Naphtha to diesel via novel routes

I
ncreasingly, refners are having to look for
alternative ways to dispose of naphtha.
Traditional markets such as petrochemical
naphtha sales are suffering competition from
Middle Eastern gas-based steam crackers. Also,
given the considerable amount of spare gasoline
production capacity in the world refning system,
opportunities to export regular gasoline to
markets such as the US will continue to decline
and reduce the opportunity to incorporate naph-
tha into the gasoline pool.
Rebalancing of the refnery product slate away
from naphtha/gasoline towards diesel is required
to meet the projected global diesel demand.
Dieselisation is a term commonly applied in the
oil refning industry to the practice of shifting
yields towards diesel by a combination of crude
selection, low-severity fuid catalytic cracker
(FCC) operation, and increased hydrocracking
and residue upgrading.
More radical options, which are explored in
greater detail in this article, include the conver-
sion of naphtha to heavier distillates via steam
reforming and subsequent middle distillate
synthesis, or polymerisation (oligomerisation) of
cracked naphtha material. Case studies based on
an average European refnery confguration and
crude feed indicate the potential that could be
achieved.
Outlook
Growth in demand for diesel is outpacing that of
gasoline, and the global diesel balance appears
to be tightening. So, if refners cannot export
gasoline, how about naphtha? Naphtha is also
under pressure and, with signifcant world-scale
ethane-based steam crackers continuing to come
on-stream, the market for export naphtha is
expected to reduce. European naphtha-based
David Gibbons Foster Wheeler
steam crackers have also become less
competitive.
1
All of these drivers come together and give
increased impetus to the shift towards diesel
production. However, rather than looking at
ways to increase diesel only, this article looks at
ways to achieve both an increase in diesel output
and a decrease in naphtha and gasoline
production.
Average European refnery
Before looking at some of the options, let us
consider an average European refnery
2
based on
average crude and downstream process unit
capacities. This refnery has both an FCC unit
and a hydrocracker, with a visbreaker for residue
www.digitalrefning.com/article/1000074 PTQ Q3 2011 1
An unconventional, synthetic approach to converting LPG and naphtha
components could boost diesel production
Capacities, kbpd OGJ average
2
Model
Crude 135.7 136.0
Vacuum 55.9 55.0
Visbreaker 14.1 19.0
FCC 21.2 19.3
Catalytic reformer 20.2 21.2
Hydrocracker 11.6 11.2
Alkylation 2.3 2.3
C
5
/C
6
isomerisation 5.3 5.3
Average European refnery confguration
Table 1
Product bpd ktpa
LPG 9280 289
Naphtha 9939 423
Gasoline 34 005 1471
Diesel 56 907 2733
Average European refnery confguration
Table 2
upgrading. This is a simplifcation, of course,
since most European refneries have only one
main vacuum gas oil (VGO) upgrading unit, but
there are a handful of sites that do, in fact, have
such a confguration.
Assuming an average crude slate of North Sea
Brent and Middle East Arab Light, and with the
chosen process units, there is a good match
between this average feedstock and the average
refnery, based on a simple generic refnery
model with typical product cut points (see
Table 1).
With this confguration, an average 135 000 b/
d refnery already produces more diesel than
gasoline, although the total of LPG + naphtha +
gasoline is about the same as diesel (see Table
2). Production of jet/kerosene is minimised.
Using average 2010 crude and product prices
(based on a typical value of $80/bbl crude),
there is around a $20/bbl differential in the
price of diesel above that of gasoline.
3
If the
average refnery can achieve an extra 10% of
diesel production, this could be worth around
$40 million annually. However, this gives us
only around $200 million as a reasonable invest-
ment (assuming a generous fve-year simple
payback). Therefore, the challenge is to fnd the
appropriate simple, low-cost technologies to
achieve the desired increase in the diesel-to-
naphtha plus gasoline ratio.
Dieselisation: conventional (easier) options
Some of the easier options that refneries can
consider are crude selection, cut points, operat-
ing mode and catalysts.
Crude selection can make a large difference,
but there are other constraints on a refnery that
can limit the choice. Refneries typically produce
diesel material from the jet/gas oil boiling range
of 180360C TBP cut point, but can effectively
go a little higher with upgrading facilities, such
as a mild or even a full hydrocracker processing
VGO, or a visbreaker, for example, processing
atmospheric or, more usually, vacuum residue.
With the average refnery confguration as
before, it might be possible to achieve up to 10%
more diesel output by the appropriate choice of
crudes, but, again, the confguration limits the
ability to process varying yields of intermediate
products and their sulphur contents, while main-
taining crude throughput.
A number of process units are designed with
2 PTQ Q3 2011 www.digitalrefning.com/article/1000074
some ability to switch from gasoline to diesel,
such as the FCC unit, or from naphtha to diesel,
such as a hydrocracker. However, there is a limit
to what refneries can achieve and how far they
can go with operational changes. Catalyst addi-
tives or complete unit catalyst inventory changes
are often required.
If we consider the FCC unit, refners can drop
conversion and increase light cycle oil (LCO)
yield, but this is a poor-quality component with
many qualities that need upgrading. A typical
LCO cetane number is around 20, compared to a
range of 4060 for straight-run and hydroc-
racked distillates, which is much closer to the
fnished product specifcation of 51 or above, and
sulphur content is usually far above 10 ppm for
the fnished product. While the FCC unit contrib-
utes around 20 vol% to the gasoline pool, LCO is
only 5% of the diesel pool, and with operational
changes a refner might achieve an increase in
overall diesel production of perhaps only another
5% overall.
Dieselisation: conventional options
bottoms-up approach
If an existing refnery has already achieved as
much as possible in terms of crude selection and
operation in diesel mode, traditionally refners
would take a bottoms-up approach. For instance,
they would look at technologies to break or crack
larger, higher boiling point components into
smaller, lower boiling point components.
If a refner already has a visbreaker and a
hydrocracker, they might typically look at adding
a coker to give more conversion than a
visbreaker, or a residue desulphurisation (RDS)
unit to produce additional distillate.
While using a coker instead of a visbreaker can
give a large increase in diesel output (perhaps
30%), it also produces more LPG, naphtha and
gasoline components, which all require addi-
tional treatment. A vacuum RDS (VRDS) unit
can also give a sizeable increase in diesel
(perhaps 20%), but, again, produces more of the
lighter components. Another option is to include
a solvent deasphalting (SDA) unit, but this
provides only a small increase in overall diesel
production (23%).
Gasifcation is rather an extreme solution for
residue upgrading within a refnery, but it does
introduce the idea of using synthesis gas, or
syngas, which is covered later in this article.
2 PTQ Q3 2011 www.digitalrefning.com/article/1000074
One fnal bottoms-upgrading
option to consider is residue FCC
(RFCC), but, on its own, that will
do the opposite of what we want
and produce overall more gaso-
line and light olefns, and lead to
a reduction in diesel make.
As the conversion level increases
in these conventional bottoms
upgrading processes, so do capital
investment and operating costs.
Many smaller European refneries
would struggle to justify the cost
of these relatively small process
units, which would not have the
beneft of economy of scale that
world-scale units would have.
Dieselisation: unconventional options
frst requirements
The previous section gave a very brief overview
of conventional investment options, but what
about some unconventional approaches? First,
refners should consider again what it is they are
looking for. Ideally, they want to convert naph-
tha and gasoline boiling range material into
diesel boiling range material, and could also
consider the use of LPG as an additional compo-
nent for conversion.
But what are they looking to create? What are
the important qualities of diesel? We have
already mentioned boiling range, but one key
quality is cetane (number or index), which is a
measure of the ignition delay in a diesel engine,
with higher values producing a shorter delay
with more effcient combustion. This encourages
refners to consider the chemical nature of the
many components that comprise a typical diesel
fuel. Cetane is the reverse of octane, such that
low-octane normal paraffns have the highest
cetane, followed by branched or iso-paraffns,
then olefns, naphthenes and fnally aromatics,
which are really the worst cetane components to
be included.
It is interesting to note that the density range
of diesel is very narrow, 820845 kg/m
3
or
0.820.845 SG. And, of course, refners want
minimal sulphur and prefer not to have any
aromatics.
Diesel quality: carbon number
Now that we are considering the chemical nature
www.digitalrefning.com/article/1000074 PTQ Q3 2011 3
of diesel, we should look at what chemistry
might be involved. If we look at the ideal boiling
range of 180360C, it is clear that we need to
consider molecules with between 1022 carbon
atoms.
Figure 1 (derived from various sources
4,5
)
shows lines for n-paraffns and 1-olefns, which
are easy to plot, but iso-paraffns and other
components fll a broad band in the middle due
to their many isomers. So, we are looking for
roughly 10 to 20 carbon atoms in our molecules.
Diesel quality: hydrocarbon species
The very narrow density range was mentioned
earlier, and Figure 2 (derived from various
sources
6,9
) shows the very small window of
acceptable EN5907 diesel quality that we are
aiming for, compared with the wide range of
cetane and density that is possible from the
different molecular species.
It is clear that there is not one component that
will work on its own, but instead we need a
blend of different components; for example,
some of the simpler (mono-branched) iso-paraf-
fns and alkyl-benzenes.
Another important consideration is that, in the
context of an existing refnery, any new diesel
components that can be created will be blended
with a much larger existing diesel pool (contain-
ing a blend of hydrotreated straight-run and
hydrocracked diesel, often with a proportion of
hydrotreated and hydrocracked kerosene), so a
refner can afford to be off-specifcation in some
properties.
300
400
350
250
200
6 8 10 12 14 16 18 20 22 7 9 11 13 15 17 19 21 23 24
C

,
t
n
i
o
p

g
n
i
l
i
o
B
Number of carbon atoms
150
1-o|ens
Mono branched parafns
n-a|ky| benzenes n-parafns
Bi-cyc|ic
Figure 1 Diesel component properties
Dieselisation: unconventional options
second requirements
So what are we starting from? Ideally, refners
want to take the LPG and naphtha components
(especially if any are in surplus) and convert
them. They would be starting from components
with between three and 10 carbon atoms, and
the sources are those streams that go to the
naphtha pool, as well as streams that go to the
gasoline pool.
Refneries produce mostly paraffnic naphtha
from a crude unit and hydrocracker, plus
aromatic and olefnic gasoline components (from
the catalytic reformer and FCC unit respectively).
Using unconventional routes, we want to make
simpler iso-paraffns (mono-branched) and alkyl-
aromatics or alkyl-cycloparaffns and blend these
new components into an existing, conventional
diesel pool.
Unconventional options: how do we get there?
Top-down approach
In contrast to the bottoms-up approach of the
refner, we can consider the top-down approach
of the chemist by synthesising desired molecules
from smaller molecules. There are two routes
and two different chemistries to achieve this.
Oligomerisation is the joining together of
molecules, and this could be thought of as poly-
mer diesel, or poly diesel, similar to poly gasoline
that has been used on a small scale for gasoline
production in some refneries. (By January 2011
in Europe, there was 47 000 b/d
of polymerisation capacity
2

compared to gasoline demand of
1.9 million b/d.
8
Polymerisation
therefore represents around 2.5
vol% of the European gasoline
pool.)
There are technologies and
ongoing research to take a light
olefn (propylene or butene in
olefnic LPG) and react it with a
heavier olefn, such as C
5
/C
6

olefns in light FCC naphtha. The
product itself is olefnic, and it
would need saturating with
hydrogen to make a normal
paraffn in order to avoid diesel
fuel stability problems through
oxidation of olefns and resultant
gum formation.
Another technology that extends existing tech-
nology (for example, cumene) is to take these
olefn components (from LPG and FCC light
naphtha) and react them with aromatics (in
reformate and FCC heavy naphtha) using
aromatics alkylation. These components would
be hydrogenated to produce alkyl-cycloparaffns.
But, as the cetane/density chart indicates (see
Figure 2), some of these components are a little
low in cetane.
For the ultimate in top-down chemistry, we
could go back to basics and consider synthesis
gas, which is available relatively cheaply from
naphtha steam reforming rather than gasifca-
tion, but downstream refners could employ
conventional Fischer-Tropsch (FT) synthesis
technologies. Such technology could be referred
to as naphtha to (other) liquids, or NTL.
Some theoretical yields
Create from two smaller molecules
Returning to the average European refnery, a
refner can take olefnic FCC LPG and light naph-
tha and create some poly diesel. The refner
could achieve 50% conversion of the FCC light
naphtha olefns, limited by the availability of
propylene, and be able to produce an additional
4% diesel production overall with, of course, a
corresponding decrease in LPG and gasoline
production.
Alternatively, the heavier FCC olefns (C
7
+)
could be reacted with aromatics (alkylation).
4 PTQ Q3 2011 www.digitalrefning.com/article/1000074
60
100
120
80
40
20
700 750 800 850 900 950
C
e
t
a
n
e

n
u
m
b
e
r
Density, kg/m
3
0
EN590
limits
1-olefins
n-paraffins
n-cetane
Bi-cyclic
Mono branched paraffins
i-cetane
n-alkyl benzenes
Figure 2 Hydrocarbons contribution to diesel quality
Again assuming only 50% conversion, and the
fact that the availability of propylene is limited,
an additional 5% of diesel overall might be avail-
able via additional alky diesel.
Of course, both steps could be taken, at which
point the availability of the heavier olefns would
set a limit, although this could be overcome by
also considering dehydrogenation of C
5
+ paraf-
fns. Based on the average European refnery
confguration, both steps might give an increase
of around 7% in diesel production overall.
Although RFCC on its own was earlier
dismissed as a residue conversion option, the
fact that it creates high yields of light olefns, as
well as heavier olefns and aromatics, could help
create the right balance of these components to
maximise poly diesel yields in a refnery upgrad-
ing confguration.
Back to basics
The other unconventional route, NTL, uses a
conventional steam reformer and a conventional
FT process, but put together in an unconven-
tional way. A steam reformer designed for
methane feed normally gives too much hydro-
gen, with a H
2
:CO ratio of 3:1 compared to the
ideal ratio of around 2:1 for FT feed. But with
higher hydrocarbons, and typically with a
straight-run naphtha feed, the H
2
:CO ratio is
closer to 2.1:1 and therefore ideal for FT.
10
While FT is not considered in detail in this
article, we can say that low-temperature FT (LT-
FT) is better suited to higher yields of diesel.
11

However, in the same way that poly diesel or
alky diesel is not ideal, FT diesel is also
constrained by what is commonly referred to as
the cetane/density/yield triangle. While refners
cannot maximise all three, they could aim for a
high yield and high cetane, and compromise on
density, as they would be blending these new
components into a conventional refnery diesel
pool, which is typically constrained more by
cetane, and where there might be an opportunity
to introduce more high-density components to
the blend.
Assume LT-FT
Considering the average refnery and taking
paraffnic napshtha to make syngas, a refner
might achieve yields based on a syngas feed of
50% diesel and 20% kerosene, with a typical LT-
FT plant targeting maximum distillate. The
remaining yields (on syngas feed) could typically
be 25% naphtha and 5% Cs and lighter, and
since the naphtha is highly (95%) paraffnic it
would make a suitable steam reformer feed.
Assuming that some of the kerosene would be
blended into the diesel, and assuming up to a
60% diesel yield from LT-FT, this would give an
overall increase in diesel of 8% for the average
European refnery.
Another point to consider is that FT processes
can create olefns as well as paraffns, and with
the optimum scheme it may be possible to
supplement the requirement of the heavier
olefns for poly diesel or alky diesel production.
www.digitalrefning.com/article/1000074 PTQ Q3 2011 5 4 PTQ Q3 2011 www.digitalrefning.com/article/1000074
Kerosene
Diesel
Naphtha
PP/BB
splitters
Steam
reformer
Oligomer-
isation
Aromatics
alkylation
LT
FT
Hydrogenate
Hydrogenate
FT
refinery
Diesel
Kerosene
Diesel
PT liquids
Kerosene
Diesel
Naphtha
Naphtha
Sat. LPG
>50%
olefins
PCC
LPG
C
3
, C
4

Naphtha
PCC
Light naphtha
>50%
aromatics
>70%
aromatics
CCP
Naphtha
SP, HCP
Naphtha
Syngas
2:l
PCC
Heavy naphtha
Figure 3 From naphtha to diesel via oligomerisation, aromatics alkylation and low-temperature Fischer-Tropsch
Maximum potential: combined oligomerisation,
aromatics alkylation and LT-FT
Figure 3 shows how to get from naphtha to diesel
with a combination of:
Oligomerisation
Aromatics alkylation
Steam reforming and LT-FT
where light and heavy olefns, and light
aromatics are converted into higher carbon
number paraffns and other components of poly
diesel, alky diesel and FT diesel, and where a
refner might be able to achieve greater than a
10% increase in diesel production, with a corre-
sponding reduction in LPG, naphtha and gasoline
production.
Conclusions
The demand/supply outlook is more positive for
diesel than for naphtha and gasoline, making
increased diesel production an attractive oppor-
tunity. However, there is a limit to what can be
achieved with an existing refnery in terms of
crude selection and operating modes.
A conventional bottoms-up approach would
look at adding a coker or residue hydrocracker,
which can yield signifcantly more diesel, but
these are also high-cost upgrades.
This article has discussed some unconventional
top-down approaches to convert lighter LPG and
naphtha components via poly diesel, alky diesel
and FT diesel, and there are some good syner-
gies between the processes that could be
exploited.
A number of supporting technologies would be
required to produce the fnished diesel compo-
nents. While the total cost could still be a hurdle
to a refner who might have only $200 million to
invest in an average European operation, it is
clear that some existing technologies and
ongoing developments could be applied in an
unconventional way to address the issue of
dieselisation.
This article is based on a paper presented at the ERTC 15th Annual
Meeting, Istanbul, 29 Nov1 Dec 2010.
References
1 Davis A, Outlook 10: Mideast naphtha capacity casts shadow
over Europe, ICIS News, 24 Dec 2009.
2 2010 Worldwide Refning Survey, Oil & Gas Journal, 6 Dec
2010.
3 ICIS Pricing 6-month delay sample spot price data, www.
icispricing.com.
4 Yaws C L, Thermophysical properties of chemicals and
hydrocarbons, 2008, ISBN 978-0-8155-1596-8.
5 Diesel Fuels Technical Review, Chevron Products Company,
2007.
6 Compendium of Experimental Cetane Number Data, NREL,
Sept 2004 (Ref: NREL/SR-540-36805).
7 European Norm (Standard) EN590:2004 Automotive fuels
Diesel Requirements and test methods, CEN (European
Committee for Standardisation).
8 Data from IEA Oil Market Report, 12 Apr 2011, www.
oilmarketreport.org.
9 De Klerk A, Fischer-Tropsch Refning, PhD thesis, University of
Pretoria, Feb 2008 (Ch 9, Fig 15).
10 Ibid. (Ch 5, Sec 2,2,1).
11 Ibid. (Ch 5, Fig 6).
David Gibbons is a Principal Process Consultant in the Business
Solutions Group at Foster Wheeler in Reading, UK, where he
undertakes refnery and petrochemical plant feasibility and
confgurations studies for clients.
6 PTQ Q3 2011 www.digitalrefning.com/article/1000074

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