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Selective Hydrogenation
Catalysts
2
Selective Hydrogenation of C2 Cuts Liquid phase hydrogenation
Raw C2 cuts contain between 0.5 and 2% LD 273 catalyst has been developed specifi-
acetylene, which inhibits ethylene polymeriza- cally to obtain high propylene yields. Through
tion catalysts. The aim of C2 cut selective hy- optimized chemical and structural characteris-
drogenation is to reduce acetylene content as tics, LD 273 achieves efficient MAPD
low as possible while maximizing ethylene conversion, typically to less than 1 ppm, and
yield and minimizing oligomer (green oil) for- propylene yields surpassing 100%, green oil
mation. formation is suppressed and over-
hydrogenation to propane is minimized.
Axens’ catalyst for selective hydrogenation of
C2 cuts, LT 279, is a promoted, low palladium LD 273’s commercial performance compares
catalyst, supported on a special high purity well with that of its successful predecessor,
alumina. The highly efficient LT 279 reduces LD 265. Both catalysts demonstrate very effi-
acetylene concentrations to less than 1 ppm at cient MAPD removal, with effluent
low operating temperatures, providing out- concentrations around 1 ppm, with typical
standing ethylene yields, typically superior to MAPD conversions exceeding 99.99%. The
100%. Moreover, it drastically reduces green catalysts, however, have different palladium
oil production which results in very long cy- (Pd) contents; LD 273 contains less Pd than
cles. In front-end operations (treatment of C2- LD 265 and yet its selectivity is remarkably
cuts), its low tendency towards runaway reac- better as Figure 2 illustrates.
tions is a further advantage.
Propylene Concentration, %
Table 1 shows the performance of LT 279 in a
96 ∆ = 1.0%
typical commercial unit. Ethylene yield is in-
creased while acetylene is virtually eliminated.
Low High
acetylene acetylene 94
content content 95.5
3
Propylene Yield, % In refineries, selective hydrogenation of a FCC
102.0 C4 cut results in reduced acid consumption in
downstream alkylation plants and increased
MON of HF alkylate. TAME unit feedstocks,
containing essentially C5 compounds, can be
upgraded by means of selective hydrogenation,
101.0 ∆ = 1.1%
in order to limit gum formation in the down-
101.6 stream TAME unit and to increase TAME
production. Axens has developed optimized
100.5 catalysts for each processing option.
100.0
LD 265 LD 273 Selective hydrogenation of acetylene com-
Figure 3 - Increased propylene yield with pounds in raw C4 cuts for butadiene
LD 273 recovery
LD 273 obtains better performance, reducing The selective hydrogenation process to convert
oligomer and polymer formation by 40%. vinyl acetylene (VAC) and 1-butyne or ethyl
These materials hinder a reactant’s access to acetylene (ETAC) improves the efficiency and
the catalyst’s active sites and stifle the hydro- economics of downstream butadiene extraction
genation reactions. Also, LD 273 maintains its processes.
high performance longer, extending the cycle LD 277 is the ideal catalyst for this application,
length. achieving high acetylenes’ hydrogenation ac-
Vapor phase hydrogenation tivities and high butadiene yields as illustrated
in Figures 4 and 5. In addition, long catalyst
Axens catalyst for vapor phase processes, lifetimes are typical. LD 277 is applied in two
LT-279, makes use of promoted Pd on a high process configurations, with or without an
purity alumina carrier. LT 279 features highly acetylene removal column in the downstream
efficient MA and PD conversion even at low extraction unit. Figure 4 shows feed and prod-
operating temperatures, outstanding propylene uct butadiene concentrations in a commercial
selectivity and a drastically reduced green oil unit having acetylene removal columns.
formation, which results in very long cycles Butadiene content, %
The following table shows the typical perform- 47
ance of a commercial LT 279 unit for vapor
phase hydrogenation of C3 cut.
Feed Product
46
Propylene,% wt 91.2 93.4
Propane,% wt 5.3 6.6
MA, ppm wt 23 000 <1
45
PD, ppm wt 12 000 < 10
Feed Effluent
Propylene yield,% 102.4
Figure 4 - Selective hydrogenation with
MAPD conversion,% 99.97 acetylene removal columns (LD 277)
Table 2 - Commercial performance of LT 279 If acetylene removal columns are available
downstream from the hydrogenation unit, VAC
and ETAC conversions can be limited to 50%
Selective Hydrogenation of C4 and as shown in Figure 5.
C5 Cuts
There are several processing options for the
upgrading of a typical steam-cracker C4 cut
containing around 50% butadiene, 25% isobu-
tene, 20% butenes and 2% acetylenes,
depending on the market for the various C4
components.
4
VAC Content, % losses by a factor of ten. Lifetimes of several
2.5 years can be typically achieved. Moreover,
2.0
LD 277 tolerates the sulfur compounds that can
appear during plant upsets and which act as
1.5
inhibitors. The initial activity can be recovered
1.0 simply by restoring the feedstock quality to its
original specifications.
0.5
0
Feed Effluent
Selective catalysts for production of
Figure 5 - VAC conversion for unit configured butenes and iso-amylenes
with acetylene removal columns (LD 277)
Butadiene Content, %
Selective catalyst for 1-butene production
100
Conventional Pd-only catalysts have poor bu-
80 tene-1 selectivity because they significantly
promote 1-butene isomerization to 2-butene.
60
Axens therefore developed LD 271, a special
40
catalyst based on Pd and a promoter on an
alumina carrier, endowing the catalyst with
20
very high intrinsic selectivity. Axens’ LD 271
0
is suitable for the two major processing options
Feed Product concerning 1-butene recovery:
Figure 6 - Butadiene content still remains high - hydrogenation of raw C4 cuts containing
without acetylene removal columns (LD 277) around 50% butadiene,
With no acetylene removal columns available, - processing of C4 cuts after butadiene ex-
the acetylenes have to be converted more thor- traction, containing around 1% butadiene.
oughly to 100 ppm as seen in Figure 7. In both cases the targets are the same: reducing
VAC & ETAC Content, % butadiene content to the ppm range, achieving
1.2 high 1-butene yields, and minimizing 2-butene
1 and butane formation.
0.8
Even for a very severe product specification of
0.6
less than 2 ppm butadiene, about 50% of the
0.4 butadiene is converted to 1-butene, as shown
0.2
100 ppm
by the following industrial results for a butadi-
0 ene-rich unit.
Feed Effluent
Figure 7 - Acetylene conversion in a unit con- Figure 8 shows relatively steady concentrations
figured with no acetylene removal columns of butadiene and 1-butene in the feed over a
(LD 277) four-year period.
Concentration in Feed, wt %
In either case, LD 277 meets the specified con-
60
version of acetylenes while attaining high Butadiene
50
butadiene yields, around 101% and 93% re-
spectively. 40
30
Beyond activity and butadiene yield, catalyst
stability is a key feature for this kind of appli- 20
1-Butene
5
step is generally over 30%, i.e., two or three Feed Product
times the concentration in the feed. The 1- Butadiene, ppm 650 <10
butene increase is around 23% which corre- 1-Butene, wt% 22.2 3.2
sponds to about 50% of the butadiene in the
Trans 2-Butene, wt% 14.1 26.7
feed. Butadiene concentration in the product
cis 2-Butene, wt% 9.3 13.6
has remained consistently less than the 2 ppm
maximum specification. i-Butene, wt% 44.8 44.1
10 1.0
Table 3 - Commercial performance of
LD 267 R Catalyst
0 0
0 500 1000 1500
6
Table 4 shows typical performance obtained by petrochemical end use. Two process schemes
pretreatment with LD 2773 on feed to a com- are possible:
mercial TAME unit. 1. First stage pygas hydrogenation – This
Feed Product involves selective hydrogenation of most
of the diolefins and alkenylaromatics in or-
Sulfur content, ppm wt 90 90
der to meet gasoline pool stability
Diolefins,% wt 0.9 0.015
specifications.
3-methyl-1-butene,% wt 1.7 0.6 2. Second stage pygas hydrogenation – fol-
2-methyl-1-butene,% wt 9.4 7.1 lowing the first stage hydrogenation, this
2-methyl-2-butene,% wt 17.2 20.7 process removes the remaining diolefins,
Diolefins conversion,% 98 alkenyl-aromatics and olefins without aro-
Reactive amylene yield,% 104.5 matics hydrogenation, followed by
desulfurization to meet high purity aro-
Table 4 - Performance obtained with LD 2773 matic product specifications.
on feedstock to a commercial TAME unit
The trend toward more stringent environmental
The results show that LD 2773, despite the regulations concerning gasoline has led to a
high sulfur content, efficiently and selectively reduction in the amount of pygas in the gaso-
hydrogenates the diolefins and increases the line pool and to an increase in its use as a
overall yield of the two amylene isomers used petrochemical feedstock.
for TAME production, namely 2-methyl-1-
butene and 2-methyl-2-butene. Axens offers highly active, selective and stable
catalysts for both options.
7
Therefore, nickel catalysts must be inhib- Axens has extensive commercial experience
ited prior to start-up, by deposition of a with both Ni and Pd catalysts, including several
sufficient quantity of sulfur on the most ac- commercial references of Pd/Ni stacked beds,
tive sites. This sulfur pretreatment can be and was the first catalyst manufacturer to bring
carried out either ex situ, making the start- both Pd and Ni catalysts to the marketplace for
up safe and quick, or in situ. first stage hydrogenation units.
The reliable and efficient ex situ pretreat- LD 265 (based on Pd) and LD 241 (based on
ment developed by Axens and Eurecat for Ni) are Axens’ first generation catalysts. They
nickel catalysts is called ResucatTM. rapidly became the industry benchmarks owing
On the other hand, Pd catalysts are intrinsi- to their successful and dependable operation
cally selective and avoid aromatics and their, having achieved consistent customer
hydrogenation. satisfaction around the world.
Based on industrial feedback and extensive
3. Sensitivity to poisons
research and development efforts, Axens has
Nickel catalysts contain 20 to 50 times more recently developed a new generation of
more active metal atoms than Pd catalysts. catalysts, Pd-based LD 365 and Ni-based
For this reason, Ni catalysts are more toler- LD 341. Through improved physical and
ant to poisons than Pd catalysts, and chemical characteristics, LD 365 and LD 341
therefore they are preferred in case of achieve highest of performance levels:
highly contaminated feedstocks. Arsenic
- high conversion of diolefins, styrenes and
and mercury can be present in pygas
indenes
mainly when natural gas condensate are
- no conversion of aromatics
used as feeds to steam crackers; such con-
- low deactivation rates
tamination occurs more rarely when
- long cycles
regular naphtha is processed. Silicon con-
- very good mechanical properties
tamination is often related to the co-
- full regeneration potential
processing of imported feedstock stem-
ming from coker or visbreaker units. Axens’ portfolio of first stage hydrogenation
catalysts is exhibited in Table 5.
4. Sensitivity to sulfur compounds
Ni catalysts are more sensitive than Pd Relative Cycle
Trade Metal activity Relative length,*
catalysts to mercaptans, disulfides and
name per LHSV years
thiophenes contained in feedstocks. For volume
feedstocks with high sulfur content, Pd
LD 265 Pd 2 1.5 - 2 0.8 - 1.5
catalysts are generally preferred.
LD 365 Pd 3 2.5 - 3 1-2
5. Cost LD 241 Ni 1 1 0.5
Ni is generally less expensive than Pd. Pd LD 341 Ni 2 1.5 - 2 0.8 - 1.5
catalysts contain in general between 0.2 - * Values obtained on full range gasoline i.e., C5-200 °C
0.5% wt of the precious metal, whereas Ni
catalysts contain between 10 - 20% wt of Table 5 - First stage hydrogenation catalysts
Ni.
Commercial experience with LD 365
In conclusion, the choice between Pd and Ni
catalysts depends on several site-specific con- There are many successful commercial applica-
straints among which are: feedstock tions of LD 365. A typical example is a pygas
characteristics, product specifications, unit unit in Germany designed by others. This unit
characteristics, Pd vs. Ni price differential. features a single first stage reactor catalyst bed
A further option is to load the reactor with with no quench and a liquid recycle stream
stacked beds: Pd catalyst on top and Ni catalyst distributed on the top of the bed. Before
at the bottom of the reactor. The advantage of switching to LD 365, the unit operated using
this option is that it combines the benefit of the LD 265. The average feedstock characteristics
Pd catalyst’s higher activity with the above- are given in Table 6 and the average first cycle
mentioned advantages of Ni catalysts. results are compared in Table 7.
8
Diene value, g I2/100 g 25 LD 365 was developed not only to improve
Bromine number, g Br2/100 g 70 diolefins hydrogenation activity but also to
Sulfur, ppm 60 improve the hydrogenation of styrene con-
tained in the pygas. Figure 11 presents
Table 6 - Average feedstock characteristics commercial results and shows that with
LD 365, styrene conversion levels are main-
LD 265 LD 365 tained between 80 and 90%. These levels are
Diene value, g I2/100 g 1 0.5
much higher compared to LD 265, for which a
maximum 70% styrene conversion was possi-
Bromine number, g Br2/100 g 60 60
ble. The improved styrene conversion is
Aromatics loss,% 0 0 beneficial for the second stage hydrogenation
First cycle, days 200 > 300 cycle lengths.
Table 7 - Effluent characteristics and first cy- Styrene Conversion, %
cle length for LD 365 compared to LD 265 100
90
The specified product Diene Value (DV) of 1.2
g I2 / 100 g was reached in the past without 80
Days on Stream
9
First Cycle Length, Months Pressure Drop, bar
0.80
10
0.60
8
0.40
6
0.20
4 0.00
0 50 100 150 200
2 Days on stream
10
- pressure drop increase is less than 0.05 bar Axens for Advanced Catalytic Solu-
- very efficient sulfur removal, as shown by tions
the outlet thiophene content of less than
0.05 ppm wt. The catalysts described in this brochure are
Reactor inlet temperature, °C enjoying considerable commercial success. In
282
fact, over the years Axens has become the
281
world’s leading supplier of hydrogenation
280
processes.
279
There are many reasons for this enviable posi-
278
tion:
277
• State-of-the-art production facilities in
276
Savannah, Georgia and Salindres, France
275
0 500 1000 1500 2000 2500 3000
• R&D support from one of the largest and
Hours on stream most capable organizations in the world
Figure 15 - Constant activity of LD 145 and • Huge bank of experience and industrial
HR 406 in stacked bed reactor system feedback acquired in a period of over fifty
years
Pressure drop, bar • Extensive and responsive worldwide sales
0.8
network
We are determined to enhance our position by
0.7 offering our customers continuously improved,
reliable, and up-to-date products and services.
0.6
0.5
0.4
0 500 1000 1500 2000 2500 3000
Hours on stream
Figure 16 - Pressure drop through LD 145 and
HR 406 stacked bed reactor system
Thiophene in Outlet,
ppm wt.
0.10
0.08
0.06
0.04
0.02
0
0 500 1000 1500 2000 2500 3000
Hours on stream
Figure 17 - Very low thiophene concentration
in effluent from LD 145 and HR 406 stacked
bed system
April2003/PPV
11