Choosing a selective hydrogenation
system
Data has shown the effectiveness of palladium catalyst for the removal
of diolefins and acetylenes in steam cracking as well as catalytic cracking
Ronald G McClung and Steve Novalany Engelhard Corporation
T
here are many applications for selective
hydrogenation catalysts and processes
within the petrochemical and petroleum
refining industries. The common source for
many of these applications is a cracking process
producing olefinic streams containing diolefins
and/or acetylenes that require removal by selec-
tive hydrogenation before further processing. For
the petrochemical industry the steam cracker is
the source of these olefinic streams and for the
petroleum refining industry the source is the
catalytic cracker.
The most common steam cracker selective
hydrogenation applications include acetylenes/
diolefins removal form C2s and C3s, vinyl acety-
lene and butadiene removal from C4s and diolefin
removal from C5+ pyrolysis liquids.
In the petroleum refining industry where gross
hydroprocessing is practised to make cleaner
fuels, the most common selective hydrogenation
applications are for the removal of diolefins from
either a C4 or C5 olefin stream. The catalyst tech-
nology applied to the treating of the C4 and
heavier streams is similar if not the same for
both industry segments. Even though base metal
catalysts are used at times for selective hydro-
genation, the majority of applications are based
around the use of a palladium catalyst.
There are some principles around catalyst and
reactor system selection that are common to
both the petrochemical and petroleum refining
applications for selective hydrogenation. In this
article, guidelines are provided for both catalyst
and reactor system selection for selective hydro-
genation of C4 and heavier streams. The effect of
contaminants, reactor flow direction, hydrogen /
reactant distribution, inlet distributor design,
www.digitalrefining.com/article/1000124
palladium loading as well as palladium distribu-
tion are discussed.
The most frequently used reactor system for
selective hydrogenation applications is a fixed-
bed system with hydrogen and liquid always
co-current but with flow direction (down-flow vs
up-flow) being the major question. Even for the
process in which a substantial exotherm is expe-
rienced, a fixed-bed reactor with attendant
product recycle is preferred over a tubular design
for its simplicity in loading, in normal operation
and in lower initial capital cost.
The primary criterion for choosing flow direc-
tion in a selective hydrogenation reactor system
with liquid and vapour mixed at the reactor inlet
conditions is gas/liquid molar ratio entering the
reactor system. Intimate mixing of hydrogen and
reactants at the point of reaction for each level
in the reactor bed is essential to making the best
use of the palladium catalyst as well as providing
good two-phase flow distribution.
Down flow reactors
A state-of-art distribution tray is needed for the
down-flow reactor system at possibly more than
one elevation within the bed. These reactor
systems are commonly called trickle bed reactor
systems because the liquid must move at a slow
rate over the catalyst particles while the hydro-
gen is co-currently moving through the bed void
space. These reactors work well in a narrow
range of flows around the original design rates.
However, as a practical matter, most operating
units in a refinery or petrochemical plant are
subject to “capacity creep” resulting in process
units being pushed well beyond their nameplate
capacities.
PTQ Q4 2002 1
 rates well above design rates are
Regeneration Off gas
E 104 limited. Operating at elevated liquid
To fuelgas
off gas or flare
to stack rates requires a much more complex
hydrogen distribution system,
E 103 including multiple injection points
C. W.
along the length of the catalyst bed.
For the most common, single-point
R 101 C. W. P 102
hydrogen injection systems, achiev-
T 101
Hydrogen ing good hydrogen distribution is
practically impossible when hydro-
E 101

Hydrogen- E 105
Steam gen rates are required in excess of
carbon
feed E 106 that dissolved at reactor conditions.
E 102 To alkylation
Poor hydrogen distribution leads
P 101
Steam to inadequate diolefin hydrogena-
C. W. tion. Consequently, at certain points
To alkylation in the reactor bed, polymer forms
causing reduced catalyst accessibility
and eventually excessive pressure
Figure 1 Upflow reactor system drop. Polymer formation leads to
shortened process cycles because of
Of course, as the liquid flow increases above premature catalyst ageing or high reactor pres-
the original design rate, the voids are gradually sure drop. Additional equipment for high
filled with liquid making it increasingly difficult temperature hydrogen stripping is required for
to maintain good gas/liquid contact. This mald- removal of polymer in order to extend the useful
istribution of reactants leads to poor catalyst life of the catalyst.
utilisation and potentially much shorter process In many cases, if a down-flow reactor opera-
run lengths. Nonetheless, the down-flow reactor tion is experiencing poor performance due to the
system does have significant advantages, includ- previously noted mal-distribution, the reactor
ing lower reactor pressure drop with un-fouled system can be converted to an up-flow reactor
catalyst bed and easier dumping for maintenance system to resolve the problem. Designs are
purposes. offered for conversion to an up-flow operation
However, the down-flow design has several requiring only a change of the external piping
disadvantages. For example, allowable liquid and no vessel welding. Having licensed over 30
selective hydrogenation process units since the
early 1980s, Engelhard has a strong preference
Symmetrical Symmetrical for an up-flow reactor design for reactor inlet
chords manifolds sectors manifolds gas/liquid molar ratios of 0.2 or less.
A typical flow diagram for an up-flow licensed
unit is shown in Figure 1. The preference for up-
flow design at low gas/liquid ratios (<0.2) is
supported by the long first cycles that have been
Concentric achieved in operations for the removal of trace
rings diolefins from a butene or pentene stream. Good
manifolds contacting of hydrogen and reactant and uniform
Vessel Vessel
wall wall gas distribution help minimise oligomers and
at bottom at bottom
polymers that otherwise would form, thereby
shortening the cycle.
Eight-year first cycles are not uncommon in C4
and C5 operations. This rationale readily extends
to higher carbon number selective hydrogenation
applications processes as long as the gas/liquid
Figure 2 Upflow hydrogen sparger system ratio is in the recommended range of 0.2 or less.

2 PTQ Q4 2002 www.digitalrefining.com/article/1000124

A summary of the merits and demerits of the up-
flow reactor system design versus the down flow
design are:

Merits 2–2.5 mm Inlet distributor

• Single point hydrogen injection works well and
simplifies hydrogen distribution system.
• Adequate design of hydrogen sparger ensures
good hydrogen distribution for hydrogen flow
rates that are in excess of that dissolved at reac-
tor conditions.
• Good hydrogen distribution minimises polymer
formation by maximising diolefin conversion.
Longer processing cycles due to minimised poly-
mer formation.
• When properly designed, capacities well in
excess of the original design (>2) are achievable.
Demerits
• Higher reactor pressure drop for the unfouled
catalyst bed.
• Reactor maintenance for dumping more
difficult.
• Reactor internals for support of catalyst are
more complex.
As previously indicated, uniform gas flow
distribution across the reactor cross section is
essential in both an up-flow and down-flow reac-
tor configuration. However, achieving uniform
distribution is made simpler in concept with the
up-flow reactor configuration. The simplest
sparger designs cover the reactor cross-section
with manifolds made of standard schedule
piping.
These manifold designs include a number of
symmetrical designs. Typical designs pictured in
Figure 2 are concentric rings, equal sectors or
chords, with each manifold containing orifices or
nozzles to ensure adequate pressure drop and
gas bubble size. Each of these symmetrical
designs represents a good common sense
approach to covering the entire reactor cross-
section. Engelhard prefers the symmetrical chord
design for its simplicity in fabrication and assem-
bly within the vessel and has developed this
inert media
Baskets
Catalyst
3–6 mm inert
6–12 mm inert
2–2.5 mm inert
media
Figure 3 Vapour phase downflow
to avoid the “bubbling bed” top layer as well as
bed lifting. If the bubbling bed phenomenon
occurs, the reactor bed is not lifted but a small
depth of catalyst at the top of the reactor churns
due to the high liquid velocities through the bed
voidage. This churning can lead to significant
catalyst attrition and precious metal loss. A good
hydraulic analysis including fluidisation calcula-
tions assures avoidance of this problem as well
as bed lifting.
Reactor vapour down-flow
Design of a reactor system for a vapour phase
operation is quite common in both the petroleum
refining and the petrochemical industries. A typi-
cal reactor is schematically represented in Figure
Flow
Extra long
longneck flange
46 cm min.

design for multiple reactor diameters. However, 1.25 cm slots,

a thorough analysis of the design must include area=2cross sect. Top of
of pipe catalyst bed
determination of sparger turndown capability,
number of spargers needed and orifice size,
placement and orientation.
Another design consideration for up-flow reac-
tors is selecting the reactor dimensions needed Figure 4 Downflow reactor inlet distribution vapour phase

www.digitalrefining.com/article/1000124 PTQ Q4 2002 3


Analysis of unregenerated palladium catalyst
History
Cycle length (months) 54
Appearance: Brown an interruption of the flows originating from the
Thermal gravimetric analysis (wt%)
Wt% loss at 20-200°C in air 1.71
Wt% loss at 200-370°C in air 5.71
Wt% loss at 370-1128°C in air 4.28
Trace element analysis (wppm)
Lead <4
Arsenic Not detected
Sodium >700
Silicon 120
Calcium 410 inlet distributor performance. More information
Chlorides <100
Sulphur 300
Table 1
3. The science around such designs is well estab-
lished. Nonetheless, the most frequent error in
reactor system design for this type of operation
is the reactor inlet distributor and its’ position-
ing relative to the top of the reactor bed.
Improper or inadequate design of the inlet
distributor can lead to catalyst attrition due to
excessive velocities or turbulence causing the
catalyst or inert bed cover to move around in the
top-most bed layer. The attendant increased
pressure drop problems can cause sig-nificant
downtime and resultant financial losses.
The most severe problems due to poor inlet
distributor design (Figure 4) can be avoided
using the following three principles:
• No process stream velocity out of an inlet
50
100 wppm S as EtSH
First order rate constant
40 100 wppm S as DMDS
10 wppm S as COS
for Butadiene
30
20
10
0
2.75 2.8 2.85 2.9 2.95 3.0 3.05 3.1 3.15 3.2 3.25
Inverse T, °K  1,000
Figure 5 Sulphur activity of various compounds
4 PTQ Q4 2002
distributor should be greater than that in the
incoming feed pipe
• Avoid excessive turbulence by having holes in
the bottom of the inlet distributor that provide
sides of the inlet distributor and rebounding
from the vessel wall
• Allow sufficient free board or distance between
the bottom of the inlet distributor and the
topmost layer of the catalyst bed or bed cover. A
distance of 46cm (18in) is the minimum.
A more rigorous and quantitative analysis
using computational fluid dynamics will give
design features that will further improve the
on distributor technology is discussed in a paper,
Reactor inlet distribution technology, presented
by R Rall at the Fixed Bed Reactor Seminar
Technological Institute at Antwerp, Belgium, in
November 2000.
Contaminant’s impact
All heavy metals and alkali metals in the periodic
chart when deposited on the palladium catalyst
used in selective hydrogenation are detrimental.
Some of the most frequently found contaminants
for selective hydrogenation catalyst are shown in
Table 1 for a commercial catalyst sample. For
long catalyst life, these contaminants should be
avoided. However if contaminated by caustic
from upstream processing, for example, while in
a liquid phase processing environment, some
recovery of activity can be obtained by water-
washing the catalyst.
The degree of recovery depends on the severity
of the contamination and the rigor with which
the catalyst is washed. Palladium cata-
lysts do not recover from heavy metals
contamination. Heavy metals (arsenic,
lead etc) are classified as irreversible
poisons to palladium catalyst.
Given the large investment necessary
for the palladium catalyst as well as the
attendant process equipment, investing
in adequate upstream feed preparation
is essential. Water-washes, sand or salt
filters, particulate filters are all impor-
tant equipment for minimising
contamination by particulate metals and
alkali metals as well. In the case where
metals are known to exist in the feed-
stock to be processed (arsenic, mercury,
www.digitalrefining.com/article/1000124
phosphorus or carbonyl sulphide), a
guard bed is recommended in front of the 140
palladium catalyst system. 0.026 kgs. of S/kg. of cat.
120
Sulphur-bearing compounds are the

First order constant for Butadiene

1.5 kgs. of S/kg. of cat.
0.026 kgs. of S/kg. of cat.
most common contaminant for palladium 1.5 kgs. of S/kg. of cat.
100
catalyst, even with all the feed prepara-
tion commonly done. Given the electronic 80
affinity of palladium for sulphur
compounds, different sulphur compound 60
structures have markedly different
40
poisoning effects as is illustrated in
Figure 5. Sulphur compounds listed in 20
order of poisoning severity on the rate of
diolefin saturation are as follows: 0
2.7 2.8 2.9 3.0 3.1 3.2 3.3
Carbonyl sulphide > disulphide >
Inverse T, °K  1,000
mercaptan.
H2S is not included because it is readily
removed from the process stream by Figure 6 Effect of sulphur on catalyst aging
either amine scrubbing or by caustic
washing. This work was conducted on pure Commercial cycle length and sulphur relationship
components doped to different concentration
levels with various known sulphur compounds.
Pilot plant of
In addition to affecting the relative activity of Commercial 1 Commercial 2 Figure 5
the selected catalyst, sulphur contamination is
the most significant contributing factor to short- Kg of sulphur per
ened cycle time or catalyst ageing. Generally, the kg of catalyst 0.076 0.05 1.5
effect on diolefin removal by feed sulphur can be Cycle length
mitigated by raising reactor inlet temperature. to date (mos) 15 54 6
However, long-term exposure to various sulphur
compounds does cause catalyst ageing and
consequently shorter cycle lives. From this same Table 2
pure component study the relationship between
catalyst ageing and sulphur exposure (as calcu- In addition to the previously mentioned pure
lated from kg of sulphur processed over the component studies, long term pilot plant runs
catalyst per kg of catalyst) can be illustrated. have also been conducted with various commer-
In Figure 6, the catalyst performance, as meas- cial C3/C4 olefin feedstocks at various butadiene
ured by first order kinetic rate constant for levels and with different levels of identified
butadiene conversion, is used to illustrate the sulphur species. Some of these feedstocks with
effect of sulphur exposure. The parameter for the hydrocarbon compositions and a breakdown of
two lines is sulphur exposure of 0.026 after 452 the sulphur compounds are listed in Table 3.
hours for the upper line and 1.5 after 3675 hours Table 4 is a summary of palladium catalyst
for the lower line. This effect is fairly dramatic performance on a variety of C3/C4 and C4 olefin
and represents significant ageing compared to a feedstocks. The effect of sulphur on catalyst
similar on-stream time for a commercial unit. performance can be seen by looking at the buta-
The lower line indicates performance that is at diene conversion on the lowest sulphur feed and
or beyond end of run for a commercial unit. the highest sulphur feed. Feedstock No. 3 with
Sulphur exposure comparisons are given in 1081wppm of sulphur has an average of 82%
Table 2 for two entirely satisfactory commercial conversion at an elevated temperature of 149ºC.
operations as well as the pilot plant runs. The In the just succeeding time period, the No. 4
inference from the data is that commercial unit feedstock with only 30wppm shows 100%
cycles will be much longer if limited only by conversion at a much lower reactor temperature.
sulphur. As an additional observation, note the perform-

www.digitalrefining.com/article/1000124 PTQ Q4 2002 5

 types and exposure duration are the
Commercial feedstocks used in pilot plant studies
most significant contributors to
catalyst ageing. Catalyst volumes
Feedstock I.D. A B C D E
Component Composition (mol/%) for commercial reactors are not
Ethane/ethylene 0.0 0.0 0.03 0.34 0.28 normally set based primarily on the
Propane 22.70 2.38 17.68 23.51 3.37 desired diolefin (or acetylene)
Propylene 24.05 1.13 22.68 27.26 1.76
conversion but on the desired cata-
Isobutane 20.34 26.56 21.80 19.52 10.47
N-Butane 10.85 9.26 14.80 8.80 17.05 lyst cycle length, which is in turn
Iso-Butylene 6.06 14.77 4.90 5.99 16.71 set by the known sulphur concen-
Butene-1 5.48 13.43 5.04 5.41 10.42 tration in the feed – assuming all
T-Butene-2 5.93 18.09 6.21 5.30 10.40
other contaminants to be under
C-Butene-2 4.27 13.16 6.30 3.58 8.14
Pentanes 0.04 0.36 0.0 0.0 10.92 specified limits.
Amylenes 0.03 0.47 0.30 0.0 7.190
Butadiene 0.25 0.39 0.26 0.29 1.05 Catalyst selection
C5-diolefins 0.0 0.0 0.0 0.0 0.72
The range of properties for
Contaminants (wppm as sulphur) Engelhard’s palladium-based selec-
Hydrogen sulphide 0.135 0.136 0.169 0.0 0.0 tive hydrogenation catalysts
Carbonyl sulphide 0.096 0.120 2.48 0.0 0.2 include:
Methyl mercaptan 0.425 0.125 0.530 14.37 63.9
Ethyl mercaptan 0.870 0.217 0.119 1.46 117.9
Densities: 673-961kg/litre
Di-Methyl sulphide 0.198 0.400 1.746 0.96 0.1
Surface areas: 5–100m2/gram
Carbon disulphide 0.292 0.448 1.157 0.59 3.1
Shapes: spheres and tablets
Dimethyl disulphide 12.191 0.0 3.337 4.96 178.1
Sizes:
Heavier Mercaptans
Spheres: 1.6mm and 3.2mm
& sulphides 0.0 0.0 0.0 0.0 717.9
Tablets: 3.2mm and 6.4mm
Total sulphur (wppm) 14.197 1.767 9.538 22.34 1081.2
Palladium concentration: 0.1–1.0wt%
Chemical state: reduced or unreduced.

Table 3 These selective hydrogenation

catalysts are offered under three
different designations that include
Palladium catalyst performance on commercial feedstocks
the HPN- series, the E-series and
the PGC-series. In view of the wide
Feed Hours Olefin Feed sulphur Reactor WHSV Feed Butadiene
ID on oil type wppm temperature butadiene conversion variety of catalyst properties from
(°C) wppm % which to choose, how is the best
1 611 C3/C4 2 81 4.5 3894 100 catalyst chosen for a specific selec-
2 2150 C3/C4 10 80 4.0 3176 98 tive hydrogenation process? In
3 4949 C4 1081 149 0.9 10585 82
4 5662 C4 30 80 4.5 8661 100 many cases, catalysts are selected
5 6274* C4 56 80 5.0 1860 95 because there is historical prece-
5 6274** C4 56 80 4.2 1875 100 dent, or a successful incumbent is
6 7430 C4 130 80 4.2 45624 100 being used in that service.
7 8246 C4 611 120 3.9 6373 77
8 8593 C4 30 80 3.5 14299 100 That kind of history is useful. On
the other hand, how was this
*At end of first cycle before regeneration **Second cycle after regeneration history established and what guid-
ing principles went into its
commercial application or its selec-
Table 4 tion for laboratory testing before
being installed commercially?
ance of feedstock No.5 before and after Several principles that can be used in determin-
regeneration. The palladium fully recovers from ing a specific catalyst to test in the laboratory or
the sulphur exposure of the previous cycle where install commercially for a selective hydrogena-
the cumulative sulphur was approximately 5kg tion application include:
of sulphur per kg of catalyst. • Palladium (Pd) metal content
In summary, sulphur compound amounts, • Pd penetration into support

6 PTQ Q4 2002 www.digitalrefining.com/article/1000124

• Support surface area
• Size and choice of the support
• Bulk density
• Unreduced vs reduced catalyst.
Palladium metal content is a parameter set
largely by the severity of service—meaning the
catalyst aging environment. Sulphur contami-
nants, types and levels in the feedstock have the
most impact on this choice in liquid phase oper-
ation. For vapour phase operation, sulphur
content and operating conditions are both
important.
Table 5 contains data illustrating the effect of
two palladium levels on catalyst performance.
The objective in pilot plant testing was butene-1
conversion to butene-2 as well as complete buta-
diene removal. Note that after a comparable time
on stream, the 0.1% palladium catalyst had
substantially deteriorated in performance. Even
though the process conditions are not exactly the
same, the kinetic rate constants account for these
differences. The rate constant values for the
0.3% palladium catalyst are over three times
those for the 0.1% palladium catalyst.
Catalyst analysis after the completion of these
parallel pilot plant runs on a commercial feed
are given in Table 6. The sulphur concentration
on the catalyst is the most important number
among those shown. Though the sulphur levels
on both catalysts are comparable, the sulphur
level on the 0.1% palladium catalyst was well in
excess of what the catalyst could tolerate and
maintain good performance.
In most selective hydrogenation applications, a
fully impregnated catalyst (metal distribution
throughout the substrate) is not required. Only
metal at a limited depth into the substrate is
needed for most applications. The combination
of palladium concentration and limiting the
depth of palladium penetration into the substrate
ensures metal accessibility for the hydrogenation
reactions.
Support surface area is a parameter selected to
minimise side reactions and assure metal access
after impregnation. The side reactions that are
to be avoided are polymerisation or oligomerisa-
tion reactions caused by the catalyst surface
acidity. In addition, size and choice of the
support is a parameter that is set based on activ-
ity requirements, and in some cases such as
vapour phase operation, the desire to minimise
pressure drop. There is more activity per unit of
www.digitalrefining.com/article/1000124
Metal levels effects on palladium catalyst performance
Palladium
Concentration (wt%) 0.1 0.3
H2/butadiene ratio 4.9 6.2
WHSV 5.0 4.6
Reactor temperature (°C) 80 79
Hours onstream 220 287
Butadiene conversion (%) 70.9 99.7
Butene-1 conversion 40.0 75.3
Butene-1 approach to
equilibrium 44.3 88
First order constants
Butadiene conversion 6.2 26.1
Butene-1 ATE 2.93 9.8
Table 5
Gas composition in a refinery using PuraTreat
continuously for approximately 15 months
Palladium
concentration (wt%) 0.1 0.3
Reactor Reactor Reactor
Reactor
Catalyst sample location inlet outlet inlet
outlet
Contaminant concentration (wppm)
Sulphur 1560 730 1700 1450
Sodium 650 700 114 700
Silicon 192 126 146 148
Iron 203 177 154 140
Table 6
reactor volume if a small diameter sphere is
used. Tablets are sometimes chosen to minimise
pressure drop and sometimes because the high
density allows much more palladium to be
installed in a fixed reactor volume. The bulk
density of catalyst chosen depends on a number
of factors. If minimising the cost of a reactor fill
is the primary criterion, choosing a lower density
support will help in accomplishing this goal. To
ensure that performance does not suffer, a higher
metals/low density catalyst could be used. If
maximising the amount of palladium in a fixed
reactor volume is the objective, the higher
density support will help in accomplishing this
objective. A higher metals concentration catalyst
will also help in reaching this objective.
The choice of unreduced versus reduced cata-
lyst is very process specific. The unreduced
PTQ Q4 2002 7

Interpretation of catalyst testing
Commercial unit Screening test
operating conditions operating conditions
Feedstock Butadiene and butenes Butadiene and butenes
LHSV 5 10
Reactor
temperature (°C) 50 50
Pressure (kg/cm2) 30 30
Hydrogen to
diolefin ratio 2 18
Feed sulphur (wppm) 20 0
Results of screening tests
Catalyst ID A B C D E
Diolefin removal (%) 100 100 100 100 100
Butene-1 Isomerisation 70 75 80 80 80
Butene losses (%) 15 12 10 9 3
Table 7
catalyst requires an in situ reduction with hydro-
gen-bearing gas and is generally more active
than the reduced version. The reduced version is
chemically reduced in the manufacturing process
and is used in applications where high initial
activity is not desirable. The chemically reduced
catalysts are best for those applications where
byproducts need to be minimised at startup or
the process equipment is not suited to the condi-
tions required for hydrogen reduction.
Role of testing
Substantial laboratory data has been developed to
assess catalyst performance in as nearly commer-
cial an environment as possible. The selection of
the conditions, the catalysts and the feedstock
were all done with the goal of the results being
directly applicable to commercial operation.
However, many operators may find such extensive
testing with multiple vendor offerings to be too
costly in both time and manpower. As a conse-
quence, many companies will use a screening test
to assess various catalysts.
This testing method is a good one as long as
its limitations are recognised and the processing
parameters are set at commercially realistic
values. If the catalysts are not tested in commer-
cially realistic conditions, the results are still
useful but care must be exercised in making
catalyst selection decisions based on the data so
generated. Table 7 contains a hypothetical case
to illustrate the need for caution in interpreting
screening test results.
8 PTQ Q4 2002
Note the commercial unit operating conditions
and the difference in those corresponding
parameters for the screening test. Space velocity,
temperature and pressure are either close or not
critically different. However, feed sulphur and
hydrogen/diolefin ratio are significantly different
and critically so, the latter being more important
in a short-term test where insignificant ageing
takes place. The question then arises, “Can these
results, though not obtained at commercially
practical conditions, be used for catalyst selec-
tion?” The answer to this question is “yes”, but
the conclusion reached without allowing for the
differences in operating parameters would be in
error.
Interpretation of data
Based on the data from Table 7, the best catalyst
would appear to be the one which meets the
commercial goal of maximum isomerization
while obtaining complete diolefin removal. The
catalyst selection guided by this principle would
be Catalyst E. However, these results (though the
ones desired commercially) were obtained with
non-commercial parameters of zero sulphur and
hydrogen well in excess of the stoichiometric
amount required to saturate the diolefin all the
way to the corresponding saturate (actually nine
times that needed).
In fact, it has to be concluded that of all the
catalyst tested, metal accessibility and dispersion
must be the poorest for Catalyst E because of the
low generation of saturates. No commercial
operation is going to consistently operate at an
18:1 hydrogen-to-diolefin ratio except in rare
cases at the end of the catalyst useful life. In
order to best interpret the data of Table 7, the
screening test must be seen not as one that will
mirror commercial performance exactly, but one
which measures the activity of the catalysts
based on palladium accessibility and dispersion.
These latter two catalyst attributes ensure, for
the commercial unit, the purchase of minimum
catalyst to achieve process objectives as well as
ensure maximum life with commercial feed and
under actual operating conditions. The correct
conclusion is that Catalyst A or B is the best for
the commercial installation. So, the screening
test is an excellent test but proper interpretation
of the results is essential.
In conclusion, catalyst selection and reactor
system selection for existing processes rely
www.digitalrefining.com/article/1000124
largely on what has worked before. The princi-
ples behind the choice being (to some degree)
irrelevant or ignored. Pilot plant testing also
serves an important role in the selection of cata-
lysts but caution must be used in the
interpretation of testing results.
Steve Novalany is Engelhard’s manager of manufacturing
technology and has extensive experience in the design and
licensing of the company’s selective hydrogenation process
technology. He has a BE in chemical engineering and an MS in
management science from Stevens Institute of Technology.

Ronald G McClung is manager of catalyst evaluation in the

Process Technology Group of Engelhard Corporation, Iselin, New
Jersey, USA. His experience includes over 30 years with various
Links
fixed and fluidised bed catalytic processes in the refining and
More articles from: BASF
petrochemical industries. He has bachelor’s and master’s
More articles from: Catalysts & Additives
degrees in chemical engineering from the University of Virginia,
FCC
Charlottesville, Virginia.

www.digitalrefining.com/article/1000124 PTQ Q4 2002 9