromium (5 to 10% wt) base.
It results in a residual COcontent of approximately 2 to 3%. The catalysts
contain little sulfur, as it is eliminated in the form of HzS during the reduc-
tion phase, Emthermicity is approximately '5'C{% of CO converted under
conventional running conditions.
The second stage at low temperature (200 to 260'C) takes place on cata-
lysts with a copper oxide (15-30% wt), zinc oxide (30% wt) and alumina
base. The composition of the base is designed to limit the growth of cop-
per crystallites, which are all the more active as they are small in size.
These catalytic systems are very sensitive to impurities, especially to
chlorine and sulfur compounds. Residual carbon monoxide can reach
0.3 to 0.8% vol

B.2.2.: Purification by Adsorption:

Pressure Swing Adsorption (PSA)
With this technology, the final COcontent in the conversion effluent can be llrn-
ttedto 2 to 3%, and low temperature conversion is no longer justified. It may
be advantageous to replace the high temperature conversion by medium tem-
perature conversion (260 to 280"C) capable of reducing the GO'to around 1%.
466 CnaDler 14. HYDROGEN PROOUC-:-,::;N

110 r Nm3(H,.coYGJ oIl.ed

10
~ % CH. (dlY gas)

100 - :~
7~

6
90
5

80 3

2 3 4 2 3 4 5
~O/C

Nm3 (CO + COz}JGJ of feed

35

30

r i
1.., 7
Te

:U.
Influence of the type of feed on synthesis gas composition. Refomling outlet
1 conditions: 850"C, 2S bar.
 C~4:)rer 14. H'ffJf'IOGE:< PRODUCTION 467

1~.U,.3 Operado, COOclitiODS for CO Conversion Flow Schemes

Equilibrium constant values for the conversion reaction versus temperature
are shown in Figure 14.8. The residual CO content in the different configura-
tions is shown in Table 14.3.

1 K;;
800
700
600

500

400
300
200
100
o '-- -J,. --'- -'--~

150 200

i Figure:.
! 14.8 Equilibrium constant(K,J for CO + H/J ;:: CO2 + H2'

!
Iff conversion i MT conversion
.
i! HT + LT conversion
Inlet stage 1 CC) i 360 I 210 360
Outlet stage I CC) ! 423 i 298 423
!
% vol CO outlet (dry gas) : u 1.6 4.1
Inlet stage:! ('C) I - - 200
Outlet stage 2 CC) I - - 230
% vol CO outlet (dry gas) i
HT: high temperature (300-560'C).
-
~fT:_medium
-
temperature (260-280'C).
I 0.5

LT: 10..... temperature (200-260 'c).

---
~ Table - - - - - - - - - - - - - - - - - - " - - - - - - - - - - '
i 14.3 CO conuersion.

J
468 Cr.a;:e" 14. HYDROGEN PROQue:",::;",

14.2.3 Carbon Dioxide Removal

After conversion, the synthesis gas contains 16 to 20% of CO2, at a pressure of
16 to 25 bar corresponding to a partial pressure of 2.5 to 5 bar. Chemical pro-
cesses employing ethanolamines and carbonates are the most commonly used
to remove the CO2,

1';.!.3.1 Carbon Dioxide Removal by Ethanolamines

Monoethanolamine (MEA) was long used despite two problems, First. the for-
mation of bicarbonate from carbonate stabilizes the carbon dioxide in the solu-
non and results in higher heats of desorption. Second. carbamates are formed
- they are even more corrosive as there is no H~ to inhibit their formation and
passivate the steel. Some degree of improvement was, however, brought about
with the development of the Amine Guard process by Union Carbide in the sev-
enties. Here. the presence of a corrosion inhibitor allowed the amine concen-
tration to be raised from 20 to 30% with energy and investment savings.
Methyldiethanolamine (MDrA) has stnce totally displaced MEA.: The weaker
bond created between this tertiary amine and the CO2 without any carbamates
being formed considerably reduces the energy cost of regeneration. MDEAwas
developed for desulfurizing gas and especially for eliminating H~ from CO2
selectively The use of a number of additives has given MDEA greater activity
with :~p.."Ct to CO2 and allowed it to be used in total CO2 removal. The pro-
cesses developed by BASF, Dow Chemicals, Elf Aquitaine, Texaco and UOP use
~IDEA-base solvents which behave like a chemical solvent at low concentrations
in solutlcn, and like a physical solvent at high concentrations. As a result. a large
amount of solvent can be regenerated by expansion, thereby lowering the regen-
erator's heating load. Consequently, old MEA units can be revamped simply by
adding a flash drum on the rich amine. Figure 14.9shows a more elaborate tech-
nology with two absorption stages: the amine, semi-regenerated by expansion,
is: fed into the middle of the absorber, while the thermally regenerated amine
allows a residual CO2 content much lower than 1 opo vpm to be achieved. Flash
regeneration is separated into two stages: the "intermediate pressure stage
':!-:$igned to recover co-absorbed hydrocarbons and the low pressure stage
where complete CO2 desorption is carried out by hot regeneration.
Note the improvement provided by Exxon's Flexsorb process which
increases mass transfer in absorption by using a "hindered amine".

14.::.3.: Carbon Dioxide B..emoval tIling Hec carboDate

Potassium carbonate absorbs carbon dioxide as shown in the reaction below:
K2 + C0 3 + CO2 + H20 :=; 2KHC0 3
The reaction is carried out at a high temperature in order to maximize the
bicarbonate concentration without any risk of crystallization. A residual CO.,
content of 1% can be achieved with a very simple flow scheme where there a~
no heat exchangers between the lean and the rich solution. Improved perfor-
mance requires adding activators and corrosion inhibitors.
 :~aprer 14. HroRoGEN .>.:;ooucTION 469

E
c::
g
en
1.1.

,~
jG-!
f.-J
!

:&ln
!!
~ GiCl>
G
o
(I.J IL I c:
rl---,--~r dl I !
E
III

l " !r~~:------~ ~~
--IeIII
c:
II: y' G
---- g'
a:

4'--1_-----.,-_)~-0

; ~ :;
~:!
'--'-- ----------'-1---
470 Chapter 14. HYOROGErv PRODUCT/Dr.

.r
 :;--,r:er 14. HYOR:GEN P'iO~!V 471

The available technologies are the Giammarco Vetrocoke process using

glycin derivatives, the Catacarb process and especially the Benfield process
marketed today by VOP. The successive process improvements have been as
follows in chronological order:
the use of two absorption stages (split 110w) with a residual CO z content
of 1 000 vprn:
the implementation of two stages for absorption and regeneration with .1
residual CO2 specification of 500 vpm:
the Hipure technology that utilizes two separate absorption-regeneration
circuits arranged in series with lean solvent/rich solvent heat exchanc-
ers, yielding a residual CO2 content of 50 vpm,
Regeneration energy corisumption is low in the Lo Heat version (Ag. 14.10)
due to successive reduction in pressure of the regenerated solution with vapor
recovery in the regeneration column. The most complex version includes
mechanical recompression of vapors. The latest development, the pressure
swing Benfield process (PSB), includes 3-stage absorption and primary regen-.
eration by double flash. with a residual C~ content of 500 vpm and very low
energy consumption.

14.2.3.3 Comparison of Different Methods of EUJDinatinc C02,

The choice between the different solutions must take the parameters belov...
into account:
specific site constraints.
available regeneration energy,
investment costs,
solvent availability and cost.
Table 14.4 shows the energy consumption of the different solvents used in
carbon dioxide removal.

Type of solvent GJt! 000 std m3 of CO:

Arnlnes:
MEA Simple flow scheme 9.2
With AmineGuard 3.8
Activated:\tDEA 1.5-3.25
Carbonates:
Conventional 5.0-6.3
Benfield Lo Heat 3.13-4.6
With recompression 2.5-3.35
I PSB U5-2.90 j
L--
i Table - - - - - - - - - - - - - - - - . . . . : . . - - - - - - - - - -

i 14.4 Energy consumption of CO:!remoooJ process with different solcents:

~c: , - - - - - - ,
til
:5
CD
::E

r------t:s=d

.~
Slii
~ '---------...,

::.
=-
-
~..;.
;,:,. -
 z-.... Ie H'tDRCGENPRooucncN 473

1,}.2.4 Methanation of Residual CO anel C02,

This step involves the followingreactions:

co + 3H:! ~ CH.f+ H:!O .:YI~ =-206 kl/mol

CO:! + 4H:! ::; CH~ + 2H20 j/[Z!s =-165 kl/moL
It takes place between 300 et 340C on a nidel catalyst, is exothermic and
practically complete. The residual COand C~ are less than 10 vpm. The tem-
perature increase is around 30C for a CO content of O.3~Q and a CO., content of
0.1% at the inlet. The final hydrogen purity is 95 to 98% vol depending on the
design of the process sequence as a whole. lbe purification flow scheme with
methanation as the final treatment step is presented in Figure 14.11.

14.2.5 Purification by Adsorption

Hydrogen can be purified by adsorption (pressure swing adsorption process.
PSA). The technology yields hydrogen with very high purity (99.9% vol) from
a steam reforming effluent after CO conversion containing 65 to 70% vol of
hydrogen. It was developed originally by UnioaCarbide and is today marketed
by UOP. Unde, Air Uquide and others.
Figure 14.12 shows the complete hydrogen production sequence with PSA
purification. Upstream, it includes the desulfurization section (hydrotreating
on cobalt-molybdenum then H~ adsorption 00. zinc oxide), the reforming fur-
nace with steam generation from furnace flue gases and the process effluent.
medium temperature conversion and the PSA purification section. ?SA is
based on the principle of adsorbing impurities on molecular sieve beds. The
operation takes place at room temperature and a pressure of 20 to 25 bar for
steam reforming.
Regeneration is achieved by expansion of dte adsorption bed and flushing
by a purge gas internal to the system, Flushing requires no heat source or out-
side fluid.The continuity of the system is provided by installing 4 to 12 beds.
. each in an individual pressure vessel. The system is entirely automatic, with
the total cycle lasting a few minutes for each bed. including adsorption.
depressurization, low pressure purge and recompression.
Figure 1U3 shows the simplest technology-for a 4-bed system:
The first bed, fed with feed gas, is in the adsorption phase and produces
pure hydrogen under pressure.
;o,leanwhile. the second. bed is in the depressurization phase. which
releases gas for purging the third bed-and 'pressurizing the fourth bed.
Final repressurization of the fourth bed is accomplished by pure hydro-
gen available at high pressure.
...The third bed is purged at low pressure ill order to eliminate impurities
as completely as possible. -
474 C/'.apref 14. H YOROGEN PRODUCT/OI:

o:lI
o .
>-

I~ ;-.

";:
 Purified
hyclrngen Pressurizaron
Deoressunzajonlre ressurization
Repressurization of purge
_I _l_ -'-'-
,,

i
'e:
'0
,..:e.
-II
F
'"
i
'CD
lC')cn
~
~
,
I
Ii
,g
''0
1<
I
1
,.
I NIl Mi~ i
l1J
l:g i 14.13
i J
Feed

PSA flom scheme with four adsorption beds.

Purgegas
(low plessure)

The last bed is recompressed first by gas coming from the second bed
and then by the pure hydrogen from the first one.
Yields are dependent on feed and purge pressures as well as on the hydro-
gen concentration in the feed. The ratio of feed and purge pressures must be
greater than 4. Industrial yields with this application are between 85 and 90%
depending on the number of vessels and the purge pressure.
Since purging is not continuous, a surge tank needs to be installed. The
purge is used to heat the reforming furnace. but usually only 85% of the heat-
ing requirement is covered by the low Btu purge gas.
Figure 14.14 gives the radiation heat exchanged versus reaction tube exit
temperature for a 10 000 Nm3Jh unit.

14.:.6 Comparison of Conventional Methan~tion

and Adsorption (PSA) Methods
Hydrogen purity seldom exceeds 98?6 volume with the conventional method
and purity depends directly on the quantity of inerts in the feed. The PSA
method yields over 99.9% volume purity whatever the feed quality. This high
degree of purity is a great asset for hydro treating units. which consume hydro-
gen (see Chapter 16).
476 Cto.aatllf 14" HYDROGENPRODUCTION

60

40 ........ -'- --'- "-- -'- --'- _

790 810 830 850 870 890
Radiation outlet (DC)

Figure i
,14.14: Coverage offumace heating requirements.

---'

Industrial PSA units can go up to a capacity of 100 000 Nm3/h, Le. in the
same range as methanation units.
Severe steam reforming operating conditions are required with the rnetha-
nation method in order to get over 97%volume (reforming outlet temperature,
steam/carbon ratio, residual CO after conversion, minimum CO2 content after
CO2 removal). The PSA method allows less severe operating conditions in the
steam reforming furnace which yield from 3 to 8% residual methane.
A comparison of feed and utilities consumption figures is provided in
Table 14.5.The consumption of natural gas feed is higher by 30 to 70% with a
PSA.Total consumption (feed and fuel oil) is roughly identical with both meth-
ods. since the PSA purge is recovered and used as furnace fuel. Exported
steam is considerable with a PSA: there is no CO? removal and the amount of
heat released is higher in the furnace. -
Small or average-size PSAunits are more attractive from the standpoint of
investments (up to 30 to 40 000 Nm3/h), whereas investment is of the same
order of magnitude for larger capacities. The oversized steam reforming fur-
nace and the cost of the PSA roughly offset the absence of low temperature
conversion, CO2 removal unit and methanation.
PSAtechnology is more reliable (there is no low temperature conversion.
methanation or CO2 removal solvent) and this. along with lower energy expen-
ditures, means a reduction of some 10% in operating costs.
 Type of feed Gas Gas Gas
Type of purification PSA Methanatioo Methanation
Hp C (mol/mol) 3.0 3.0 4.5
Process steam (t/h) 9.4 7.4 9.9
Feed (GJ'h) 137.8 117.1 99.6
Fuel oil (GJ/h) 17.8 49.S 5-1.0
Total 1556 166..'" 1436
Reforming:
Temperature ('C) 850 850 870
Pressure (bar) 24 24 24
I i
Residual CH 4 (% mol) ,I 5.6 5.6 1.9
i
Outlet CO (% mol) 13.2 I 13.~ 12.1
Radiant energy demand (GJlh) I 39.3 , 33.4 if 34.7
Type of CO conversion ! HT I MT+LT LT
Residual CO (% mol) 4.1 I
T
0.5 0.3
Outlet CO2 (% mol) 15.6 I 18.6 19.4
H1 purity (% vol) ! 99.9 i 92.8 9;.2
Exported steam (t/h) 8.5 0.:- I 1.9
Hydraulic flow rate Base 100 : 85 I 95
I
Conditions: Feed preheating to 5.J{j'C. air preheating to 3OO'C. lu~(oi1 preheating to 200'C.
Lsteam exported at 44 bar. 1,\i th tile PSA. the purge is used as reforming furnace fuel.

Table
H.5 Comparison of methanation and P;S;4 (for 10 000 MnJ/h ofpure H:J.

In conclusion. PSA units have practically replaced conventional units.

which may be preferred. however, in the following instances:
limited hydrogen purity is acceptable given the overall optimization of
the process configuration;
the furnace can be heated by less expensive fuels than the feed;
CO2 recovery is planned;
the excess steam is inadequately exploited.

. 14.2.7-, Ongoing Devdopments [21

1-+.:.7.1 Steam ReformiJlc Catalysts_
Catalysts are being developed with increased activity and lower pressure
drops. Better activity along with less resistance to heat transfer results in
lower tube skin- temperature and a closer approach to methane conversion
,.

-==-=-...: : :. . ~.:~. . . =-.~:e. reduced pressure drop in' the catalytic bed with no
"'==- -.-, :.. :.'".e ca~:'"St's ::nechanicalstrength allows:
~ a ~ifjca:lt ea:t1 in hydrogen recompression.
zr =e :.;...<.:: rA iess severe operating conditions which lengthen tube life-
:.=e ';;s:;~ly cesigned for 100000 hours).

- _ - ~ !i~ Steam Reforming now Schemes

-i : .: ~.~ ;:_:.t::-;~-S :;'i:.:.:.:; aim to improve the heat balance of the steam
-:;:r-~ .mit.

?:-eteformiDg mg. 14.15)carries out part of the conversion in an adla-

:.c::::c reactor after preheating of the feed. It reduces the endothermicity
t: ~c':ons occurring in the radiation zone. This set up converts virtu-
L7 ail~"le heavy hydrocarbons into methane. hydrogen and CO2, The
:--r:on is endothermic for natural gas. thermally neutral for LPG and
4.-t:rly exothermic for naphtha
Combined reforming (Fig. 14.16) uses the high thermal level heat at the
:c~ <:.: the steam reforming furnace in posHeforming. The post-reform-

Steam from
steam drum

....,..- Y
.-----~.*~-_._--------------
:.::;;;;;;, '!lxpor: 4~~\:r
lL.J
T
~
To waste
heat recovery

:':'.:: Steam reforming with prereforming.

 C!".apfef 14. HYDROGEN PRODUCT/CN 479

Hydrogenator Sulfur guard

Sleam from
steam drum

- - - - - - - I - - - - - - ...

,
.
Steam
export
.
____ '
I
I

I
1.. .1I __
.
-+-------

To waste heat
recovery and
conversion

ing exchanger-converter consists of a set of concentric dual tubes. with

the inner tube containing the catalyst converting part of the fresh feed.
The heat required for the reaction is provided by the (primary) steam
reforming effluent filling the annular spaces between the concentric
tubes. The cooled gas is collected in the shell of the exchanger and sent
to heat recovery at between 620C and 780C mixed with the synthesis
gas which exits the reaction tubes at 550 to 720C.
Oxygen post-conversion can also be contemplated downstream from the
primary furnace if oxygen is available in economically attractive condi-
tions.

H2. i 3 carbon Monoxide Conversion

New catalysts operating with lower steam/carbon ratios and at temperatures
closer to the gas dew point are being developed. Development work is also
being done on iron-chromium catalysts working at very high temperature (550
to 650=C), allowing higher level heat recovery and a lower CO/C02 ratio alter
conversion. This limits hydrocarbon formation in the conversion that follows
at lower temperature.
480 c.-..t.=~~ 14. HYOROGEN PRODUCTION

I-f.3 Hydroge~ ..~oduction ~y Partial Oxidation [2}

This technology can process any gaseous feed. whether .liquid or solid. In
actual practice, heavy feeds are the most attractive ecOnomically speaking.
These are the heaviest fuel oils. petroleum residues either from solvent
deasphalting or from deep conversion. Petroleum coke and coal can also be
converted into synthesis gas, a process usually termed gasification in this
case.
Two major technologies have been implemented industrially, the Shell
(SGP) and the Texaco erGP) processes.

14.3.1 Synthesis Gas Production

l-U.l.1 Reaction Kinetics and Thermodynamics
Partial oxidation consists in introducing a hydrocarbon, an oxidizer and a tem-
perature moderator (most generally steam, sometimes carbon dioxide) into a
pressurized vessel clad with refractory material by means of a specially-
designed burner. The overall reaction is written as follows in a simplified form:
n m
CnHm+ 2' O2 -t nCO + '2 H2 .
It shows the overall result of a large number of reactions which occur
schematically speaking tn three phases:
In an initial step, the hydrocarbons are dispersed in a mixture of oxygen
and steam and subsequently vaporized. The gaseous mixture is then
heated by radiation of heat from refractory walls, Cracking reactions
occur with the formation of carbon. methane. hydrogen and hydrocar-
bons.
In the second step, a part of the hydrocarbons is transformed as soon as
the ignition temperature of the mixture is reached:

c.a; + (~2 + ~)
2
O? ~ n~O + ~ H,O
- 2-
This highly exothermic reaction shifts the equilibrium to the right. At the
same time endothermic reactions occur between the hydrocarbons. the CO2
and the steam:

C17Hm + nH20:::; nCO + (I+ n) Hz

It is essential for the hydrocarbon/oxygen mixture to be homogeneous so
that the endothermic reactions absorb the heat' of oxidation and thereby limit
the temperature to between 1 300 and 1 500C.
 .. - "- .. . r':'~
In the third step. at very high temperature, side reactlons occur such Ci$:'.
- hydrocracking: . .' . ~ : .

. CnHm+(2-:.Il~2~.~H4-;(R:i):C
- steam gasification- of carbon: . ~.~
HzO+C~~~CO

- reforming:
CH-I + H:P ~ 3H1 + CO
- gas conversion with water:
CO + H20:; H!+ CO
- sulfur conversion:
H~+CO:::; COS + H2

(The H~/COS ratio is around 10 to 25 depending on conditions.)

- decomposition of nitrogen compounds into ammonla, in tum decom-
poses into nitrogen and hydrogen. As ammonia is very soluble in water,
it concentrates in the recycled water which eliminates the soot and
holds the pH at 9. preventing the development of carbon dloxide cor-
rosion.
Chemical equilibrium does not include carbon formation, but equilibrium
is not reached for any of the liquid and solid feeds. The non-converted carbon
is a reactor effluent in the form of soot. It can be recycled to the reactor or
mixed with fuel oil and burned.
Except for methane. the concentrations of the main products are close to
equilibrium. Thus the gas composition can be readily calculated when the non-
converted carbon and methane yields are estimated.
The composition of the raw gas (H,/CO) and the methane content depend
on the feed e/H ratio and the type of moderator chosen. A lower HIe ratio pro-
motes carbon production. so the injected steam flow rate must be increased
when the amount of water produced by combustion is insufficient, even at
high temperature.

H.3.l.:: Partial Oxidation Tedmologies

The Shell and Texaco partial oxidation technologies include:
a burner where liquid hydrocarbons. oxygen and steam are injected and
partial oxidation takes place;
a section to recover the heat contained in the synthesis gas either by
direct contact by quench. or in a steam generator;
~. section where soot is eliminated by washing and filtration before being
. recycled.
 In addition to the specific burner design, the Shell and Texaco processes
also differ as to hydrogen production. Shell always uses heat recovery by con-.
tact (convective boiler for stearn production), while Texaco usually uses cool-
ing by quenching.
Burners. often arranged in pairs to facilitate regular inspection and main-
tenance, have unit capacities of approximately 150 000 std m3/h of synthesis
gas. .

a. Quench Cooling (Texaco)

In this now scheme (Fig. 14.17), the feed is pumped to the burner, preheated
in order to reduce its viscosity, and mixed with steam. This atomizes the feed
and allows the reaction temperature to be controlled. Oxygen is fed into the
central part of the burner. The energy released in the upper part of the reac-
tor which is clad in refractory material keeps the reaction products at high
temperature, 1 200 to 1 400C. The hot gases which contain solid particles
(non-converted carbon, soot and ash) go through the combustion chamber
and then undergo quenching by contact with water in the lower part of the
gasifier. The synthesis gas is subsequently washed to remove the last traces of
solid particles. Most of the particles are recovered at the bottom of the reac-
tor and treated in a carbon recovery unit.
Naphtha is then mixed with the soot laden water (Fig. 14.18). The naphtha
recovers the soot at the top of the settler and is then mixed with part of the

Oxygen
ReSidue . . . - - - - - - - - - Synthesisgas

r
...---l..---,
Acid gas

Soot
extraction

Soot recycle To water

treatment

Rgu~i
I 14. 17 l Quench cooling (Texaco).
 0rapttIr 14. HYDROGEN PRoDucTION 483

Naphtha

Naphtha + soot

Fractionator

1----1- Steam

Water
.
loaded
with soot

Stripper

L- figure - - - - - - - - - - - - - - - - - - - - - - - - - - - - - '
. H. I8 Soot extraction (Texaco).
I

feed residue and fractionated. The bottom of the fractionator containing the
soot can either be recycled to the reactor to increase the carbon yield or used
as fuel.
The naphtha soot extraction- step can be avoided by recycling the soot
directly to the gasification reactor suspended in a slurry with water. Additional
oxygen consumption is then necessary, Part of the soot can also be discharged
in order to prevent accumulated ash in the recycle circuit.
Table 14.6 shows the unit's performance for various feeds. The CO and H2
yields and the feed and oxygen consumptions change with feeds. For example.
3 points lower yield, 4% wt more feed consumption and 12% wt more oxygen
consumption can be expected when a deep conversion residue is processed
instead of a vacuum residue. Meanwhile. the ~CO ratio goes from 0.8 to 0.9.

b. Cooling by Waste Heat Boiler

Figure 14.19 shows the principle of the Shell technology where the gases are
cooled by a waste heat boiler. The synthesis gas is cooled to about 350C while
generating saturated high pressure steam. An economizer is usually placed
downstream from the convective boiler, which is specifically designed to main-
tain very high velocities and minimize the problems of sour environment.
484 CI'.aoJer 14. HYDROGENPRODUCTION

II
Residue From From From s-ou
characteristics -Vacuum - visbre8king deasphalting process

sp.gr, dZf!
Composition (% wt):
1.04 I 1.05 1.17 1.08

C 83.8 I 85.45 85.94 84.33

H 9.65 ! 6.5 9.49 8.89
f'\ 0.31 I 0.8 lAO 1.12
4.2 5.56
5
0
6.20
-
2.40
0.47
I
Ash 0.04 0.05 0.3 0.1
Heating value (kJ/kg) 9628 9665 9642 9480
e/H ratio (wt) 8.68 8.99 9.06 9.49

Consumption for
1000 Nm3 (dry) gas: I

Hydrocarbons (kg) 346.1 347 349 361

Steam (kg) 173.1 141 142.1 146.9
Pure oxygen (Nml) 245.0 258 265.6 270.7
..,
I 1
Products (mol %):
CO
H2
48.3
44.2
50.4
43.4
I 50.7
42.94
51.16
41.4
CO 2 5.2 4.6 4.94 5.28
CH4 I 0.6 0.2 I 0.30 0.3
N2 + Ar 0.2 0.3 0.53 0.46
H~ 1.4

i 0.55 1.32
1
COS 0.1 0.1 0.03
I 0.08
.. f
Consumption for
1 000Nm3 (H2 .oj. CO): I Ii
Oxygen(Nm:l)
Hydrocarbons (kg) I
264.8 275 "
369.9
I 283.6
372,8
292.5
390
,
--- I
374.1
!
I !
! Table I
; 14.6 I Partial oxidation. Properties and performance with various feetk.

c. Carbon Extraction
The free carbon which accounts for approximately 1% wt of the feed is
extracted with the ash in a two-stage washing section. Ninety-6ve percent of
the carbon can be extracted by water injection, and complete elimination can
be achieved using two beds of packing with water recirculation on the lower
bed. The upper bed is fed with water from the carbon recovery section.
 ---------------------------~-----_.. ---..--.. __..

Wolo heal
boiler
Washor
oC-~----l

.J=-:f-e ~~
._J~--

Sleam -I f>
H
Recycled woler ~
.l:
Feed

Melals Waler ~
and.th
~
11
~
11il:Ufl:

H.19 \ J',trljlll (lxjl!(lliorJ. Stietl proces iscn.
I""
486 Cr.apler 14. HYDROGEN PRODUCTION

d. Carbon Recovery
With soot recycle
The carbon is recovered using the same principle of naphtha extraction as
described previously, but with a slightly different technology. Pellets are
formed by placing the solid particles in suspension with small amounts of
hydrocarbons. Then they are separated from the water by filtration and mixed
with the feed oil after preheating. Afterward the naphtha is separated by dis-
tillation for recycle, whereas the feed oil containing the soot is recycled.
With soot extraction (Fig. 14.20)
Another solution for heavy feeds, developed by Lurgi, consists in filtering the
slurry to a moisture content of 20% wt. The-residue undergoes controlled mild
oxidation in a rotating hearth furnace so as to limit melting and corrosion prob-
lems. The resulting product is high in vanadium (75% wt of V20y, which can
itself be upgraded in the metallurgical industry. In this flow scheme the soot is
not recycled and this reduces the corrosion and erosion effects due to the pres-
ence of large amounts of metals (vanadium and nickel) in the convective boiler.

To sulfur To incineration Gas to

unit .t. sulfur unit
Filter

Soot Cake
slurry

Carbon
combustion
Waste
water

T
Concentrated Water recycled Waste water
vanadium to oxidation stripper
process

. Figure:
. 14.20 Soot recovery. Lurgi process.

14.3.2 Hydrogen Production Sequencinc

Depending on whether the oxidation technology includes a quench or a waste
heat boiler. the resulting synthesis gas exits partial oxidation under different
conditions (water content. temperature) that lead to different production
sequences. (Fig. 14.21).
 '-~"--------~--~~'--

Flow scheme with quench

2
Hu:;iduo
~--..
C! "a,lIa' '
oxidation
wllh quench
Schemo 2

~ FG

Flow scheme with waste heat boiler

','
l'l
~
. Scheme 3 <:
:t
~

~
~
H2
}
.~ .
PSA Schcmo4 }]
q
tl
('

r
FG :<:
''
-' Flllurc T~---- _._-
',<:" itJd",ge" ,,,,,/,,'1/,,,, />J' txtrtial ",'I<h,';"", ~
1
436 r:Il'l1l11f 14. HYDROGEN PRODUCTiON

In the quench version. the conversion of carbon monoxide is followed by

desulfurtzation, and CO2 removal before purification by either rnethana-
tion or PSA(flow schemes 1 and 2). With PSApurification. CO2 removal is
unnecessary if the low BTUPSApurge gas (2 500 kl/std m3) can be used
as fuel in the unit.
In the waste heat boner solution. conversion is located downstream from
desulfurization and uses' conventional Iron-chromium catalysts.
Purification by methanation or separation by PSA is preceded by CO2
removal (flow schemes 3 and 4). As in the quench version. PSA purifica-
tion can be carried out without prior CO~ removal.

14.3.2.1 Quench Teeha.logy

a. With Final Purification by Methanation (Flow Scheme 1)
On exiting the quench carried out with preheated condensate. the CO in the
synthesis gas (50 to 70 bar and 230 to 250'C) is converted by steam injection
(steam/gas ratio: 1.4 to 1.5) on a sulfur-resistant (5 to 800vprn) cobalt-
molybdenum catalyst (4 and 10% wt respectively) on a magnesia/alumina
support. The most commonly used catalysts are K 8-11 by BASF and SSK by
Topsoe.,
Three beds with intermediate cooling are generally necessary to achieve a
residual CO content of 0.5% corresponding to 99% conversion. The tempera-
ture of the first bed is kept higher than the gas dew point and the residual CO
is then 3 to 4%. The heat released by the first stage is most often used to pro-
duce high pressure stearn. Condensates can be injected to cool the second
bed. Preheating the boiler feed water can also be contemplated.
In this unit. the ammonia is decomposed and the COS present at the oxi-
dation outlet is hydrolyzed (residual content 20 vpm). After CO conversion,
the synthesis gas has a CO2 content higher than 30% vol and a H~ content
ranging from 0.5 to 1.5%vol depending on the feed. The final purification unit
requires sulfur removal to lower than 1 vpm. Physical solvent washing is the
best suited technology under these conditions.
Cold methanol washing allows the sulfur content to be lowered to 0.1 vpm
and exhibits high CO2 selectivity. The enriched acid gas can be treated in a
conventional Claus unit. The Rectisol process, jointly patented by Lurgi and
Linde, is presented in Figure 14.22.
Deacidification. which includes simultaneous elimination of H.$ and COS
then CO2 removal. takes place in two stages at low temperature -(-30C and
-50'C). The first absorber absorbs the sulfur compounds with the solvent
presaturated in CO:? The second absorber performs CO:? removal of the
synthesis gas by using two grades of solvent, One. partially regenerated by
pressure reduction and nitrogen injection. absorbs most of the CO2 while a
thermally regenerated solvent achieves the CO2 specification later at the top
of the column. The sour stream is enriched in H~ (15 to 40% vol) by an
absorber/stripper. A residual CO2 content of 10 vpm can thus be achieved
before methanation.
490 O.a;;ter 14. HYDROGEN PRODUCTION

Other physical solvents such as N-methylpyrrolidone (7\~tP). dimethylfor-

mamide (DMf) (Fig. 14.23) and "Selexol" can also be used aldose to ambient
temperatures. The selective properties of these solvents allow the acid gas to
be enriched. with a final sulfur specification of a few vpm however. requiring a
final guard vessel before methanation. Final methanation is similar to the pro-
cedure described earlier in Section 14.2.4: the pressures of 50 to 60 bar
required by partial oxidation havelittle influence on performance.

b. With Final Purification by PSA (Fig. 14.21, Flow Scheme 2)

The CO conversion catalyst is the same as in the previous flow scheme. In con-
trast, the residual CO content is not governed by either produced hydrogen
purity or methanation requirements. Economic criteria might prompt the
choice of 2 reactors (1 to 1.5% vol of residual CO). or even one single reactor
(4 to 6% vol of residual CO). The technologies considered for CO2 removal can
be confined to those that use physical solvents at ambient temperature (NMP.
DMF. Selexol, MDEA). The PSA purification process operates in this case at
high pressure and treats a feed gas slightly richer in CO2 than in steam reform-
ing. Recovery yield can not exceed 85 to 88%.

14.3.2.2 Wute Heat Boiler Technology

a. With Methanation Purification (Fig. 14.21, Flow Scheme 3)
Located between desulfurization and CO2 removal. carbon monoxide conver-
sion takes place on iron-chromium catalysts. The steam required for conver-
sion (the gas here is saturated only at low temperature) is generally supplied
indirectly by means of a saturator with make up Jive steam so as to get
between 0.5 and 1% vol of residual CO depending on the number of stages
selected (minimum of 2).
The gas to be desulfurized contains between 1 and 6% vol H2S and only 4
to 6% vol CO2, The appropriate washing technologies are those discussed in
Section 14.3.2.1: the cold methanol process presented in Figure 14.23 can often
be.replaced by physical solvents operated at positive temperatures or mixed
solvents, given the lower H:!S/C0 2 ratios.

b. With PSA Purification

ln carbon monoxide conversion. the residual CO content can be from 5 to
6% "0) with a single reactor. Synthesis gas can be treated by MDE.-'\, often a
competitive technique (low HzS/CO z ratio. less stringent residual sulfur specifi-
cation). The PSA process operates at high pressure. which. along with a feed
gas slightly richer in CO2 than in the case of steam refonning. limits recovery
yield to 85 to 88%.
 OJaprar14. HyCRC$E."/ P'iCCUCTTC:I 491

'.------'
I---J.-_-&.-
.. - - - - - -

~
~
~
::.-
s
..:::

--I--
~

L~
I ~
~
::':

~
~
,.J....,..-,.-L~::__~,~

1 a
I
----~I-._------------
..
<5
:a'~ -_~_
1_
aE'
:n:j -
"8 I
,-"----

.~~
'"
:: -
N

~ ~ -:. 1

_--.:._---------------------------'~
 492 Cna&tr., 14. HYDROGEN PRODUCTION

14.4 Hydrogen and Electricity Copr'.ld~c~ion

The partial oxidation unit for heavy residues can be used as a basis for pro-
ducing hydrogen as well as for generating electricity from the synthesis gas
minus its pollutants (sulfur and nitrogen compounds). Figure 14.24 shows the
flow scheme for a hydrogen/electricity coproduction unit processing 800 000
to 1 000000 t/year of deasphalting residue and producing 4 to 500 MWof elec-
tric power and 20000 to 40 000 Nm3/h of hydrogen. Here the hydrogen is recov-
ered from the synthesis. gas which has been selectively desulturtzed bya com-
binaUtm of processes including membrane separation and adsorption (PSA).
Under these conditions. membranes recover 40 to 50% of the potential hydro-
gen and the 80 to 90% pure permeate is fed into a PSAwhose recovery is opti-
mized. The residual gas is recycled to the gas turbine. For large scale hydro-
gen production. i.e. 60 000 Nm3(h and more. a flow scheme with' carbon
monoxide conversion is recommended (alternate of Fig. 14.24).
IIi these flow schemes, the pressure difference between the synthesis gas
from partial oxidation (50 to 70 bar) and the fuel gas powering the gas turbines
(12 to 20 bar) is used for additional electricity production. Thermal effidency
in these combination units varies considerably: between 40 and 44% for elec-
tricity production and 70 to 80% for hydrogen production. When both hydro-
gen and electricity are produced simultaneously, efficiency ranges somewhere
between the two sets of values.

14.5 Other Technologies

14.5.1 Hytex Process (Fig. 14.25)
.-This 'process is derived from Texaco's partial oxidation process and can be
.applied to refinery gases to produce hydrogen under pressure. It is a thermal
process
..,
~
which includes: .r

-, ~. a Texaco gasifier with a quench:

carbon monoxide conversion;
a PSA;
a boiler running on low Btu gas.
The light. non-sulfur containing feed allows simplified technology to be
used. As practically no soot is formed during oxidation, a conventional con-
version catalyst can be used. The advantages are:
There is flexibility with respect to the feed which can contain olefins.
It is possible to operate at high pressure.
No nitrogen oxide is discharged during absorption.
The low Btu gas may be recycled to the gasifier.
 a.pw 14. HYDRCGEN PRCCi.JC:::', 493

G
.' o>
E
l!!
oo

.1

___ .1

rill----,
y: ,. .
;-a

o
al ..

\.Ul!~~
~.o
!;: l--~--------_+_I
l::
II -sS
I I e-
I .~.
T

i:
I! i..~
.L--
.._ .,.N
::l -i-
L- ~~
494 ~ 14 HYDROGEN PRODUCTION

Gl
Cl<ll
... Cll
6:. 01

c:

"*~
c:
o
U

1~1
~-~D I

I
I
 ChaplIN 14 I+IDRcG&I P.Q(XU;7':C~ 495

14.5.2 Catalytic Alltothermal Process (Fig. 14.26)

This process was developed jointly by the Societe BeIge de l'Azote and Haldor
Topsoe in the fifties. It consists of mixing gases from a burner with steam and
sending them both to a fixed bed reactor containing a nickel base catalyst.
Pressure can be relatively high (20 to 60 bar) with an exit temperature between
950 and 1OOO:C. The feeds processed must not contain any heavy components
that couJd produce carbon deposits. Carbon deposit formation can be limited
by injecting steam and installing high-efficiency burner/mixers. Any soot
formed can be regasified on a catalytic guard.
A large number of companies have recently worked to improve the tech-
nology by operating it at steam/carbon ratios lower than I, whereas present
industrial references work-with ratios of around 2. The composition of the
resulting gases is presented in Table 14.7.
In comparison with steam reforming, the need to have oxygen available
must be weighed against
lower vulnerability to heavy hydrocarbons and
lower natural gas consumption because there is no surplus steam pro-
duction.

Type of combustion With oxygen

I I
Type of feed
I Natural gas Naphtha
I
Components (% vol):
H:? 68.3 62.6
CO I 20.3 16.4
1 co, I 10.5 20.6
II
I
I
CH4
N:?
A
I
1
0.4
0.2
0.3
0.1
0.1
0.2
I
I Total 100.0 100.0
I
Table I
14.i I Typical composition of gasesu:ith (he SBA-Topsoe process. .

1-+.6 Economics
1-"-6.1 Process Licensors .
a. Steam Reforming
There is no licensor as such for the hydrogen production unit. All the major
engineering companies can design and build one by resorting to specific tech-
nologies for some sections. .
496 :;-~:~. 14. HrD,~OGEN PRODUCTION

c:
e
III

"0
>-
:I:

dJ
iil
:>
0
0o E
!
0o

t-- --Jr-If-----
--.!

.~
~
s
a
..l..--

_____________________________ ---l~
 C~t'" 14. HroROGc'. P=iODt.:CC.'J 497

Furnaces: among steam reforming furnace designers, Foster Wheeler.

Humphreys & Glasgow. KTI, Lummus and Topsoe should be mentioned.
BASF. CCE. ICI, and Topsoe.
Catalysts: the most well known suppliers are
They give sizing data and performance guarantees for conversion and
primary steam reforming catalysts.
PSA process: Air Uquide, Linde and COP have the required know-how.
Waste heat boilen: are licensed by Borsig, BalkeDiirr; and Strutherwells.
b. Partial Oxidation
Processes: Texaco and Shell/Lurgi can license the processes.
Waste heat boilers: zhe Texaco technology is available from GHH.
Steinmuller, and Stiegener, while the Shell technology can be obtained
from Bronswerk.
Conversion catalysts: these sulfur-resistant catalysts are available from
BASF and Topsoe,
Add gas removal units: are theoretically under license but some engi-
neering companies can design them without any outside help. The major
players are:
- for activated MDEA: BASF, Dow, Elf, Huntsman. and UOP;
- for physical solvent washing: Linde, Lurgi, and Technip.

L4.6.2 Investments
Investment costs are provided as an indication as of the first half of 1999.They
assume that the hydrogen production unit is included in a refining complex
Where utilities and infrastructures already exist.
a. Steam Reforming
The investment of M 40.5 (1999) for a unit producing 60 000 Nm3jh of hydro-
gen corresponds to a PSA purification technology (85% yield) based on desul-
Iurized natural gas feed. The same capacity based on desulfurized naptha or
LPGfeedentails an increase in investments of 7 and 5%respectively.
The reforming furnace and its related facilities account for over 55% of the
installed costs. The exponent n to be considered for capacity change 1 is 0.75
but can not be applied to small capacity units with production lower than
:; 000 Nm3/h. This is because smaIl units may have a specific furnace, i.e. a
single burner generating hot flue gases with tubes distributed in a crown
shape in a cylindrical shell and a simplified PSA with 3 or 4 adsorption
vessels.

1. tu; = (clcor.
498 c-dDleT 14 HYDROGEN PRODUCTION

b. Partial Oxidation
Investment for a capacity of 60 000 Nm3;h rs M 65 (1999)without any air sep-
aration unit and ME 91 (1999) with one. Investment in the partial oxidation
unit is highly sensitive to the following factors: .
type of feed (feed flow rate variations of around 6% depending on the
characteristics of the heavy residue):
energy recovery mode (convective boiler or quench);
allowable 502 content in effluents. and
gas washing technologies (around 5?o of the cost of the installation).

14.63 Production Costs

Tables 14.8 and 14.9 show hydrogen production costs for the two processes.
Maintenance costs are higher for partial oxidation (4%of the investment) than

Consumption
for 1000 Nm 3jh
Units II
Amount /unit jl_Nm3/h ! /t
i
I
Inputs: I!
Natural gas GJ 15.5 1.7 I 26.35
I

Catalysts and 1
I !
chemicals - - - 0.97 II I
I
Utilities:
Natural gas GJ 1.85 i 1.7 3.15 I I
Steam
Ele<:bicity
t
kWh
(-)0.9
20
I
, 6.4
0.05
(-)5.80
1.0
I !
Cooling water m3 1 i 0.16 0.16 I iI
I
Demineralized water
I
m3 1.6 0.8 1.28 !
I
1
\mable costs
I r
1
27.11 I

Maintenance 2.50
i
Manpower 120
Overheads and insurance I I 1.37 ,
fbced costs !
I
I 5.07 56.8
!

Operating cost I 32.18 360.4

Depreciation i I 8.38 93.8
Production cost i i 40.56 453.4
Cost of H2 with 15% ROI ,I I 584.2
CapacIty: 60 000 Nm3/h. Battery Ilmits investments: 40.5 loG (mid-I99!J).
1...-'--
I Table
i 14.8 Hydrogen (99.9% ool) production by natural gas steam reforming.
,-'--
 for steam reforming (3%) provided the same service factor of 8 000 h/year ::5
applied. Production costs exclude loans and financing during construction.
but include 100year ~eprecjation of the unit.
Note that considering a return on investment (ROI) of 15%. capital budget-
lng-would advise against partial oxidation. However. this does not take other
eifeets into account (reduced atmospheric pollution. product quality) which
canbe included only for a specific project.

\\lthout oxygen unit \\llb oxygen UQit

I
Coasumption for
1000 Nm:l/b Uuits /Unirs
t:uits i: /1000 Nm3 1
Units
/1000 :'tat'
, 1000 :'Om:! , 1 1000:'\m3
olH~
I
Inputs:
Residue t 26.6 OAi
I 12.5 OA; 12.5
Oxygen
CataJyst and
t 35.5
I
0.5-1 19.2 - -
chemicals
Utilities:
i
I
- - 0.97 - 0.97
i ;
Fuel I GJ I.;{) . (-)2.26 (-)3.8 (-)2.26 (-)3.9
HP steam t 9.70 H'lOa (-)0.8 (-)0.i.l8 (-)0.8
LPsteam t I
6.40 ; (-:>0.35 (-)2.3 (-)0.33 (-)2.1
Electricity k\Vh i
0.05 ; 53 2.6 270 13.5
Cooling water m3 0.16 IS 2.9 -10 6.-1
Demineralized water m3 0.8 0.S5 0.7 0.81 0.6
,

I
Variable costs !
I 31.0
i 262

I ,
I
I
: :\taintenance 5.3 8.0
~ ~tanpower 1.6
I
2.0
. Overheads
!
and insurance 2.2 3.0

Fixed costs 9.1 13.0

i Operating cost 40.1 39.2

! Depreciation 13.3 IS.S
Production cost 53A -17.1
H! cost with 15"~ ROI i3A 76.0

Capacity: 60 000 :"m;'h.

Battery limits investments (mid1m):
Oxygen unit: )1 90.5 (1999). Partial oxidation: )IE: 63 (1999).

Table
14.9 Hydrogen (99.9 n ,j L'ol) production by partial oxidation 01 dsbreakittg residue.
 Figure 14.27shows production costs versus material costs and production
capacities for the two technologies. In this calculation, the oxygen is assumed
to be available at 35.6/t. As soon as it reaches 40.5jt, production In the
refinery can be contemplated. Note that if hydrogen production is less than
50000 Nm3/h. it is necessary to have a virtually zero-cost heavy residue and a
gas energy cost greater than Euro 2.G/GJ in order to justify partial oxidation.

llol
~

~ 1050 !

c
&
a
-g,
950
::t:

-- --
---- -----
750

650 '-- "'"'"- --:......... ......... -'-__

40000 60000 80000 100 000 120000
Capacity (Nm3/h)

Natural gas - - - Residue

A 3.51GJ 1 35Jt
B 2.S1GJ 2" 171t
3 0It
,Rgure,
!14.27
I t
Production costs (ROt" /5%). Natural gas reforming. Residue oxidation.

14.6.4 Cost of Other Sources of Hydrogen

a. Revamping catalytic reforming can increase hydrogen production from
5 to 15000 Nm3{h in an 8 Mt/year refinery with a virtually zero hydrogen pro-
duction cost, if the new reformate quality is credited. The cost of this type of
revamping can reach 50 to 60% of the cost of a new unit and can only be justi-
fied if the increased amount of reformate is allowed in gasolines.
 b. Hydrogen can be recovered from hydrorefining processes at high
pressure by using membrane separation. The potentially recoverable amounts
are small in units supplied with impure hydrogen and operating at less than
100bar. Production costs lower by 20 to 30% than those for a new unit very
often justify the hydrogen recovery investment. but only for small capacities
of between 2 and 5 000 Nm" h.
c. Refinery outside sources. Hydrogen make up can also be provided by a
system outside the refinery. Here. supply flexibility is related to the "back up
effect" of the system which is supplied by multiple sources (petrochemical
and fertilizer plants. the steel industry. specific units). The hydrogen available
in this way is almost always at high pressure and high purity. It may be advan-
tageous to involve outside sources to make up for any production deficits in
refinery units.

References
Raimbault C.. Abrassart P., Espelllac M. (1994) L'hydrogene : Bilan actuel et
perspectives en raffinerie, Petrole et Techniques 390. p. 37.
2 Chauvel A. Lefebvre G.. Castex L (1985) L'hydrogene, les gaz de synthese et
leurs derives. Procedes de petrochimie. Caracteristiques techniques et
economiques. Editions Technip, Paris.
3 Le Gall A. Vaporelorrnage : developpernents recents et amelioration des
performances. Petrole et Techniques 390. p. 44.
 ---1-'"~~
.~~ .
White Products Refining by Sweetening

Claude Marty

,.

Generally speaking, crude oils undergo basically two kinds of treatment in

refineries: physical separation processes and conversion processes (ther-
mal/catalytic). The result is a range of intermediate or end products that then
need to have finishing operations called "chemical refining", White product
sweetening is among these operations whose aim is to partially or totally
remove or convert small percentages of unwanted substances found in these
products. The substances may be hydrocarbons (diolefins) 'or molecules
containing heteroatoms (sulfur and nitrogen derivatives, phenols. etc.),
Table lfi.l Ilsts the main types of compounds that need to be removed or con-
verted.
Mercaptans, essentially present in white products (LPG. FCC and visbreak-
ing gasolines, kerosene cuts), are eliminated by sweetening (see new tenden-
cies elsewhere in the text). Sweetening is necessary since mercaptans are cor-
rosive, detrimental and foul-smelling products (see the different families listed
in Fig. 15.1). They result in engine fouling and have an unfavorable effect on
octane number when gasolines are leaded.

15.1 Mercaptan Distribution in Petroleum Cuts

~Iercaptans are mainly present in light and middle fractions:

butane.
gasolines (light and heavy).
solvent cut.
e.kerosene cut (lamp oil),
gas oil, to a lesser degree.
504 Chapre-:; WHiTE PRODUCTS REFININGBY $wEEiEN/{';3

I
1. Hydrogen sulfide
I
! Exists In some crudes. but is mostly formed from sulfur
compounds in the feed during thermal and cataiyttc crack-
Ing operations, and obviously during hydrotreatmg opera-
I tions.

2. Elementary sulfur Is seldom present. but is usually formed by oxidation of

H~. especially during product storage.

3. Mercaptans IHave the same origin as H~.

4. Carbonyl sulfide ISeldom present In crudes, COS Is probably formed during
I operations such as thermal and also catalytic cracking.

5. Neutral sulfur The sulfur compounds present originally in the crude

compounds undergo numerous transformations dUring operations.
and this explains the presence of sulfides. disulfides. thto-
phenic and other similar derivatives.
6. Nitrogen bases Probably come from thermal or catalytic decomposition of
complex, nitrogen compounds existing previously in the
crude.
7. Organic peroxides Are formed by oxidation of hydrocarbons and particularly
of oletins and dtoleflns. They are very troublesome as they
decrease storage stability of gasollnes and promote engine
fouling by forming carbon deposits.

8. Naphthenlc acids Are present In some crudes called "naphthenic crudes".

Furthermore. they are also formed by thermal decomposi-
tion of complex oxygenated compounds that are present
in the crude.

9. Phenols Have the same origin as naphthenic acids. High tempera-

ture hydrolysis reactions have also been reported to occur
during catalytic cracking operations with formation of
phenols.

10. Ammonia liS formed during thermal pr catalytic cracking and obvi-
ously during hydrotreating operations.

11. Hydrogen cyanide ! Is formed during catalytic cracking of petroleum cuts that.
Icome from crudes containing nitrogen compounds. :
I
12. Compounds altering This group probably Includes a very large number ofcom~l
product color . plex molecules such as sulfur and nitrogen compounds.
! phenols. and even some hydrocarbons (fulvene series). I
i
These products are mainly formed during refinery opera-
! tions.
I

]3. Existent and The compounds forming gums are probably cyclic conju-
potential gums gated diolefins. Other sulfide or acid compounds and
metallic contaminants formed during treatments can
accelerate gum formation.
'--'~.--

Table I'
15.1 List of main unwanted compounds with their probable origin.
I
 I I Primary
-C-C-SH
aliphatic
I i
SH Aryl. Example:
Ii; Secondary
thiophenol
-C-C-C- aliphatic
! ! I
I
-C-
I I Tertiary Naphthenic
-C-C-SH afiphatic
I I
-c-.,.
L--~
I --,- .....
. Figure;
15.1
_ _I
i Different mercapftln families in petroleum fractions.

There are none in the fractions heavier than gas oil. Additionally their
concentration depends OIl the type of crude, as indicated in Tables 15.2. 15.3
and 15.4.
Mercaptans account for 40 to 100% of total sulfur for light cuts of distilla-
tion (gasollnes, butane). As an illustration, Table 15.5 giws a distillation bal-
ance for an Iraqi crude along with the "sulfur" and "mercaptan sulfur" distri-
bution. When a catalytic cracking balance (see Table 15.6) is examined. the
significance of mercaptans can be noted in the butane. and the light and heavy
gasoline cuts.
From a more general standpoint. note that thermal conversion processes
without hydrogen (e.g. R:C. coking. visbreaking) produce mercaptans in the
light fractions.

, '. j Heavy upt jt

i Gas oil bmp oil Solvent i i i ' a.soIiDe'Butane PropaDe*
i ' i gaso ne: g j

IRSH sulfur (gtt) 2;5 302 377 287 233 200 0

j Total sulfur (% \"1) i 1.23 0.34 0.14 0.063 0.030 0.02 0.015
i 5 (RSH) x 100 : 2.24 8.9 -,
?- 0
78 100
! 5 (total) ,
46

i The propane cut contains ~sulfur alone, but little or no mercaptans.

L Table
15.2 Type of erode: 1nIftKirkuk. Transfer temperature to atmospheric distillation:
360'C. Total su'flITcontenL' 2.057:..
506 Ctra:>!er 15. WlirrE PRODUCTS R2FINING BY SWffTENIN:;

- Heavy tight
Gas oil lamp oil Solvent
I
I I gasoline
i gasoline

RSHsuliur (gIt) 2.2 1.4 1.9 1.2 1.6

Total sulfur (% wt) 0.18
I 0.026 I 0.021 0.013 0.012
S(RSH)
0.1 0.5 0.9 0.9
I
1.3
5 (total) x 100
--,
I
I I
I
I
Table i
" 15.3 I Type of erode: Hassi-Messaoud. Transfer temperature to atmospheric distilla-
I tion: 360C. Total sulfur content: O.14'JO.

I
!
Gasoll i Lamp oil I Solvent
Heavy
gasoline
tight
I I gasoline
i
I ~

RSHsulfur (gil) 240 246 256 250 475

Total sulfur (% wt) 0.83 0.11
I 0.06 i
I
I
0.05 0.06
5 (RSH) x 100 2.9 22.4 43 ,
I
50 80
5 (total)
---, , I
I

-:T....
: 15.4
I Type of crude: Qatar. Transfer temperature to atmospheric distillation: 365C
! Total sulfur content" 1.19%.

15.2 Background Data

.c
The aim is to eliminate rnercaptans by converting them lnto disulfldes by oxi-
dation as follows:
1
2RSH + - 0., ~ R-S-S-R.;. H.,O
2 - -
For economic reasons, air is the mercaptan oxidation reactant, but most
mercaptans have a rather weak reducing activity with air. To make them more
reactive. it is necessary to transform them into salts (called "rnercaptldes") by
treating them with a base. This lowers the redox potential of the system.
thereby favoring oxidation. To carry out a sweetening operation. two types of
operation are required:
Transform mercaptans into mercaptides. For economic reasons aqueous
caustic soda is used industrially.
Oxidize the mercaptides to disulfides. During this operation the caustic
soda is regenerated and can therefore be recycled.
 ::-.::r r5. Whv1c PRooucrs RF1flJJIIG 8'1' S.:$EN/NG 507

Yield SaIfur ! (RSH) s 0

(% WI) lS) feed (% wt) ~ (S) total (% wt)

I
GaS 0.2 II 0.17 I
0

F
IC Butane
\
Propane

; Light gasoline
0.5
1.8
9.3 I
0.27
1
0.16
0
100
78
Heavy gasoline' 9.7
I
I
2
f
:
46

Feed ~~
::-: :=; I
Solvent 6 I 0.5 27
~ ~ ~ Lamp oil
jr---l- 7.5 1.2 9
Iraqi crude sa ;;; ~ Gas oil 24 14
I 2.2
S(%wt)'2~ i'
~ c Distillate 6 5.7
I -
j
Atmospheric -
residue
35 75
I
I
100 100
~-
I
T:lbl~ :
. 15.5 ' Atmospheric distillation. Emmple of sulfur balance.

I
Yield Sulfur !(RSH) S
(%wt) I
<.S) feed (% wt) (S) total (% wt)
! I
Gas 5.35 23.44 -

~
! -
CJ cut
C4 cut
Light gasoline
I
5.89
10.17
35.12
22.56
0.44
1.92
II 99.9
10
Heavy gasol_ I
5.25 1.15 I 25
i ,.l-----; I
~ cl- LCO I 18.63 20.37 I 0.3
,:;
Feed !-"z i
-7 ~:::~~i ,
,
S(% \\1):2
~ 5r- HCO 12.42 14.24 1

L Fuel (slurry) 7.17

100
15.88
100
)

i
.
-
--
Table
15.6 Catalytic cracking. Example ofsullur balance.
508 Ct'!aD:6' 15. L'V,..{:TF PRODUCTS ReFINING BY SWEmNlNG

15.2.1 Recapitulation of Process History

The importance of chemical refining in petroleum 'product fmishing operations
has led to research and development on a large number of sweetening pro-
cesses in the past fifty years. Before discussing modern technologies in depth.
a few of the older processes are presented briefly below. Since they are now
outdated. the presentation will be confined to a description of the principle of
each one and its major drawbacks. without going into detail about the process
itself.

15.2.1.1 Doctor Sweetening or Plumbite Process"

The process includes three reaction sequences:
(a) Plum bite treatment. Pb0:zNa2. with lead mercaptide formation:
2 RSH + PbO 2+ H20 -t Pb(RS)2 + 20H-
(plumblte)

(b) Oxidation of the lead mercaptide into disulfide by sulfur:

Pb(RS)2 + S ~ PbS + RSSR
(disulfide)

(c) Regeneration of the plumbite by oxidation with air in an alkaline

. medium (caustic soda):
PbS + 202 + 40H- ~ 504 + PbO; + 2HP
(regenerated)

The drawbacks are as follows:

dissolution of the sulfur in the reaction medium;
separation of aqueous and hydrocarbon phases;
plurnbite regeneration. causing the solution to age.

15.2.1.2 Sulfuric Add Treatment

The process includes two sequences:
(a) Formation of a sulfuric diester as illustrated below:

/OH
RSH + H"sO. -t S02 -;- H.,O
-.. 5R -

/OH /5R
RSH + S02 <, ~ 50 2 <, + H.,O
SR SR-
(sulfuric acid diester)
 ~ 15. ""ITE PRoDuCTS REFINING B~" S.~NG 509

(b) V~omposition of the sulfuric diester, with formation of disulfide and

502:
/5R
SO., ..... - R-S-S-R + SO.,
- 'SR -
Tze sulfonation side reaction of the aromatics present in the feed is:
aromatics + H.::SO~ ~ sulfonic acids + H:P
The process has the following drawbacks:
severe corrosion by sulfonic acids:
disposal of the viscous acid sludges that are a by-product of the opera-
tion.

15~.!': "Inhibitor SweeteniDc" Process

(Sweetening with an ADriolddant)
'Ibis process uses oxidation by air in the presence of an amine inhibitor and a
strong base, The reaction sequence tan be summarized as follows:
(a) Formation of the mercaptide and a free radical:
RSH -to OH- ~ RS-+ H20
RH+ 02 ~ ROO
{feed (free radical)
hydrocarbon)

(b) Action of the amine inhibitor in the following way:

R1:i- R1N-

2RS-+O ~RSSR+
R1NH"
(regenerated)

The process results in severe. unacceptable gum formation and color

change.
510 C/laD:s-15 WHIlE PRoouCTS R~FINING BySWECTENING

15.2.1.4 Copper Sweetening

.. - .
The feed is treated with a copper salt (CuCli). The process includes two stages:
(a) Oxidation of mercaptans by the ion Cu2+:
4RSH + 4Cu2+ --+ 2RSSR + 4Cu+ + 4W
In this reaction the cupric ion Cu2+ is transformed into a cuprous ion Cu".
(b) Regeneration of the cupric salt by the oxygen in the air:
4Cu" + O2 + 4W --+ 4Cu~" + 2H;?O
(regenerated)

The presence of even traces of copperin gasoline is unacceptable (gum for-

mation and color change) and is a major drawback.

15.2.1.5 Hypochlorite Process

After the mercaptans have been transformed into salts. the attack by
hypochlorite is direct and rapid:
2RSH + 20H- --+ 2RS-+ 2H20
2 RS-+ CI0- + H20 --+ RSSR + CI-+ 2OW
(hypochlorite ion)

The drawbacks come from a large number of side reactions caused by the
strong reactivity of hypochlorite, with the formation of sulfonates, suHones
and chlorine derivatives in particular. As a result, pollution phenomena occur
and reagent consumption is significant..

15.2.1.6 "'Soluc:iser" Extraction Process

Developed by Shell after the Second World War, the process consists in dis-
solving the mercaptans in an alkaline solution. Dissolution is made easy by the
addition of some organic compounds such as fatty acids. aromatic acids and
alkylphenols. The reaction proceeds as follows:
(a) Extraction of mercaptans by the alkaline solution:
RSH + OH- ~ RS-+ H:P
(b) Oxidation of rnercaptldes to disullides and regeneration of OH-:
1
2RS- + 2" o, + H20 --+ RSSR + 2\>H-
(regenerated)

The extractive solution, called "solutizer", is a solution of potassium

hydroxide and tricresol in water.
The following drawbacks can be noted:
several extraction stages;
disulfides difficult to separate from the solution:
 smell problems due to tricresol:
large volumes of solution in operation.

Ij.2.2 Current Tedmologi~_5

Generally speaking. thesweetening feed (LPG, gasolines. kerosene) is treated

"by air in the presence of caustic soda with a soluble catalyst. It is a catalytic
oxidation process working in liquid phase. The pressure is adjusted so that the
air required for the reaction is dissolved in the medium. In a later improved
version of the process. the catalyst was adsorbed on a solid support. thereby
giving rise to the second" generation of processes.

15.2.2.1 Reaction Steps. Types of Catalyst

Mercaptan sweetening requires the use of a catalyst active at low temperature,
as the reaction is usually carried out between 30 and SOeC. Of all the catalysts
that have been studied in the past thirty years, organic chelates have proved
to be the most effective. Today the catalytic formulas generally used in indus-
try have a cobalt phthalocyanine base 1 (Fig. 15.2), where hydrophilic groups
have been grafted in order to make the catalyst soluble in aqueous alkaline
solutions.
The catalyst's mode of action determines the reaction mechanism of this
type of oxidation: i.e, the dyestuffs redox properties. In the presence of mer-
captides (reduced form of RSH), cobalt phthalocyamne oxidizesthem to disul-
fide and thus goes into its reduced form (called the "leuco" Iorm in the
dyestuff industry).
The air present in the medium reoxidizes the dye and the catalytic cycle
continues. The determining step is therefore the dye reoxidation rate.
With these considerations, the mercaptan oxldatlon reaction sequence can
now be described. It rakes place in three steps:
(a) Transformation into mercaptides by aqueous caustic soda treatment:
:!RSH + 20H- ~ 2RS- + 2H:?O
(caustic soda) (mercaptide)

(b) Conversion into disulfide by means of the dyestuff in its oxidized form:
2RS- + catal? ~ RSSR + cataF-
(oDdized form of dye) (reduced form of dye)

(C) Reoxidation of the catalyst by the oxygen of air and regeneration of the
caustic soda for recycle. This is the slow step of the process.

- cataI!- ... ~ 0, ... H-_,O ~ catal" +2.0H- ."

2 -

I. Other dyestuffs thaD phthalocyanines have also been proposed. for e.umple sulfur
dyestuffs.
512 Cna:::e- IS. WHITE PRODUCTS REFINING BY SWfEJENING

:~~I
o Cobalt phthalocyanine. Sweetening catalYst base.

The sum of these three reactions gives the overall reaction of the process:

15.2.2.2 Process De.igo

Two types of approach have been developed for the reaction sequence pre-
sented above:
Sweetening oxidation: here the "mercaptan" sulfur is transformed byoxi-
dation into "dlsulllde" sulfur, which remains in the medium. In other
words. after this chemical refining process the total sulfur remains
unchanged. but the mercaptans have disa.ppeared.
Extractive oxidation: this process uses Dhysical extraction of mercap-
tans. and the extractive solution (i.e.. the alkaline solution containing the
phthalocyanine) is regenerated afterward by air oxidation.
The extraction coefficients of mercaptans by industrial caustic soda are
examined versus their carbon content (Table IS. i) for the second approach.
The mercaptans in light cuts are extracted satisfactorily, contrary to heavy
 K Bolling range at 1 atmosphere caC)
- 1000 6
220 35
30 52-68
5 64-98
1-2 105-125
0.2-0.3 150-160
0.1 170-180
- Table
15.7 Equilibrium constants (caustic soda/hydrocarbon) 01 mercaptans (C I to C,.).
K '" RSH concentration in the caustic soda "/RSH coacenmuion in the hydro-
carbon. expressed in u:eightlr:olume.
~1easurements made with industrial soda.

rnercaptans. especially the C6+' In actual practice, extraction is possible up to

C5 mercaptans.
Consequently:
The extractive process is sufficient. for LPG to obtain a product comply-
ing with spectflcations 2.
Extraction can be performed lor light gasolines, but the operation must
be supplemented by a sweetening oxidation to make products comply
with specifications.
Extraction can not be used to treat. heavy naphthas and jet fuels
(kerosenes). The first technique, Le. sweetening oxidation. must be
applied.

15.3 Industrial Processes

There are two main types of processes:
The first uses technologies of the liquid/liquid contact type.
The second is more conventional and implements a fixed bed catalyst.

15.3.1 LiquidJLiquid Contact Technologies

Two technologies of different design have been developed in this area: one by
COP (Merox process) and the other more recently by Merichem (Thlolex anc
Mericat processes).

:!. According the sodium plurnblte test (Doctor Test).

 --------------'-------------------------- U'I
Extraction tower ~
TreatedLPG or gasoline
, ~
w
~
i);

I
Regenerator Dlsulrlde separator ~
(Rashig rings)
Flame
arrester
Furnace or flare
(
~
.. iR
~
~
OJ
-c
tIJ

~
20
Gasoline - - j
I

orlPG ,, ~
I

Steel
wool
,
I
I

Catalyst 'make up

Caustic soda circulation

---r::
Figure
_~5 .~_. Extructiue process (Men: extructioe).
 :;'2=:~ 'S. WrllTE PRooucTS RE;:",':::IJ(; BY S.'/FTE'!lNG 515

15.3.1.1 UOP TechDolocy (Merox) [6]

Q..J1eroxExtractive Process
The Merox extractive process unit (Fig. 15.3) comprises three sections:
The counter-current extraction touier. It extracts mercaptans with caustic
soda and is generally equipped with perforated trays. Operating conditions
are as follows:
- apparent contact time: 15 to 20 min:
- linear feed velocity (LPG. gasoline): 0.5 crn/s:
- caustic soda 12-18% wt (expressed in pure caustic);
- caustic soda/feed ratio: 15 to 2590 vol;
- sufficient pressure to p,revent evaporation phenomena;
- the lowest possible extraction temperature to achieve better extraction.
Nolabene:
(a) E..<tractive caustic soda ages with time due to the formation of carbon-
ates and phenates, as well as thiosulfates from the oxidation of traces of HzS
present in the feed (less than 10 ppm). In any case, the caustic soda concen-
tration must be kept above 11% wt by make up with the solution or with pure
soda.
(b) The feed must contain the least possible dissolved oxygen to prevent
side reactions.
The extractice solution regenerator. Here the alkaline solution coming
from the bottom of the extraction tower (and charged with mercaptides) is
regenerated by air oxidation with disulfide formation. It is packed with Raschig
rings. The operating conditions are as follows:
- contact time: 40 min;
- linear velocity (in empty vessel): 0.1 to 0.2 cm/s:
- air: approximately 1.9 Normal mJIkg of RSH sulfur;
- temperature: 20 to 60'C.
Nota bene: The "active" catalyst content varies between 100 and 250 ppm
in the solution. Excess catalyst results in regenerator fouling. i\loreover. fresh
catalyst make up must be added at regular intervals.
- The disulfide separator. Disulfides are separated from the alkaline solu-
tion in a horizontal drum that operates under the following conditions:
- contact time: 25 to 30 min:
- linear velocity: 0.3 to 0.5 cm/s:
- a steel wool coalescer improves the disulfide/alkaline solution separation.
,'Iota bene: The disulfides exiting the separator are sent to the gas oil
hydrodesuifurization unit or to the atmospheric distillation overhead hydro-
treating unit.

b. Merox Sweetening Process

The Merox sweetening unit (Fig. 15.4) includes three sections:
-The mixing touter: Gasoline, the alkaline catalytic solution and air are
injected in the bottom of the tower. The reaction takes place in the tower and
 ~
Ol

Sand filter
t
Mixing tower
~
~

I
XI
~eline~l
aIr FHler.
y Gratel~
i
ll>
"'(

~~o~ __ Refined gasoline en

I
10 ~

Fo"d gll'olln.. ...

I-~~
t
I
~ 'Caustic soda
make up!
y
f
t
I

Catalytic sohnlon
circulation

Figure
1S.4 I Suieeteuing proces (lIfem.\").
 the lota) effluent is recovered at the top and sent to the separator. The tower
is P~cked with Raschig rings or equipped with perforated trays. It operates
UJ1 d "er the following conditions:
'"" contact time: 3 to 12 min:
'"" catalytic solution/gasoline ratio: 10 to 20% vol:
'"" linear velocity: 0.5 to 3 CIDiS:
'"" temperature: approximately 40C.
~ The separator. The gasoline is separated from the catal}1ic solution in a
ho n zontal drum that operates under the following conditions:
<, contact time: 25 to 30 min:
-... linear velocity: 0.3 to 0.5 cmIs.
After settling. the catalytic solution is recycled to the mbdng tower. while
the ~asoline is sent to a sand filter.
" The sand filter. The settled and sweetened gasoline is sometimes cloudy
(3 stight emulsion due to caustic soda solution entrainment) and the sand Ill-
tet' ~cts as a coalescez In the sand filter vessel. the linear velocity is approxi-
m8.t~)y 0.3 to 0.5 em/so The refined gasoline is drawn off laterally in the lower
p~t: of the sand filter.
Iyola bene: Despite the sand filter. soda entrainments can sometimes be
oVs~rved in the gasoline due to surges in flow rate or pressure.

the possible areas of application for Merox technology are summarized in

Tzt-ble 15.8. '~

CombiDaUon Merox
Merox Merox
Feed extraction then
e.~ctiOD sweetening p-mening

vP~ +
t- igbt straight
t'ttn gasolines + +
Catillytic cracked
!Sasolines + +
1"h~rmal cracked
~asolines + +

'-t'"
Jet fuels"

;
+
~N'Jte that the ~lero.x extractive process can also be applied to treat sour gases.
Possible but not done in actual practice.

-------
: table - - - - - - - - - - - - - - - - - - - - - - - - '
l5.8 Possibleareas 01 application lor Merox liquid.'liquidtechnology.

'l'his table requires some comments;

'1 . RSH extraction is accomplished to 98-100% for LPG (C3iC4 cuts).
518 cr.ao!er 15 WI/I1EPRODUCTS REFINING BY SWE=r~NIN:;

2. Sweetening or the extraction + sweetening combination are possible for

light straight run gasolmes, but hydro treating is
currently preferred
(Chapter 16).
3. A sweetening operation is generally performed for catalytic or thermal
cracked gasollnes. However. it may be advantageous to implement extra-
ction before sweetening in anticipation of lower sulfur specifications for
gasollnes. Experience has shown that the mercaptans present in the C5
cut (l.e, the light gasoline overhead) can be extracted satisfactorily.
4. Jet fuels can be sweetened by means of a soluble catalytic solution and
with this technology. However, as discussed later on, a simpler solution
uses a catalyst adsorbed on a fixed bed under a slight trickle of caustic
soda and in the presence of air. .
From a refining standpoint as such. the resulting products have an RsH sul-
fur content lower than 3 ppm (in general). However. two major drawbacks
about this type of process should be pointed out:
1. Use of large volumes of aqueous soda, leading to spent alkaline solution
disposal problems.
2. Soda can sometimes be found entrained in the refined products.

15.3.1.2 Mericbem Technology [1. 3, 4]

This technology is also of the Iiquid/liquid type, but of a totally different
design. The process uses the principle of the fiber contactor patented by
Merichem in 1975.
The hydrocarbon feed and the alkaline solution are sent to a cylindrical
contactor (Fig. 15.5) packed with stainless steel fibers. The metallic fibers are
wetted with the aqueous phase which runs down along them. The hydrocar-
bon phase flows parallel to the fibers. In this way. the contact between the
hydrocarbon and the aqueous phase films is excellent, The resulting mass
transfer is highly efficient without any problems of emulsion or pressure loss.
The two phases can be separated without any entrainment in either one.

a. Process ROID Scheme (Thiolex, Mericat)

There are two possibilities: mercaptan extraction by caustic soda (Thioiex
process) or sweetening (Mericat process) (Fig. 15.6).A combination of the two
processes can also be used if the aim is to sweeten while eliminating maximum
RSHsulfur from the medium at the same time. The flowscheme represented in
Figure 15.i illustrates treatment of a light coking gasoline. It includes three
main sections:
A caustic soda prewash to remove the HzS present in the feed.
A mercaptan extraction section with two in-seriescontactors (Thlolex
process).
A Mericat catalytic sweetening section for the mercaptans that could not
be extracted in the Thiolex section.
~-----------------
_ Acid hydrocarbonfeed
i
I
.~
r-::..:.-o:::::='...l.
I =~~
il~:1
Alkaline I I
Treated hydrccamon
solution I Fiber contactor

Separator

Spentaqueous solution

1 Figure
15.5 ' Basic diagram of the Merichem technology.

" Results
t-he advantages of this technology can be summarized as follows:
(1) Very high efficiency achieved in mercaptan extraction and sweetening.
(2) Minimumcaustic soda and catalyst consumption.
(3) No caustic soda entrainment in the refined product.
(4) Simple operating conditions.
\. Areas of application: the Merichem technology can treat a wide range of
hite products:
LPG(as well as gases) with the extraction process;
straight-run. or catalytic or thermal cracking gasolines:
jet fuels.
~ Table 15.9gives the results for treatment of a light coking gasoline .by the
\.~mbination of soda prewashing + Thiolex + Mericat processes. Despite the
~ ~ high mercaptan sulfur content of the feed (2400 to 2 700 ppm), the result-
t)gefficiency is excellent and the product complies with spedfications.
 Feed TrealBd hydrocarbon

Oxidation
air

Causticsoda
____
Fiber
contaetor
-+~i-+--------'-
I __

recycle

~=-====..:::;;==:=-
Spent caustic soda Fresh causticsoda

Figure
15 6 MeTicat sweetening process.
1

Test , Design
I
Flow rate (ms/d) 256 i 318
I
Feed: ~
Sp.gr. dfl 0.675 0.690
:
Initial boiling point ("C) 31 30
End point Cc) 86 100
H~ (ppm) 7-8 20
Mercaptan sulfur (ppm) 2400-2706 3000
Total sulfur (ppm) 3500-3700 4020
I
Product:
Sodium (ppm) <1 ~5

H~ (ppm) 0 0
Mercaptan sulfur (ppm) < 1 15
Total sulfur (ppm) I 15(1...1280 1300
Doctor test Negative Negative

Efficiency (~,,): I

Prewashing section 100

RSH extraction section 94
Sweetening section >99
- ----,
! Table I
15.9 Treatment of a light cokinggosoline. Combined process [i].
_ _I
 ~' g -a.E ,'g.s

'~I
Ig
.~ l~
~
I'll ClIiii'8
U:~<Il
:J ~ i! g
a: 0. _ CJ o fI : - 10..2
C :i 1i
ig'
0'
Cl
C. a:: 0
(/J
'--------1

~~----'
l
I
I

,r --JC:D-..5 A --'
I I ~

~1
CDl
III
u..
-r--
'-----------------------
522 c.1atJ:fr 1S. WHITe PRoouCTS REFINING BY SW""~NlNG

1j.3.2 Fixed Bed Catalyst Processes

This type of process uses cobalt phthalocyanlne as its catalytic base.
adsorbed on activated carbon. Industrial processes were developed around
this formula. for example Minalk and Kerox (VOP) and later Mericat II
(Merichem).

15.3.2.1 Process Flow Diagrams

The processes involve mercaptan sweetening rather than extraction. The fixed
bed of catalyst (impregnated activated carbon) is wet by a trickling solution of
caustic soda.
a. Minalk Process (Minimum Use ofAlkali) [6]
The process was designed especially to treat light and heavy gasolines from
catalytic: cracking. The flow diagram (Fig. 15.8) is simple: after the gasoline is
mixed with dilute 3% weight caustic soda and air. it is treated in a reactor con-
taining a bed of activated carbon previously impregnated with Merox catalyst.
The soda itself is injected at a very low flow rate (5 to 20 ppm of NaOH in rela-
tion to the gasoline). The fixed bed reactor also serves as a soda settler and
coalescer, so there is one single vessel with a slow flow velocity. The tempera-
ture ranges from 40 to sOGe and the pressure from 8 to 20 bar. depending on
the type of feed.

3% caustic
soda

Catalytic
cracking
,

=='=~,:,o,ca~,,,
gasoline

0~lr~
. :::".' ".:

r-~-"i--....---- ..... Treatedgasoline

I 4-----.... Antioxidant

L- ; Figure 1
~ _ _~ Witho:awaf of
water pH 912 _
! 15.8 ! Minalk process (UOP).
I
 The refined gasoline is withdrawn from a side stream and sent to storase
after an oxidation inhibitor is added on line. The settled caustic soda. with a
pH between 9 and 12.is withdrawn at the bottom of the reactor. The Merox cat-
alyst.has a lifetime of one to three years. The procedure of reimpregnating the
catalyst on the bed of activated carbon requires a series of washing
sequences.

b. Kerox Process [6. 2]

The process was designed especially to treat kerosenes. It comprises seven
sections (Fig. 15.9):
Prewashing with dilute caustic soda removes the acidity due to naph-
thenic acids and phen6ls from the kerosene.
The sand filter removes suspended particles and emulsions. In some
cases an electrosettler is used to perform these two operations.
The reactor works with caustic soda recirculation (10 to 15% wt), an
operating temperature between. 40 and SO"C and a pressure ranging from
5 to 10 bar.
The settler separates out the spent caustic soda exiling the reactor. The
soda is recirculated back to the reactor two or three times at the most
and then routed to the refinery's spent caustic circuit
Washing with water eliminates entrained caustic.
The salt filter dries the kerosene.
The clay treatment, with a clay filter, winds up the refining process by
eliminating polar compounds.

c. Mencal II Process [5]

Developed to treat jet fuels. this process uses fiber contactors with several
stages. It includes (Fig. 15.10):
A caustic soda pretreatment to eliminate naphthenic acids and phenols.
A fixed bed sweetening section (Mericat II).
Washing with water without any settling vessel, which is not considered
necessary in this process.
Kerosene drying on salt. followed bya final clay treatment.

15.3.2.2 Results

a. Jlinalk Process
The process allows production of gasoline with characteristics that meet the
doctor test (plum bite test) specification. During normal operation. the exiting
mercaptan sulfur concentration is less than 3 ppm. Neither the copper corro-
sion test nor the color is affected.
524 C~:ir:~ ~', -,~ PFlOtJUCTS REFINING i3y $,"EETENING

~J
I ( \"0
~~~

~~
;ii:
________________________-..J1- -
 Caultlc aoda treotment Merlcat II Woter waah Salt Cloy
towor tronhnenl
Air

Koroscnc IllUtl

Recycle
fl II

Ii
~
~

~
iil

~
til
~
Spent cnusuc ~
soda Waler Troulod kcroecno (;)
I Caustic soda
---- ... u,
...;

~.l~
. I .
Hl:urc - -
15.10 AIlrimlll/l/Uc(!Ss. Treatment of aviation grade kerosene.
~
U1
~
526 C~:::tef 15. WHln: PRODUCTS REFINING BY SWEETENING

. If the process is compared to the liquid/liquid Meroxsweetening process..

three major advantages can be noted:
a dramatic reduction in caustic soda consumption;
a decrease in alkaline solution entrainment in the gasoline;
a simplification in the process (see Section 15.4) which results in lower
investments and operating costs.
b. Kerox Process
The process allows production of kerosenes that meet present-day specifica-
tions:
negative plumbite test with an RSH sulfur content lower than 10 ppm on
exiting the unit;
free sulfur content E; 0.2 ppm;
acid number ~ 0.012 mg KOH/g;
Saybolt color ;a. 20;
WSIM (water separometer index modified) .,.. 85 (without additive);
silver corrosion :!iii 1.
However,some kerosenes are more difficult to refine. Table 15.10classifies
crude oils according to how readily the kerosene cut can be refined. UOPhas
proposed a new catalyst, Merox 10, for the most difficult cases.
e.: Mericat II Process
Like the Kerox process, the Mericat II process allows production of kerosenes
that meet present-day specifications.

15.4 Economic Data

15.4.1 General Inform~tiOn-
- ":"

Table 15.11 gives the areas of application of chemical refining and hydrotreat-
ing processes for various white products.
This table requires two comments:
1. Fixed bed sweetening is in competition with hydrotreating for the kero-
sene cut (jet fuel). Today one of the essential specifications laid down
for jet fuel is on mercaptan sulfur. It is therefore preferable to perform
chemical refining because hydrotreatlng consumes hydrogen, which is
never in very abundant supply in the refinery. Moreover, with the
increasingly stringent sulfur specification on diesel oils (sulfur 0.05%),
there may be a risk in some cases of a shortfaU in desulfurization capac-
ity. Sweetening kerosene should therefore be a good way to make more
desulfurizatlon capacity available or maintain it the same.
 Ch!:Jrttr 15. itlt-iir.: PF;cOUCTS REFA:,3 sy S.~ 527

Possible refining Difficult refining

Arabian Light Adma AghaJan
Arabian Medium Basrah lambur
, Arabian Heaw Basrah Medium Tujrnaza
I Hassi-~tessao~d Fereidon Eocene
I Kuwait Gash Saran
Kirkuk Ain Zala
Murban ~ Darius

I Qatar Laad
, Qatar ~1arine
, Souedieh
Ural
i Belaym
Kirkuk Blend
Zuetina Basrah Heavy
ZarzaitiDe Abu AI Bukhoosh
Berri
Dubai
Slrtica
Oman
Brass River
Safaniy~
Sahara
Anew
Khan
i Table'
i 15.10' Kerox unit. Effect of the parent crude oil on refining the corresponding
~'_ _ kerosene. .

Uquid/llquid
dlemical refining
F"o:ed bed
Hvdro-
Feeds chemical
~tiDg Extraction
Sweeteuing with or without refining
sweetening

l
LPG 2 :!
Straight run
light gasolines
Conversion
gasolioesu 2 I 1
Kerosene 3 4 I I
Notes: 1:Commonly applied. 2: Possible application. 3: Probably possible applica-
tion but DOt yet tried..1. Impossible application.
.. Except for special cases, hydrotreating is currently preferred."
** These include ca.talytic cracking. coldng and visbreaking gasolines.
- Table
ly.ll Areas of application for hydrotreating and chemical refining processes.
528 c:-.aQ~ 15. WHITE PRODUCTS RI;FINING BY Sl"lEfTENING

2. Today conversion gasolines (from coking, catalytic cracking, visbreak-

- lng) are' generally chemically refined rather than hydrotreated. Here
too, with the increasingly stringent sulfur specification on the gasoline
pool. chemical refining technologies by extraction should gain popular-
ity since the investments and operating costs are lower than for
hydrotreating. Furthermore. for the same reason some fractions of light
catalytic cracking gasoline (middle cuts) are hydrotreated. while the
overhead cut is treated by sweetening, generally of the extractive type.

15.4.2 Process Licensors. Treatment Capacity

The market for white product chemical refjni~g by sweetening processes, Le.;
mercaptan extraction units,
chemical sweetening units,
combined units with extraction followed by sweetening,
is today mainly dominated by two l1censors: VOP and Merichem. The first.
VOP, had licensed over 1 500 units worldwide by 1994 for a total treatment
capacity of more than 680 million m3/year of various products (LPG. gasolines
of all origins) (Appendix 15.1). The second, Merichem, had licensed 280 units
by mid-I994, accounting for a treatment capacity of 160 million m3/year of
white products and 30 milHon m 3/year of gas (Appendixes 15.2,15.3 and 15.4).

15.4.3 Basis for an Economic Estimate

15.4.3.1 Investments
Investments in white product chemical refining units depend on the feed to be
treated and the type of process. Table 15.12 gives battery limits investment
ranges for refining three types of feeds (kerosene..catalytic cracking gasoline,
LPG). .

15.4.3.2 Operating Costs

Operating costs can be estimated as shown below lor two typical cases.

Q. Kerosene Refining
An estimate of operating costs for fixed bed sweetening ranges from 0.25 to
0.4 per ton ( 1999), and is broken down as follows:
(%)
Utilities (kWh, cooling water, instrument air) 2
Catalyst............................................................................. 7
Chemicals (NaOH, salt, clay, reaction air) 45
Manpower 46
 Feed to Flow rate Type of Investments
Commeats
be refined (tId) refining (10' 1999)

Investments depend
Kerosene 1 700 Sweetening 4.0-5.5 on the type or tech- ,
nology used I

1.~1.9 Liquid. liquid tech--

i Light catalv": nology
cracking gc.sc"- 1 700 Sweetening
I line 0.8-1.0 Minalk type fi-xed
bed technology
j
I , Extraction
iI LPG 800 without 1.4-1.6 , Merox e:rtractive
type
sweetening
L- Table
I~5.12 I lncestmentsfor u:hite product chemical refining units (battery limits).

b. Gasoline Refining
Table 15.13 gives an estimate of operating costs for two kinds of process
(Merox and Minalk). The use of a fixed bed technology reduces operating costs
substantially:
caustic soda consumption is lower by half.
catalyst consumption is also halved.
manpower is divided by three.
Overall. calculation shows that operating costs for fixed bed sweetening
are an estimated 2.5 times lower than for Ilquld/liquid light gasoline sweeten-
ing.

Uquid/liquid process (Jlerox) Fixed bed process (MiBaIk)

Utilities 0'\\n t) 0.09 0.07

Caustic (g;t) 30 15
Catalyst (g f\ 1 0.5
-i Manpower (h d) I::! -\.
~ Table - - - - - - - - - - - - - - - - - . : . . . - - - - - - - - - - - - '
15.13 Sueetening of a light catalytic crackInggasoline. Estimate of operating costs.
530 Chaaler 15. WHITEPRODUCTS REFINING BY SWEETENING

Referenc:es_
Mueller T.. Rosenstock G. (1983) Sweetener lowers' costs. Hydrocarbon
Process. into Ed., o, 10. 95.
2 Verachtert T.A, Staehle B.E., Salazar J.R. (1985) Merox catalyst innovation
solves difficult kerosene treating problems. Nod. Petr. RefinersAssoc. Annuo
Meeting, San Antonio.
3 Vasquez R.G. (1989/1990) Reduced operating costs by caustic treating jet
fuel stream. Hydrocarbon Technology international.
4 Maple R. (1994) Caustic treating of MTBE and TAME feedstocks.
Hydrocarbon Technology International 91.
5 Francoise G., Varadi T. (1993) A new kerosene mercaptan oxidation process.
Hydrocarbon Technology international 63.
6 Holbrook D.L., Arena BJ., Verachtert TA. Brick J.e. (1983) Merox processes
for caustic minimization and management. Natl. Petr. RefinersAssoc. Annu.
Meeting, San hntQnio.
7 Wizig H.W. Vasquez R.G., Maeda K. (1986) Increase lead susceptibility of
sour coker naphta stream via caustic treating. Nail. Petr. RefinersAsso.Annu.
Meeting, Los Angeles.

Appendixes

Capacity
Operating companies Place
(m3jd)

Conoco Inc. Billings. USA 1875

Chevron Canada Ltd. Burnaby,Canada t 350
Petro BrasiIeiro SA Paulinla, Brazil 2700
3000
of
1000
Petrox SA Concepcion, Chile
Admin. Nacl. Combustibles Montevideo. Uruguay 950
Alcoholy Portland SARAS SpA Sarroch, Italy Extension
ERTOILSA

Kukdong Oil Co. Ltd.

Huelva, Spain

Seosan, South Korea

620
940
300
I!
480
2385 !
Kyung.in Energy Co.
Thai Oil Ltd.
Inchon. South Korea 875 !
Sriracha. Thailand 3020
BP Kwinana Rfy. Pty. Ltd. Kwinana, Australia 1590
3510
" l ~ r - --
i ....:..- ---.J

I 15.1 I Units using Merox process (UOP).

' (Source: HPl Construction Boxscore Hydrocarbon Processing (1992/997)).
 Operating Capacity I
companies
Place
(arId) i Feed

Ai'HC Gela.ltaly 480 Pentenes

ARCa OlL & GAS Bakersfield. C5A 205 Condensate
BP Grangemouth. l"K i95 Heavy cracked gasollne
1750 Ught cracked gasoline
! Champlin RockSprings. [SA 160 Condensate
! Chevron EIPasu.l"SA 2385 Light crackedgasoline
I
I Chines Petroleum Co. Kaohsiung. Taiwan 2580 Cracked gasoline
j OTGO Lake Charles. [SA 3180 Heavy cracked gasoline
3180 Heavy cracked gasoline
i Conoeo . Comm~rce City. USA 1190 Xaphtba
Cosmo . Chiba. Japan 400 Ught cracked gasoline
IKyokuto II Chiba.Japan
1430
1190
light naphrha
Light naphtha
UquidEnergy Bridgeport. VSA 320 Naphtha
UttleAmerica I Casper. l:SA . 1910 Cracked gasdine
Marathon 1 Robinson. USA 1590 Naphtha/cokiDg gasoline
Mobil i Chalmette. USA 400 Naphtha/coking gasoline
I
4610 Cracked psoline
I
:'Iavajo I Artesia. USA 1810 Cracked gasoline
NesteOy j Porvoo. Finland 2780 Cracked gasoline
Pemex IiSalina Cruz. ~Ie.'tico 2385 Naphtha

I ;arpom
L~
Petrosar
I:
, Samia. Canada
Trecate, Italy
PuiauBukom. Singapore
510
1670
1525
LPG
tight cracked gasoline
Heavy cracked gasoline

Appendix;
/15<2 I Units using .\lericatI process.
i (Source:HPlConstruction BoxscoreHydrocarbon Processing (]992-1997)).

Operating Capacity
Place feed.
companies (rr/d)

I Derby Wichita. USA

j
480 Kerosene
i Hydrocarbons GreatBritain Barrow-in-Fumess. UK - 1_ 960 Condensate
: CS Oil & Refining - - TacomaUSA 555 Jet fuel
i --- ,;....- --'
-; Appen.iix-
! .15.3 (Jnits using .VerieatII process.
.L - - (Source:HPIConstruction Boxscore Hydrocarbon Processing(1992-/99f)).
532 c-,, . ~ 15 WHi:= P;;OOUCTS REFINING BY SWEETENING

Operating Capacity
Place Feeds
companies (m3/d)

Enterprise }It. Belvieu. USA 780 Butane

1600 Propane
3200 Butane
3200 Butane
Exxon,USA Baytown. USA 480 Aromatic naphtha
FlnaOil& Chemical Port Arthur.USA 1030 Butane
Fletcher Oil Carson. USA 480 C3iC~
GulfCoastFractlonators Mt Belvieu. USA 2420 Butane
5090 Propane
IdemitsuKosan Aiehi. Japan 1530 LPG
Javelina Corpus Christi, USA 490 Butane
Koch CorpusChristi.USA 400 LPG
Marion Theodore, USA 525 Naphtha
Mobil Chalmette.USA 9900 Fuel gas
480 Propane
Texaco \\ilmington. USA il5 Butane/buteues
TexacoOil&Chemical Vidor. USA 11300 Fuel gas
TOA Kawasaki. Japan 1160 LPG
Tonkawa Arnett. USA 28300 Fuel gas
UDS Arkansas. USA 1160 C3/C~
UltramarCanada 51. Romuald, Canada 1110 C3/C4
Union Lemont.USA 2700 C4 for a/I..'ylation
Valero Corpus Christl.USA 2860 C3/C4
Warren Petro Venlce, USA 1670 C4 for alkylation
Yukong Ulsan. South Korea ,1>10 LPG

Appendix
15.4 '. Enits using Thiolex process.
~ (Source: HPf Construction Boxscore Hydrocarbon Prtx::essing (1992-1GYi)).
 16
Hydrotreating

Gerard Heinrich
Sladk Kasztelan

Hydrotreating processes consist in treating a petroleum cut under hydrogen

pressure with a solid catalyst. They are designed for all the petroleum cuts in
a refinery from light gasoline to vacuum residue. A distinction is made
between hydrorefining and hydroconversion processes. Hydrorefining aims
mainly to remove impurities. e.g. sulfur, nitrogen, metals. etc. and increase the
HIe ratio by hydrogenating unsaturated compounds. Hydroconversion is
employed to modify the hydrocarbon skeleton by cracking and isomeriza-
tion [1].
This chapterwilJ essentially cover distillate hydrotreating. Distillate hydro-
cracking and residue hydrotreating are dealt with in Chapters 10 and 13
respectively.
The main hydrotreating reactions are hydrodesulfurization (HOS), hydro-
denitrogenation (HON) and hydrogenation (l:ND). In some cases the feed to be
treated contains a small amount of oxygenated compounds 'which will be
decomposed by hydrodeoxygenation (HDO) and some metallic compounds
which will be decomposed by hydrodemetaJlization \.HD~I). In other cases. a
little conversion to light fractions is sought by hydrocracking (HOC).
Hydrotreating operating conditions are highly variable depending on the type
of feed and the prevailing reaction. Pressures vary from IOta over 200 bar and
reaction temperatures range from 250 to 450'(.

16.1 Objectives of Hydrotreating Processes

Hydrotreating processes are by far the most commonly found in refinery flow
schemes. They have two basic functions. One is to improve the characteristics
of finished products so that they meet specifications in terms of quality and
emission standards (sulfur content in particular). The second is to prepare
534 ChaPlet 16 H'tDROTFlEATING

feeds for other processing and conversion units in the refinery (isomerization.
reforming. catalytic cracking. hydrocracking) whose catalysts are sensitive to .
impurities: sulfur for metallic catalysts, nitrogen for acid catalysts and metals
for all types.

16.2 Impurities and their Origins

16.2.1 Heteroztoms and Metals
Crude oil naturally contains impurities, particularly sulfur. nitrogen, metals
such as nickel, iron and vanadium and sometimes oxygen. These impurities
are an integral part of various heteroatomic compounds. whose nature and
amount depend greatly on the origin of the crude. As a general rule, the impu-
rity content increases after distUlation from light cuts to heavy cuts, as shown
in Figure 16.1 for the sulfur and nitrogen content of an Arabian Light crude.
The type of compound containing impurities also depends on the distilla-
tion range of the petroleum cut. This is illustrated in Table 16.1 for sulfur com-
pounds. For example. light distillates - naphtha and kerosene - contain sul-
fur in the form of mercaptans, sulfides, polysuUides. thiophenes and
substituted thiophenes. Middle distillates - gas oU and vacuum gas oil- also
contain heavier molecules of the benzothiophene and dibenzothiophene type
alkylated to a greater or lesser extent. The residue contains even heavier sul-
fur compounds such as benzonaphthothiophenes and heterocyclic polyaro-
mattes with one or more thiophenic rings [2].
Nitrogen is present in different types of compounds such as: aliphatic
amlnes, compounds containing a five-atom ring or non-basic compounds
(indoles, carbazoles), and compounds containing a slx-atom ring or basic com-
pounds (qulnolines, acridines and benzoquinolines) [3. 4]. All these com-
pounds exist in forms that are substituted by alkyl groups to a greater or lesser
degree. "

I Distillali ISulfur
' Sulfur compoWltk ('; .-t total S)
! 001
Petroleum
t l"lI.DIe 'cootent, j
cuts
CC) I
(% ..1) Men:aptans , Sulfides : TbiopbeBes
, I
Beazothiophenes
aDd heal)' sulfides

Naphtha 7/}-lSO 0.02 50

ii
50 i

iI
'Traces -
Kerosene 160-240 0.2 25 .J$ 35 15
! i
Gas oil ! ~350 0.9 IS 15 33 35
Vacuum gas oil i 350-550 1.8 5 I
Vaeuwn residue i 551)-"
I 2.9 Traces I
I
Tra:es I
j
30
19
55
90
"-; Table i

1 16.1 Distribution 01 sulfur compounds in the cuts from distillation of a crude with
! 1.2% u;t sulfur.
 PC} S (% wf) (ppm N)
550 -. ---------------oy---- 5 ;- 2500
I
Arabian Lignt C:ude
34.2 :API
s. 1.65'; wt
N: O.05'~ wt 1I 4 - 2000

: I
!
"
350 3 ~ 1500

I
2 r- 1000
I
I
I
I
I

~5oo

0 !O
I o 25 SO 75 100

l- ! Figure
: 16.1
"~distilled volume (TBP) or distilled volume
mid-poinf (sulfur and nitrogen)
-----'
Sulfur and nirrogen rontent cersus dislilJation range. Arabian Light crude
(suitur: I.65.~ uit: nitrogen: O.OS",J uit).

Oxygenated compounds are generally present only in particular hydrocar-

bon cuts from coaL tar sands. oil shales and certain heavy crudes. The main
oxygenated compounds are alcohols, phenols. naphthols. Iurans, benzofurans
and alkylated dibenzofurans [5}.
Nickel.vanadium and iron are essentially chelated in organometallic com-
pounds such as resins and asphaltenes and in particular in structures of the
porphyrin type present in the heavy oilIracttori [6]: Iron is also cornplexed in
aromatic structures oi the naphthenate type for example. These complexes
are decomposed under hydrotreatlng conditions by reacting with hydrogen on
the catalyst surface. Then they are deposited in the form of Nit V and Fe sul-
fide in the catalyst pores. .
536 Chaptef 16. HYDROmEATlNG

I ..
Impurities Soun:e
I Main Ca~'St
Muimum
content
cut
I !
poison ~ (~wt)

i'\i, V Crude I Distillates

Residues
Strong, deposit inside cata-
lyst and plugging
to
30-40
As ! Crude !All Strong, deposit at top of
reactor !
0.2-2

Hg I Crude I Naphtha Slight, only slightly retained Traces

NaCI Crude I Residue> i Strong, deposit at top of
reactor, generates pres-
;
1.0

sure loss I
I

Fe Crude and cor-

rosion I PJI
Slight. deposit at top of
reactor, generates pres-
!
j
I
I

;
sure loss I

CI SOlvents and I Very slight, promotes i. 0.1-0.5

!
recycled slops , coking and corrosion
Si Anti-foaming IDistlllates Very slight, deposit inside , '>-10
agents catalyst and plugging
Pb IRecycled
line
gaso- ; Gasoline Strong. deposit at top of
bed
!
0.1-1.5
I

CO/CO2 Hydrogen
make up
IAll Very slight. formation of
carbonyl N"l. Co. Fe at
< 0.05 % vol
low temperature
I
:--- I I
I Table
: 16.2 Origin of impurities and their effects on hydTOlreating catalysts. Maximum con-
i
L-- tent on spent catalysts.

!
Straigbt
run !b~ngl Delayed
cokiDI
fluidized
i
Catalytic
coking i cracking I
TBPcut point CC) ! 150-350 150-350 150-35{) 1S()....350 210-300
ii
Sulfur (% wt)
l'\itrogen (ppm)
1.31
70 !
I
1.35
300
0.95
600
3.0
900
2.33
530
Bromine number (&/100 g) 1 20 30 45 14
Sp.gr.~s 0.880
Aromatics (% wt)
I 0.846
27
0.865
29
0.865
30 45
0.958
87
,

~~
I

,I 16.3 Impurities. and unsaturatedcompounds in gasoil cuts produced b.vr:arious con-

versionprocesses.
 Another type of impurity is sodtuz; chloride, even though it is usually
removed by desalting. It is sometimes :\)und in small amounts in the heavy
cuts and particularly in the residues.
Other impurities are present in very small amounts. such as mercury and
arsenic in the form of alkyl-mercury azd alkyl-arsenic. Mercury compounds
are usually decomposed during hydrcceatlng. but the mercury - gaseous
under the temperature and hydrogen pressure used - is not deposited on the
catalyst. Arsenic compounds are decomposed on the catalyst causing arsenic
sulfide to be laid down mainly at the tcp of a catalyst bed.
Other impurities should be added r: this list of heteroatomlc compounds
and impurities naturally occurring in crude oil. They can come irom recycling
various petroleum wastes ansi hydrocarcons that may contain numerous trace
metals, particularly Pb, P. Cu. etc. They can also come from antifoaming addl-
rives containing silicon that may also poison catalysts.
The petroleum cut can also contain solid particles such as carbon from
furnace tube coking and iron sulfide ,generated by corrosion in the units.
Lastly, the presence of impurities in hydrogen gas should also be meutioned.
such as CO and CO!. CO and CO2 are hydrogenated to methane and water by
reacting with hydrogen on the catalyst. COhas an inhibiting effect 00 catalyst
activity and can moreover form carbonyl compounds at low temperature with
the active catalyst elements such as cobalt and nickel.
Table 16.2 summarizes the origin of me impurities present in the various
different petroleum cuts. It also indicates the main effect on the hydrotreating
catalyst and typical content values determined on spent" catalysts Fl.

16.2.2 Unsaturated Products

Aromatics and polyaromatics are the main unsaturated compounds present in
oil. The number of aromatic rings increases with the distillation temperature
of the cut. Unsaturated mono and diolefins and aromatic amines are among the
compounds originally absent from crude oil but present in certain hydrotreat
ing feeds. They come from processing ;:-=tToleum cuts in catalytic and thermal
cracking units. Today the increase in :.:nsaturated products in cuts sent to
hydrotreatlng is basically due to the inccrporatlon in refinery flow schemes of
thermal or catalytic conversion processes. These conversion processes
mainly include: visbreaking (Chapter 10. coking (Chapter 12). and catalytic
cracking (Chapter 6) of heavy products :rom vacuum distillation.
Table 16.3 shows the nitrogen and olefin content commonly found in gas
oils from thermal conversion processes. The values are considerably higher
than for a straight run gas oil.

16.3 Hydrotreating Processes

There- are. two major categories of hycrotreatlng processes according to their
aim: meeting finished product speciticanons or preparing the feed for other
 ~ processes. Figure 16.2 shows how distillate hydrotreattng processes
~ =ccr.,omed in the refining flow scheme. The main hydrotreating units are
:.-::!';~:o improveend product quality by reducing the impurities and unsat-
:=-~ ;.r:.<iuc: CO:it':::nt.

.7.~'!21le hydmtreating:
-~e!:S mercaptans, sultunaromatics,
- :z::pw."es smrJke point.
:.~ : if .'::.drr.-treating:
- :~:X.'l:S <;,ulfJT. nitrogen. aromatics. olefins,
- =?TOV!S cetane number, thermal stability.
~. oil h}"drMinishing: ~
- ~uces sulfur, Conradson carbon (CCR),
- ~roves color. oxidation stability.
:-:-.e :Jain hydrotreating units that prepare feeds for other refining pro-
~ are naphtha and vacuum distillate hydrotreating. Naphtha hydrotreat-
~ .s i ~tment for isomerization and catalytic reforming processes. The
~;~~~~ is to reduce sulfur, nitrogen
0.5 ppm wt) and olefins 0.1% wt).
-~"U!D distillates such as straight run,visbreaking, coking. deasphalted
:': ~ ::ydrotreated residue vacuum distillates are hydrotreated as pretreat-
:::.~.: 'cs FCC and hydrocrackers.

?;':2iment of flUid catalytic cracking feeds:

- "~uces sulfur, nitrogen, oleflns, polyaromattcs, metals (Ni, V) and
:Onradson carbon (CCR),
- .=-pr1)v~ hydrogen content, crackability,
- results increased conversion, reduced impurities (sulfur) in products.
:rJ.....er SOx and NO., emissions in gases exiting the regenerator.
?:";!!'".&.tment of hydrocracking feeds (or the first stage in the hydrocrac-
6g process): .
- :,,~uces nitrtJgen 10 ppm) and aromatics content.
.' .

: :.~ Background Information

: ~"~-: Hydrotreating Reactions
?~ ~:iierent heteroatomic compounds present in petroleum cuts are trans-
:'j~r.:d by reaction with hydrogen on the catalyst surface. The reactions lead
tCl :orrnationof hYdrocarbons that are saturated to a varying degree and elirn-
i:.ationof S. 0 and N ill the form of H:zS. H20 and NH3 The hydrogen sulfide is
".:2:racted from the gaseous effluent by an amine treatment unit and then con-
~ed into elemental sulfur in a Claus unit. The ammonia is extracted from the
~:.u-!:!lt by washinJ:with water. The water is recovered in separator drums. At
th~ same time as the hydrorefining reactions, the unsaturated hydrocarbons,
<J;~i:'.s and aromatics are partly hydrogenated.
 ------ -----------------_..
-~- --f .e,c'-I -- -~-: ::~:,~.
I n---fT"'c
nlr
"lJ J a
c

'
~I ----)ttr ,,"""m

Crudo
G,,~
-
.--

--t.
01 ~.~:~.. .
em" ~I_I--U Healtr~OII

".m.Ra. 1 [.rr= vac.018.1

J
FILllll.
.1.
III
-{f~~NhM3-6-TJ-- . .
g.... L r'; __ ~
- ...

~~.~. breaking
--t;J~-J- :--EiI-- J oj

~
(g
:'1
~

H\:llrC I --l_ . . .__..

.....Fueloll
!

16.2 I /)j:~'ilialt! Ityclmtretlting processes incorporated in a refinery flow scheme. J1)'dn)/realillg lit/its are shoum ill way.
~
 540 C/tapltK 16. HYDROTREATING

16.4.1.1 Thermodynamic Characteristics

Reactions that break carbon-heteroatom bonds are exothermic as indicated by
the negative values for heats of reaction in Table 16.4. The reactions are com-
plete under usual hydrotreating operating conditions.
Hydrogenation reactions are highly exothermic (Table 16.4) and reversible
under hydrotreating operating conditions. Hydrogenation is promoted by an
increase in hydrogen pressure and a decrease in temperature. Olefin hydro-
genation is generally almost complete under hycrotreatlng conditions. In con-
trast, aromatics hydrogenation reactions can reach thermodynamic equilib-
rium under certain conditions. such as those usee. ;or hydrotreating kerosenes
and gas oils. Figure 16.3 shows an example <;If thermodynamic limit reached
during gas oil hydrogenation. A rise in reaction temperature causes an
increase in the aromatics content. Figure 16.3 also shows that the heavier the
aromatic compound. i.e. the larger the number of rings, the more the thermo-
dynamic limit will be shifted toward a low ternperature for a given hydrogen
pressure. Deep hydrogenation of aromatics therefore requires a high hydrogen
pressure [10].

Heat
Reaction of reaction
(kJ/mol)

I 2propanethiol + Hz..... propane + HzS -54.3

1 R-S-R+ 2H z -+ 2RH + H~ -117.0
I R-S-S-R + 3H z ..... 2RH + 2H~ -209.0
I Cyclohexanethiol + H2 -+ n-butane + HzS -112.8
! Thiophene + 4 Hz ..... n-butane + HzS -284.2
I Dibenzothiophene + 2H! ..... biphenyle + H~ -46.0
I R-NH 2+Hz RH + NH3 -79.4
I o-Ethylanlllne H2 --- ethyl benzene + NH3 -58.5
Indole + 3H 2 ethyl benzene + NH3 -204.8
Quinoleine + 2H! 1.2.3.4-tetrahydroquinolelne -133.8
Quinoleine + 4H z propylbenzene + NH3 -2;1.7
R-OH + H2 RH H20 -100.3
Phenol + Hz benzene ... HzO -66.9
Furane + 4H:! n-butane + H20 -351.1
Benzofurane 3H! ..... ethylbenzene ...H20 -104.5
Benzene ... 3 Hz ..... cyclohexane -209.0
Naphthalene + 2 H:! -+ tetraline -125.4
:....-
Table
i 16.4
!
!! Heat of reaction for a number of pure cotr::c:..ids treated by hydrogen [8, 9}.
L-.....:
 g 100- Monoaromatics.
Diaromatics
~ Polyaromatics
~ 80-
.5
60 -
.~
CIl
.!.!
~
E 40 -
e
I";

l- __
20,.
!
0 I I i -e.==
250 300 350 400
Temperature eq
I Figure .
i 16.3 : Thermodynamic limit for hydrogenaliDlr of aromatics in a gas oil. Catalyst
I
=
NiJfolalumina. PH! 60 bar. J- 000 p,. ofS in the feed.

16.4.1.2 Reaction Mechanism

Hydrotreating reaction stoichiometry is highly dependent on the nature of the
heteroatomic or unsaturated compounds. Note in Table 16.4 that hydrogen is
always consumed in these reactions and that hydrogenating aromatics rings
consumes more hydrogen than breaking carbon-heteroatom bonds. Which
reaction should be promoted depends on tbehydrotreatlng objective. the type
of petroleum cut and therefore the type of heteroatom or unsaturated com-
pound that needs to be removed. The selected reaction wiJI require a different
catalyst formulation and different operating conditions.
The hydroreflnlng reaction sequence is of a varying degree of complexity
according to the type of heteroatomic compound [8]. Decomposition of mer-
cap tans. alcohols and aliphatic amines is easy and involves only reactions that
break carbon-heteroatom bonds. The bond-breaking mechanism is still a sub-
ject of debate. but the two most probable ones are elimination and nude-
ophilic substitution as illustrated in Figure-I6..4.
When compounds contain aromatic rings. the reaction sequences can be
very complex with a large number of intermediate compounds and a network
of parallel and consecutive reactions involving hydrogenation of aromatic
rings and unsaturated bonds. and breaking of carbon-heteroatom bonds. This
- type of sequence is represented in Figure 16.5 in a simplified form" for
hydrodesulfurization of dibenzothiophene (DET). which is a molecule repre-
sentative of the sulfur compounds present in gas oils. The main DBT
hydrodesulfurization reaction is direct breaking of aromatic carbon-sulfur
bonds without prior hydrogenation of the aromatic rings yi~!ding biphenyl
542 Cr.acter 18. HYoRoTREATING

(process 1, Fig. 16.5) [2.12]. Other products are obtained in small proportions
by hydrogenation. particularly phenylcyclohexane and dicyclohexyl. As such, -
one of the specific features of hydrodesulfunzatlon is low hydrogen consump-
tion. since desulfurization does not require complete hydrogenation of the sul-
fur compound.

A. Elimination (E2)

BH+C=C + NH3

B. Substitution (S~)

~ Figure
16 4 Mechanisms of carbon-heteroatotn bond breaking by elimination or
1 1
substitution.

Tetrahydrodibenzothiophene
(THDBT)

;;b7 (Ie()
~ S ""- Phenylcyclohexane
-........ (PhCH)
Oicyclohexyl
(OCH)
OBT
~
V~V
s "U~O-O
~ /
r
Biphenyl (BP)
I'-
l---
i Figure ---.J

: 16.5 I Reaction sequence for hydrodesuliurization of diben.::othiophene (DST).

 o-rer 16_ ~TREATi!lG 543

The numerous sulfur compounds present in petroleum cuts do not all react
in the same way. Figure 16.6 gives a Qualitative comparison of the desulfuriz-
ing difficulty for various sulfur compounds in a gas oil cut. It also shows that
COQlpounds of the alkyl-dibenzothiophene type are the most difficult to deal
~ith. They are-identified in thoroughly desulhirized gas oils [2].
The reaction sequence for quinoline decomposition is shown in Figure 16.7
[3. 4].lt represents the-type of nitrogen molecule that is present in gas oils and
is difficult to decompose. Complete denitrogenation of quinoline involves
steps with carbon-nitrogen bond breaking as wen as hydrogenation reactions.
Cor1trary to hydrodesulfurization. hydrodenitrogenation requires prior hydro-
genation of aromatic rings in order to free the carbon in a position of the
nbogen.
,-

OR Easy
:f'S S R-f"']-R
g
I
5 R{JcJI ~Ult
5 R-0=O-R Verydifficult
R-(')-()-R
AYlfA
- S

TS~

F"lgUR
j 16.6 Reiatice reactivity of su/furcompounds in a gas oil.

0 l.2.3,4.THQ OPA PB

ro ~I ..-:
N
~
ro NH ~
NH 2
~
!lI !) !)
I' I, i!
I,
00 N

5.S.7.S-THO
4
co DHQ
q:-U
PCHA .PCH -!
Fi';lUrt
16.i Reaction sequence for ~Tirodenitrogenation of quinoline (Q). (THQ: tetraity-
droauinoline, DHQ: decaitydroquinaiine. OPA: orthopropylaniline. PS: propyl-
benzene. PCHA: propylcydohe.\)1amine. PCH- prop.v1cyc!ohexone).
544 Cnaorer 16, HYOrior;:=.:;:-;,\';;

Figure 16.8 gives a qualitative comparison of the reactivity of the various

nitrogen compounds in a gas oil and shows that compounds of the alkyl-quino-
line type are the most difficult to denitrogenate.
The diolefins in thermal conversion process products are highly reactive
compounds which tend to polymerize and generate a hydrocarbon or coke
deposit on the catalyst surface under hydrodesulfurization conditions. It is
therefore preferable to hydrogenate the diolefins beforehand with a specific,
noble metal base catalyst or a hydrotreating catalyst with very low acidity.
Generally speaking. olefin and diolefin hydrogenation reactions are easy.
Polyaromatics hydrogenation takes place by successive hydrogenation of
each aromatic ring. It is relatively easy to hydrogenate the first ring. However.
the last one and in general monoaromatics are difficult to hydrogenate. The
reactions will be strongly promoted by increasing the hydrogen pressure.
Sulfur, nitrogen and aromatics molecules have different reactivity.
Compared reactivity of molecules with one aromatic ring gives the following
increasing order of reactivity:
toluene < aniline < phenol < thiophenol
and for reactants with two aromatic rings:
tetrahydronaphthalene < quinoline < dibenzofuran < dibenzothiophene
Generally speaking the order of increasing reactivity among the different
hydrorefining reactions is:
HYD < HDN < HDO < HDS
Hydrorefining reactions generate H~. NH3 and H20 that can influence cata-
lyst reactivity. H~ has a complex effect on the various hydrorefining reactions.
It is an inhibitor for hydrogenation and desulfurization and a promoter for the
carbon-nitrogen bond-breaking reaction [4. 8J. NH3 is an inhibitor for all the
reactions and its effect is more powerful than that of H~. Water has a slight
inhibiting effect on hydrogenation and desulfunzation, but seems to promote
carbon-nitrogen breaking slightly.
Hvdroreftning reactions take place simultaneously when a petroleum cut is
hydro treated. The different reactants present in the cut are more or less
strongly adsorbed on the catalyst surface and therefore compete with each
other for access to catalytic sites. Consequently, inhibition phenomena are
very significant in hydrotreating. They explain the differences in reactivity'
between petroleum cuts even more than the differences in reactivity between
heteroatomic molecules. For example. nitrogen compounds inhibit hydro-
genation and desulfurization very strongly and can additionally influence each
other mutually. Figure 16.9 shows an example of orthopropylaniline HDN inhi-
bition by &-methylquinoHne [4J.
Generally speaking. the reactivity of a cut is conditioned by the quantity
and reactivity of its heteroaromatic compounds and by the presence of other
more strongly adsorbed reactants. The heaviest fraction of the cut therefore
has a very important effect on hydrotreating severity. The heavier the
petroleum cut. the more heteroatoms there are. The more complex the het-
 Difficult

~R. Very difficult

, ~..)J...J
N ~
~ R~ .~-RI~A
!
N ~J
I I N

I H R~~-R
~.~
L~-~~--
N

figure,
16.8 I Relatice readirily of nitrogen compounds present in a gas oiL
LJ

80 - I- - - - - : - - - - - , - - - - - - - - - . , . - - - - - - - - ,

II A B I
I
t \. I

(I) 60 L \..... :
~all~
a.ffi~
e 1i:.s: I I: I
~ [~

l
r
:
40 I
a,g~ I

~8~
I

20 ~
Ii I
I
I

aI Li --l ---'--L. ~

o 10 20 30 40
lime (11)

Figun:
16.9 Orrhopropylaniline hydrodenitrogenation (HDN) inhibited by 6-ml:!thylquino-
line. A. and D~ pure orthopropyiandine HD.\'. B: 6-methylquinoline plus ottho-
propylaniline HDS C: pure Bmemyicainoline HDN. Catalyst: .WAfo/alumina.
-;0bar. 3-;O'C

eroatomic compounds are. the lower their reactivity is and the more strongly
adsorbed they are on the catalyst surface. As a result. hydrotreating severity
increases greatly (Table 16.5).
 ,
Petroleum cut
!
I
Cut
point
;
Spa", I H,
vt'loc:ity pressure,
Temperature
at start of!
H~C .
ratio
H:
' consumption
I ('C) (h -I) (bar)! run ee) \ (std m3/m3) i c:~ wt) !
I
;";aphtha I j~180 4-10 5-10 2ro-300 100 0.05-0.1
Kerosene )160-240 I 2-4 15-30 300-340
I 150 0.I-c.2 I
Gas oil
Vacuum gu oil
1230-350 '
1~550
1-3
1-2
15-40
40-TO
320-350
360-380
I 150-300
300-500
0.3-0.5
O.4-C.T
Ij
Atmospheric residue ! 350- 0.3-0.5 100-130 3ro-3SO 1.000 1.0-1.5
i Vacuum residue ! 55{1- 0.15-0.3 120-160 360-3S0 I 1.000 1.5-2.0

Ta.ble I
: 16.5 I Typical operating conditions for distillale and residue nydrodesudurization.

16.4.1.3 Reaction Kinetics

A large number of kinetic equations have been proposed for HOS, HDN and
HYD reactions using "model molecules" as reactants [1. 8J. They depend on
the type of reactants and the operating conditions among other parameters. A
generally accepted equation for simple reactants is:

(16.1)

He stands for the reactant, H2 the hydrogen, i the inhibiting compounds. P; the
partial pressure and K; the adsorption constants for products i, k the rate con-
stant and f a more or less complex function of the hydrogen partial pressure P.
In the presence of HzS and of strongly adsorbed and therefore inhibiting
compounds, the rate equations are often first order in relation to the hydro-
carbon and hydrogen and are of the Iollowing form:
v =k'PHCPH~ (16.2)

16.4.2 Catalysts
Hydrotreating catalysts comprise an oxide support and an active phase in the
form of molybdenum Or tungsten sulfide promoted by cobalt or nickel. The
commonly used formulas are associations of CoMo, NiMo and !'\iW for the
active phase and 7 alumina with a large specific surface area for the support.
Metal content is usually approximately 9% wt of Mo and ~.5~~ wt of Co or Ni.
Today catalysts have an increasingly high metal content. e.g, 12 to 15% wt of
Mo and 3 to 5% wt of Co or Ni. Generally speaking, the Covlo type formula is
employed for hydrodesulfurization, the NiMo type for hydrogenation and
hydrodenitrogenation and the NiW type for hydrogenation of very low sulfur
cuts. Some of these catalytic formulas are sometimes doped with phosphorus
or fluorine. Other oxide supports are used such as the silica-aluminas or tita-
mum-oxide aluminas. Formulas containing three metals are also found. for
example ~iCo~lo or FeCo~lo.
A bydrotreating catalyst is manufactured with its metals in the oxide form
and then activated by sulfurization in the hydrotreating unit reactor. It is avail-
able in the form of beads. cylindrical and polylobed estrudates, rings. etc. The
most commonly used form is the cyimdrical or poIylobed extrudate with a
diameter of 1.2 to 1.6 mm. There are numerous methods of preparing this type
of catalyst. The most widespread are impregnation of the preshaped oxide
support or coblending and extrusion of the mixture of oxide gel and active ele-
ments.
The oxide support has several functions. It must first provide a large spe-
cific area to allow the deposit of a large amount of highly dispersed active
phase- It must also give the catalyst mechanical properties such as crushing
strength and attrition resistance. Other important support characteristics are
the size of the grains (beads. extrudates, etc.) and of the pores. These last two
characteristics are optimized to overcome diffusional limits. particularly when
heavy cuts are hydrotreated, while maintaining a satisfactory specific area and
good mechanical properties. Figure 16.10 shows two different types of pore
size distribution. One is monomodal with mesopores and is generally
employed for light distillate hydrotreating. The other is bimodal with macrop-
ores and is better suited to heavy distillate and residue hydrotreating.

- - Bimodal
- - Monomodal

10 100 1000
Pore diameter (om)

Figutt
16.1\1 Pore diameter distribution for ffDo catalyst suppodS.

Another importantsupport characteristic is its acidity. Acidity promotes

hydrogen-consurnlng cracking reactions as well as heavy hydrocarbon deposit
on the catalyst surface (coking). which is the main cause of deactivation for
this type of catalyst. Hydrotreating catalyst acidity must therefore be limited
to a minimum. In contrast the cracking and isomerizing properties can be
sought in some cases such as hydrocracidng and hydroisomertzation.
548 ChaDter 16. HYDF/CiiFi:ATlNG

The hydrotreating catalyst active phase is produced by sulfurizatlon of the

oxide precursor, generally represented by a formula of the CoO-.\lo03/alumina
type for a CoMo catalyst for example. The supported oxide phase of the oxide
precursor consists of what is called a polymolybdate phase with the cobalt in
the form of surface cobalt aluminate. The sulfurlzatlon reaction is highly
exothermic. it consumes hydrogen sulfide and hydrogen and generates water
as shown below:
1 5 t
Mo0 3 + -2 CoO + -2 H.-.,5 + H?- H COO.5 MoS?~.:2
5 + - H.,O
. (16.3)

Sulfurization therefore changes the oxide-phase into a sulfide phase with a

totally different structure.
The hydrotreating catalyst active phase is made up of a mixed sulfide
phase comprising crystallites of molybdenum or tungsten sulfide. Mo~ or
WS2 Cobalt or nickel is associated with the Mo~ or WS:z in the form of ions
0

fixed at the perimeter of the crystallites [13-17]. These mixed phases are often
written CoMaS, NiMoS and NiWS [16]. The molecular structure of the active
phase is that of molybdenum or tungsten sulfide (the two sulfides have
the same lamellar crystallographic structure). High resolution electron
microscopy has shown that hydrotreating catalysts contain smaIl particles of
MoS:,! (WSiJ of an average length of 3 to 4 nm with 1 to 3 layers (Fig. 16.1 1)
deposited on the surface of the alumina support. Adding cobalt or nickel

.:
!

I
1
!

Fill6guf.lle I:

II
Anal),'sis of a sulfurized NiMolalumina
hydrotreating catalyst by transmission elec-
tron microscopy.
 ~
~ 40.0-
o
E

~ o COMo:A~O;
"5
.s.o 30.0-
+ NiMo/AI203

ec '* NiW'AI203
.g
Cll
C

~
i
..c: 200-
.
lit
as:::I
~

10.0 L

0.0 ;'-- ---'I --I._ _.......,.---L._-.....;;...;;:,_ _

0.0 0.2 0.4 0.6 0.8 1.0

Ratio ~ or .a, or 2!L-

Co+Mo Ni+Mo Ni+W
iF~'
116.11: Influence of actit:e phase composition. Ni.~fo. CoJfo. N;n~ on activity for
L-.J =
toluene hydrogenation (60 btu. JS()0c. space velocity 2 h -ij.

greatly increases the activity of molybdenum or tungsten sulfide, whether for

simple reactants or for petroleum cuts. Figure 16.12 illustrates this effect for
the hydrogenation of an aromatic, toluene, under pressure and in the presence
of sulfur. Generally speaking the optimum Mo and Co or Ni composition is
achieved for a Co;"(Co + Mo) or Ni{(Ni + Mo) atomic ratio of 0.3 (Fig. 16.12).
This ratio is related to the location of Co or-Nion the surface of the ~IOS2 crys-
tallites, and therefore to the size of the crystallites.

16.5 Process Information

16.5.1 Catalyst Reaction Kinetics
Petroleum cuts are composed of a complex mixture of different compounds.
Allthat is known about them is the overall initial and final concentration in sul-
 550 ChaPler 16. HYDROTREATING

. fur, nitrogen and olefins for example. Based on feed and effluent analyses, con-
version is determined from the initial and final concentration such that:

(16.4)

Here for HOS.So is the sulfur concentration in the feed and S the sulfur con-
centration in the product. Empirical rate equations, generally of apparent
order n = 1 to 2 are used to calculate performance from conversion. For HDS,
there is the following type of relation [1J:

(16.5)

E. is the apparent activation energy of the reaction. T the temperature (K). R

the ideal gas constant (R =8.31 J/molK), k o the apparent rate constant, So the
sulfur content in the feed. X the sulfur conversion and n the apparent order of
the reaction. The rate of reaction v can also be expressed in the form:

v =AlliSV.s" (16.6)

LHSVis the hourly space velocity in m3 of feed/m J of catalyst per hour and A
the activity or performance of the catalyst depending on the initial and final
concentration, and therefore on conversion. The expression of A depends on
the order of the reaction as shown by the different formulas in Table 16.6.

Order of n",l
1 1.5 2
reaction
I I I
A(S) Ln~
S
I [1VS vS;;1] I, S-~ II n:t1[1
2 ---
i'
!
;
1 1]
sn~1 - SrI
i

I A(X)
'-__
ILn - 1
I-X
Ij -=-2 [ 1
YSo
-=-1
V 1 -X
]JI Su(l-X)
-1- I en - 1 (1 -1J
I)So
I>-I
(l - X) ...I

Table'
16.6 Expressions of performance (A) in hydrodesulfurization l'I~I3US the initial and
final sulfur content. So and S. or versus the conversion X '" (So- S)/St.

Generally speaking, a first order is found for light narrow cuts (naphtha
HOSt kerosene HYD). An order of n > 1 is the result of a wide reactivity spec-
trum of the various components. The longer and heavier the cut. the higher
the apparent order (order = 1.5 to 1.7 for gas oil HDSand 2 for residue. heavy
gas oil and vacuum distillate HDS, for example.)
16.5.2 Operatin~ Variables
The main thermodynamic and kinetic operating variables for hydrotreating
processes are:
the hydrogen partial pressure (PH! in bar);
the weight average reactor temperature (Tm in 'C):
the liquid hourly space velocity (LH5V in m3 of feed/m:: oi catalyst per
hour).
Two secondary variables are also important:
the recycle ratio and purity of the recycled hydrogen:
the H~ partial pressure,
The choice of these variables leads to determination of:
the operating pressure;
the process flow scheme;
the investments and operating costs.
An important factor in defining operating conditions is the type of feed. A
number of parameters can be used to describe the feed, such as specific grav-
ity, refractive index. temperature at 95% distillation, etc.

16.5.2,1 Hydrogen Partial Pressure

Since hydrogen is one of the main reactants, the choice of its pressure is cru-
cia! for the process to run properly. Figure 16.13 illustrates the influence of the
hydrogen partial pressure on hydrodesulfurization performance on a middle
gas oil. Zone OA indicates that the hydrogen concentration on the catalyst sur-
face increases when the hydrogen pressure rises, causing acceleration of the
rate of reaction. Zone Be shows that the hydrogen pressure has little influence
on the desulfurization rate as the catalyst surface is saturated in adsorbed
reactants and hydrogen.
Hydrogen pressure therefore aims to shift reactions in the right direction
and minimize side reactions such as gas production and coke deposit on the
catalyst surface. In this way-it promotes long-lasting stable catalyst operation.
The heavier the feed, the higher the hydrogen pressure needed: for a given
feed (for example straight ron gas oil) it varies according to the performance
required:
hydrodesulfurizalion 15-25 bar .
hydrostabilization (mild hydrogenation) 25-35 bar
-hydrodearomatizatlon (deep -hydrogenation) 35-60 bar
An improved cetane number and reduced aromatics content demand par-
ticularly high hydrogen partial pressures. Chemical hydrogen consumption.
which depends on the performance required. is also important as indicated in
Table 16.7.
552 ena"ter 16. HYoRO;;:;.ATtNG

A Middlegas oil

20 40 60
p~

---,f----------------------------'
. Figure
. 16.13
Influence of hydrogen partial pressure PH. on hydrodesulfurization perior-
___, mance on a middle gas oil. -

Hydrogen partial
pressure
Aromatics content
I Chemical hydrogen
I
I
in effluent consumption
(bar) (%wt)
I (%wt)

30 25.7 0.4 i
40 20.0 0.6
65 I
I
10.0 0.9 I
L-
--- 85 r
i
Tal:>t- -----~----------------------'
5.0 '1.1
I
16.7 Hydrogenation ofa primary distillation gas oil containing 26. 796 ur of aromot-
ics and 1.3% wt of sulfur.

The hydrogen partial pressure is therefore chosen with the following aims
in mind:
increasing activity to minimize the amoeat of catalyst and consequently
the reactor size;
insuring stable operation all throughout the run;
minimizing thermal cracking and coke formation.
 16.5.2.2 Weicht Averaae Catalytic Bcd Tcmperarure (WAJI'I)
Hydrotreating units are operated at constant performance and pressure. Given
the gradual deactivation of the catalyst, the performance level is maintained
by increasing the reaction temperature. A start-of-run and end-of.nm temper-
ature are defined (TSOR and TwJ. Additionally. since nydrotreatiog reactions
are exothermic. a rising temperature gradient is established in d1e catalyst
bed. Even though the temperature can not be known at every poiDt in the cat-
alytic bed. installing thermocouples allows the temperature of several por-
tions of the catalyst bed to be measured. In this way a weight .werJ.ge tem-
perature of the catalytic bed (\\'ABT) can be defined by:
T- t lvl + t2 v2 + ... +- tno n (16.7)
rrt- V
V is the total catalyst volume and vi the volume of each portion:
V =VI + 02 + ... + Vn (16.8)
The weight average catalyst bed temperature characterizes abe thermal .
status of the catalytic bed by a single 'value. Nevertheless. the temperature gra-
dient of the catalytic bed is obviously determining for chemical reaction kinet-
ics.
Several other temperatures can be measured lor a hydrotreatiog unit reac-
tor. particularly:
the outlet temperature of the feed heating furnace;
the reactor inlet temperature (te):
the reactor outlet temperature (tJ.
More simply the weight average temperature can be defined roughly for a
catalyst bed by:
te + t, I 1
Tm = - - =te + -M:::t$--M (16.9)
2 2 2
with:
06.10)
or the Iollowtng equation can be chosen to take the gradient into account:

T = te +2/s =1 + ~At=t - ~M (16.11)

m 3 e 3 3 $

Tm must be used in all calculations involving the effect of temperature.

a. Weight At'erage End-of-Run Temperature

-The weight average end-of-run temperature (T~ is the ma-mnum tempe~a
ture that the catalyst can withstand and is generally between 400 and 410'C
depending on the feed. When the temperature is in excess of UO=C. thermal
cracking becomes severe and can no longer be moderated by increasing the
hydrogen partial pressure. At high temperature. hydrogenation of polyaro-
matic coke precursors becomes limited thermodynamically and furthermore.
 unsaturated compounds tend to condensate. This leads to accelerated cata-
lyst deactivation by coke deposit. The maximum temperature' defines the tem-
perature for the end of the catalyst run. It depends on the type of feed and the
required product quality (sulfur content, thermal stability, aromatics content,
etc.).

b. WeightAl:erage Start-of-Run Temperature

The weight average start-of-run temperature (Tm SQR ) is selected in order to
insure stable operation of the unit for one to three years. In general, taking the
weight average end-of-run temperature into account, a run duration of two
years is chosen. This requires a minimum var!ation in weight averagetemper-
ature of JO"C during the run, i.e.:
6.T= TlIIOR - TIJ1SOR = 30C (16.12)
The weight average start-of-run temperature depends on the physico-
chemical characteristics of the feed. For example, the higher the average
molecular weight of the feed, the more sulfur compounds there 'are and the
more difficult desulfurization is. This means a drop in hourly space velocity
and a rise in start-of-run temperature. The weight average temperature at the
beginning of the catalyst run is therefore the main variable in an operating
unit. It has a very strong influence on performance and catalyst run duration.

16';.2.3 Li'IUid Hourly Space Velocity

The liquid hourly space velocity (LHSV) is used to define the amount of cata-
lyst needed to get a specified performance. It is expressed in m3 of fresh feed
(at 15'C) per m3 of catalyst per hour. The inverse of LHSV is generally called
residence time. The LHSVdepends on the catalyst activity, the type of feedand
the hydrogen partial pressure. As a result, for a given feed there is a trade-off
between P~, LHSV and aT between the beginning and the end of the run. The
influence of residence time on the HDS ratio is represented by the curve in
Figure 16.14 for a light gas oil and a CoMo/alumina catalyst.

16.5.2.4 Hydrogen Ratio or Recycle Ratio

Optimum catalyst use demands relatively high hydrogen partial pressures. It
is therefore necessary to let the feed in with a much larger amount of hydro-
gen than that required for chemical consumption. In order to minimize hydro-
gen requirements, gas is recycled- from the separator drum which is supple-
mented by make up. The hydrogen partial pressure therefore depends on the
relationship among:
the hydrogen recycle flow rate,
the hydrogen purity, and
the hydrocarbon flow rate,
for a total fixed pressure and a given make up gas purity and hydrogen con-
sumption.
 99.9,

catalyst CoMo/alumina
PHz: 20 bar
%HDS
Tm=340"C
rHz:150 std mJ/mJ
So= 1.2% wt

S =0.3O"Yo wt
5Oh~---------------i

OL.... --'
Residence time(h)

'Figure:
i 16.H; /n/luence of residence time on pertormance for light gas oil hydrodesulfuriza-
L--.J lion (23D-360C).

Besides maintaining the hydrogen partial pressure. the recycle gas also
produces the turbulence required for the reactants to come into contact in the
reactor. Moreover the gas recycled to the unit inlet Increases turbulence in the
.heat exchangers and the furnace, improves heat transfer .condttions and pre-
vents the deposit of Ioulants in these apparatuses to a certain extent.
When reactions are highly exothermic. it is also necessary to control the
thermal gradient in the reactor by distributing the catalyst onto several beds
and by injecting enough cold gas between each bed to cool down the hydro-
carbon by quenching. This allows operation as close as possible to the
isotherm and minimizes premature catalyst aging by reducing the high tem-
peratures in the bottom of each catalytic bed - particularly in the first one.
Figure 16.15illustrates the effect of injecting hydrogen between two catalyst
beds.

16.5.2.5 Hydrogen Sulfide Concentration in Recycle Gas

The recycle gas also contains hydrogen sulfide which has an inhibiting effect
on desulfurization and hydrogenation reactions. Depending on the perfor-
mance required (deep desulfurizatlon, aromatics reduction) the rec)~cle gas
556 Cnaprer 10 HYOROTREATING

~
L4Q.C2. _

J
I- '200C
~r--- I

I 2nd bed
1/LHSV
_ Catalytic bed _ }--350:C

Figure,
16.15 i Temperature gradient controlled by hydrogen quenching.
---l

can be partially or totally washed with amines. However, it is useful to retain

some H2S partial pressure to keep the catalytic phase sulfurized.

16.5.3 Implementing Catalysts

16.5.3.1 Loading the Catalyst
Loading the catalyst in the reactor is an important step because the mass of
catalyst loaded in relation to a definite reaction volume depends on how well
packed it is. Packing depends not only on catalyst characteristics (specific
gravity, grain shape and size) but also on the loading method. The catalyst
must be uniformly packed all throughout the volume, both vertically and radi-
ally in order to prevent channeling. The tighter the packing, the more catalyst
is required and consequently the greater the activity of the reaction volume.
However, there is also a greater risk of pressure loss problems. The two main
methods of catalyst loading are the "sock" method that gives loose packing
and the "dense" method that usually causes an increase of 15% in packing
density.

16.5.3.2 Sulfurbing the Catalyst

The active phase of hydrotreating catalysts is produced by sulfurizing the
oxide precursor. It is an exothermtc reaction which consumes hydrogen sul-
fide and hydrogen and forms water. 5ulfurization conditions must allow the
metals present to be totally sulfurized without being too severe. so that no
large particles of sulfide are formed.
Several sulfurization methods are employed industrially. Gas phase sulfur-
ization generally uses a mixture of hydrogen and hydrogen sulfide or some-
times an organic sulfide such as methyl mercaptan, dimethyl sulfide and C52.
The drawback of this method is that it allows a considerable temperature
increase to develop during sulfurization due to the exothermic nature of the
reaction. Liquid phase sulfurization consists in injecting a heavy naphtha or
gas oil cut under hydrogen pressure to which an organic sulfide may also be
added, The cut used for sulfurization must not contain any olefins in order to
prevent premature catalyst coking. The advantage of this method is that it sets
a limit on the catalyst temperature increase during sulfurization. .
Lastly. another increasingly common method is ex-situ sulfurization. i.e. the
catalyst is activated by a specialized company, Usually a heavy sulfur corn-
pound is laid down by impregnation followed by heating to activate the cata-
lyst. The advantage here is that the method requires only thermal activation
of the presulfurized catalyst.loaded in the reactor.

:d-33 RegeneratiDg the catalyst

Hydrotreatlng catalysts become deactivated with time mainly because of coke
deposition. Deactivation is rapid at the begilming of a run and then slows .
down afterward. Carbon deposits are promoted by a high reaction tempera-
ture and a low hydrogen pressure. This type of deactivation is reversible since
the carbon can be burned during regeneration.
Another important source of deactivation is the deposit of metallic impuri-
ties such as Nl,V, Si, Pb, As, etc. These poisons are irreversible but are gener-
ally laid down at the top of the bed because of. their high reactivity.
Consequently. the top of the catalytic bed can be "skimmed off' and new cat-
a.yst can be added if the aim is to save on catalyst.
One way of measuring a hydrotreating catalyst's resistance to deactivation
:s the duration of the run. It usually lasts several years for light cuts such as
;:.sQline. kerosene and gas oil but is considerably shorter for heavier cuts or
cuts that are seriously polluted by metallic impurities (Table 16.8).
Distillate hydrotreating catalysts are regenerated several times durtng their
::fetime. Regeneration consists in burning the coke "C)-Iy" and the sulfur and
:-..trogen it contains, and removing the su!f,,;!' from the sulfide phase
- :o').5MoS~.5 by oxidation as shown below in the <verall reaction:

(16.13)
1 Y 5
~ - CoO+Mo03+ - H,O+.rUJ,+ -SO.,
2 2 - - 2 -

When regeneration is carried out in the hydrot!'~atingunit reactor, the com-

custlon stages must be. very carefully controlled, r~ombustionjs performed by
.:-.jecting a mixture of steam and air or nitrogen er.d air. In both cases the OX}"-
ren content must be very low to prevent runaway cornbustton due to the very
:::ghly exothermic combustion reactions. The procedure is generally to
.zcrease the oxygen concentration and the temperature very gradually. Ex-situ
:-~eneration is increasingly practiced. since it she-tens downtime for the units
558 cr.ap;er 16. HrDFlOiiiEA':i:.:;

and simplifies shut-down procedures. It also guarantees better control of com-

bustion.:With regeneration. the' lifetime of a hydrotreating catalyst can be
extended up to ten years (Table 16.8). .

Petroleum cut Ruo duration (years) Ufetime (years)

Gasoline/kerosene 2 to 4 4 to 10
Gas oil, vacuum gas oil 1 to 2 2 to 6
Residue 3 months to 1 year 3 monthsto I year
'"t Table 1 - '- - - - - - - - - - - - - - - - - - - - - - - -. . . . . . . . . .

16.8 Run duration and lifetime of typical hydrotreating catalysts.

16.6 Process Technology

The process technology and catalyst are adapted to the performance required
for the different feeds sent to hydrotreating. In the range of equipment that
makes up hydrotreating processes (reactors, furnaces, compressors, separa-
tors, heat exchangers), the reactors and their internals are the heart of the
technology.

16.6.1 Reactors
Fixed bed reactors are used in distillate hydrotreating units. There are two
types: .'
reactors operating in the gaseous phase, used with light feeds such as
naphthas and kerosenes:
reactors operating in combined liquid and gas phase. used with heavier
feeds such as light and heavy gas oils. vacuum gas oils. lube oils and dea-
sphalted oils.
Besides the outer shell. reactors have a large number of internals
(Fig. 16.16) that are designed to control reactor temperatures and pressure
losses and achieve the desired performance. Table 16.9gives a list of internals
for the two types of reactors.

16.6.2 Process Flow Schemes

A distinctlon is usually made between two parts of the flow scheme. the reac-
tion section and the distillation or separation section.
 H:;--E3-....;:;-;-::;;.,..j. Alumina beadsdiameter31'4-

Distributortray

- Alumtna beads diameter3'4"

\---+-----I-"I~

- '-
..",;; Aluminabeads diameter 1/4.

r-....~IH."'"IQ.l""\.- Alumina beads diameter:r4-

- - - - - Outletcollector

Figure
16.16 Hydrotreating reactor and its internals:
 560 Cllap:r, 16. HYOF;OTREATII.3

Type of hydrocarbon-hydrogen mixture

Reactor internals Combined liquid
Gas phase
+ gas phase

Inlet distributor x x
Liquid-gas distributor tray x
Baskets x x
Bottom collector x x
~ measurement devices x x
Catalyst drain pipes x x
Temperature control devices x x
Quench system if needed x x

U Catalytic bed support

,.-..--,....
i
'

T.bl< I-------------------'-----------'
x x

t, 16.9 Internals for hydrotreating reactors operating in a gas or a liquid and gas
I phase.

16.6.2.1 Reaction Section

The section comprises the reactor. the furnace, the heat exchange train, the
booster pump, the compressors and the separator drum. If need be. there is
also water and hydrocarbon washing and an amine H~ absorber. Two types of
reaction sections are used. the cold and the hot separator process. The crite-
. ria fOT choosing between the two are based on the type of feed, the feed
temperature, the risks of foaming and the problems of water-hydrocarbon
separation.
The cold process is illustrated in Figure 16.17. It includes elaborate and
complex waste heat recovery circuits at the reactor outlet. Part of the heat of
reaction is used to heat the reactor feed. The thermal range chosen for the
separator is controlled by the air-cooled exchanger. In most cases, the tem-
perature is low enough to get recycle gas directly with sufficient purity to
make hydrocarbon washing unnecessary. However.amine washing is installed
for the recycle gas when deep hydrodesulfurization and aromatics saturation
(kerosene and gas oil) are required. Here. the hydrogen sulfide concentration
must be lowered as it inhibits these reactions. Due to steam injection. strip-
ping works at sufficient pressure so that the recovered gases can be sent
directly after amine washing to the refinery fuel gas network.
The advantages of the cold process are:
purer recycle gas and therefore lower operating pressure and less hydro-
gen loss;
greater simplicity;
the possibility of treating light feeds.
561
 -_._~-

U1
~
Rem:lor
i
It
j;;

I~
~

Heat exchange Crain

Mako up
I
hydrogen gas
lrr-r-J -
Fresh
leed
FI"url'
I Ct. 1H
I "I/o'" 11)'(/mtles"If""'=((ll(JlIllm(C'.~.~.
I
 The drawbacks are:
a larger heat exchange surface area:
a greater heating load on the stripper furnace;
a large settling drum (separator).
The hot process is illustrated in Figure 16.18.This set up indudes a hot sep-
arator on the reactor effluent circuit. The separator temperature is generally
set at the level necessary for proper stripping. The hot gases are cooled and
washed as described for the cold process:
with water to eliminate salts (ammonium chloride and suiiide);
with hydrocarbons to purify the recycle gas;
with amines to remove the hydrogen sulfide.
The advantages of the hot process are:
a great reduction in the heat exchange surface area;
the possibility of treating hot feeds;
a lower heating load on the stripper furnace;
the possibility of feeding direCtlyinto the stripper.
The drawbacks are:
use limited to heavy feeds;
greater hydrogen loss and lower hydrogen partial pressure;
the need to purify the recycle gas by washing with amines or hydro car-
bons.

16.6.2.2 Distillation Section

The section is made up of the distillation column, with reboiling by a furnace
or by heat exchange with the reactor effluent for light feeds such as naphthas
and kerosene (Fig. 16.19). For heavier feeds (gas oils, residues, deasphalted
oils), steam stripping is used, which mayor may not be followed by vacuum
drying (kerosene. gas oil) (Fig.-16.2().

16.6.3 Selecting ConstnKtion Materials

The choice of materials is crucial for hydrotreating process equipment to have
satisfactory resistance. The chemical substances that dictate this choice are:
sulfur-bearing hydrocarbons. hydrogen. hydrogen sulfide, ammonia and water.
Furthermore, the reaction section is at high hydrogen pressure and different
thermal levels. At temperatures over 260'C and high hydrogen partial pres-
sure. the basic materials are chromium-molvbdenum steels in order to with-
stand decarburizing and cracklng phenomena, Moreover, the baSic materlal is
covered with a protective layer of stainless steel (18Cr-l0Ni) in order to con-
trol sour corrosion (H.,S). The thickness of the stainless steel layer is deter-
mined by the temperature. the ~ partial pressure and the required equip-
564 Cnamer 16 HYDRom.,;,j/NG

Purgeto amine
treatment
Stabilization
column

t-----~Ojstillate

From reaction
section (Fig. 16.18)

J----- Product
- i
Figure
. 16.19: ROUl scheme of a light feed hydrodesulfurization unit. Distillation section with
i reboiling by a furnace.
.r

ment lifetime (10 to 20 years). At temperatures lower than 260'C. carbon steel
or steel with a low Cr-Mo content is chosen. However, in the presence of free
water and hydrogen sulfide. the material should observe NACE recommenda-
tions on the subject. The same is true for the distillation section.

16.7 Industrial Performance

16.7.1 Feed Pretreatment for Gasoline Catalytic
Reforming Units
Naphtha cut hydrodesulfurization is designed to prepare the feed for isomer-
ization units and mainly for catalytic reforming. The aim is to achieve a sulfur
 565

6
1

-I
'J
i

C?
~

1
566 Cr.mter16. HrDRomEAT1NG

and nitrogen content lower than 0.5 ppm. Table 16.10 indicates the typical
properties of a stralghtrun naphtha sent to the hydrodesulfurization unit and
those of the resulting desulfurized products. For this type qf feed. hydrogen
consumption is low because the operating conditions. hydrogen partial pres-
sure and space velocity are not very severe. Taking dissolution and rnechanl-
cal losses into account, total hydrogen consumption is approximately 0.05 to
0.1 % wt in relation to the feed.

Naphtha Product for Product for

feed isomerization reforming

TBpcut point ("C) Cs-l7S CS -e6 85-175

P (% vol) 55.6 82.5 47.8
0(% vol) 0.2
N (% vol) 37.5 16.5 48.6
A (% vol) 6.7 1.0 8.6
ASTM 086 distillation ("C):
ffiP 19 95
50% vol 120 135
EP 180 180
Sp.gr. dl s 0.726 0.643 0.750
Sulfur (ppm) SOO < 0.5 <0.5
Nitrogen (ppm) 1 <0.5 <0.5

' .. 16.10
Table I Characteristics of feed for naphtha pretreatment by hydrorreating and of result-
ing effluents for isomerization and refonning processes.

-'

16.7.2 Hydrotreatinl Kerosene and Gas Oil

Kerosene and gas 011 feeds for hydrotreating units are straight-run distillation
products. products from conversion processes (vis breaking, coking, fluid cat-
alytic cracking) or mixtures. Kerosene hydrotreating allows a reduction in
total sulfur. mercaptans and in some cases aromatics in order to improve the
smoke point. The aim of hydrotreating the gas oil fraction is mainly to reduce
the sulfur content and sometimes the aromatics content. to improve the
cetane number, color and thermal stability. Improving the cetane number and
reducing the aromatics content require higher hydrogen partial pressures and
therefore result in more hydrogen consumption. For example, a catalytic
cracked gas oil (or LeO) demands a chemical hydrogen consumption of 3.4%
wt to lower the aromatics content from 78 to 20% wt for a final cetane number
of 40. Table 16.11 lists the properties of feeds and resulting products for vari-
ous typical cases of kerosene and gas oil hydrotreating.
 C1Iap/w 16. HYDROTREATrNG 567

I Kerosene
StraJcbt
nm
Gas oil +
LCD
I
I
LCD I
gasoD I 80/20 I
j
I i
I Feed propet-ties:
Sp.gr. etiS II 0.793 0.846 0.863 0.941
Sulfur (% \vt) I 0.15 1.31 1.50 I . 2.24
Nitrog~n (ppm) I - 70 245 940
VISCosity at 50'C (rom 2/s)
I - 3 2.8 2.4
Aromatics (?{, wt) 21 27 37 78
Cetane number - 53 47 20
Smoke point (mm) .. 19 - - -
Freezing Point rei -50
! - - -
Bromine number (g/loo g) - 1 4 15
AST~1 b86 distillation ("C):
10%vol 175 257 253 236
50%Vol 215 294 288 276
90%vol 244 341 338 346
EP 259 358 358 374
rle1d aft~ hydrotreating:
H~+N~(% wt) 0.15 1.34 1.55 2.45
CI-C~ (% wt) 0.20 0.30 0.35 0.50
C~150"C (% wt) 0.50 3.50 3.60. 4.50
15O"C+ (% wt) 99.30
i, 95.26 95.0 93.9
Total (% wt) 100.15 100.40 I 100.50 II 101.35
Hydroget} COnsumption:
Chemi~al (% wt)
I I

i DiSSOlution and losses

0.15 0.40 I 0.50
I
1.35

(% wt) 0.05 0.1)6 0.06 , 0.10

Total (% wt) . 0.20 , 0.46 0.56 1.45
Product Ilropertles: 1
I 1_
! Sp.gr.d/ 0.788 0.833 0.848 0.898
!
Sulfur (PPIll)
Nitrogen (Ppm)
YISCosity at SOC(mm 2js)
Aromatics (% wt)
Cetane number
Smoke point (mm)
. \STII Color.
Color stability

!.- Tablt----------~---------:.--------
16.11 HYdrotn!Oling kerosene and gas oil. Feed and product properties.
568 C-.a::net 15. HYDROTfiEATlNG

16.i.3 'Hydrotreating Va,cuum Distillates

Vacuum distillate hydrotreating involves the feeds from primary vacuum dis-
tillation and from conversion processes (vtsbreaking. coking). Its main objec-
tive is to prepare feeds for further conversion, generally by catalytic cracking
or hydrocracklng; This type of hydrotreating is essentially designed to reduce
the sulfur and nitrogen content in vacuum distillates. Sometimes a certain
degree of conversion to middle distillates is sought (mild hydrocracking).
Reducing the sulfur. nitrogen and metals content (Nl, V), and having a low
Conradson carbon in the catalytic cracking feed greatly influence cracking per-
Iormance and products by:
boosting conversion;
lowering the sulfur content in products;
reducing SOx and NO.1' emissions.
Table 16.12presents the properties of two vacuum distillates whose yields
after hydrotreating are listed in Table 16.13.The properties of the products
from the two feeds for two different types of operation, hydrodesulfurization
and mild hydrocracking, are given in Table 16.14.

Original crude Iranian light Kuwait

TBP cut point CC) 385-570 385-570

Sp.gr.dJ5 0.927 0.926
SuUur (% wt) 1.80 3.02
r\itrogen (ppm) 1400 950
! CCR (~; wt) 0.5 0.5
: Viscosity at 100C (mm 2{s) 12 9
: Aniline point CC) 86 81
I ~i v (ppm)
-+- 3 3
I Pour point CC) 44 32
, ASTM 01160 distillation ("C):
Ii IBP10~" vol
300
395
300
395
! 30<'~ vol 417 417
I 50,;vol 445 445
! 70"" vol ~81 481
I 90"', vol 538 538

~:c-content (" vol)

585 585
8 8
Table i

16.12 Typical properties 01 vacuum distillates.

 C"~oter 16. H!cROTReAT/NG 569

! HDS ~mdHDC

i~ Iranian light II Kuwait : Iranian light : Kuwail

I Yields (":, wt): !

I
H~

:-':H3
1.82
0.08
II
3.05
0.05 ,
1.88
e.io
i
:
3.17
0.07
c. 0.10 1 0.05 i 0.24 0.20
j
c, 0.15 ! 0.12 ! 0.35 0.30
C3 I 0.1t 0.15 DAD 0.40
;.(:4 I 0.07 0.03 aso 0.26
n-e.
~
I 0.11 0.09 0.40 0.34
Cs-80'C 0.30 0.28 1.30 1.20
8I)..170C 0.90 0.81 3.80 3.60
170-385C 13.50 14.50 25.93 25.86
385"C" 83.30 81.55 66.00 66.55
Total I 100.50 100.75 100.70 100.95
I;
Hydrogen ceesumptton (% wt):
Chemical 0.50 I 0.75 0.70
I 0.95
Dissolution and losses 0.15 0.15 , 0.15 ! 0.15
Total 0.65 0.90 0.85 UO
~c I
I
ThM,
16.13 1f}'tlrotreating cocuum distillates. Yields and hydrogen consumption for two
:1'

f}pes ofoperation: hydrodesulturization (HDS) and mildhydrocracking (HDC).

16.8 Economics
. 16.8.1 lavestments
A feed pretreatment unit for gasoline catalytic reforming with a throughput of
770 000 t/year (20 000 bpsd) of total naphtha requires battery limits invest-
ments of 12.5 1()6 (1999). This cost includes licensing, engineering and the
first load of catalyst. For this 770 000 t/year unit. the utilities costE including
light and heavy naphtha separation are estimated in Table 16.15.
Table 16.16 gives economic information for a straight run gas ol]
hydrotreating unit with a throughput of 1.3 Mt/year (30 000 bpsd), for three
desulfurization levels.
Economic information for a 2 Mt/year unit (40 000 bpsd) for hydrotreating
vacuum distillates is listed in Table 16.17. Investments do not include the
amine washing unit and the waste water stripper.
570 Cr.aorer 16. HYDROTREATING

HDS __ MildHDC

) Nap
I . hth a
Sp.gr. dls 0.730 0.730
!
Sulfur (ppm) < 120 < 50 I

Nitrogen (ppm) < 20 <10

Bromine number (g/100 g) <2 <2
RON clear

Gas oil
58

1,0-385'C
I! 60

Ii0-385'C
Sp.gr. dJ5 O.~ 0.883
SuUur (ppm) 200 100
Bromine number (gJ100 g) <2 <2
i
Cetane number j 40 43 i
Flash point co 65 65
I

Pour point C"C) I -9 ':"12

Viscosity at 2O'C Cmm2/s) i 6 5.6
Vacuum distillate 385'C+ 385'C+
Sp.gr. dls 0.901 0.895
Sulfur(% wt) i 0.18"-0.30'" I 0.12"-0.20**
Nitrogen (ppm) 840"'-560** 600*-400.....
CCR(%wt) 0.1 0.1
Viscosity at l00'C (mm 2/s) 11*-8 .... 8.5*-7.5**
Aniline point CC) : 92..-90.... I 97..-96 .....
Ni + V (ppm)
Pour point CCC)
0.5
45"-36**
!
1
0.5
97..-96 .....
Refractive index 70C 1.483"-1.484** t 1.478*-1.478.....
ASTM 01160 distillation ("C): t

I IBP 320 I
I 320
t
! 5?; vol 380 ; 375
"" vol
IV"" -
39;) -
39;,
30%vol 415 410
50% vol 440 435
70% vol -179 475
90%'-\101 535 530
95~6 vol 558 550
EP 585 575
.. Iranian light ..* Kuwait
, Table
L--~'' - I- - - - --.J

'. 16.141 Hydrotreating vacuum distillates. Product properties for two types ofoperation:
hydrodesulturization (HDS) and mild hydrocrackitJf (HDC).
 Battery limits investments (base 1999. 1()6 ) 12.5
, Total hydrogen consumptton (% wt) 1).05-Q.l
Utilities (per ton of fee-:n:

I Fuel oil (kg)

: Electricity (k\\11)
lOA
6.6
I MP steam (t) 0.1
' Coolmg water J.T= 10'C (m3) 2.4
j
I Catalyst operating cost ('t of feed treated) 0.03
~ Table
i 16.15 Hydrotreating naphtha. Economic data lor a capacity of ;iO 000 t/year
i (20 000 bosd).

I
Case 1 Case 2 CaR 3
I
Sulfur content in product (ppm) 500 25 10
Aromatics content in product (% wt) 25.7 20 10
Battery limits investments (base 1999. 1()6 ) 16.5 30.0 37.0
Total hydrogen consumption (% wt) 0.46 0.155 LO
Utilities (per ton of feed): \
Fuel oil (kg) I
I
5.17 4.52 3.32
Electricity (k\\ih) 12.9 25.2 33...8
MP steam (t) i 0.02 0.02 o.oz
Cooling water em3} 0,46 0.61 0..80
Catalyst operating cost (it of feed)
r----- I 0.05 0.20 0.20

H)'drotreating gas oils. Economic data for different cases of inC11'OSing

ltydrotreatmeruseemty for a throughput of 1.3.lit/year (30 000 bpsa).

HDS Mild HOC

Battery limits investments (base 1999.lOti ) 54.0 54.0

Utilities (per ton of feed):
Fuel oil (kg) 6.9 8.2
E1ectridty (k\\-11) 212 24.0
MP steam consumption (t) 0.03 0.04
MP steam production (t) 0.04 0.03
Demineralized water l:m3} 0.04 0.03
Cooling water (m~ 0.22 0.26
1 Catalyst operating cost (,'t of feed) 0.3 - - 0.3
LTable
-- -1... ---'

16.1i H.:rdrotreating L"acuum distillates, Economic data for the HDS and mild
HDC operation from Tables /6,13 and /6.14 lor a capacity of 2 ,'Ilt/)"f!ar
(40 000 bpsd).
572 Ci'>a!JIer 16 HYDROTREATING

Regions Capacityq.lt/year)

Lruted States 320

EtJ 180
Asia/Pacific 140
Rest of the world 160
Total 900
- Table,lr- -'- ---J

16.18: Hydrotreating capacity in different regions in the uxuid.

---l

16.8.2 HydrotreatiDc Capacity Worldwide

World hydrotreating capacity excluding residue hydroconversion amounts to
around 900 Mt/year (23 Mbpsd) [18]. The geographicaJ distribution is approx-
imately as indicated in Table 16.18. Over a thousand hydrotreating units are
generally estimated to exist in the world. They can include several reactors of
widely varying size: 10 to 300 m3. Yearly hydrotreating catalyst consumption
excluding residue hydrotreating can be assessed at 30 000 tjyear.

16.8.3 Process Licensors and Catalyst Suppliers

There are a large number of hydrotreatmg process licensors in the world. The
main ones are listed below as a guide:
ABBLummus Crest Inc. (United States) .'
Chevron Research and Technology Co. (United States)
Exxon Research and Engineering Co. (United States)
Foster Wheeler (United States)
Institut Francais du Petrole (IF?) (France)
Union Oil Products (UOP) (United States)
Kellogg (United States)
The major catalyst manufacturers are:
Procatalyse (France. United States)
AKZO Nobel (Netherlands)
BASF (Germany)
Catalyst Chemical Industries Co. (CCIC) (Japan)
Criterion Catalyst Co. (Netherlands-United States)
Haldor Topsoe (Denmark)
Orient Catalyst Co. (Japan)
United Catalysts Inc. (Vel) (United States)
References
Le Page J.E (1981) Applied Heterogeneous Catalysis. Edltlons Technip.
Paris.
2 Gates B.C.. Katzer l.R.. Schult G.C.A (l9f9) Chemistry of Catalytic Process.
McGraw-HiIl. p. 390.
3 Ho I.C. (1988) Catal. Rev. Sci. Eng. 30. I. 117160.
-t Perot G. (1991) Catal. Today 10. +Ii.
5 Furimsky E. (1983) Catal. Rev. Sci. Eng. 25. 3. .J21--t5S.
6 Quann R.G.. Wave RA, Hung c.. Wei J. (1988) Adcances in Chemical
Engineering 14. 95. ~.
j McCulloch D.C. (1983) Applied IndustritJI. Catalysis. 1. Academic Press. 69.
8 Girgis :\t.J.. Gates B.C. (1991) Ind. Eng. DIem. Res. 30, 2021.
9 Thonon C. (1972) In: Wuithier P., Le pitrole. Raffinage et genie chimiqtJ.e,
2nd Edn., tome 1,ch. Ill.9. ditions Tecbn.ip, Paris.
10 Marchal N., Kasztelan S., Mignard S. (1994). In : Chemical Industries Series
58. 17. 315. Marcel Dekker, Inc.. New York.
11 Nelson N.. Levy R.B. (1979) J. Catal. 58. 485.
12 Vrinat M.L (1983) Appl. Catal. 6. 137.
13 Chianelli R.R.. Daage M. (1989) Stud. SBrf. Sci. Catal. 50. L
14 Delmon B. (1989) Stud. Surf. Sci. CataL 53. L .
15 Prins R.. DeBeer V.HJ.,Sornorjai G.A. (1989) Catal. Rea-Sci. Eng. 31. 1.
16 Topsoe H.. Clausen B.S.,Topsoe N.Y.Zeuthen P.(1989)Stud. Surl Sci. CataL
53. i7.
17 Kasztelan S., Toulhoat H.. Grimblot J.. Bonnelle J.P. (1984) Appl. CataL 13.
12/.
 Acid gas treatment

Christian Legrand
Joelle Castel

"

In refinery installations. acid gas treatment essentially comprises absorption

of H~ by a solvent and its conversion into elementary sulfur. Some specific
applications, such as the purification of gases from partial oxidation
of residues (Chapter 1-1), may require Simultaneous removal of H~. CO2 and
COS.
There are many sources of H.,.5-containing fuel gases in refinery units: atmo-
spheric distillation. hydrodesullurization units, etc. These gases are generally
combined to be treated in a single unit. However, there are special cases that
entail a treatment specific to each H~ source. Here it is advisable from an eco-
nomic and operational standpoint to use a single absorption solvent. The aim
is to be able to regenerate the solvent streams loaded with acid gas from the
different absorption sections in one single unit. 1bis type of arrangement is
shown in Figure }7.l.lt does not include the treatment of hydrogen-rich gases
from partial. oxidation which require a different solvent from the one used in
the purification units discussed in this chapter.

17.1 Absorption of Acid Gases by a Solvent

The acid gas treatment processes used in refineries consist mainly of scrub-
bing with regenerable solvents. Processes involving solid beds are not covered
in this chapter.

17.1.1 The Different Solvents

There are three families of solvents: chemical. physical and mixed solvents.
 Sulfur-eonlaining fuel gases Treated
...
fuel gas

Solvent

- - - -... Treated gas

Solvent
Solvent+H~

' - - - - - - - ' - - - - - - - - -.... Treated LPG

b
i~i~~l Typical block diagram of Hz5 removal facilities in a refinery.

1~ .1.1.1 Chemical Solvents

These solvents react chemically with H~ and CO2 by equilibrium reactions.

Absorption reactions are promoted by high pressure and low temperature.
The solvent can then be regenerated by inverting these conditions. The most
common chemical solvents are:
aqueous amine solutions such as N-methyldiethanolamine (f\IDEA).
mono and diethanolamine (MEA and DEA) and diisopropanolamine
(DIPA);
solutions of hot potassium carbonate (Benfield or Catacarb processes)
(see Chapter 14);
diglycolamine (DGA) in an aqueous solution (Fluor process) which
behaves like ethanolamines.
Chemical solvents. especially amine solutions. are the best suited to the
operating parameters in refinery treatment units.
 C't::6 " Aao G,;,s TREATMENr 577

rr.i.r.; Physical So)veats

These solvents allow the absorption of the acid compounds without any chem-
ical reaction. The differences in H~ and CO2 physical solubilities give the sol-
vents a selective H~ absorption property. as H~ is more soluble than CO2,
Such solvents are usually applied to synthesis gas treatment (see Chapter 14),
but seldom or never in the refinery.

li.l.lJ Mixed Solvents

These solvents are mixtures of a physical and a chemical solvent. The most
well known is "Sulllnol"developed by Shell. a mixture of sulfolane and an
ethanolamine (MDEA or DlPA). The use of mlxed solvents remains limited in
refinery units.

17.1.2 Simplified now Sc:h~me of a Solvent Washing Unit .

Figure 17.2 shows the typical flow scheme of a solvent scrubbing unit for
gases. It includes:
an absorption column;
a rich solvent flash drum (optional);
a regeneration column and its related equipment (reflux. reboiler);
ancillary facilities (storage. solvent filtration).
The operating principle is the same whatever the type of solvent:
The gas to be treated is fed in the lower part ol an absorption column
where the acid compounds (H~, COl> are removed by counter-current
scrubbing with regenerated (lean) solvent. The gas exiting from the col-
umn is treated gas and is sent to users.
The rich solvent at the bottom of the absorber is loaded with the acid
compounds. It is sent to the regeneration section via a flash drum which
is optional. The flash drum's function is to degas part of the hydrocar-
bons coabsorbed in the rich solvent. It is therefore only useful when
absorber pressure is high and/or when several rich solvent streams are
fed into the same regeneration section.
The rich solvent is preheated in the rich/lean solvent heat exchanger, and
then feeds the top of the regeneration column which operates at low
pressure. Here the acid compounds are desorbed by steam stripping.
The heat required to generate the stripping steam is supplied by a
reboiler. generallyheated by low pressure steam or sometimes by a heat-
transfer fluid. The acid gas produced at the top goes through a condenser
where the steam is condensed and separated in the reflux drum. The
...water is sent back to the regeneration column. The cold acid gas is then
routed to tze acid gas treatment unit (see Section 17.2).
 Acid gas
Oondonsor ~
Trentod
gas
w
ijj
...
:t>-
o
6
~
Absorpllon
column Hydrocarbons
~
~
.~

Regenerator ~
~

L~

Untreated
goo . -
f-,Y

'-1 Fi~url1
17.2 Simplifi,'d n01l1 scheme of ({ sour Ras scrubbing unit in a refinery.
 The hot regenerated solvent in the bottom of the regenerator is cooled
by exchange with the rich solvent. then !lows to the lean solvent storage
tank. It is pumped back from the tank into the absorption column.
The treatment unit also includes a solvent filtration section to filter part
of the solution (generally 10 to 20%) conrtnuously,

il.l.3 Background Iaformation

17.1.3.1 TbcVariou5 AmiDes
Amine solutions, which have been used industrially since 1930. are Widely
applied to acid gas treatment in refineries. The most commonlyutlllzed are:
Monoethanolamine, or ~IEA. a primary amine with the formula
(C2H.OH-NH;D.
Diethanolamine, or DEA. a secondary amine with the formula .
(~40Hh==NH.
Diisopropanol amine. or DlPA, of the same type as OEA.
"Tertiary" amines such as triethanc.amlne (TEA) and N-methyl-
diethanolamlne ~IDEA). TEA has seldom been used in refinery applica-
tions. MDEA. (CH3(C/f,PH)2=N), orlginally developed for treatment of
natural gas and synthesis gas, is today more and more frequently
employed in refinery treatments. MOEA has undergone many develop-
ments: besides generic MOE>.. chemicais manufacturers and process
licensors propose formulated iv1DEA-bas~ solvents containing additives
(see Section 17.1.3.4).
Lastly, diglycolamine (DCA). which behaves like DEA. DGA was mainly
developed by Fluor.

MEAwas the first amine to be Implemented because it was easier to manu-

facture. However, compared to secondary and ';rtiary ammes, the drawback is
that it is more corrosive. This is why MEA concentration is limited to 15-18% wt,
Despite MEA's lower molecular weight this ger.erally results in a higher solvent
flow rate than with OEA or ~IDEA. Furthermore, MEA is more prone to form
degradation products than secondary or tertary amines, particularly in the
presence of COS. As a result. a "reclaimer", i.e, ::c solvent purification system for
removing degradation products. must be empoyed when MEA is used. For all
these reasons. MEAis much Jess applied in refzertes nowadays. ;"Ianyunits ini-
tially designed for l\JEAhave been converted ~:. DEA or MDEA.
DEAis commonly present in refinery treatzents. Less corrosive than ;"'lEA.
it can be employed in concentrations of 2S t~ 35% wt in water and does not
form significant degradation products in the ;::==sence of COS.
Lastly, MDEA allows amine solution concentrations as high as 50% wt
because of its lesser corrosivitv. Due to its chenical structure. ;..tDEA exhibits
an absorption selectivity for H~ rather than :02 (see Section 17.1.3.2). Its
580 C!:aDtIJf' 17. ACID GAS TREATMENT

main advantage is to allow a lower solvent circulation rate thanks to the higher
concentration limit of the solution. This justified its introduction in refinery
H.:.S removal units.

17.1.3.2 Chemical Reactions

a. Reactions with H 2S and CO2
The absorption reactions of H~ and CO~ with amine solutions are exothermic.
They are similar for primary and secondary arnines and can be written as fol-
lows fora secondary amine such as DEA:

H~ + R2NH :::; R2NH; + HS- (17.1)

CO2 + 2R2NH :::; RzNCOO- + R2NHi (17.2)

CO2 + H20 + R2NH =::; R2NHi + HCOi (17.3)

Reaction 1 is instantaneous. Reaction 2 occurs at an intermediate rate

whereas reaction 3 takes place at a slow rate. In order to reach the equilibrium
of the amine/C0 2 reaction. a longer contact time is therefore necessary than
for HzS.
The direct reaction with CO2 is not possible with tertiary amines due to
structural reasons. The reactions are as follows:

H~ + R2R'N ::; R2R'NW + HS- (17.4)

CO2 + H20 + R2R'N =::; R2R'NH+ +.HCOj (17.5)

Since reaction 5 is kinetically slow, tertiary amines such as MDEA allow H~

to be absorbed selectively in the presence of CO2, It is enough to limit the con-
tact time between the amine and the gas to be treated for CO2 absorption to
be only partial (kinetic limit). This property is riot particularly useful in stan-
dard refinery systems where the amount of CO2 in gases is negligible. but it
finds its best application in the treatment of natural gas or synthesis gas such
as produced by conversion of heavy refining residues (see Chapter 14.).

b. Reaction u.:ith COS

While COS is generally not a problem in refinery fuel gases. it may have to be
removed from liquefied petroleum gases (LPG). COS reacts with arnines after
hydrolysis to H2S and CO2:

This equilibrium reaction has relatively slow kinetics. it is thermodynami-

cally limited by a high H~ or CO2 concentration in the product to be treated.
As a result, COS hydrolysis requires low H~ and CO2 concentrations and
enough contact time to occur at a significant rate.
 17.1-_: J ~De Properties. Equilibrium. Curves
Table 1';.1 below shows the thermodynamic properties of MEA.DEA and :\1DEA
that can b~ used under commonly practiced operating conditions.

~IEA DEA ~mE.\

~k:eculat- weight (pure amine) 62.1 105.1 119.2

Hee: of ~action:
H':s(kJ/kg H"s) 1450 1190 ?50
C~ {kJ/kg CO:J 1915 1520 950
/
L--
T~ ---
1i'.1 Thermodynamic characteristics of reactions between acid compounds and
amine solvents.

The main properties of amine solutions are shown in Figures 17.3 to 17.11
(specific gravity, specific heat. viscosity of aqueous solutions of MEA. DEA and
~IDE.\). lne data come from a compilation of values provided by the various
amine SUppliers;
The ~uilibrium data for H>5 reaction with .\IEA. DEA and ~IDEA are
presented in Figures 17.12 to 17.iS. These curves can be used to calculate the
flow rate of solution required for the treatment of gases with a given composi-
tion. ~e also that simulation sottwares are also a\-ailable to represent these
equilibriQ..

1i. L+ 'technology and Process Data

Figure 1';'.16 describes the flow scheme of a conventional refinery installation
includin~:

high pressure treatment 0; hydrogen-rich gas recycle from hydrodesulfu-

maUon;
fuet gas treatment;
liqt1id LPG cut treatment.
In this flow scheme. the ric:' solvent regeneration unit is common to all the
absorption sections:
The rich amine flash drum is used to mix the three solvent streams
~fore regeneration.
The liquid LPG cut treatment presented is the simplest that can- be
~talled. It includes the H:S absorption section and a coalescer designed
to recover the-entrained amine. In some applications. a more sophisti-
cated arrangement is required for LPG treatment (water wash at the out-
let. specific design for COS removal).
 d~5

1.06 t -.... 1000.0 ' 1.02 -' I'

1.04~OO-""_-...._ ,
1.00
0.98." _.__ .1
1.02 ,~;g~i
......
J0.96
1.00
0.98
'~".~!~~.
~
'""-..~'-""':-----"'_
Deti)t - ............ _ ~ 0.94
0.96 I
0.94 '---'-_'-----'-____Jo__........----' ..l...---'-_""---'-_'---'---J
20 -10 0 10 20 30 40 50 60 70 80 90 100 110 120
Temperaturerc)
Figure
17.3j Specific gravity ofMEA solutions..

1.10

1.08
1.06 '~40
1.04 \-30
7-20
1.02 ';-10
i 1.00
~\M
0.98
1 0.96

I_---r- -10 -20 -10 0 10 20 30 40 50 60 70 80 90 lOll 110 120

Ti_em_peraue {~C_) ____J

1.06

1.04

1.02 r-
I
1.00 t 50--....
100
<,
0.98
0.98 1
-10 0 10 20 30 40 50 60 70 80 90 100
Temperature("C)
~ Figure I
; 1 r.s ! Specific gravity of MDEA solutions.
 4.00 ~.~
_ _ '5 ~
P
~
2
3.50
--~ =--------------
_ _ 50

3.00 :..

2.50
--
100------------
-'- -'----'-
Temperature I'C)
_
o 10 20 30 40 50 60 70 80 90 100 110 120

Figure
16 Specific heat ofM4 solutions.

"
~.wtOEA

4.00 _ 10
?
f 3.50:"
;
I.
_20 ---------

30
40~
==-----===
. 50 _ _ _ _ _ _ _ _ _ _ _ _

3.00 70

I 2.50
o
100-------------Te~rel'~
..- , ,
L-~ 10 20 30 40 50 60 70 80 90 100 110 ~20
--l

iF~:
17.7 Specific heat of DEA soluuons:

4.00 -

~I ,~
3 . 5 0 : - - 50
j
I
3.00 :..

,
2.50 -
.
'____
2.00 _ _--....;.
100~
-'-
---------

---'-
Terr:o:-a:J;~ ('C)
_
I -- o 10 20 -....".
30 40 :-J 60 70 80 90 100 110 "20 --'
! fi:ure,
: 17.8 Specific heat of .lIDEA solutions.
I.
584 Cr:a::Jlet 17. ACID GAS TREATMENT

____________________-:.._-l-r-

'-- ..:J,--
 O!Jler 1T. A;;;OG::S TREATMENT 585

-.;.
::;
- ~< t::
.\ . =-
::: i :::;..
~ "-
::! i ~
4

-I =~
~
~
~

~
01
Q

~
~ S
'"
., "t:
..
Q
,.;
~
~
;::-
~ ~

~
~
~.

I s:cU
!::
_
N
l"-
-
i \.l.. -

I
I
/
7 (

---------~---____;_-...........__--'---------___:o

-------------------------'1!~,
--------------------------~

!.~ ~
L- r--
I \.l.._
586 Chapter 17. ACID GAS TREATMENT

<
til
0

I
-
-:,
~
;;; ..,.
- :::

. -., I ~
'-"')
~

. ..
.,
;:j

...
,., ~
;0
ia
I.,
.. "E
=e
.,; ::::
:::
.,; ::::-
~

~
.,;
.,; ~
;. ~ ,..
:::::
. -e-
~ r-:
~

,r
 c.~.ac:Y. '-. -cs: G..s TReATMENT 587

10000 - - - - - - - - - - - - - - -

/ /
/ / I

i 100'C / /
)

I . j

Figure I, I !
H/MDE-l equilibrium 17.15 i / I
cun;e. 50:'.; ur (2fJ.'.
t' I 1
G G.t 0.2 0.3 0.4 0.5 0.611: II.! 0.9 1.0 t.t t.2 1.3 U t.5 t.'
~ !.Ioles HzS{mole MOEA

17.1.4.1 Opcra~ Parameters

a. Amine Solution Flow Rate
For gas treatment applications:
The amine solution flow rate is calculated at the absorption column bot-
tom temperature. Because the chemical reactions are exothermic. this
temperature is generally higher than that of the lean solvent feeding the
absorber. The equilibrium curves between the amine and H~ and/or CO2
define the theoretical acid gas absorption ratio per mole of amine. It is.
however. necessary to provide a solvent circulation flow rate higher than
the theoretical quantity in order to take into account the approach' to
equilibrium. Lsually a factor of 1.15 to 1.3 is applledto the theoretical
flow rate computed from the equilibrium curve.
The absorber bottom temperature. which is used to determine the equi-
librium data is checked by thermal baJance induding the heats of reac-
tion given in Table 17.1. '
 _G~~ recy'~I~ . __ .. Fuel To fuel gas system LPG Treated LPG
fin:;
toilOS I + I + 'I en
C
CD

~
i
~
:h.
s
~
~

:;;
~
~
~

c_ I
I

I
L~l
<:
I I
I

I
l
I

I
)

r--~ Fuel
I
I
l
I
)
I

ik-- j Solvont
X-I
In
1 I...-Waler
I

gas I regenerator

Solvent recycle

F11l1lrl'
17. J 61 How srheut of l/ retlnery 1111I;/1(' treatment.
 The czculated amine solution flow rate must aJso consider the residual
amount of H~ and/or CO:! presea: in the lean soln'!tl fed into t:-te
absorber, For a properly regenerated amine. the residual. H~ content
commonly achieved ranges from 5l\1 to 2 000 ppm wt "i.e. Q.005 to O.lt~
mole ~i H1S per mole of amine for J 30% \..1 solution of OE.\). A value vi
0.1 mc.e of CO~ per mole of amine .s often considered f,lr CO2, which is
more diiicult to regenerate.
The r:.:j solvent loading at the bottc:n of the absorber gt'nerally amounts
to O.3~ and 03 mole of acid gas pt'~ mole of amine edt'pending on t~t"
absorber pressure and the acid com::lound content in the gas). Note th:\t
a loading of 0.5 mole of H~ per mole ~)f amine should not be exceeded tor
:\-I..t Above this limit. cbrrosion prottlems can be experit'nced in the rtch
solutlcn circuit.
When liquid CUts are treated. the required flow rate of amiDe solution is
estimated using a circulation rate of 3 moles of amine per mole of acid com-
pound. Afterward the flow rate wt1l be checked to ensure that it is high enough
to provide good contact between the amine and the liquid hydrocarbon:".
since their acid gas content is often low.
b. Solvent Inlet Temperature
The lean solvent inlet temperature at the top of the absorber must be as low
as possible in order to minimize the flow rate of solution t(l be circulated.
However. this temperature must remain above the dew point of the gas treated
in the absorber to prevent hydrocarbon condensation. Common practice is to
feed the lean solvent at least SoC above tilt' feed gas dew point temperature.
When treating liquid cuts, the solvent temperature must remain below tilt.'
bubble point of the hydrocarbon cut. If needed. either the solvent temperature
or the treatment pressure must be adjusted to comply with this constraint.

c. Rich Solcent Regeneration

Regeneration must be carried out at the lowest possible OPt'f:tting pressure
compatible with:
routing the overhead acid gas to downstream treatment:
Ilowing the lean solvent to the storage tank .
..\S a general rule. the operating pressure ranges from 0.5 to 0.9 bar g at the
reflux drum. The lower the pressure. the better the quaJity of solvent regener-
ation. In addition. by limiting operating pressure, the temperature of the 501-
vent in the regenerator bottom is minimized. Therefore. the risks of thermal
degradation and corrosion are reduced. The operating temperature at the bot-
tom of the regenerator is between l~O and 130:C. depending on the pressure
or the column.
The regenerator reboiler duty is computed by thermaJ balance around the
column taking into account:
The rich solvent preheating in the lean/rich solvent heat exchanger (l (/
to 25"C approach to the temperature at the bottom "f the column
590 ChaDler 17. AciD GAs TREATM~NT

~ depending on the type of heat exchang~r selected and the n':lmber of

shells installed).
A temperature at the top of the column approximately 5 to 10C above
the rich solvent inlet temperature. This generally corresponds to a reflux
ratio from 1.5 to 2.5 moles of water per mole of acid gas (depending on
the rich solvent loading).
The amount of low pressure steam required in the reboiler ranges from
100 to 130 kg per m3 of solution (l.e, around 200 000 to 275 000 kJ/m3 of solu-
tion).

17.1.4.2 Conceptual DeSieD anel Tec:hnololY of InstallatioDs

a. Absorber
The absorption column is equipped with trays or packing. Valve trays or per-
forated trays as well as random or structured packing are suited for this ser-
vice. The number of trays depends on the final specification to' be achieved
(generally 15 to 25 real trays are adequate for refinery treatments). The foam-
ing tendency of amine solutions must be taken into account when sizing the
column. A foaming factor of 0.75 to 0.8 must be applied.
b. Regenerator-Reboller
Trays or packing can be used in this column. The number of real trays installed
is 20 for standard treatments. A foaming factor of 0.85 must be applied when
sizing the regenerator. The design must also take into account the low allow-
able pressure drop in the column. The solvent is withdrawn to the reboiler by
a tight seal chimney tray.
The regeneration column has to be protected against the risk of vacuum
that can occur in the event of reboiler shut down. Protection can be achieved
either by column mechanical design under vacuum conditions or by installing
a vacuum-breaking device. The reboiler is generally a kettle with natural
circulation. Reboiler mechanical design must include precautions against
the risk of excessive tube bundle vibrations, since they may cause tube rup-
ture. Furthermore, the heat flux and the tube skin temperature must be limited
in order to reduce solvent thermal degradation and subsequent corrosion
problems.

c. Rich/Lean Solvent Heat Exchanger

The heat exchanger can be of the conventional TEMA type. with two or three
shells in series allowing an approach of 15 to 25'C on the hot side. or it can be
of the plate type. The plate type is more compact and less expensive. It also
allows a reduction of the thermal approach to 10-15'C.
d.. Lean Solvent Storage
The lean solvent storage tank serves both as a surge tank between the absorp-
tion and regeneration sections and as a storage capacity to hold the unit sol-
vent inventory during maintenance operations. It operates at atmospheric
 ChatnlN 17. ACJO G.=-s TRC.-W.IENT 591

pressure. An inert gas blanket (preferably nitrogen) Is required since amines

tend to form degradation products when in contact with oxygen,

e. Solvent Filtration
Filtration is necessary to eliminate the impurities that tend to accumulate in
the solvent circuit (solid particles, degradation products. heavy hydrocar-
bons. etc.). The nitration system generally treats 10 to 20% of the total solvent
flow in circulation. The filters are either of the cartridge type for small units or
precoat filters for larger ones. Self-cleaningfilters without any precoat are also
available (e.g. "backllush" filters). Filtration on activated carbon is effective in
removing heavy hydrocarbons, The activated carbon bed is replaced once a
year on the average.
~'

f. Foaming Tendency
Amine solution foaming tendency can cause serious operating upsets, espe-
cially in absorption columns. This is because it can result in massive amine
solution carry-over with the treated gas and a significant reduction in the treat-
ment capacity. .
Foaming is generally due to the presence of excessive amounts of impuri-
ties in the circulated solvent (solid particles, liquid hydrocarbons, chemicals
carried along by the feed gas. etc.), Besides proper sizing of column internals
taking into account this foaming tendency, the best protection against foaming
is to limit the impurity content in the solvent. This can be accomplished by
proper filtration of the solvent, selection of appropriate operaneg'condttlons,
efficient separation of liquid hydrocarbons and, if need be, filtration of the gas
at the absorber inlet. It is advisable to equip the unit with anti-foam agent
injection facilities so that the operator can stop any incipient foaming.
Silicone-based emulsions are tile: most commonly used anti-foam chemicals.

g. Metallurgy. Corrosion
Corrosion in amine units is the result of the presence of acid components (H~
and/or COi). The most sensitive zones are therefore those handling rich sol-
vent as well as the regeneration section. As a rule, carbon steel metallurgy is
satisfactory! provided an adequate corrosion allowance is specified (3 to
6 mm). Post \Veld Heat Treatment (pWHT) must be applied. Special care is
required in selecting the grade of steel and its implementation due to the risk
of sulfide stress cracking (SSC) and hydrogen induced cracking (HIC) corro-
sion in the presence of HzS in it wet environment. Generally stainless steel is
preferred for the hot rich solveet feed piping to the regenerator:

h. Preparing and JHo n itoring Amine Solutions

Commercia! amines are generally available as pure products. Consequently.
fresh solvent must be diluted to the desired concentration. It-is mandatory to
use demineralized and deaerated water for amine dilution to prevent mineral
salt accumulation in the system and solvent degradation by oxygen. The water
must also be free of chlorine. since it can cause many corrosion problems.
especially with stainless steels.
592 ChaPter J7, ACID GAs TRWMEr:r

During operation, the concentration and quality of the amine solution in

the ctrcuitmustbe monitoredregularly Periodic water make up (continuous
or intermittent according to the unit's water balance) is usually required to
maintain the adequate concentration. The control of the solution includes
visual examination (limpidity) and laboratory analyses of the amine content
v.
and residual acid compound content (H~. CO Such monitoring enables the
operator to check that the unit is operating properly.

17.1.5 Process Performance

In gas processing, the treated gas residual H:zS content depends on:
the pressure and temperature at the top of the absorber;
the quality of amine regeneration.
At low pressure (5 to 10 bar), the residual H~ content that can be achieved
in the treated gas is around 100 to 250.ppm vol. Meanwhile, high pressure
operation (such as natural gas processing) allows H~ specifications below
4 ppm vol,
The residual CO2 content (which is not very significant for refinery treat-
ments) varies according to operating conditions: from 50 ppm volume for
severe high-pressure applications, to 1 000 or even 5 000 ppm vol when no
stringent specification needs to be complied with.
In LPG cut processing:
The residual H2S content is some 10 ppm wt. Note that these cuts usually
require a finishing treatment in order to meet commercial specltications.

The residual COS content is around 10 to 50 ppm wt depending on the ini-
tial amount of COS in the feed and the processing scheme arrangement.
FOT the downstream conversion of H~ into elementary sulfur, an important
parameter is the hydrocarbon content of the H~ rich gas produced by the
amine unit. With amine solvents, this hydrocarbon content is generally lower
than 1% vol (expressed as equivalent methane).

17.1.6 Safety and Environmental Issues

The major safety hazard in amine treatment units is related to H~ toxicity.
even when H~ is present at low concentrations. As a result specific precau-
tions must be taken: metallurgy selection adequate for wet H2S service. non-
destructive testing, zero effluent discharge to the atmosphere, leak detectors
and specialized training for operators.
The unit must not discharge any gaseous or liquid effluent directly into the
environment. Gaseous effluents are sent to a close flare network and liquid
effluents, consisting of solvent drains. are recovered and recycled. Solid
wastes, such as used activated carbon and filter cartridges, are rinsed or lncin-
erated.
 .
17.1.7 Process Licensors
The use of aqueous amine solutions to desulfurize sour gases is public prop-
erty. As a result. it is not usually necessary to involve a process licensor.
However; a number of companies have undertaken specific developments,
especially in the area of :\lDEA appllcatioes:

Elf Exploration Production: "high concentration- DEA process (up to

40o~ ~1:)1' ~lDEA process, (selective H~ removal and activated ~lDEA appli-
cations).
UOP: "Amine Guard" process famil}" using formulated :\IDEA (""Ucarsol"
soteents), l.e, ~tDEA-base solvents with a specific additive that can vary
according to the type' of treatment desired (selective HzS' removal, low
pressure treatment, etc.). Note that UOP is also process licensor for the
Benfield process (see Section 17.1.1.1).
Dow Chemical: Gas/Spec process involving a family of formulated MDEA-
based solvents. ~

E:aon: FIexsorb processes.

Fluor: DG.-\. process.
Shell: ADIP process (using DIPA solutions).

17.2 Sulfur Recovery Units

The objective of sulfur recovery in the refinery is to convert the hydrogen sul-
fide generated in solvent scrubbing into sulfur. a storable, marketable and non-
polluting product. Additionally, the sulfur dioxide emissions that would be
produced by incinerating hydrogen sulfide are limited. Refinery sulfur recov-
ery units mainly treat the acid gases from solvent absorption unit regenerators
(see Section 17.1). They also process the gaseous effluent from the stripping
unit for H~ and ammonia-eontaining process water. Sulfur is recovered in the
refinery by one or more sulfur plants implementing the Claus process which
achieves recovery ratios of 94 to 98~. When higher ratios are dictated by
administrative standards, an additional installation called tail gas treatment is
added and gives recovery ratios of 99 to 99.9?~1'
Refinery sulfur plants are characterized by:

smail sulfur production capacities (from a few tens to a few hundred

tons, day):
of
-~'erY subst~tial operating flexibility, from the standpoint capacity (up
to 5 to lO~~,_~ with loads Widely varying over time) as well as the fluctuat-
ing quality of H2S-rich gas that may also contain hydrocarbons, ammonia
-" and steam:
high reliability that often justifies coupling two units.
594 ChaD:>:, ir. ACID GAS TREATMENT

1i.2.1 SuJIu.r R.ecovery with the

Vapor Phase Claus Reaction [1, 11]
1, .2.1.1 Typical Feeds
Feeds to the unit are usually:
The main acid gas stream from absorption units. that contains basically
H2S (89 to 94%), water (about 5%) and carbon dioxide (0 to 5%). It is avall-
able at low pressure (0.4 to 0.7 bar) and at a temperature of 40 to 55C.
The effluent from the process water stripper. that contains ammonia, H2S
and water, generally at socC.
When the refinery includes a' hydrocracking or deep conversion unit, the
acid stream from the water stripper can amount to up to 30% of the main
.stream.

1i .2.1.2 Chemical Reactions

The overall reaction is:
H~ + 1/22 :::; lin Sn + H20 AH248 =-186.6/221 kl/mol (17.6)
The reaction is in fact carried out in two stages:
The thermal phase:
H~ + 3/2 2 :::; 50 2 +. H20 Mfi9s =-518 kl/mol (17.7)

The Claus reaction:

2H~ + 52 :::; 3/n S, + 2H20 M/ 298= -41.8 kl/rnol (52 gaz) (17.8)
-146.3 kJ/mol (58 liq)

A thermodynamic study of the Claus reaction (17.8) shows that at atmo-

spheric pressure, conversion is practically total at approximately 200C.
Conversion drops rapidly as the temperature rises. reaches a minimum at
around 550C:C and then picks up slowly to about 80~b (Fig. 17. 17). In industrial
units. reaction 2 takes place in the combustion chamber of a reaction furnace
where 1/3 of the H25 is burned to produce SO~. Reaction 17.8 begins with low
conversion in this furnace where the temperature is high and continues in the
catalytic converters that operate at lower temperature.
Reactions other than those mentioned above are due to impurities
included in the sour gas sent to treatment. e.g.:
light hydrocarbons if the upstream scrubbing units use a chemical sol-
vent of the alkanolamine family, or heavy hydrocarbons including aro-
matics if the units use a physical solvent:
CO") coming from catalytic cracking units;
ammonia generated in hydrotreating conversion units (hydrocracking
and hydroconverslon) that achieve a high denitrification ratio (30 to
"'0/)
i 10:
 hydrocyanlc acid produced in conversion units. but generally in very
small amounts.

100.

Dewpoint of
/ st.:if'Jr vapor

60

50 -_-J--

l- ------'
Io....- _

100 300 500 700 900 1 100

Temperature (=C)

: Figure
: li.li H~S conversion. ~fect 01 pressure and temperature {12f.

During the thermal phase these impurities lead to the following side reac-
tions:
y' y
eli"., + ( x + :....)
4 o?::;
" xCQ.,.. + -2 H.,O
.. (17.9)

.. 3
o? =: NO).. + 3H?O
2NH3 + -2" .. (17.10)

2 liNe + ~
2"o?:::; ~....
+ H?O + zco,.. (17.11)

CH4 + 252 == 2H~ + C5 2 (17.12)

I
HzS ::: -
n
s." + H~ (17.13)

.- . - CO2 -+ H2 :::: CO -t H20 ___ (17.14)

1
CO + -2 s.,.. = COS (17.15)

(17.16)
596 ChaD:,":;- ACt.J GAS TREATMENT

Reactions 17.9 to 1i .11 are exothermic. They consume oxygen and gener-
ate inert gases (HzO,- COi), thereby diluting the reaction medium. The other
reactions generate organic sulfur compounds. carbonyl sulfide (COS) and car-
bon disulfide (CSi). which are not 'converted by the Claus reaction. thereby
reducing the final conversion to sulfur. The dissociation of hydrogen sulfide
(reaction 17.13) takes place in conversion during the thermal stage due to the
high temperature (1 300C). Reactions 17.13 and 17.14 supply the reducing
gases that will be utilized in certain types of processes (see Section 17.2.3.3).
Downstream from the thermal phase, the Claus reaction takes place on a
solid catalyst. It is carried out in a sequence of several stages with intermedi-
ate separation of the resulting sulfur. Since the reaction is exothermic. con-
version to sulfur is promoted by low temperatures.. However, a high enough
temperature must be maintained in order to:
promote Claus reaction kinetics;
prevent liquid sulfur condensation on the catalyst;
favor hydrolysis of organic sulfur compounds (COS and CS?, formed dur-
ing the thermal stage of the process) by means of high tern-perature:
COS + H20 =:; H20 + CO2 (17.17)
CS2 + 2H20 =:; H~ + CO~ (17.18)

17.2.1.3 Technology and Process Data

Q. Process Features
Refinery sulfur plants are made up of the following main sections (Fig. 17.18):
A thermal section where one-third of the hydrogen sulfide contained in
the unit feed is burned with process air to produce a gas called "Claus
gas" which contains hydrogen sulfide and sulfur dioxide in the stoichio-
metric molar ratio of two, which is the optimum for the Claus reaction.
Combustion occurs in a flame where a minimum temperature and suffi-
cient residence time are required to insure good flame stability and com-
plete combustion of impurities (hydrocarbons. ammonia and hydro-
cyanic acid). Depending on the type and amount of impurities present.
the temperature varies from 950 to 1 350:C and the residence time from
0.7 to 1.5 seconds. These two parameters are essential in reducing alu-
minum salt laydown in the cold parts of the installation. and soot deposits
and traces of oxygen eventually sent to Claus catalysts. Sulfur production
in the thermal phase ranges from 60 to 70% of the theoretical figure.
A condensation section located immediately downstream from the ther-
mal section where the Claus gas is cooled in order to condense the pro-
duced sulfur. The heat recovered usuaUy generates saturated medium
pressure steam (18 to 40 bar) in the waste heat recovery boiler along
with 10\\' pressure steam (5 bar) in the first condenser. In small installa-
of
tions (less than around 80 tons sulfur a da~..). medium pressure steam
production is often omitted for economic reasons.
------_ __ ._--.--------- --'.' ------_.
.. ~

Thermal section Catalytic section

1st heater
[~l

Add 1jilti
..- .... " " ,
Boller
c~ t -,_-;J
/"'":;" J.
'

15t reactor
,
,>c
2nd reactor
.... J 11""Ii"~ IJ].,.
gal __
Air- ..

... tnctnoralar

AI~~l~~~U~.L-~t ~ J
contuintnq [
I _ '_ _

J IT I i
_ -.

l
1st condenser
CC-r- I I 3rd condenser
'(.-;.----1
Air ....... ~S'J- . '\-L__[-"1
I r~ 1-' LL-=I~
I.--~-
~ -~-r
I
. .
\l

I
o.

Donunoralized
wator,
-._- ....
--_._~-----~-----._---
j
I

I
~
III f Sulfur lank
Liquid lullm
-_.-.... ,
~
.:;
) ...

~~J_
q
{j

i;i~':;c
L~-t2;~i?L ~~
Dega'llng
iLtJ-
Sloreoe
~
~

l
. _ - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - _ ... _ - - - - !

UI
17.IM 7)'II/cul flu'" schenu: uf u sultur uui! uutl; two cutulytic .,\/u.t!(','i. ...,
co
598 ChaDre" 17. A=::: GAS TREATMENT

A first catalytic stage that includes heating the Claus gas. catalytic con-
version as such, cooling and condensation of the
sulfur. This stage imple-
ments the Claus reaction to produce sulfur but also takes part in the
hydrolysis of COS and C52, which are undesirable compounds formed.
upstream as shown in reactions 17.17 and 17.18. This Is made possible by
operating the reactor at a temperature high enough to promote hydroly-
sis at the expense of a lower sulfur conversion at this stage.
One or t\4/0 further catalytic stages that include heating. conversion on a
catalyst and sulfur condensation. These stages complete the treatment
that allows the Claus reaction to perform at ever lower temperatures
while maintaining sufficient catalyst. activity and preventing sulfur from
condensing on the catalyst.
The recovery yield in these units can vary from 94 to 96% with two reac-
tors, 95 to 97.5% with three and 97 to 98% with four. .
An incineration section (either catalytic or thermal) where all the resid-
.ual sulfur compounds are converted into 502 before being discharged
into the atmosphere. If specifications on residual H~, COS, (52' CO and
H2 content are stringent, thermal incineration limits H~ to a few ppm
(10 mg/std m 3 usually) at around 600 o e. An incinerator operating at 800C
is required to destroy completely all the compounds mentioned above.
At this temperature the heat can be recovered by heat exchange. between
the incinerator off gases and the tail gases entering the incinerator. It can
also be recovered by generating/superheating medium orhigh pressure
steam. catalytic incineration is possible too and generally operates
between 300 and 500C. However, the residual CO and COS content is
higher than with thermal incineration.
A degassing section for the H~ in the liquid sulfur (approximately
250 ppm \\1:). since HzS can create serious risks during storage and trans-
portation due to. its toxic and' explosive nature. Sulfur degassing to
10 ppm of H2S can be achieved by various processes, including the
Aquisulf process from Elf Exploration Production. Here degassing is per-
formed by spraying recirculated sulfur and injecting a small amount of
catalyst [16].

b. Impurities Removal in the Thermal Phase

Maximum Hydrocarbon Content
The presence of hydrocarbons in the acid gas feed causes more air to be con-
sumed (6.5~~ for 1% more C;?Ha> and can lead to carbon formation. This can
foul the catalyst of the following stage and lower the quality of the resulting
sulfur. As a result, it is recommended to limit the hydrocarbon content to
0.5-1 % vol of methane equivalent.

Ammonia Destruction
The presence of ammonia in sulfur units causes plugging (ammonium sulfides
and sulfites), catalyst sulfation and equipment corrosion. These problems
 o-..,tM 7' AC:O i.:-s TREATMENT 599

occur with an ammonia content of a few tens of vpm. A few hundred ppm of
~H3 can usually be allowed in the feed of a burner operating at a minimum of
1 250=C. If the ammonia concentration is higher. three types of configuration
(Fig. 17.19) can be contemplated:
if ammonia amounts to a few percent a high efficiency burner is used
with preheating of the acid gas and the air (Fig. 17.l9A):
if the acid gas H~ content is low (15 to 30% H~), a single burner is used
with a bypass for part of the feed so as to raise the temperature of the
first zone (Fig. 17.19B):
when the ammonia content is very high because of the input of water
stripper gases. a two burner system is used (Fig. 17.19C).
In any case, ammonia destruction requires efficient burners such as the
ones made by Duiker, John Zink and Lurgi (Figs. 17.20A. B and C) [7].

c.. Catalytic Coneersion

The aim is to continue HzS and S02 conversion beyond the 65% figure which is
generally achieved at the exit of the thermal phase. The reaction must also
enhance the hydrolysis of COS and CS2 In order to do so. it is necessary to:
shift the thermodynamic equilibrium by condensicg the sulfur;
operate at a temperature lower than 300:C to approach thermodynamic
equilibrium (Fig. 17.17):
use active catalysts to improve the kinetics of approaching" equilibrium.
In actual practice the unit comprises a sequence of in-series reactors work-
ing at decreasing temperatures. Each one is associated wtth a sulfur condenser
and a gas heating system to raise the gas to the temperature of the next
reactor.
In the first reactor. thermodynamic equilibrium is yractically achieved at
around 400:C. In the second one and sometimes in the thrrd working at a lower
temperature. active catalysts must be employed (for example, titanium oxide
base CRS 31 from Procatalyse). The catalysts must witr__stand deactivation by
traces of oxygen that produce sulfates which are cataly.t poisons.
After sulfur condensation, the gases can be heated '.lSing a number of dif-
ferent methods (Fig. 17.21) [3]:
a hot bypass, by taking part of the effluent frorz the thermal furnace
(between 500 and 700~C) and mixing it with the r:ffluent from the con-
denser;
an on-line burrier: the gas is mixed with the hot ~ases generated by a
burner that is fed with acid gas or network gas;
heat exchange between the hot gas exiting the Iirst catalytic reactor and
.the feed gas entering the second and third .reactor!:
reheating with hot oil, steam or electricity.
600 Cna.,ref 17. Ac:O GAS TREAT.\1ENT

Preheating
A
Burner

Acid gas

Water
stripper
Preheating

Air - - -~

Bypass
B
, ~
Acid gas r-- Burner
Water I ,....

stripper
Air U

C
.r
Acid gas

Water
stripper
: I Burners

1
-
~
Air

! Figure 1
, 1-;.19: Ammonia destruction. A Acid gas and airpreheating. B. Combustion in a sin-
; !
, l gie burner (bypass). C. Combustion with two burners.
 0:atJ!~ 17. AC;v G.:.S T;:::..?:e:';j 601

r--T-L ~ (0\
'rlW,il7>~
~'l/f7)
..
,:'
., tJ!

~
..~
~

'.. ,
r. ~..
rzt:-.
--! ~j
I I
.
~,I.
~ ~ ====:
I~~ .~ I " ,~ C!J'-'. II
.:
... '?I :

.. ~ I I I
. ~~;.'
~CI.{Q ICJiI ~ I
,
'. \ " Y.: --. ..... ,

- JIoc:b!".: I
I ..

... . "'~ ........

~'

t ..Jl ',; '1

!
I
.;~.,
-~~
\j~/X(2Zd
~.

- Figure
,17.20..-\ Duiker type 40 burner: maximum sour gas capacity: /2.4 t/h.
i

Observation ~

~'J'
l .~
-T----:::::::::~~ i

Combustion gas
LtDci
.U
/V'
~Pj Air Inlet .: ~ I !

Ignition ""
~~JA !
system ~j~
i
~
Ii' -
j
;
Fi~re
17.20B John Zink JHTR burner.
602 Chaprer 17. ACID GAS TREATMENT

Plssau~.r-
m T"jl~
Fuel gas
<,

Steam -I n
:" ~
Acid gas /
IIr

Combustion air ~:: ; : i -~

Oxygen

I
; Figure
,17.2OQ Lurgi burner.
I I

In some cases, the different heating methods can be combined depending

on economic conditions [5]. .t

Controlling the. H~/S02 ratio in the feed of each of the reactors is an essen-
tial operating parameter for getting the best performance. The ratio must be
kept strictly equal to 2. The curve in Figure 17.22 shows that in a unit sized for
94% recovery, 1% excess air causes a 6% loss in yield. By means of new ana-
lyzers (diode array photometers for example), the air/acid gas ratio at the unit
inlet can be adjusted so as to have an H~/SO~ ratio equal to 2 :!: 0.1 at the cat-
alytic conversion inlet.
This type of unit must be able to operate at much less than its nominal
capacity so that it can adapt to variations in refinery operations: crude oil sul-
fur content, changes in refinery production and acid gases from various
sources. Generally speaking, sulfur recovery units can wOrk at 30% of their
nominal capacity. In the event it becomes necessary to go as low as 5 to 10%.
special devices must be used to keep a 25to 30% hydraulic flow rate in the
unit: special blowers to recycle gases and gas make up by burning refinery fuel
gas.
 A B

Air Air
!

I
Acid:1
1........----0--
gas ........- 1....._ _-
h, .~
,

, I
e
I
I.-'- -

[I I ,
I I
1
Sulfur

I
T
Sulfur

c o (Steam)
(Hot oil)
.
X
Jl
ltJJ
J
T
,
Sulfur

Sulfur
Sulfur
----{ OQ)QQ J--
Elect..:: heating

I c~onl
gases

!-
. Figure
17.21 Heating conuerters: ..t Hot bypass. B. On-line burner: acid gas or fuel gas.
C. Gas/gas heat exchanger. D. External heating medium.

d. Special Configurations
These configurations can be included in the following cases:
When it is advantageous to replace the combustion air in the thermal
stage by oxygen or enriched air. this technology can be contemplated.
604 Cr.4.;J:et 17. ACID GAS TREATMENT

100

- 99
fI.
c
0
...
"iii
(D 98
>
c:
0
(J
97

96

95

94

93

92

91

-8 -6 -4 -2 0 2 4 6 8
Excess air (%)

I
--: Figure
1i.22 Sulfur units. Yield reduction due to excess air. Each curve corresponds to a unit
designed for maximum yield without excess air. -

when the acid gas has a low heating value (e.g. gas from partial oxidation
of heavy residues) or to increase the capacity of existing units without
heavy investments {4].
Omission of the thermal phase when the acid gas contains less than !Q...
12% of acidic compounds (e.g. gases from partial oxidation).
Operation with recycle of the gases exiting the first condenser to the last
converter after sulfur condensation. thereby achieving maximum flexibil-
ity (down to 5-10% of the nominal capacity).
17.2.1.4 Sulfur Storace, Transportation, and COllclitioning
Storage
After degassing, the liquid sulfur is stored in the liquid state either in metal
tanks or in pits clad \\ith acid resistent concrete. The temperature is held
within a 125-135=C range where viscosity is at an optimum.

Transportation
Sulfur can be transported by truck. train or ship with a heating system to keep
it in the liquid state. In the refinery it is dispatched in the liquid state from a
truck loading facility. since small amounts are involved and as it is often used
nearby.
I

Nota bene: Liquid suUur can be transported by pipeline over long distances
as long as suitable heating is provided (electric tracing. pressurized hot water
or steam lining). Heating must not be accidentally stopped for more than 4 to
6 hours.

Solidification
In some cases sulfur is exported in the solid state using a non-dedicated means
of transport. Historically speaking. the most common solidification technolo-
gies have been conditioning 1:1 flakes or slates and by spreading.
Flakes are produced by cooling the liquid sulfur which is deposited in the
form of a film on the outside of a rotary drum. A cutter is used to cut the solid-
ified sulfur up into flakes (Fig. 17.23). .

Water Air
Liquid
sulfur

\i
L --=--
t
Overflow I
Solidified
sulfur to
Y
loading area
to sulfur I
stOrage r
.. i

Figure
Ii.23 I r
Production ofsulfur zses.
 606 Cf'IGc;e~ 77. AciD GAS TREATMEWT

Slates are produced by cooling the liquid sulfur that has been laid down on "
a moving belt several meters long. It is cooled by spraying with water-
(Fig. 17.24).

Liquid sulfur

Product
Steel

,0I
belt
~

o
I I , , r I Cutting into
" I ... I "I, I ,,' ... I " I ...
slates
TIffiTf "1.~-r OL

!
Sulfur to
storag~

Water to.....
sprays --J

Water return ........- - - - - - - - '

Production ofsulfur slates with a Sandvik bell.

,I

Spreading consists in letting the sprayed liquid sulfur cool down in air and
form stacks of solid sulfur one on top of the other.
All the above methods produce crumbly sulfur which creates environmen-
tal problems when handled. Its moisture content after storage is often high. A
large number of processes (some twenty including around ten marketable
- ones) have been developed in an attempt to produce pellets or granules that
are more attrition resistant Some processes involve cooling with water. others
with air (Table 17.2).
The two most widespread processes are the Rotofonn Sandvik and the
Procor GX. The first (Fig. 17.25) pelletizes the solidified sulfur (module from
50 to 150 tid) and the second (Fig. 17.26) produces beads in a revolving
cylinder by injecting liquid sulfur that cools down in an air draft (300 tid and
more).
 ._------~--~-------_ .. _----------
\

art gas
scrubbing

Liquid foed
sulfur
--' ...

Mixur

\1'

I
,:j

8
~
~
~

-l Fil;lItc r'--- - .,. ~

1~+,25 U(,~c'('Jr", /'I'tU'CSS. en
~
608 Ct'.aoter 17. Ac:: GAS TREATMENT

~
--
.~
.....
 #

T~-pe of product Xame of process

Slates Procor. 5andvik

PeUets Rotoform 5and\ik
Water cooled beads Chemsource. Rl~t (ex-Fletcher Process).
Sulpel (H and G)
Air cooled beads Cornineo. Intcan. PEe. Procor G.\..
Stamtcarbon, Windgate
L TaHt --J

li2 Liquid sulfur solidification technologies.

~'

17.22 Sulfur Recovery by OXidation [2.6]

When a very small amount of sulfur is recovered. i.e. 2 to 30 tId at the most,
recovery can be carried out by a direct oxidation process. This serves as a
substitute for solvent scrubbing followed by a Claus operation and its associ-
ated treatment of residual gases (see Section 17.2.4).
Small amounts of sulfur can be found in:
small capacity refineries (SOO 000 to 2 000 000 t 'year) processing low-sul-
fur crudes with a low-complexity flow scheme:
lubricant production units;
or possibly in synthesis gas production units of moderate capacity using
partial oxidation. where the lo~HtS sour gas can entail costly scrubbing
enrichment units.
~Iodem technologies implement a redox process using iron chelates as a
substitute for the old Stretford vanadium process.

17.~.2.1 Stretford Process

The treatment feed gas is contacted with a solution containing pentavalent
vanadium ions (\"5-) and anthraquinone disulfonic acid (ADA) in a solution of
sodium carbonate (Fig. 17.27).
The H~ is absorbed in an acid/base reaction with the S:!- ion :eing oxidized
to sulfur by the pentavalent vanadium. The vanadium pentavalence is reduced
to ... in this reaction" The sulfur is recovered by notation in an oxidizer where
the initial vanadium valence is restored by a set of oxidation reactions using
.-\0.-\ and dissolved oxygen (air regeneration).
610 Cr.a~!e,~ tr. ACID GAS TREATMENT

_ - - - - - - Treated gas

Air

Feed
gas
Reaction

Sulfur
s+~ (ADA) recovery

Vanadium Oxydizer
solution
storage

FIgUre I
II 17.27 I

i
Stretford process.

Treated gas
Air
-t I
T
.1
Absorber:~
I I I

I Oxy~hzer t
I

rn
Steam !

Scrubber I U
C::==::J---r--...::~..o-----....
.. Sulfur
separator

, L

L-
II
FIgUre I - - - - - - - - - - - - - - - - - - - - - - - - - J
17.28 l
I,
Conventional ARJ LOCAT process.

"
 c."~:::~~ ~:-, AC:o GAS T~EATMENT 611

17.2..2.~ Chelate Processes

These processes use Fe:!+/F~ as a redox pair.
The ARl LOCAT process utilizes '10\\1' Iron concentration (1 500 ppm) with
high solvent circulation. It is \\l'ell suited to low' pressure gases but rather
uneconomical for high pressure scrubbing (Fig. 1i .28). A self-circulatmg
alternate integrates the absorption and oxidation iunctions. Other develop-
ments are under way to adapt the process to use with high pressure gases.
The 5ulfint process. developed by Gaz Integral. works in a similar way.
The Sullerox process. developed by Dow Chemicals and Shell, uses high
concentration chelate solutions
I
(2 to 3% iron). It can treat high pressure
gases if certain specific installations are provided (Fig. 17.29).
The Bio-SR process. developed recently by NKK. uses a non-chelated iron
ion that is regenerated microbiologically.

17.2.3 Tail Gas Treatment Units

Incinerating the residual hydrogen sulfide after recovering the sulfur signifi-
cantly increases the refinery's 502 emissions. As a result, further sulfur recov-
ery from the sulfur plant tail gases often becomes necessary. It is one of the
first methods of reducing these 502 emissions. Final sulfur recovery can reach
99 to 99.9~o by implementing supplementary units. At the outlet of the sulfur
recovery unit (see Section 17..2.1)t residual concentrations of the various con-
stituents vary according to the number and age of catalytic reactors.
Concentrations are indicated in Table 17.3.

Constituents Concentrations

COS 50 to 1 000 vpm

CS 2 50 to 1 000 vpm
H,S 0.3 to 1.5% vol
S0,, 0.15 to O. ,5'Y. vol
Vapor sulfur 10 to 100 vpm depending on the temperature
j of the gas
Vesicularsulfur 0.5 to 1 g/std m3
Table
17.3 Composition of tail gases from a sulfur unit.

Figure 17.30 presents the three main types of processes using different
principles:
A. Claus reaction on solid or liquid catalysts.
B. H~ or 501 recovery section with recycle to the Claus unit. 502 may not
be recycled.
C. H~ oxidation reaction.
612 C'':3D:e~ 17. ACtO GAS T=!4iMENT

11
0'

...
.2
"3
(J)

.1

o
m
...
2
o
a
e
a:

,
-~:-,
,.
=i_i
--...;".-.-
.....
C '
U T

L '

I
 C!&::;~- AC:.? GAS TFo~fENT 613

Sold
eabllrsts
A. Low ter:":::erar..;re eaus
Acid :
n
/:
Suifreen
\ HydmsWfreen

E =It
Claus
gas C"a~s cata.....;,. .. ; \ DolO suffreen
~ lJU'" I-----~ Inclneranon ~ CBA
----~I LJ
adsorption

SUlfur .,I
r\
II

liquid phase

=-1 , n C:aus
i
l
Claus
liquid
phase
----,
.
Inc,r.e,anon
.
rLJ
;
J
t \ Causpof n IF?

Sulfur I I
r
II

B. HzS and S02 recovery

- - - HzS recycfe - - ---4- """"
I
T
Scot

~
HCR
! Claus Incineration
Result
Sulften
8fapur
Sulfur
01
,
~ - - S02 recycte - - --e.- ~

Acid
, Cintox
gas Solvent 1-- ....
Lucas
C:aus UCAP
saubbing weHman-Lord

Sulfur ,! I
-----~
C:O
.... 2

Vapor phase c:ae.tytic oxidation

Modop
Acid I Parsons high
gas Catalytic activity
-... I

I
Claus ~ Hydrogenation
oxidation
lncr.eration Setectox
i
L
I Superdaus
Sulfur
.. T

Liquid phase oxidation

~
BeavoniStretford
Acid i i i~ . I C1eanair
gas

_ _ _ _-;
.

""- -
I Direct
------ Claus f""""'; HYdrogenation... . ' oxidation
by solvent
'"'" ' " n I i
i Incmeratlon H .
I
Sulfur
;
i
" "
l-.
, Figure
, 17.30 Tail gas treatment. Different types of-techniques. A. Low temperature Claus.
B. H;..S and SO! recouery. C H::S oxidation.
614 ChaDter 11. co GAS TREATMENT

Out of some 500 tail gas treatment units installed in the world, over 2/3 use
one of the following three processes:
Sulfreen (Claus reaction on solid catalysts); _.
Clauspol II (recent development of the Clauspol 1500) with a liquid phase
Claus reaction;
SCOT and its derived processes (H~ recycle).

17.2.3.1 Sulfrecn Process and its Derived Technologies [13,14]

Developed by Elf Aquitaine and Lurgi, the process has given rise to several
derived technologies (Amoco's CBA Delta Hudson's MeRe, Davy McKee's
Maxisulf). It operates at low temperature (below the sulfur dew point so that
the reaction equilibrium is shifted toward production of sulfur which accumu-
lates in the liquid form in the catalytic bed). It uses a Claus type catalyst (see
Section 17.2.1.3.b) in a fixed bed reactor.
The unit generally includes two reactors operating cyclically. The gases
from the Claus unit with an H:zS/S02 ratio of 2 are fed to the first reactor at
between 120 and 135C. At this temperature, the reactants are practically
totally converted into sulfur. The sulfur is adsorbed in the pores of the cata-
lyst, which is regenerated by thermal desorption after reaching a specified sul-
fur ratio. In this way the sulfur is vaporized at 300 using part of the residual
ClC

gases which are heated indirectly and recirculated by a blower operating in a

closed loop (Fig. 17.31).
The desorbed sulfur is recovered by condensation. Regeneration ends with
the catalyst being cooled by the residual gases treated in the first reactor. The
second reactor then goes into the reaction phase and the treated gases are incin-
erated. Sulfur recovery of 99.5% is possible. and a higher recovery ratio can be
achieved by adding a further stage and intermediate cooling of the gases.
The Sulfreen process can be implemented with several variations:
Hydrosulfreen includes a pretreatment reactor which hydrolyzes the COS
and CS2 and oxidizes the excess H2S to sulfur in air on a titanium oxide
catalyst at 300 eC. The resulting gas (HzS/S02 = 2) is then treated in a
Sulfreen unit.
Doxosulfreen is a finishing process for the Sulfreen process. The residual
H~ is oxidized to sulfur on activated carbon. The adsorbed 502 is oxi-
dized to sulfuric acid. Catalyst regeneration allows the sulfuric acid to be
converted into sulfur. Sulfur recovery can exceed 99.S~o. A development
under way with Procatalyse win yield recovery of oyer 99.9~h.
Oxysulfreen includes a unit to hydrogenate sulfur compounds to H-S. It is
followed by an air oxidation unit that converts 1/3 of the H~ into -50 2 in
order to provide the gas required by the Sulfreen unit
The principle of the Sulfreen process has been utilized by other companies
by combining the Claus reaction and adsorption (CBA Process developed by
Amoco, MeRe by Delta Hudson, Maxisulf by Davy McKee).
 ~ I
(~ I Sulfreen

., I
f
Healer
I
raactors

!
tt
Fueloit Air
Tail gases
t I
6~~1~
Blowe!' ,
Sulfur

~ Figure
; 17.31 Sulfreen process.

17.2.3.2 Clauspolll Process [9)

First marketed by IFP uncer the name Clauspol 1500. the process was then
improved and called Claurpol II. It allows 99.8% of the suHur to be recovered
over the whole process s-:-~'.lence. It is based on the Claus reaction carried out
in a solvent that absorbs :--: ~5 and 502 but is almost immiscible with liquid sul-
fur. Consequently, the corverslon equilibrium is shifted in the favorable direc-
tion. The Bmiting factor t: :he reaction is the H~ transfer to the solvent. The
process feed gas is contacted counter-currently on ceramic Intalox packing
with polyethylene glycol .nolecuiar weight -tOO) containing the sodium salt of
an organic acid as a catalyst. The produced sulfur accumulates by settling in a
boot where it separates cut from the solvent. The treatment is performed at
120:lC. a temperature at ":'lich conversion is at a maximum. In addition, COS
and CS... are hydrolyzed ;:-d the vapor or vesicular sulfur entrained in the tail __
gases .IS recovered (F'19. ,.. -3?)
. .. .
The process results j, a tail gas sulfur content of less than 300 ppm
expressed in sulfur. It alsc allows for greatIlexibillty with respect to variations
in feed characteristics (~:w rate. H~~ ratio), due to the properties of the
616 Chaprer 17. ACID GAS TREATMENT

Treated gas
to incinerator

Catalyst

I I
I
~-_u-B
I, !

I
f
I
I I
I f
I

:@
I
I
Tail gases --~ I
I I .
I
I OrganIC
I
I ~---- . phase

l_rt_:
I I

Sulfur 4' _
Figure
17.32 Clauspol nProcess.

solvent and of the dissolved catalyst which can absorb excess H~ and 502 at
close to the stoichiometric ratio of 2. As a result, only an H~ and 502 analyzer
needs to be provided in order to control the Claus unit inlet regulating the air
injection. The process is insensitive to the presence of ammonia in the unit
feed gas and it can work with extremely low feed flow rates. A development
allows 99.9% recovery by limiting the sulfur concentration in the recycled
solvent.

Ii.1.3.3 The SCOT Process (Shell Claus Offgas Treatmc) and

Derived Processes [10]
The process includes (Fig. 17.33) a section to reduce sulfur compounds (SO~.
COS. CS2 and elementary sulfur) to H2S on a cobalt-molybdenum catalyst. It
operates at 300::C in the presence of hydrogen or of a hydrogen/CO mixture.
After cooling in two stages (steam generation then scrubbing with water). the
reactor effluent (3% H2S and up to 20% COl) is scrubbed counter-currently in
a selective absorption column by diisopropanol amine (DIPA) or l\1DEA. The
treated gas, which contains only traces of H~, is incinerated. The concen-
trated HzS is stripped from the rich solvent, recovered at the top of the regen-
 ~

---.: Compressor
Tail
gases
II Treated gas Acid gas
.
Burner ! ~ Reactor .1
---
rr.I
i Absorber J

l Regenera:or I

Fumace I
Nr
Fuel
oil

.,f
Condensates

: 17.33 Scot process.

I

erator and then recycled to the Claus wit. SCOT unit performance aBows an
overall recovery of 99.9% of the potential sulfur present in the Claus mit feed
(250 vpm in the off gases).
Two variations on the process yield even lev.. er discharges:
The SuperSCOT uses two stages for the stripper and works at a lower sol
vent temperature. It can achieve 50 vpm of 502 in the off gases.
The 1..5 SCOT uses an additive that reduces emissions to 10 vpm of 502.
Several processes have been developed based on the SCOT process. They
differ in the reduction technique and the solvent:
The BSRjAmine (Beavan Sulphur Removal) process, developed by Ralph
Parsons. uses selective amine absorption.
The HeR process. llcensed by
~-IGI.holds the' H2S/Sb2 rano at 2.5 in .
order to reduce the 502 content to 300 vprn in the effluent sent to treat-
ment. thereby making hydrogenation unnecessary.'
The Sulften process. developed by Union Carbide, Ford and Bacon &
Davis. uses,50% promoted ~IDE.\. to improve H~ absorption.
 618 CMprer 11. AcJD GAS TREATlrfE/Jj

17.!3.4 Other Technoiocies

Other processes are combinations of the ones described above. Among them
the following can be mentioned:
502 recycle processes (Weiman-Lord and Chiyoda) better suited to desul-
furization of flue gases (see Chapter 18);
selective processes that oxidize H~ to sulfur (Superciaus process from
Cornprimo, Seiectox from Unocal, Modop from Mobil, BSR/HI from
Parsons), by means of specific catalysts;
liquid phase oxidation processes (BSRP by Union Oil, Clean Air by
Pritchard).

17.2.4 Process Performance Figures

The usual characteristics of liquid sulfur are:
purity (% wt) 99.9 min.
ash content < 0.05% wt
carbon content < 0.025% wt
acidity < 0.01% expressed in sulfuric acid
water content < 0.5% wt
H:zS < 10 ppm (non systematic)
In some cases, there may be a maximum content requirement on specific
products (arsenic, selenium, tellurium, etc.). Acidity is representative only at
. battery limits. Depending on storage, conditioning and transportation condi-
tions, the oxidizing action of bacteria can increase acidity by an order of mag-
nitude, especially for solid sulfur. Particular specifications are laid down for
solid sulfur (grain size, shape and distribution, brittleness, bulk density, angle
of repose, etc.).
Recovery' efficiency, defined as the ratio between the amount of sulfur pro-
duced and the amount of potential sulfur in the feed, depends on the different
parameters mentioned previously (feed characteristics. options selected - in
particular the number of reactors for a Claus unit. type of tail gas treatment if
any, etc.), Recovery of 97.5% with a 3-reactor Claus unit can be boosted to
nearly 99% if a selective oxidation catalyst is used and can reach 99.9% with a
high-performance tail gas treatment.

17.2.5 Economics
The number of sulfur recovery units installed worldwide in refineries must be
greater than 1 000 with over 500 tail gas treatment units. The amount of sulfur
recovered from refinery streams amounts to some 1.5 million tons/year in
Europe. In France. refinery sulfur production was around 245000 tons for 1995.
Aging and replacement should allow for construction of about twenty units per
year worldwide.
17.2.5.1 Process Licensors
Around ten Claus type processes are in competition. with the most well known
proposed by Amoco, Comprimo.. EEP (Elf Exploration Production), Ford.
Bacon & Davies, Goar, Lurgi, Parsons and TPA. These technologies use either.
proprietary burners (Ford. Bacon. Lurgt, TPA) or burners marketed by equip..
ment suppliers such as Duiker, John Zlnk, Pillard. etc.
There are about thirty processes for tail gas treatment. The three major
ones are C!auspol (45 references in 1995). SCOT (150 references) and Sulfreen
(50 references).
The main catalyst manufacturers are as follows:
Procatalyse, which cov~rs virtually the complete range of catalysts used
in these units:
- alumina based catalysts: CR.. DR, iron doped AM; ,
- CRS 21 catalysts (titanium oxide) and CRS 31 on a Ti02 support.
Alcoa Catalysts and Chemicals. Discovery Chemicals, Kaiser. La Roche
Chemicals and United Catalysts Inc.
Engelhard Corporation, which markets the oxidation catalysts imple-
mented in the Superclaus.
Unocal, which sells the Selectox catalyst.

17.2.5.2 Investments
Q.. Claus Units
Investments depend on feed characteristics, treatment capacity, recovery effi-
ciency, desired hydraulic fle.."dbility and regulatory requirements and stan-
dards. For reference purposes. the battery limits cost of a 100 ton/day, 3-reac-
tor Claus unit is approximately ME 12.5 (1999). The skid model for units of up
to 200 t/day allows substantial savings to be made on construction costs.

b. Tail Gas Treatment

Depending on the technology selected. the added cost of a tail gas treatment
unit is as follows in comparison \\ith the Claus unit:
Superclaus: 15 to 20%
Sulfreen: 35 to 45%
Clauspol: 40 to 50%
Hydrosullreen: 60 to 70%
H:S recycle process: 80 to 110% according to the degree of integration
with .the other units in the refinery.

1;.~.5.3 Utilities, Catalysts an. Chemicals

Utilities consumption is given in Table 17.4. expressed per ton of sulfur pro-
duced.
620 ChatJter 17. ACID. GAS TREATr..fE'....r

;
.
I

- Claus ( Sulfreen i Oauspol I SCOT

I
Electricity (k\Vh) !I 45 to 80 10 25 to 35 28
I
LP steam (t) j -0.4 to -0.7* I -1.8 - 0.46
HP steam (t) i -2.4 to -2.6
!
- - -
Fuel (lOS kJ) '0.20** 0.4 - 0.8
t
1.7 to 2.9**
I

l
I

!
Cooling water (m3)
The symbol - means production.
Without line tracing.
Catalytic incineration.
-
- -

_... The~mal incineration: 0.8 to 1.5 with gas/stack gas 'heat exchanger.
I 3 to 4 -

, Table
i 17.4 Utilities consumption per ton ofsulfur produced.
i

The initial catalyst load is 0.3 to 0.6 ton per ton/day of sulfur for the Claus
process and 20 to 50 tons for the Sulfreen process. Catalyst lifetime is around
3 years. In the Clauspol process, 10 to 15 m3 of solvent is circulated per
ton/day of sulfur.

References
1 The status of Claus sulphur recovery process. Sulphur 187~ Nov.lDee. 1986
Supplement.
2 Lagas J.A., Berben P..H.~ Borsboom J. (1988) Selective oxidation catalyst
improves Claus process. Oil Gas 1 86, 41, 68-71.
3 Optimum furnace configuration for sulphur recovery units. Sulphur 198~
24. Sept./Oct. 1988.
4 Reviving an industry work-house - Oxygen enrichment in Claus process
sulphur recovery units.. Sulphur 195, 24, MarchiApril 1988.
o Nedez G., Jaeger P., Ray J.L (1995) A new Claus catalyst with improved sul-
fur recovery, 2nd Tokyo Advanced Catalytic Science and Technology
Conference. Studies in Surface Science and Catalysis 9~ 395-399.
6 Johnson 1.E., Tzap SJ. Laczko LP. (1993) Options narrowed to Claus or
redox processes. Oil Gas J. 91, 47, 70-il~ 74-76~ Nov.. 22-
"i Leading burner design for sulphur plants. Sulphur, Jan./Febr. 1993, p. 23.
8 Oxygen technology in Claus plant. Sulphur, Nov.lDee. p. 75. 1994~
9 Dezael C., Kerdraon L (1994) Clauspol300 : une avaneee de 1'lFP dans le
traitement des gaz de queue des unites Claus. Rev. lnst. Franc. du PeJzole
49, 5, 491-493.
 C"a.:::er 11. ACIO GAS TRCArMNT 621

10 Recent dev.pments to the Scot process. Sulphur 227. July/August 1993.

11 Paskall H. (1982) The Claus Sulphur recovery process. Sulphur 160,
- May-June.
12 Gamson B.\\:. Elkins R.H. (19..\9-1953) Sulphur from hydrogen sulfide.
Chemical Engineering Progress 49,4,203-215.
13 LeU R.. ~ougayrede J. (1990) Improving the reduction of 50 2 emission with
the 5ulireen Process. Sulphur 90 Conference, Caneun.
I-t Nougayrede J.. Ruhl E. (1986) Industrial experience and nev.. developments
of the 5ulfreen Process. S..vmposium Stutgart 86.
15 Nougayrede J. Voisin R~. (1989) Liquid Catalyst efficiently removes H~
from liquid sulphur. Societe Nationale Elf Aquitaine. Oil Gas 1 17, 65-69,
July.
16 Muhlbauer H.G., Monaghan P.R. (1957) Swetening Natural Gas with
ethanolamine solutions. Oil Gas J, April 29.
17 Jones J.H.. Froning H.R., Clayton Jr E.E. (1959) Solubility of Acidic Gases in
aqueous monoethanolamine. Journal of Chemical &: Engineering Data 4, L
18 Lawson J.O., GarstA.\V. (1976) Equilibrium solubility of hydrogen sulfide
and carbon dioxide in aqueous monoethanolamine and aqueous diethy-
lamine solutions. Journal ot Ciiemical & Engineering Data 21, 1.
19 Lee J.I.. Otto F.D. Mather A.E. (1973) Partial pressures of hydrogen sulfide
over aqueous diethanolamine solutions. Journal of Chemical & Engineering
Data 18.4.
20 Lou F.Y.. ~1ather A.E.. Otto F.D. (1982) Solubility of H2S and CO2 in aqueous
methyldiethanolamine solutions. Ind. Eng. Chern. Process Des Dec. 21,539-
544.
 -.f stack- Gases

Yves Barthel

The sulfur oxides present in stack gases generated by the liquid fuel oils used
in refineries account for a large part of the sulfur discharged within total emis-
sions. This sulfur is even larger if Claus unit off gas desulfurization units are
incorporated in the refinery. The main characteristics of liquid fuel oil stack
gases are given in Table 18.1.

Pressure (bar)
, Sufficient for natural draft
Temperature CC) 12~150
!
j
Sulfur in the fuel oil (~ wt) 1 2 4
!
Stack gas composition:
Sulfur oxides (ppm vol) 600 1150 2300

l
I
i
1
I
Ox-ygen (10% excess air) (% vol)
H:=Q C"~ ~"OI)
CO2 (;, \-01)
N~(%,U)
Ash (mg-std m3)
;

II

i
1.8-2.0
10-12
12-13
i3-75
<50
Table
18.1 Characteristics of stack gases generated by liquid fuel oils.

Sulfur oxides consist mainly of sulfur dioxide (SO!), along with sulfur triox-
ide (S0i> in very small proportions compared to 502 (a few percent at the
most). They are difficult to analyze since it is almost impossible to handle.
stack gases without 502_ oxidizing to SO:!. Roughlyspeaking the ash content
depends on fuel oil characteristics (a heavy fuel oil will produce more ash than
 624 ChaPter 18. DE5ULFURlZAnON OF STACK GASES

~. a light one when burned) and sulfur content. A large part of the ashis made
up of carbon, but metals can also be present in the form of oxides (nickel,
vanadium, titanium) or impurities (of .sodiurn and other alkaline or alkaline
earth metals). Other impurities may have been incorporated during refining
operations. For example, silica or aluminum salts may come from catalytic pro-
cesses. Ash can also result from the accidental introduction of water contain-
ing dissolved minerai salts.

18.1 Legislation
Recent European Commission initiatives valid Europe-wide on sulfur emis-
sions from combustion facilities are listed in Table 18.2. .

Aolaximum
Capacity
(thermal MW)
(mg SOz/std m3) (ppm SOz) .
Solid fuels 50-100 2000 700
II 100-400 2 QOO-8OO 700-280
>400 800 280
100-500** 2000-400 700-140
1 > 500** 400 140
Liquid fuels 50-300 1100 595
300-500 1 700-400 595-140
>500 400 140
II
Gaseous fuels I all 35 12
i
liquefied gas i all 5 1.8
Low Btu gas' all .' 800 280
1 I

Running time under 2 200 h/year.

... Running time over 2200 h/year,

I, Table I
! 18.2 , 502 emissions for new combustion facilities.
(Directive 88/609 & Proposal COJI (92)563 final).

The European Commission's decision is now pending on combustion facil-

ities with less than 50 MW thermal capacity. The directive is obviously not con-
fined to the refining industry as dealt with in this chapter, but is applicable on
principle to refinery energy production units. There is no Community legisla-
tion on 502 emissions in the refining industry other than the directive "Sulfur
content of certain liquid fuels", which is in fact applicable to diesel fuels. The
Commission seems to be moving toward a framework directive that would
leave it up to each member country to adapt legislation to local situations.
 C1",ap:fJf 18 CES~1F:..lRfZAT!CN CF Si':'CK 6uEs 625

Note that France has decided to limit overall 501 emissions to 1 000 mg/std mJ
for all stack gases from a new refinery (350 ppm vol) and 1 iOO mg/std m3
(595 ppm vol) for an existing refinery beginning in the year 2000- In other
words, the "bubble" ( concept will be applied.
In addition to being nonproductive by definition. desulfurizatiOll of stack
gases is considered to be a very expensive operation and rightly so. Before the
refiner resorts to desulfurizing stack gases he \vill search for other solutions
compatible with the refinery configuration to the extent authorized by regula-
tions. Some possibilities for the refiner are as follows:
energy requirements met as much as possible by gaseous by-products
(whose sulfur is easy to eliminate) and by liquid fuel oils with the lowest
sulfur content;
unit combustion facility capacity limited to 50 thermal MW (to comply
with European standards);
desulfurization of the catalytic cracking feed (and/or use of a sulfur trans-
fer mass in the cracker regenerator):
desulfurizatlon of Claus unit gaseous effluents (see Chapter 17), a less
expensive solution than desulfurizing stack gases.

18.2 Principle of Stack Gas .

Desulfurization Processes
Since the first stack gas desulfurization processes came into operation in the
seventies. a considerable number of techniques have been proposed. They
have given rise to numerous industrial applications, mainly in purifying stack
gases from (usually) coal-fired thermal power stations. To this authocs knowl-
edge, there is only one refinery installation of representative capacity
(660000 std m3{h) located in Europe (see Section 18.4.4.3). In the United States
and Japan there are a great many desulfurization units, some si~ mainly on
the effluents of cracking catalyst regeneration.
Various possible classifications have been proposed for stack gas desulfu-
rization processes on the basis of:
the choice of the chemical agent reacting with S02.
the operating conditions of the reaction.
the processes foreseen to r.egenerate the chemical reactant and recycle it
at the end of the cycle, whereas the recovered sulfur is in a concentrated
- . marketable form (sulfur, 502' sulfurtcacld). __
Note that a few processes also accomplish stack gas denitrification, which
can be a decisive advantage (see Section 18.4.4.4).

I.' The bubble concept consists in setting emission limits for the whole industrial site
rather than for an isolated installation.
 1.8.2.1 Choice ~f Sulfur 9lrlde .Chemical Reactant
Virtually all desulfurization processes were developed from Cl!1 acid-base type
of reaction.. The acidity of SO:? (or SOi) is neutralized by a base. usually lime or
limestone (the most common processes) or sometimes caustic soda, magne-
sium hydroxide or ammonia. Sometimes a base in the form of a metallic oxide
(calcium. copper, etc.) has been proposed.
The elimination of sulfur oxide can also be carried out by selective adsorp-
tion with activated carbon or selective absorption with an appropriate solvent.

18.2.2 _Operating Conditions

Conditions obviously depend on the choice of active agent. "Wet" processes
essentially consist in neutralizing sulfur oxides by a base in solution or sus-
pension. The stack gases are scrubbed with this solution or suspension and
therefore the processes necessarily involve cooling the gases to their dew
in
point (they can be cooled by heat exchange or vaporizing water the gases).
Processes based on adsorption are by definition "dry", operating solely in the
gas phase, i.e. above the gas dew point. The advantage of these processes is
that they produce gases at a sufficiently high temperature so that no heating
is needed before they are discharged into the atmosphere by natural draft in
the stack. "Semlwet" processes have also been proposed, where the amount of
water introduced to contact the gases is limited in order to get a'gaseous efflu-
ent alone as purified stack gases.. Their temperature is slightly higher than the
dew point so as to minimize heating (or even make it mmecessary). Here the
. effluent contains neutralization products in the form of fine solids entrained in
the stack gases.

18.2.3 Regenerative Processes and Throwaway Processes

.r
"Regenerative" processes treat the sulfur dioxide neutralization products so as
to regenerate the reactant, recycle it to the reaction section and produce the
sulfur in a sufficiently concentrated form as sulfur, concentrated sulfur dioxide
or sulfuric acid. These methods have proven to be costly and are mainly used
in refineries with smaller treatment capacities. The typical example in this cat-
egory is a wet process, the Wellman-Lord process (see Section 18.4.4.3).
Another type of regenerative process also used in refineries is based on the
use of activated carbon as an 502 adsorbent, generally at the stack gas pro-
duction temperature. The SO., is catalytically oxidized to sulfuric acid and then
adsorbed on the activated carbon. During regeneration, the sulfuric acid is
desorbed and then reduced to concentrated S02 by a fraction of the activated
carbon. All of the activated carbon is recycled to the SOz absorption section.
This is a dry process.
Inorganic impurities present in the stack gases can act as poisons for regen-
erative processes, especially for wet processes (in dry processes, the impuri-
ties behave like any solid). This is because they can become dissolved, even
 Ct:ac!1Y- ~8. D~SUt..R.JRIZATlON OF S-:',),CJ( GASES 627

partially, in the solution sent to the reactant regeneration section. Oneor more
purges must then be performed, causing large amounts of reactant to be con-
sumed. Here the most commonly recommended way of avoiding or attenuat-
ing this drawback is-a prewash at the stack gas dew point with or without neu-
tralization to eliminate a maximum amount of impurities before the
regeneration section..
Moreover. the possible impact on a regenerative process of the impurities
present in the water must be checked any time the temperature is lowered by
vaporizing water in the stack gases.
A great difference used: to be made between regenerative processes (where
the sulfur impurity is produced in the form of sulfur, 502 or sulfuric acid) and
throwaway processes. However, today the second type of process has evolved
toward discharges that can be upgraded. For instance. processes usingBmeor
limestone (the least cost effective neutralization agent) to neutralize sulfur
oxides could originally be considered only as throwaway processes (the first
units in 1975-1980 in the United States were designed to treat coal combustion
stack gases and the solutions from the scrubbing operation were just stored in .
dedicated pits for the lifetime of the unit). Since then the processes have
changed and usually include a step to oxidize calcium suIfites to sulfates. This
is the solution chosen in Japan in any case. where the end product, gypsum
(caS0..1' 2 H20 ), is marketed. The country has only little natural gypsum and an
ex-factory price is therefore possible. Likewise in Germany, the gypsum pro-
duced in stack gas desulfurization units is beginning to replace the natural
product. It is only a question of product specification (the gypsum produced
from stack gas desulfuri-zation is inferior in quality to natural gypsum, often
from the standpoint of color) and of price to be adapted to the market price.
The process can no longer be considered to produce discharges toda~ but can
not be termed regenerative either.

18.3 Characteristics of Stack Gas

Desul.furUation Processes
Before discussing the most common stack gas desulfurization processes
(including the ones used in refineries), it might be useful to review process
characteristics. This will help situate them in the general context of refinery
sulfur oxide emissions.

18.3.1 Stack GasJReactant Contactor

First of aIL burning a fuel oil -generatesconsiderable gas flow rates. approxi-
mately 1 000 to 1 100 std m3/h per thermal ~I\V with around 10% excess air. In
other words stack gas flow rates of 300 000 and even 600 000 std m3;b can be -
encountered and therefore require, large-size contactors.
. In wet processes. 502 is neutralized by a base in a gas..llquid contactor
where the amount of scrubbing liquid is very small compared with the amount
 628 V.dPIBf 18. DESULFURJZATION OF STACK GA.SES

of flue gas. In order to improve contact, the amount of liquid in the contactor
Is increased by outside recirculation of part of the liquid which is sent back to
a higher level by a recirculation pump.
Packed columns are seldom used due to the high flow rates involved. Tray..
type columns may be preferred (gas velocities approximately 2-2.5 m/s) for
relatively moderate liquid recirculation ratios. Otherwise liquid spray-type
columns may be selected, with very low pressure drops (in comparison with
tray-type columns) but high gas velocities (up to 4-5 m/s) and liquid circula..
tion ratios. An economic optimum must therefore be sought on a case by case
basis between the two types of column. The tray-type column requires a fan to
achieve a greater differential pressure in stack gas circulation. Meanwhile, the
spray column needs more efficient systems to recover the liquids entrained by
the high stack gas flow rates, in addition to the specific equipment around the
contactor (columns, stack gas fans, pumps).
Dry and semiwet processes use specific contactors whose sizing rules
involve proprietary licensor information. All that is known is that the contac-
tors in semiwet processes are much larger than the ones in wet processes.
Whatever the type of stack gas/reactant contactor, it causes a pressure
drop along the stack gas path. When a stack gas desulfurization unit is antici-
pated during construction of the combustion facility, there will theoretically
be no need for a gas circulation fan in the desuJfurization unit. This is because
the required pressure level is provided for upstream in the liquid fuel oil and
combustion air feed system design. If a desulfurization .unit is incorporated
after construction of the combustion facility, a gas circulation fan is necessary.
Depending on the process and the contactor constructor, the fan may -be of
. two types: blowing at the outlet of the combustion facility or sucking at the
outlet of the desulfurization unit after gas heating in wet processes. The fan
will be located so that it operates on gases that are sufficiently far from their
dew point to prevent any condensation or corrosion.

18.3.2 Heating the Stack Gases .'

The temperature of the purified stack gases must be high enough 'to insure nat-
ural draft by the stack. It is widely accepted that the temperature must be
around 15C or more above the gas dew point in order to prevent condensa-
tion. Dry processes fulfill this condition in theory. Semiwet processes, which
generally operate at a temperature relatively close to the gas dew point, may
need only partial heating.
The amount of heat required for wet processes is considerable: on the
order of 1 340 kJ per :C per thermal ~1\V, i.e, for example 6 106 kJ/h to heat up
300 000 std m 3/h of stack gases by lS cC. Accordingly, various solutions have
been studied to minimize or eliminate this utilities item. A number of facts
must be taken into account in designing heating equipment:
The corrosive characteristics of the stack gases (see Section 18.3.3) mean
that sophisticated materials must be used for any surface in contact with
them.
 ;.~a::. 74 D:::UUVRIZATiCN OF S:-':'CK G~ES 629

Heating by steam (involving a pressure drop that must be taken into

account by the gas fan) or by a burner (with a sulfur-free fuel) results in
considerable utilities consumption.
The drawback of conventional feedleffluent tubular heat exchangers- is-
that they cause Quite a significant pressure drop even with a mediocre
exchange coefficient. They quickly become very large in size. For the past
few years sophisticated design heat exchangers have been proposed that
take the particular characteristics 0( this application into account: i.e.
high gas flow rates, -corrosive nature of the gases. low differential pres-
sure between the two streams.
Rotating heat exchangers of the LjUogstr6m or Rothemiihle type are
being used mainly in Germany and seem to be giving satisfaction.
The possibility remains of heating the gases by mixing them with other
sufficiently hot stack gases in the refinery.

18.3.3 Corrosive Nature of the Slack Gases

The stack gas analysis presented in Table 18.1 shows that it is possible to oxi-
dize 50 2 to 503' The ash - part of which is in the form of metallic oxides -
can catalyze oxidation in the preser.ce of ~ and water vapor. So there is in fact
a certain rate of oxidation. even mere so as the temperature is not a negligible
parameter. Therefore. aJl the cond.tions exist for it to be necessary to cope
with the sulfuric acid dew point ;.henomenon. if not continuously, at least
intermittently. Depending on their ;articular conditions, the equipment mate-
rials (for the stack gas scrubber, :.eat esehangers, gas fans) will have to be
selected with the phenomenon in mind when wet or semiwet processes are
involved. The recommended mate::a1s are at least 316 L steel or more sophis-
ticated steels. Carbon steel coated with resins. rubber or other inert products
can also be employed. Besides the :onventional temperature limits for the use
of such materials. another limit may be the abrasive nature of suspensions in
relation to these materials for .rme- or limestone-base wet processes.
Theoretically. dry processes at su::'ciently high temperature are not exposed
to the sulfuric acid dew point phe-.0menon and do not require very sophisti-
cated materiaJs in this respect.

18.4 The Main Processes

IS.of.l Processes Using Lime or Limestone
This type is the most common of III the stack gas desulfurization processes.
including for coal-fired power pl~.1ts (they account for 90% of the- existing
installations). Their use is very lir:ited in refineries except in Japan.
Generally speaking. the proces: stages include the following sections start-
ing from the electrostatic preclpiuzor outlet:
Scrubbing in the contactor ~: such and the recirculation pumps.
630 Ct".a:ne: 18. DESULFUFlIZATlON OF STACK GAsEs

Preparation of the chemical neutralization agent (lime or limestone in

suspension). . - -. -, . - - - -.
The sulfite to sulfate oxidation section. This operation is necessary for
these products to be disposed of (sulfate COD2 is theoretically zero).
Oxidation is now increasingly carried out in the scrubber.
The stack gas circulation fan (at the inlet or outlet of the installation).
The stack gas cooling and heating section (see Section 18.3.2).
A simplified flow scheme is presented in Figure 18.1.

Steam
......-------4 I'r--~ Stack
Heater (2)

Scrubber
Stack gases
Electrostatic
precipitator

Product
treatment

Additional
Ash air (1) ...----'

Figure ,
IB.l Simplified flow scheme of a wet process for stack gas desulfurization with dis-
charges.
Nota bene: (I) It may not be necessary to introduce air. (2) The gases can be
healed by a feed/effluent heal exchanger.

Stack gas desulfurization is in fact more a question of know-how than a typ-

ical process giving rise to a licensing contract. It is usually offered by various
contractors specialized in the construction of thermal power stations or utili-
ties production units. These companies have already solved the specific prob-
lems of plugging, scale formation, corrosion and abrasion and have often
added their own special improvements.
Today desulfurization efficiency can reach 95% for a Ca/S (calcium/sulfur)
molar ratio of less than LIto 1.2. The use of this type of process is very lim-

2. COD: chemical oxygen demand.

ited in refineries.. It obviously involves importing the chemical reactant into
the refinery and exporting the neutralization product. For example, with a SO:!
recovery of 90% and a Ca/S ratio of 1.. 1, desulfurization of the stack gases pro-
duced by burning a 3% sulfur fuel oil for a 50 thermal MW capacity means han-
dling substantial quantities:
U t day of lime or 8.2 t/day of limestone imported;
some 15 t/day of gypsum equivalent (presumed dry) exported,
\vet process desulfurization techniques yield gypsum (95% purity on the
dry product) which can replace natural gypsum in certain applications.

lS.4.. Z Semiwet Processes

The reactant, an alkaline, lime-base suspension, is introduced into the contac..
tor by spraying or atomization.. The resulting neutralization products are
entrained in the purified stack gases in the form of fine particles recovered by
batteries of bag filters at the installation outlet (the water introduced with the
neutralization solution is in fact insufficient to cool the gases to the dew
point), A simplified flow scheme is presented in Figure 18.2.

Water
+ lime
I

o ISla~

Slack ~ ---'
gases Atomizer Bag
filter

Ash and
sJudge
Figurr
182 Simplified flow scheme 01 a semiuiet stack gas desulfurization process,
Nota bene: The gas fan can also be of the dralt type (otter the bag filterJ- The
stack gases may have to be heated
632 Crao;ar 78. D:SUU=URIZATION OF STACK GASES

It is difficult to upgrade the mixture of solids laid down on. the filter: pres-
ence of fly ash, incomplete oxidation of sulfites. The Ca/S ratio (1.3 minimum)
is generally higher than for wet processes for an efficiency of 85 to 90%.

18.4.3 Dry Processes with.l;)ischarges

Desulfurization associated with a boiler can be mentioned in this category
(Fig. 18.3). The process includes an entrained bed desulfurization chamber
incorporated between the boiler furnace and the convection exchange zone. It
operates at around 1 OOOr.:C and uses lime or limestone as a desulfurizing
agent. The adsorbent is injected between the furnace and the desulfurizing
chamber and is entrained in the off gases. It passes through the convection
exchange zone and is finally recovered at the final dust collector. Part of the
adsorbent can be recovered and recycled to boost performance and curb dis-
charges.

Absorbent recycle Steam out

To
stack
..

Fresh
Boiler
L absorbent
Lime
injection

- Figure
18.3 Simplified Ilou: scheme of the Aude boiler.

This type of boiler is' proposed by Institut Francais du Petrole and Babcock
Enterprise. Desulfurization efficiency of 80% and more can be achieved with a
Ca/S ratio of 1.5 to 2. Adding NH3 helps insure some NOx elimination (see
Section 18.4.4).
 c.""40_ 18. D:S:.:U:URlZAnON OF SrACK (i.:,SEs 633

1:3.4.4 Relenerative Processes with

Production of Concentrated 501
l~AA.l I1paradJlII tbe Extracted Sulfur Dioxide
"" .

In the processes that result in the production of concentrated S02' fhe refin-
ery's Claus unit. can be used to transform it into sulfur. The most common
method consists in replacing a fraction of the air in the Claus unit thermal
stage by an 502 recycle. It is widely accepted that 502 make up can amount to
up to 15-20% (in moles) of the H~ entering the Claus unit.
Another solution also used industrially is thermal reduction at high tem-
perature of the 5~ by pure hydrogen when the amount of recycled 50 2 is too
large compared with the H~. Here the H~/S02 ratio of 2 is sought to recycle it
to the Claus unit thermaJ stage (Redotherm process licensed by Lurgi) (see
Chapter 17).
These are the solutions used in a refinery.
. In other industries the SO?- can
be upgraded either in the liquefied form or by being transformed into sulfuric
acid (when this type of unit exists on the site) or sulfur by means of the Allied
process where the 50 2 is reduced by fuel gas. The resulting effluent is treated
in a Claus uni t.

15.4.4.2 Processes on Activated Carbon

This is the main dry process that has been used in refineries. It is based on the
useof activated carbon to adsorb 50 2 and also allows stack gas NOx to be elim-
inated. The license for this process, developed by Bergbau Forschung, is avail-
able from several contractors (Mltsui, KTI, Uhde). The stack gases at a tem-
perature of 100 to 2OO~C are contacted with circulating activated carbon. In an
initial stage the sulfur dioxide is adsorbed by the activated carbon and then
converted to sulfuric acid by the oxygen and steam present in the stack gases
as shown in the reaction below (Fig. 18.4):
1-
501 + 2 1 + H20 ~ H~O.\
In a second stage, ammonia is fed in the reactor so as to reduce the NO.,; by
means of the catalytic properties of coke:
4NO + 4NH3 + O2 - t 4N1+6H20

The sulfuric acid-rich activated carbon is then sent to a regenerator at

400:C where the suUuric acid is desorbed and converted into 502 by a fraction
of the carbon in the activated carbon according to the reactions below:
H2S0~ ~ H20 + 503-
250 3 + C,~ 2S0~.;. CO:!

After concentration. the resulting 501 is treated as indicated in

Section 18.4.4.1.
634 Chapter 18. DESULFURlZAnON OF STACK GAsES

Stack CycJone

Activated carbon
502 to
treatment
I
Contactor Regenerator
Stack
gases -----+-I
NH 3 ----~F__--+-....

Activated Burner
carbon cooling
Fuel gas
------------------------
; Figure I
1,~I 18.4 I Simplified flow scheme for stock gas desuliurization and denitrification by acti-
vated carbon.
Nota bene: The feed/effluent heat exchanger is not included in the figure.

The major advantage of the process is that it carries out desulfurization (at
a ratio of 90%) and denitrification (at a ratio of 70%) at the same time. In con-
trast, the process seems to be limited by the large contactor size required in
large capacities. It is used in Japanese refineries mainly to treat the effluents
of catalytic cracking catalyst regeneration. .'

18.4.4.3 The Wellman..Lord Process [1]

This process, now licensed by Lurgi, has given rise to some twenty industrial
installations in around twenty years, some of which have been in refineries
(including one in Austria at the Osterrische Minerol Verwaltung refinery in
Schwechat). It .conslsts in (Fig. 18.5) neutralizing 502 by caustic soda. in fact
by sodium sulfite, and produces sodium hydrogenosulfite in solution. The
solution is then treated to regenerate the sodium sulfite and produces SO:!.
The reactions are as follows:
Adsorption of SO:?:
50 2 + Na~03 + H20 =:; 2 NaHS03 (18.1)

(18.2)
 ........ _ ..... _ _ ~_~ __ .~. _ ."r" . ~.. ._~~_

Stack

Stack gase~
)0

Electrostatic Sloam
proclpltQIOr Lfung.tr~m
exchanger

Prewashinq
Purgo
Washing
-fJ-
Evaporator
J

1. _ [}"
-
Steam o
ti~
!h

fi?
5 Cooling
Causllc
2 "

water
(
Sulfate
purge i
~
Q
(J)

Fi~lIrc
.. ~-~----
,~------ f
Itt&) Sim/Jlitii'd IV".lIl1uml.urd 1"'UCf'S.'l flow scheme. PJ
U1
Nul it heue: 'lh If", run I)e' i1ll'o'1JUIl,/t't/ "".Ii/ream "'ill' otl"''''Y/Jt',.. or t'.rf"tIllH(~":('
636 Cnac!er 18. DESULFUR1ZATfO.~ OF STACK GAsES

Regeneration (at a higher t~mperature):

2NaHS03 -+ 50 2 + Na2S03 + H20 (18.3)
Treatment of SOrrich gas:
2502 + 6H 2 ~ 2H2S + 4 H20 (18.4)
2H~ + 502 --7 35 + 2H20 (18.5)
The process includes the following sections:
The adsorption and stack gas circulation section comprising an electro-
static precipitator, a feed/effluent heat exchanger (of the Ljiingstrom type
in the Schwechat unit), prewashing and then the scrubbing column.
The regeneration section with 2 parallel, forced circulation evaporators
where the sodium sulfite is regenerated as shown in reaction 3 above.
The water and 50 2 are then treated so as to concentrate the 502" The
sodium sulfate is extracted from the system on an evaporator operating
on a regeneration section' bypass. .
The SOrTich gas section with treatment by pure hydrogen in order to
reduce 2/3 of the 502 to H2S. A certain amount of sulfur is produced in
this high temperature operation. The effluent from the section is routed
to the thermal stage of the Claus unit.
Na2S0.. is inevitably produced by oxidation at the scrubbing stage and is
minimized by adding EDTA in the scrubber. However.. a purge is required to
eliminate it from the system.
The Stackpol-S02 process, developed by IFP, works on a principle similar to
the Wellman-Lord process, but uses ammonia instead of caustic soda. It has
resulted in an installation in Russia. The adsorption and regeneration reactions
are similar to the ones in the Wellman-Lord process where the ammonium ion
fulfills the function of the sodium ion. The advantage of the process is that it
reduces the sulfate produced in the adsorption stage in a new way (self-reduc-
is
tion of the sulfate in a molten salt medium). but it costly in terms of energy.

18.4.4.4 Stack Gas Denitrification Processes

Denitrification techniques are often applied at the same time as stack gas
desulfurization. In addition to the precautions that need to be taken with the
burners to limit NOr formation at the source, the processes mentioned in
Section 18.4.4.2 (and 18.4.3) are the only ones that can eliminate a large pro-
portion of the NO x at the same time as the 5 2-
There is, however, an independent denitrification technique: Selective
Catalytic Reduction (SCR). Here ammonia is injected as a reducing agent into
the stack gases in the presence of a metallic oxide-base catalyst (titanium,
tungsten. vanadium. chromium/iron). The catalyst is deposited on a support
or in bulk form with a regular honeycomb structure so as to prevent fouling by
fly ash. The reaction is as follows:
4NO + 4NH 3 + O2 -+ 4N 2 + 6H~ (18.6)
 The operating temperature is approximately 300-400~C. This solution is
used in almost all the installations on stack gases. obviously wlth some varia-
tions as to catalysts,

Reference
Janda H,. Reichel P. (1993) The \Vellman Lord process, Ol\-tv refinery
Schwechat. Petrole et Techniques 383. Oct.. 4&-51,
 19
Water Treatment

Francois Decoopman

Water is important in the operation of a refinery for cooling in certain pro-

cesses and for producing steam. which is a source of energy in refining.
Reffnery water consumption has been considerably reduced due to technical
progress and closer attention to wastage.
french decrees of 1 March 1993 dictate new limits on discharging refinery
waste water. These limits go far beyond simple water conservation, they
require recycling in service and fire systems and in cooling system make up
water. Legislation also places constraints on the concentration of carbon com-
pounds and suspended solids in waste water. In addition it introduces a limit
on nitrogen compound discharges.
\Vater must be purified for both recycling and discharge. Water treatment
technology has improved with the development of biofiltration, membranes
and. micro- and ultrafiltration. Better understanding of reverse osmosis and
electrodialysis has also been of prime importance. Technological evolution
helps meet the legislator's new demands and allows zero discharge which is
technically feasible. but high in cost (3 to 5 of the price of a refinery).
1;6

Table 19.1 shows mass flows authorized by French legislation according to

refinery category.

19.1 Source and Type of Water

Requiring Purificatit:n
The design of refining effluent treatments depends on the structure of the refin-
ery: its capacity. the type of units (thermal or catalytic cracking units, lube oil
plant. solvents required. tanker debalJasting). Generally speaking, if water
treatment units are to be effective. they must be as close as possible to the ori-
gin of pollution. The main sources of contamination are discussed below,
 640 Ctupl~ 19. WATER TREATME-\7

.. ~

Refinery categol1" ! 2 --
I 3
Consent mass Dows*
I
Water flow rate (m 3It) 0.2 0.5 0.8
Total suspended solids (gIt) 5 12.5 20
COD (gIt) 20 I 50 80
BOD f.Rjt) 5 12.5 20
Total nitrogen (g/t) 4 10 16
Hydrocarbons (g/t) 1 ; .,
_.=>- 3
Phenols (gIt)
I 0.05
.... I 0.125 0.2

Yearly average.

"'--

~
t. Table
19.1
I Mass flows consent level from French legislation (as of / ~Uarch /993).
i
I

19.1.1 Waste Water from Refining Processes

19.1.1.1 Crude Desalting
The desalter reduces the water and salts content of the crude to 0.1 to 0.2%
and less than 1 to 10 mg/J respectively before distillation. It proceeds by wash-
. ing with water (see Table 19.2). The washing water must be only slightly min-
eralized, neutral and if possible soft. The amount used depends on the crude
viscosity and the desalting temperature. The desalting circuit purge corre-
sponds to 5 to 6% of the volume of processed crude.

19.1.1.2 Process Condensates ,I

This waste water stream comes from the condensation of vapors that have
been in contact with oil products.

a.. Distillation Condensates

Atmospheric distillation condensates come from steam stripping of distilled
products and amount to 2.5 to 3.5% wt of the feed flow rate. Vacuum distilla-
tion condensates amount to 3 to 4% wt of the feed. The degree of contamina-
tion of these condensates is low.

b. Sour Water from FCC, Hydrocracking; and Hydrodesuiturixation

This category of waste water comes from the steam from the demineralized
water used for thermal cracking and hydrotreating. \\"hen heavy products are
cracked, sulfur is converted into H~ and mercaptans. During hydrotreating,
nitrogen compounds are converted into NH3 The reaction between steam and
cyclic hydrocarbons produces phenol. These condensates are called "sour
 C.":30t81 19. WATE:~ T~J,TMENT 641

Desalter capacity (m 3 'd) 12000'

Crude before treatment:
Salt content (mg I) 300
Water content C, \\1) 0.4
Treated crude:
Salt content (mg 1) 10
Water content (". \\1) 0.2
Water injection to crude ratio (0,;) 6.0

Volume of water blown down (mJjd) 744

I
Amount of salt extracted (kg/d) 3480
Salt content of the blowdown (g:l) 4.67

TabI~
19.1 Characteristics of a crude desalting URit.

condensates" or "sour water" and are ricb in NHt. HS- and phenols. They
amount to 6 to 12?6 wt of the feed and can not be discharged into the sewer
without prior desulfurization.
c. Steam Cracking
Steam cracking discharges reach 15 to 35% .1: of the feed. In contrast however..
the degree of contamination is lower. The presence of aldehydes, acetic acid
(pH 8 to 9) and phenols can be noted (fable 19.3).

Atmos. Vac, Steam

fCC GOHDS
dlst, Dist. crackiDC
wt of
t.l{l
the feed ')- .,-
_.~-,j .) 3-1 6-12 3-6 15-35

pH 6-7 6-7 5-9,3 5-6 6-8.5

HS-. RSH 20-200 10-50 500-3000 : 3000-5 000 10-20
i
CI- 5-100 5-50 10...50 10-30 10-30
C:'-!- 5-200 5-10
NH; HMO 5-30 300-3000 1 500-3000 Traces
Phenols 10-30 5-10 ~300 10-20 20-30
He 30-00 ~20 5-60 5-20 30-50
CH:~CO~H :
: 5D-l00
CH,~CHO

- Tabl~

19.3 Example of process condensate composition in milligrams per liter.

542 ChaPter 19 ~VA7CR TREATMEIfl

19.1.1.3 Solvent Discharges

This type of discharge comes from lube oil plants in the refinery. The main sol-
vents used are: .
Furfural or N-methylpyrrolidone (NMP) for aromatics extraction.
Methylethylketone (MEK) or methylisobutylketone (MIBK) for dewaxing.
These solvents are very soluble in water and specific bacteria are required
to ensure biodegradation in an aqueous medium. Production units must have
effective recovery systems because of the high cost of the solvents. However,
large amounts of solvent can be accidentally discharged, causing COD con-
tamination peaks that are difficult for biological systems to absorb
(Table 19.4). A surge tank is usually installed on these discharges to regulate
accidental discharges and better treat them with biological processes.

I NMP Furfural MEl( I

.
I AIIBK

Boiling point CC) I 201 161 79 US

I
sp.gr. dis
4 1.02 L15 0.82 0.80
Water solubility High 83 gJ-I 320 gJ-I 18 gJ-l
TOO 2.5 1.66 2.44 2.72
BODs (mg/mg) 1-1.5 O.3-{).8 L5-L8 0.6-2
COD (mg/mg) 2.5 1.6 2-2.3 2.1-2.4
Biodegradability I
i
- Good Good -
I 1
Table

.
. 19.4 Characteristics of solvents used in lube oil manufacture.

.r

19.1.1.4 Special Effluents

Waste water from bitumen blowing is in the form of an emulsion that can be
broken only by coagulation or acidification. Waste water from catalytic alkyla-
tion can have a high sulfuric acid and/or fluoride content. They can be elimi-
nated more or less easily by precipitation with calcium.

19.1.2 General Refinery EMuents

19.1.2.1 Oily Waste Water
This heading mainly covers:
Drainage from crude oil or refined product storage" containing hydro-
carbons and from 1 to 10 mg,tl of phenols.
 Chapter 19. W4TE.=i T=4TMENT 643

Rainwater that has fallen on allthe paved areas in the refinery, which
may cover 5 to 10 ha.
Rainwater that has fallen outside paved areas. The Dow rate can be con-
siderable and there may be accidental contamination during storms. Flow
rates may reach 3 000 m3/ h. an amount that can not feasibly be treated at
its instantaneous flow rate. As a result. it must be stored and treated at
low flow rates. Storage tanks 01 20 000 m 3 capacity are common, but they
can go up to 60 000 m3 in certain refineries that extend over a large area.
\Vater used 'to wash the ground.
Deballasting water from oil tankers. Depending 00 vessel size. it may
account for 25 to 33% of effective tanker capacity. The hydrocarbon con-
tent is around 1%. Theinstantaneous deballastlng flow rate is very high.
so the water must be stored and then treated at a low flow rate.
Deballasting water has the following usual characteristics after storage:
- high salinity (seawater),
- a hydrocarbon content of 50 to 100 mg/l,
- a suspended solids content of about 50 mg/l,
- dissolved hydrocarbons present from previous transportation of
refined products.
- rarely phenols. XH~ and HS- ion contamination.
Tanker cleaning water. Cleaning before periodic tanker maintenance
involves powerful streams of water, often massive and variable doses of
detergents (0.1 to 3.0 gil) and sometimes caustic soda. Emulsions of
hydrocarbons in water are very stable and concentrated and require spe-
cific treatment. The discharges from tanker cleaning are not usually
incorporated in refinery effluents.
Heat exchanger leakage. This category of waste water is accidental in
origin and may amount to a large proportion of the total discharges (from
50 to 500 I/t of crude processed).

19.1.2.2 Nonoily Waste Water

This type includes:
Sanitary waste water: showers, toilets, canteen. etc.
Laboratory water,
Beiler blowdown when it is conditioned with POt
Already neutralized ion exchanger regeneration eluates. They are highly
salty and must not be incorporated with other effluents. This is why they
need a separate discharge flow line.

19.1.2.3 Spent Caustics

~Iost of the spent caustics come from nonregenerative gasoline sweetening
processes (Merox), or from alkaline washing of LPG. kerosene, etc. (Chapter 5).
It is a highly specific effluent. small in volume (0.1 to 8 m3/h) but quite trouble-
some due to its S 2 and phenol concentration. When it comes from washing
 644 C~-2:::e~ 19. ~VAr.E'R TREATM(Jj

operations it is low in phenols but rich in Na~, and when it comes from gaso-
~ -- line sweetening it is rich in thiophenols as well as phenols or cresols that are
insoluble in water.

19.2 Purification Treatment Method

19.2.1 Segregation of Discharge Streams
The only way to comply with the most stringent standards at the lowest cost
is to separate discharge streams. In Section 19.1 the various sources of waste
\~..ater were seen to include: "
Discharges related to refinery processes, whose general characteristics
are as follows:
- relatively low flow rates: 50 to 100m3/hr. .
- low salinity for condensates, higher for the desalter, but when com-
bined the result is on the order of 500 to 800 mgjl as average, mainly
NaCI,
- a high NH 4', 5-, phenol and dissolved hydrocarbon content,
=
- relatively high soluble COD and BOD (BOD 200 to 500 mg/l and
COD =500 to 1 500 rng/l) 1 t

- a relatively low hydrocarbon content (20 to 100 mgll).

When these effluents are treated separately from theothers, the most strin-
gent nitrogen, BOD and COD standards can be complied with under the best
conditions since the concentrations are high enough. A specific sewer network
. is therefore necessary. It will include preliminary sour water treatment by strip-
ping and oxidation due to the very high ammonia and phenol concentration.
General refinery effluents, with the following characteristics:
- relatively high flow rates: 300 to 1 000 m3/h and more,
- variable salinity, which is high when the ejfluents include deballasting
water,
- a low NH!, HS-, phenol and dissolved hydrocarbon content.
- relatively low soluble COD and BOD (BOD = 40 to 80 rng/l and
COD = 120 to 250 mgjl) 1,
- a relatively high insoluble hydrocarbon content (200 to 1 000 rng/l).
Treating these effluents by biofiltration separately from refinery process
discharges allows better adaptation to dilute BOD and NH~ contamination and
high salinity.
Spent caustic soda, which requires specific pretreatment before it is
incorporated in the other discharges.
Ion exchanger eluates, which will be discharged directly after they are
neutralized.

1. See Sections 19.2.2.3 and 19.2.2.4.

 C/'r:IJpMr 19. WATER ;:;EATl.IENT 645

The organizatloa of discharge sewer networks must be completed by a

large storage capadty..lt is designed to deal with accidental contamination due
to upsets in processing units, storms. maintenance shutdowns. etc. Refineries
usually have storage tanks ranging from 20 to 60 000 m3 . Their holding capac-
ity must be greater than 24 hours ot flow from the discharge network on which
they are independently installed. Specific tanks are located upstream from the
water pretreatment section and accommodate surges in accidental contami-
nation. In this 'Kay they minimize the damage that could be done to down-
stream treatments and also allow an off-specification effluent to be recycled
back upstream.

19.2.2 Characteristic Parameters

of Waste Water Treatments
19.2.1.1 Suspendal50lids (55)
Suspended solids are measured in France by the AFNOR T 90-105 standard
using a Millipor':! AP20 filter. They can be free (sand corrosion products, inor..
ganic prectpitates, ete.) or colloidal. .
Colloids (cr)nsiderable specific area. diameter of a few microns. elec..
tronegative cMrges) are subjected to electrostatic forces of repulsion that
keep them sus;;ended indefinitely. They are measured by turbidimetry or by
observing the ".olar of the" water.
In refinery ',,;aste water, two points are critical when suspended solids are
measured: '.

When th:: water is very salty. the sample must be diluted or the cake
formed 0", the filter must be washed before measurements are made.
The hydr .carbons, oils. greases (total He) are for the most part included
when the filter cake is weighed. thereby giving total suspended solids.
Dlssolutr..n of He by a solvent allows determination of nonoily sus-
pended ~")iids, called "true SS".

19.2.2.2 Hydr.,canons (He)

In France mea~urements are made today by infrared (IR) absorption. as stipu-
lated in standsrdlzed methods:
AFNOR T ,:..203: absorption at 3.42 urn,
AFl'\OR T ;(-114: cumulative absorption at typical wave lengths: 3.29 J.1m.
3.38 "urn. 2 <2 um and 3.50 .urn.
These twc methods measure Total Hydrocarbons: soluble and insoluble
tpatticle size ~reater than 1-2 micrometers). -To measure soluble hydrocar-
bons. the anavsis can be carried out on the filtrate obtained after passing the
sample on a ~"~illipore AP 20 filter which is used to measure the 55. The insol-
uble hydrocarions are calculated by subtracting soluble He from total hydro-
carbons. Prio- to measurement, both methods specify elimination of polar
646 ChaDter 79. WATER TREATMENT

compounds by FlorisiI. Calibration is performed on representative products

from the refinery waste water, -- -- - -
Since there are other standard methods of measurement. the hydrocarbon
content in water should always indicate the method used.

19..2..2.3 Chemical OXygen Demand (COD)

COD is measured in France by the AFNOR T 90-101 method and corresponds
to the oxygen consumption of a solution of hot refluxing potassium dichro-
mate over a period of two hours. It represents most organic compounds and
oxidizable inorganic salts such as many sulfur compounds.
After the sample has settled for two hours and the settled suspended solids
have been separated, the COD measurement of the settled water is called
CODad2 It corresponds to dissolved and colloidal material. The chlorides that
are oxidizable to chlorites must be precipitated out beforehand by mercury
sulfate in a ratio of 10 to 1 to prevent any interference. The COD equivalence
of the main inorganic reducing compounds is given in Table 19.5. ..
,

I Sulfides
Compound Ion COD (mg 0z.mg- 1)

2
Sulfur S 1.5
Thiosulfate S20~ 0.57
Tetrathionate S40~ 0.5
SuHite SOj- "0.2
Thiocyanate
i SuHocyanide SCN- 0.6-1.5
i CN-
f Cyanid~ 1-2.9

~ uble :"'i---------------~-----------'

19.5 i COD equivalence of inorganic reducing compounds.

19.2.2.4 Biological OXygen Demand (BOD)

BOD shows the ability of waste water pollutants to undergo biodegradation.

Exact BOD measurement is necessary in order to size a biological treatment
facility. It is measured in France by the AFNOR T 90-103 method. 80D 5 corre-
sponds to the oxygen consumption of a preseeded sample at 20C in darkness
during a five-day incubation period. A fraction of the carbon organic matter,
said to be biodegradable. is measured in this way.
 Seeding is usually carried out with municipal waste water sludge. but
should be done with biological refinery sludge to be strictly precise. The a.ro-
matic compounds, sulfooates and compounds that are only sUghttiv
biodegradable or have slow kinetics, or are- subject to particular inhibitic>n~
would then be taken into account. Only the soluble BODs is of any real inter-
est. since it aDows the biological treatment facility to be sized.

19.:.:.5 Odlu Charactcrisdcs

The theoretical oxygen demand (TOO), the total organic carbon (Toe) and t:.~e
permanganate oxidizability are also useful characteristics (Table 19.6).
.
19.2.2.6 Ni.....en Compaaads

These compounds include the following:

ammonia nitrogen (NHt) measured by the AFNOR T 9O-nlS method,
organic nitrogen (mainly DEA In refinery' waste water and urea in l.he
petrochemicals industry),
inorganic. nitrogen, mainly nitrates NOi and nitrites NOi.
Total Kjeldahl nitrogen (rKN) gives the sum of ammonia and organic nitlto-
gen. The total nitrogen is the sum of the TKN and the inorganic nitrogen. In
refining. the FCC condensates are the effluents most loaded in nitrogen.

19.2.2.7 Sullides and Mercaptans

These compounds are measured by silver electrode potentiometry with a
plateau at -700 mV for sulfides and -200 mV for mercaptans. Sulfides are fOUltld
in the form of HS NH4 in FCC condensates, and Na~ in spent caustic sodla
Sulfides become dissociated in water in the form of H;zS, HS- and S- (Fig. 19.11).
At a pH of 8.5-9, the dissociation of H~S is almost total (> 99.8%), odor is
slight and the risk of HzS stripping is low, -

19.2.2.8 PbaIols
Phenols are present in sour water, desalter 'blowdown and spent caustic so<ia.
Analysis methods can separate:
Phenols that can be stripped by steam. The standard measurement is
AFNOR T 90-204. These are the phenols that are usually measured ;:in
refinery waste water.
Total phenols, which also include heavy compounds that can not be ca..r-
ried off by steam.
Phenols are easily biodegradable. the required content (0.5 to 1.0 mgtI) ~s
easily achieved. -
648 Ctlap!er '9, WATER TREATMENT

! !
Compound !---- TOO - COD L BODs- I TOC
I -(mg C.ing-I)
I f'
Acids: ! I
Formic acid 0.35 0.35 0.25 0.26
Acetic acid 1.06 1.0 0.8 0.4
Benzenesulfonic acid 1.62 1.5 0-0.5 0.45

r
Aldehydes:
, !
Fannie aldehyde 1.07 1.06 0.6-0.8 0.4
I
Acetic aldehyde i 1.82 1.8 1.3 0.54
Benzaldehyde
Furfural
I! 2.42
1.66
1.9
1.6
1.5
0.3-0.8
0.79
0.62
I

Alcohols:
I
!
TBA I 2.59 2.2 - 0.64
Isopropanol 1 2.4 2.2 1.2 0.6
!
Methanol 1.5 1.4 0.9 O.3i
Ethyleneglycol I
I
1.3 1.29 0.8 0.39
I
I
Amines: !
MEA (monoethanolamine) \
1
2.49 1.3-2 0.8-1 0.39
1
DEA (diethanolamine) ! 2.13 1.6 0_2-0.4 0.46
I

j
Phenols:
i
Phenol 2.4 2.3 1.8 0.76
Cresols 2.52 2.4 r 1.6-1.8 0.46

Miscellaneous: I
I
II
i
I I
MEK 1.44 I 2.3 1.5-1.8 0.66
Acrylonitrile
Caprolactam
3.17
2.1
I
I
1.4
0.4
j
j

f
0.7
0.4
I
I
j
0.68
0.6-4
I
!
Ethylene oxide 1.82 1.74 1 0.1 I 0.54
Propylene oxide 2.21 ! 1.8 0.2
1
0.62
t 1
I
I
Isopropylether 2.8 1.5-1.7 0.2 I 0.7
MTBE 2.72 2.5 f - 0.68
I
j
"-

jTabk
19.6 I TOD. COD and BODsequivalence of various OX)'!JefIOIed compounds
(mg O2 per mg of compound).
 Non~ssociated
fraction

0.01 r
I
!

3 6 9 12 pH
It
: Figure
19.1 Dissociation ofH",s' HS- and CH]-<:H at 25'C

19.2.3 Process Condensate Stripping (Sour Water)

This operation is a pretreatment before recycle to the desalter or discharge to
the main water treatment section. It is required because of the very high ~~4
and H~ content in process condensates. It consists of (Fig. 19.2);
a. Preacidification with a strong acid (H2S04 or in some cases HCJ) in order
to achieve a pH of 5.5 to 6. At this pH, HS~H4 is dissociated into H~ and
0Hv2S0 -t 0

b. Steam stripping of the H2S and NH3. Since H~ is more volatile than ~1i3~
QC.
it can be stripped at 80 NH3 requires a temperature of 105C.. A packed
or trayed column is used with steam injection of 85 to 130 kg per m3 of
condensate.
Stripping is designed to eliminate 90 to 98;[ of the sulfides and 92 to 97?Q of
the volatile ammonia. Phenols are only slightly entrained and only 3O?o of the
combined ammonia is carried off. In order to remove the ammonia completely
a further stage must be imple-mented with a pH > 11 which aIIows the com-
bined ammonia to be converted into free ammonia. After stripping. the sour
water is mixed with the rest of the process waste water. Sour water raises
the sulfide content from 20 to 100 mg/I and the ammonia content from 100 to
200 rng I.
650 Chapter 19. WATER TREATMENT

Jncineration
Mists~ or
Claus

--+--of- Steam

L-- ....
Desulfurized
condensates

!~~~f
U Steam stripping of process condensates.

19.2.4 Oil in Water Separation

This is the first stage of the refinery's general waste water treatment opera-
tion..
The first function is to eliminate insoluble floating hydrocarboDs and
some of the very unstable mechanical emulsions. The aim is to protect
the systems located downstream (surge tan]; flotation) and keep them
running smoothly. .
The second function is to remove free, Don colloidal suspended solids
such as sand. corrosion products, inorganic precipitates. fine clays, etc.
These solids would alter proper operation of downstream systems (sed-
imentation in the surge tank, bottom sludge in the flotation sectlee), .
The third function is to accommodate.and store upsets and sometimes
massive amounts of He or 55 generated by accidents or improperly con-
trolled maintenance operations.
The amount of insoluble hydrocarbons at the preliminary oil separator
outlet can vary from 50 to 200 rng/l (100 rng/l on the average). The 55 con-
tent can range between 50 and 200" mg/l (100 mg/l on the average)..
Preliminary oil separation is commonly carried out by graviq oil sepa-
rators, which include two types:
- longitudinal "API" and circular separators,
- lamella "CP!", "TPS" and "PPI" separators.
 Chapltlr 19. WATER T~ATMENT 651
i
I
,lit !
(
. t
i

The first type are of simple design and provide good management of 5S and .,
bottom sludge management. However. the oil droplet cut is from 100 to
150 11m.. The second type are more compact and have an oil droplet cut point
of approDmately 50 JIm. However. it is more difficult to manage SS and sludge
since they require frequent cleaning.

t9.2.';'.1 LOngitudinal API Separators

These separators are designed according to an API (American Petroleum
Institute) standard. applied to the sizing and design of conventionallongitudi-
nal settlers (Fig. 19.3). Sizing takes the size of the oil droplets into account. The
cut point is usually from 100 to ISO J.1Dl.
:i

_____ Decanted
water

;
L ' Sludge
, Fi!!'llre:
I eo
i 19.3 API separator with a bottom scmping device.

Calculations define the length, width and water depth in the settler based
on the water and oil specific gravity and viscosity:
the width ranges between 1.8 and 6.0 m,
the water depth ranges between 0.65 and 2.40 m.
Most separators are fitted with surface oil skimmers, and API standards
recommend installing an extra separator basin to allow for drainage and main-
tenance. The surface oil is evacuated via .adjustable troughs or oleophilic
drums. Bottom scraping is always incorporated in new APIseparators and can
be performed with a chain driven or scraper bridge device (Fig. 19.4). These
separators are very commonly used in refineries.

1~.2.-f.~ Circular Separators

It is also possible to build circular separators similar in design to thickeners

with the oil recovered on the surface. This technique is increasingly appreci-
ated as a complement to old API separators without scrapers whose mainte-

!
t
L
652 Chamar J9. WATER TREATMEtvr

Screening

1 Isolating
penstock

.~_ OIeophiliC

F.=~~ S==~ drums

Oil Sttldge
bay hoppers

r-+1--- Adjustable trough

or drum
T

;~i:U~ I General layout of API separators (From API Manual).

~

nance is difficult and costly. The circular separator is installed as a bypass of

the API separators and deals with the permanent refinery flow rate.
Meanwhile, accidental discharges and storm rains flow to the old API separa-
tors. The circular separator provides good protectipn for downstream systems
and also allows bottom sludge to be recovered' in a single point and sent
directly to dewatering.

19.2.4.3 Lamella Oil Separators

These separators of the CPI (Corrugated Plate Interceptors), TPS (Tilted Plate
Separators) or PPI (parallel Plate Interceptors) type" use a set of parallel
plates, set at an angle of 45 to 60, incorporated in an oil separator (Fig. 19.5).
The advantage of the system is its compactness and oil separation effi-
ciency. The parallel plates reduce the average vertical rising route of the
oil droplets, thereby reducing the distance covered by a droplet before its
recovery. The plates also distribute the wafer better and promote droplet coa-
lescence.
In this system, a high density of plates with an in-between plate interval of
4 to 10 em makes the separator sensitive to deposits and wax, Consequently,
the plates have to be removed frequently for cleaning. The separators are suit-
 Oil Screen _

"I .....
) Rawwale<
-~, r- - -
1:1\! f1'
f"'\
II::;- \
~
\U
IH = f
I
I .... r---
i Decanted
-.. I: 0
I

~
:~
i water }

;I

J
!

I~ :
:
i
:
I I
/ ...I
~ - - - - - -1- - - - - - - - - - -
I
< I
t
.TraYieung
I drain
I I
ParaDel sand
plates pit

f10...- :.-' ---.1

:Fi~,
I
19.5 PPI separator.

able for treating clean process condensates. Preliminary oil separation also
protects surge tanks (see Section 19.2.1).

19.2.5 Catalytic OXidation of Sulfides with Air

Section 19.2.3 mentions a residual sulfide content of 20 to 100 mgfl in mixed
process waste water. This figure is too high to be compatible with proper oper-
ation of downstream treatments: it does not allow organic coagulants to be
used in flotation and is toxic for biological treatment. It must drop to 5 to
10 mg/l. This can be accomplished by catalytic oxidation of sulfides to thiosul-
fates S20j- with air in the presence of a ~1n:?"'. Fe>, C02+ or Fe 3+ as a catalyst.
Oxidation can be carried out either in the surge tanks or in an in-line reac-
tor with two in-series compartments and a residence time of one to three
hours. Surge tank oxidation allows for a long residence time (at least 24 hours),
which insures 90 to 95% efficiency both for sulfides and for mercaptans.
Additionally, a reduction of 20 to 40% in the effluent COD is also observed. The
pH is held at 8.5-9.0, thereby preventing H1S stripping during the operation.

19.2.6 Physicochemical Treatment

This treatment process follows preliminary oil separation and catalytic oxida-
tion of sulfides. It must be carried out before the biological treatment stage,
since biological treatment would not operate properly due to the over-content
of nonbiodegradable S5 (50 to 200 mg/l). Moreover, the insoluble hydrocarbon
content would not allow the bacteria to breathe. -The process assoclates a
chemical reaction and physical separation.
Mention will be made only of the most widely used treatments today, i.e.
coagulation-flocculation with one or two polyelectrolytes, separation by dis-
solved or induced air flotation and filtration.

19.2.6.1 Action of Chemical Substances

Chemicals allow conoidal suspended matter and emulsified insoluble hydro-
carbons to be eliminated. Coagulation is, performed by introducing a strong
cationic polyelectrolyte (type 2) or a Fe3+ or...A13+ salt. It breaks the electro-
static bonds of colloids and also breaks up fine hydrocarbon emulsions. The
destabilized micelles then come together by coalescence. Coagulants are used
in doses of 0.2 to 3 mg/J of active matter. Flocculation by adding a slightly
cationic polyelectrolyte (type 1) helps the oily "floes" grow (Table 19.7). The
flocculant dose is 0.5 to 1.5 mg/l as active matter. These chemical reactions
result in the formation of a sludge called "floc" that must then be separated
from the water by physical means.
Organic polyelectrolytes have an advantage over inorganic coagulants
(FeJ+ AI 3+) in that they do not increase the mass of sludge and induce good
t

sludge concentration. The most effective system is made up of two polyelec-

trolytes and a smaU dose of Fe-l+. However, the use of a type 1 polyelectrolyte
alone in flocculation is generally considered sufficient for a simple refinery.

Type Structure
I Molecular weight
I Commerdal form

Acrylamide and
t
i
Anionic
I
acrylic acid
copolymers
II .r
!
Nonionic
I
1
!
Polvacrvlamides
- II'
!
~ 106 to 107
I
, Hocculants
j Powders or emulsions
j Copolymers of ~ ,I
Type I cationic , acrylamides and 1

a cationic mono- i I!
mer
i : I
; ;

I Coagulant
Type 2 cationic : Melamine formal- ,
(coagulant) i dehyde ; 10 4 to 10 5 Aqueous solution or
I EPIDMA pol} l
emulsion
! DADMAC
EPIDMA: Epichlorhydrin dimethylamine.

--:I Table
Main types ofpolyelectrolytes.
i
I 19.7
 Chapter 19. WATeR TREATMENT 655

19.2.6.2 Physical Separation

a. DissolDftl Air Flotation (DAF)
This is by far the most commonly used system in Europe as it is the most effec...
tlve in retaining suspended solids and produces concentrated sludge that is
easy to handle and dispose of.. The association of chemical action (see
Section 19.2.6..1) and a OAF flotation unit is often called a flocculation flotation
unit. FFU. The treated water contains less than 5 mgjl insoluble hydrocarbons.
10 to 20 mg/I total hydrocarbons and 20 to 30 mgtl Suspended Solids. The sol-
uble fractions of hydrocarbons. COD and BOD and nitrogen compounds are
not treated when they go through physicochemical treatment. "
The OAF system works by sticking very fine air bubbles onto the "Iloc" (50
to 100 urn) and forming a very light sludge with a fast rising velocity, approxi...
mately 7 to 15 m/h in water. These fine air bubbles are produced by recycling
part of the treated water (20 to 50%) under a pressure of 4 to 6 bar, dissolving
compressed air in it to saturation, followed by controlled pressure release of
the water. The flotation cell is circular or rectangular, equipped with a device .
to skim off surface scum and scrape bottom sludge (Fig. 19.6).
DAF flotation units are advantageous in that they can perform a remarkable
thickening function with oily sludge, but also with biological sludge that may
be incorporated in the system, if the two types of sludge are given to serve the
same end use.
b. Separation by Filtration (Fig. 19.7)
Filters are of the downflow type on granular filtering material.. The filtering
material may be made up either of a homogeneous layer of sand or a layer of
anthracite on top of finer sand or garnet. Filtration usually proceeds under
pressure, in depth and retains suspended solids and insoluble hydrocarbons.
The cycle duration ranges from 8 to 24 hours depending on. design. An organic
coagulant or Fe3+ insures cohesion of the "cake" (fable 19.8). The SS/insoluble
hydrocarbon ratio must be higher than 2.
c. Induced Air Rotation (lAF)
This technique is more often used in North America, despite its inferior perfor-
, mance compared with the DAF system. After addition of a polyelectrolyte, insol...
uble hydrocarbons are eliminated by foaming through several in-series reac-
tors. Very high mixing energy is developed .in each reactor by a stator-reactor
that mechanically induces the formation of very large air bubbles (0.5 to 2 rom).

19.2.7 Aerobic Biological Treatment

At the outlet of the physicochemical treatment section, dissolved compounds
need
"still "to beremoved. i.e.: - -- -" ~ - - - "
soluble hydrocarbons,
soluble COD and 800,
phenol,
nitrogen compounds.
 en
(,J1
G)
Coagulation Scraper system Surge
tank column
Raw
waler i
!Ii

1
~
r
L ~
Treated
water
.. I ~
';}
c ~
"'
"3 ~
CJ)
ra
o .... ~
U S!
~
C'I1

Coagulated water
::
Heavy sludge Pump u

J
'(1)
disposal <3
Recovery of ~
ComP~esse~ .... ~<:ated sludge .. ~
air I '
I
Expansion I
valve
Dosing -..
pump

lLJ
Coagulant
Pr.lsurlzed
water
, ..
storago

FiKurc
19.6 I Flo/aZUl" industrial waste untter Ilotation unit.
 Filters

II I.
I
I ,. /0' "(" V "\ tV". ,
~ I n. _ .y_
_ I
f

I,
i 1
"--JI'----J
'
I
II
; I I
t---=---i

6
1 j I ~
A
I Raw

waler
I
Washing effluents
j
-
o
(

e:::::: 9

W WGil..--_---.-\
Dosage OAF unit for
Burning

Sloptank

Coagulant Flocculating washing efftuens

agent
L--- --J

Figure
19.7 Oity uiater filtration.

j 1
Insoluble He 55 J
Sz-
I
Type of emulsion (mg/I) (mg/l) I (mgJI)
\ Separation
.
I I
I

Cold mechanical
I
I
~

i I I Organic coagulant
20-100 20-50 < 10 I
+ filtration or fio-
i
emulsion i

,
i
I
I
tatlon

i ~
I Organic coagulant
Hot mechanical emul- ;
sian (4Q-90:C) 50-500 I <20 !, - + coalescence or
flotation < SO'::C
;

! i
i

I
t
I
20-300
Oxidation
I AI-Fe coagulant +
flotation
Chemical emulsion 50-200 , 50-100 : ;
;
10-50 I Fe coagulant -+- fIo-
i - -- -- i Precipitation I -tatton - ...
L! Table.
I I
~ ...19.8 i Range of physicochemical purificatioo processes for oily waste water.
658 C"':aD:~ 19 WATER TREATMef:7

19.Z.-;.1 Objectives
The soluble organic compounds in refinery waste water are highly biodegrad-
able. Based on the considerations in Section 19.2.2~ the following comments
can be made:
Soluble BOD is by definition biodegradable within the limits of efficiency
of the system used. .
Soluble COD comprises a biodegradable fraction, including certain com-
pounds such as MEK or furfural with slow degradation kinetics.
Depending on the biological system, these compounds may not be com-
pletely degraded. Soluble COD also contains a residual hard core 000-
biodegradable fraction, which varies depending on the refinery from 40
to 100 mg/l, This fraction is related to a low total organic carbon (fOC)
and can usually not be adsorbed on activated carbon any more than
around 30%. The precise nature of this residual COD has not been
researched but it is probably made up of sulfur derivatives.
Steam strippable phenol is highly biodegradable, with a residual content
of 0.5 to 1.0 mg/l. Heavy phenols and polyphenols are slightly biodegrad-
able.
Total nitrogen (TKN) is usually quite biodegradable. NH! is easily
degraded to NOj, and the DEA making up most of the organic nitrogen is
also degraded quite well. The final values depend on the efficiency of the
biological treatment system used. .
NOi is easily degraded to N2 Efficiencies of 80% have been achieved in
denitrification by activated sludge in anoxic tanks.

:9.2.7.2 Activated Sludge

"he principles of this well-known system, widely used in treating municipal
vaste water. can be summarized as follows. It is sometimes called DNB: deni-
.nflcanon, nltriflcation, biotreater; It can operate under reliable conditions
mly for a BOD content of over 150 rog/l, and this limits its use to process con-
lensates (see Section 19.1.1) in the refinery. It includes an aeration tank where
.acteria develop in suspended growth in the presence of air or oxygen, fol-
rwed by a secondary settler o~ clarifier. The clarifier has a dual function: clar-
ving the water and concentrating the activated sludge so that it can be con-
.nuously recycled upstream the aeration tank. Recycling allows an
ppropriate bacterial concentration to be kept in the tank (Fig. 19.8).
This technique treats carbon compounds measured by BOD, and TKN as
.ell when design and operating conditions allow. The TKN are usually
egraded to NOz and then to N0 3 by means of specific nitrifying bacteria.
hese degradation processes occur in the same tank. The oxygen required by
00 degradation and nitrification is provided by surface aerators or sub-
.erged air diffusers. Biological degradation of the BOD and TKN produces
-eycled biological sludge, which is periodically bled off to maintain the
eslred level of concentration.
 Aeration S~ndary
tank clarifier
.,
j\
Raw I \ j
J: TreateC
water
/ water

\ 7
SSrecyde
10 9.- 1
_- - Excess sludge
T
Dewatering ~ Thickener
~

2Og-I-1

IF' ~l
T
-..1

I 1':; i Biological treatment by actiuatedsludge.

Production of excess sludge, expressed in dry solids (OS), is estimated as

follows:
0.35 kg of DS per kg of BOD degraded,
0.23 kg of DS per kg of TKN degraded.
The excess sludge is usually bled off at a concentration close to l~. It is
then thickened by settling (static thickener) or by flotation (OAf) and then
dewatered with a centrifuge or a filter press.
Biological denitrification degrades the nitrates to gaseous nitrogen as
shown in the reaction below:
2NOj + 12H+ -+ N2 + 6H20

Degradation is carried out by activated sludge in an anoxic _tank.

Denitrifying bacteria use the oxygen from nitrates and feed on an organic sub-
strate. Biological denitrification therefore occurs:
in the absence of oxygen,
in the presence of assimilable COD with-a CODjN-N03 ratio of 3.6 mini-
mum.
To get maximum benefit from the assimilable COD in the raw water. the
anoxic tank is located upstream from the aeration tank. However; since
nitrates are produced during reactions in the aeration tank, 200 to 250% of the
activated sludge exiting this tank is recycled to the inlet of the anoxic tank to
provide nitrates (Fig. 19.9).
660 C-.at>cer 19, WATER TReATMENT

100 to 150~:; recycle Sludge at 1%

~------------------
I I Excess
:
r
200 to 500% recycle t -$iudge - ......
(
I
'f
Raw Anoxic Aeration
water tank tank

t
Figure
< 19.9 Activated sludge in nitrification-denitrification.

The design and calculation of activated sludge treatments in a refinery

must take the following into account:
the presence of phenols and compounds with slow degradation and spe-
cific seeding (MEK, furfural. DEA);
nitrification, which must operate in the presence of phenols and certain
inhibitors;
denitrification, which has only a slightly assimilable COD;
degradation. which must also involve aromatic compounds.
. Biological treatment by activated sludge is suited to process discharge
streams. After stripping, preliminary oil removal, catalytic oxidation of sulfides
in the storage tank and physicochemical treatment, waste water has the solu-
ble contaminant characteristics indicated below (fable 19.9). These values
comply with the most stringent legislation.

Before treatment After treatment

Soluble BOD (rng/l) 200 to 600 < 10

Soluble COD (mgjl) 600 to 2 000 < 100
TK.'" (mg/l) 50 to 200 < 10-15 Including NH, < 51
Table
19.9 Efficiency of biological treatment by activated sludge.

!~.2.;.3 Trickling Filters

These systems were widely used around 1980 and many refineries are
equipped with them. They are suited to the treatment of effluents with low
 C/'JapW'" WArc:.:l TREATUENT 661

BOD 100-150 mg/I), such as when all the effluents in the refinery are mlxed
in a common sewer. They are also suited to biological treatment of deballast-
ing water from oil tankers that have previously transpor(ed refined products.

a. Principle
Water trickles continuously through media in towers where air circulates
counter-currently by natural draft. The material needs to have a large specific
area and not be subject to clogging. It supports a thick bacterial film com-
posed mainly of aerobic cells similar to activated sludge along with anaerobic
cells from the digestion of part of the excess sludge.
Plastic packing is generally used. combining light weight and a large spe-
cific area. There are two types:
"
loose fill material, made up of rings or discs several inches in size (Pall-
ETA, Norton, etc.) (Ftg. 19.10),
ordered fill material made up of tubes (Cloisonyle) or frames (FIocor,
Plasdek).
Water is dispersed on the surface" of the bed by a rotating jet device, the
sprinkler, giving a hydraulic load of 1 to 4 m/h, Volume loads are from 0.5 to
2 kg of BOD per cubic meter of packing per day.

b. Operation with RefiJr.ery Waste Water

The simplicity of the system, often without a secondary settler. and the
absence of measurements and controls made trickling ~ers attractive in the

Sprinkler

_.....of+- FilHng material

Floor

---- - -......----......,~.
-J -
Air blowing
- ~ Treated_water

Figure
19.10' Circular trickling filter with loose fill packing.
662 C'7!:)te~ 19. WATER TREATMENT

past. This was despite some drawbacks which are less well accepted today.
such as.:
high clogging risks, especially with loose fill material, due to inadequate
treatment upstream or because the .anaeroblc bacteria produced by
sludge degradation have disappeared;
high probability of odors;
lower performance in terms of carbon contaminant degradation. espe-
cially with ordered fill material: efficiency between 50 and 70% of the
80D5 or the phenols;
nitrification is impossible or very difficult.
The last two points above result in waste water characteristics in the range
listed below for final discharge, depending on the refinery's complexity;
BODs: 20 to 40 mgjl
KTN: 10 to 50 mg/l
55: 20 to 40 mg/l
They do not allow compliance with stringent standards.

19.2.7.4 Biofilters (Biofor)

Biofilters have recently appeared on the market and can be compared to trick-
ling filters. However, the major drawbacks of trickling filters, i.e. odors and
clogging, have been overcome. The principle is to distribute the effluent from
a bottom distribution floor upward through a mass of granular material. A dis-
tribution system for air, supplied by air blowers, provides the oxygen required
for bacterial growth (Figs. 19.11 and 19.12).

,r

t-
i

t 02t 02t

__~:I~~?~~=
Process air f Washing water
1 _
SCouring air . ~ Raw water

Fiptre
; 19..11 - Principle of Biotor biofiltration.
- Figure j

.19.121 Biofor mod'*s.

The biological sludge produced is stored in the granular material. which

results in a low level of suspended solids in the treated water, The granular
material is periodically washed to remove the accumulated sludge. Biotor type
biofilters can be used:
As a substitute for trickling filters for better elimination of COD, BOD and
phenols (yield over 90%). They also allow retention and partial nitrifica-
tion of suspended solids (5 to 15 mgjl).
As a tertiary treatment. following activated sludge in nitrification-denitri-
fication, to recover periodic operating upsets to a certain extent and
thereby make performance more regular.

19.2.8 Tertiary Purification for Very Stringent

Discharge Standards. Recycling
The most effective way of meeting very stringent standards is to separate
refinery sewers into two categories: process related and general (see
Section 19.2.1). Biological treatment by activated sludge is then used on pro-
cess related effluents. Tertiary treatment by filtration of the Biofor type. sim-
ple filtration, activated carbon and ozone allow compliance with the most
stringent standards. 1bey also allow recycling to-be anticipated- . - .-
The simplest recycling treatment is performed for re-use as service water
and fire-fighting water circuits or as make up water in cooling circuits.
Approximately the same salinity and quality as new water can be restored to
the treated effluent by-using reverse osmosis or electrodialysis. The effluent
664 Cr.ac:er 19 WATER TREATMENT

can then be fed into demlnerallzatlon systems for boilers. -Total recycling is ~

technically possible. However, implementation requires a perfect understand-

ing of end-user circuits and a case by case approach to the problem.
Figure 19.13 gives a typical example of a treatment sequence in a refinery
whose effluents can comply with the most stringent standards.

Process-related General Deballasting Demineralized

effluents effluents water eluates

API

- Oily water
filtration

Activated sludge
nltrifteation Biofortype
denitrification biofUttation

,I
Simple
t
filtration
,.
!

~~; ~Pe- -:_ ~: - ~~~e-a;",~~t -~

:--blOhltfatjon -)0-

If JI If JI 1I

I _ _ _ _ _ _ _
---------L __T
Reve~e
I
t
t

., I1 OsmoSIS I
..1 ...

Demineralization
system recycle

o..-:----- ...J
I
' Figure
,19.131 Treatment scheme (or compliance with stringent standards.
t
 Chap. '9. WATER TREArien 66S

References
I Berne-E. Cordonnler J. (1991) Traitement des eaux. Editions Technlp, Paris.
2 Schleck 0.5. (1990) iVPRA Annual meeting. San Antonio. Vol. 4. 25/03/90.
3 Spencer C.L.. \Vatson L.A. (199;) Process optlmisatlon conference (Houston
8-10 Aprtl 199i). Hydrocarbon processing. 76. 6. 77-80, June.
4 Levenberger E. (1997) Informations chirnie 386. 74-79, March.

~.
 668 INDEX

supports, 8&88 Etherification. 291319

test pilot. 73 catalysts. 301
Catalytic cracking, 8. 169-227 economic data. 314. 316
catalysts, ]77. 185.210,211,214,21&-222 feed stocks. 294. 297
coke combustion. 208 processes. 298,303,305. 309. 310,313
conversion, 189 reaction mechanism. 298
economics. 223 reactors, 313
feeds. 2Q6..209 thermodynamics. 301
nuidization,l84-187 Ethers. 291.292, 295. 314
pnoducts, 173,174.179
reaction mechanism. 199204 Flexicoking.398-407
regenerator, 176. 183.208 chemical reactions. 399
severity, 189 economic data. 406
technologies. 192198 feeds.-399
thermal balance, 181184 processes. 400
yields. 191 products. 402
Catalytic cracking flue gas treatment. 177 yields, 400, 401
_ Catalytic reforming. 8. 101168 Fluid catalytic cracking. 17(}..198
catalyst coking. 128 feeds. 171
catalysts. 111, 121. 135, 138 products. 172, 174
continuous regeneration, 135. 153 reactor. 176
economic data. 163 regenerator, 176
feeds, 105, 106, 148 yields. 172. 173
industrial results. 124, 126, 157 Fluid coking. 398.400
pnocess. 104, 142, 145, I5~156. 158 economic data, 406, 407
reaction mechanism. 122. 123 feeds, 399
reactors, 148 low Btu gas. 405
reformate characteristics, 159 products. 400, 402
technology. 148, 153 yields. 400,401,403
thermodynamics, 113, 114, 117
Chemical oxygen demand. 646. 648 Hydrocracking, 44, 333-364,533
Chemica! reaction catalysts, 342. 346
- advancement (or molar extent), 13 economic data, 362
conversion, 14 feeds. 338.347.356,357. 359
selectivity. 14 processes, 334, 337.348
yield. 14 products, 354-357.359
Claus reaction, 594. 596 reaction mechanism. 340
Coke. 385.392,396, 406 thermodynamics. 341
fuel,387 Hydrodearomatization. 417
needle. 386 Hydrodemetallization. 413. 416. 533
Coke calcination. 396 Hydrodenttrogenatlon. 416. 533
Crude desaJting, 641 Hydrod esulfunzation. 46. 65. 413. 414. 533.
water Irom-, 640 542.551
catalysts. 424
Deasphalted oil. 359.360 processes. 562. 565
DeasphaJting,444 Hydrogen.444.451~501.492.551
Delayed coking. 381. 387. 389 by catalytic autothermal process. 495
economic data. 397 by partial oxidation. 480-491
feeds. 381, 388 by steam reforming. 455-465
products, 384. 387. 388 economics. -495
yields. 387 Hydrogenation. 533
DesuUurized fuel oils. 409 Hydrogen transfer. 202
Hydroisomerization,339
Enthalpy, 17 Hydrotreating. 66, 5~573
partial molar, 18 catalysts. 536. 546. 549. 553.556
variation ln-, 18. 19 chemical reactions. 538. 540
Ethanolamines. 468. 579-587 economic data. 569
 INDEX 669

feeds. 564. 566. 567 continuous stirred taDk. 34, S2

performance. 56-l emlllating bed, 437
pnJcesses.533.537.549.55S.568 entrained bed, 441
products. 536.. 53:. 567 fixed bed. 148.429
reaction mechanism. 341 for catalytic c:rackilJl,. 176
reactors. 558 moving bed. 153,435
thermodynamics. 540 one-phase. 47, 50
sesakontinuous, 52
Isomerization. 229-25d thfee..phase,47
catalysts, 231. 23;. 252 two-phase, 47
economic data. 2-17. 254 Refinery effluents, 642
performance. 239 Residue catalytic cracking, 196. 222
processes. 237. 2-11. 253
Residue hydroconversioa. 409449
reaction mechanism. 233. 252
catalysts, 418. 419
therrnodynaRdcs.231
cooversion, 427
economic data. 448
Low Btu gas. 405 feeds. 412
lube oils. 358~ 361 performances. 434..44l
Lumping. 13, 26. 44. ~5 processes, 411, 429.. 435,437,441
products, 441. 443
~ercaptans.503 reactor. 430
Metals in petroleum products. 173. 382. 53-t
Methanation of CO. -165. 473, 475. 488 Scrubbing
with amines, 579.. 5I'i
Nitrogen compounds. 347, 535. 543. 545. with a solvent. 578. S79
647 501 emission. 410. 624
Solvent. 575. 576
Octane number, 103. 110. 158. 174. 230. 259, discharges. 642
271. 293 regeneratton, 590
Oil separation. 650. 652 Spent caustics. "643
Oily water. 640 Stack gas denitrifica~ 636
Oligomerization.321-331 Stack gas desuJfurizatioo.,. 623-637
catalysts. 322. 323 processes. 625. szs, 627, 629. 631. 632.
economic data- 331 633,634
processes. 324.326. 328. 329 Stack gases, 625, 627
Oxidation of sulfur compounds. 609 Standard state, 17
Oxygenated compounds. 294. 297 Steam reforming, 455.. .fi8
catalyst. 457. 477
PartiaJ oxidation (see also HYdroge~) economic data, 497~ 498
feeds. 456. 466
economic data. 499
soot recovety.-I86 performance, 463
technologies. 481 reaction furnace. 461
thennodynanUcs.480 Sulfides. 647
PIN/A (paraffins. naphthenes. aromatics), catalytic oxidation. 506. 653
106. 122 Sulfur. 593. 604
Production production economics. 618
of aromatics. 162 recovery processes, 596-604, 609-611
of LPG. 163 storage. 605
tail gas treatment. 611-618
Radical. 30 transportation. 605
Reaction rate. 36. 1:!6 Sulfur compounds, 503.534.543
influence of temperature on-. 3:- Sulfur oxides. 623. 62-1. 626
with a solid catalyst. 39 Suspended solids (55).. 645
Reactor. 4j. 49 ..00 5~eetening.S03.509.510,532
batch. 33.51 catalysts. 511
continuous piug How. 31. 35. 52 economic data. 526-529
670 iNDEX

ftxed bed catalyst technology. 522 Visbreaking. 8. 365-379

liquid/liquid technology. 513. 518,0, ---
- economic data. 378 -
processes. 508-510. 512. 515. 518. 522. equipment, 373. 376
523.525 feeds. 365
processes. 366.3il
Synthesis gas. 455. 480
products. 368-370
composition at equilibrium. 480 reaction mechanism. 366
methanol washing. 488. 489 yield. 368
production. 455.480
Waste water. 657
Tail gases. 611 Water treatment. 639..fi65
treatment processes. 614-618
Thermal cracking. 414. 41 i' I Zeolites. 210-213. 216-219. 345