Overview on C2 and C3 Selective Hydrogenation in Ethylene

Plants

Edgar L. Mohundro
Consultant

Prepared for Presentation at the

American Institute of Chemical Engineers
15 th Ethylene Produces Conference
2003 Spring National Meeting
New Orleans, LA
March-April 3, 2003

Session: Ethylene Plant Technology

C2 and C3 Hydrogenation Technology Review
64a

Unpublished

AIChE shall not be responsible for statements or opinions contained in papers or primed
in its publications

531
Introduction

This paper will provide an overview on C2 and C3 selective hydrogenation operations in

ethylene plants. The primary focus will be on selective hydrogenation of acetylene. The
reason for this is that most C3 selective hydrogenation units installed since the mid-late
1970's are liquid phase units. For the most part, the details about the design and
operation of liquid phase processes are proprietary, licensed technology.

This is an overview paper, providing background information for the succeeding papers
in this session. The following papers will cover in more detail some experiences and
know-how with acetylene and/or C3 selective hydrogenation within ethylene plants.

Acetylene and C3 hydrogenation units are purification steps for ethylene and propylene.
Trace levels of acetylene, methyl acetylene (MA), and propadiene (PD) are formed in the
steam cracking furnaces. The amount of acetylene and MAPD formed is a function of
the furnace feed, along with furnace design and operating conditions. Acetylene will
fractionate with ethylene; MAPD will fractionate with propylene. These components are
only tolerable at < 1 ppm in polymer grade ethylene and propylene.

The overwhelmingly dominant method for removal of acetylene and MAPD is through
selective hydrogenation. With few exceptions, acetylene hydrogenation is carried out, in
vapor phase, adiabatic fixed bed reactors. The number of beds ranges from 1 to 4, with
intercooling. Acetylene hydrogenation is also done with isothermal tubular reactors.

Liquid phase C3 hydrogenation became the "process-of-choice" around the mid-70' s.

The dominant process is an adiabatic, fixed-bed, liquid phase system. Some C3 liquid
phase hydrogenation units have isothermal, tubular reactors. Many vapor phase C3
hydrogenation units are still in service.

During past Ethylene Producers Conferences (EPC), there have been several papers that
deal with acetylene and C3 hydrogenation and the impact of contaminants on these
operations. These are good reference documents. They are given in the "List Of
References" for this paper.

This paper will cover the following items"

Acetylene Hydrogenation
¢" Options for locating hydrogenation units within ethylene plant sequences
¢' Pros/Cons for Each Location
¢" Operating Strategy
¢" General Design Comments
¢" Promoted Catalysts
¢" Theory of Acetylene Hydrogenation
¢" Green Oil
¢" Comments on Contaminants
¢" Regeneration Considerations

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 General Comments on C3 Hydrogenation

Safety Considerations

Acetylene Hydrogenation

The basic requirements for acetylene hydrogenation units include the following"

• Safe operation; e.g., no exothermic runaway reactions; no "hot spots" during

operation
• Maintain acetylene in ethylene product below specification. The typical
maximum is 5 ppm; however, ethylene customers may expect the acetylene level
to be maintained below 1 ppm; perhaps, below 0.5 ppm.
• Do not be the cause of interruptions to continuous operation of the ethylene plant;
e.g., a target for continuous operation may be 5+ years.

Some secondary requirements or "very strong wishes" are:

• Operating with a net gain of ethylene; the higher, the better.

• "Low investment cost"---within the context of the overall cost considerations for
ethylene plant investment, project execution, feedstocks, energy, etc.
• Good catalyst life and reasonable catalyst cost

L o c a t i o n w i t h i n the E t h y l e n e P l a n t P r o c e s s S e q u e n c e

An acetylene hydrogenation unit can be located at one of several locations within the
ethylene plant sequence. There are two major designations for these locations: These
are:

• Front-end
• Tail-end or Back-end

In the Front-End category, there are several possibilities. These are:

• DeC2 overhead in a DeC2-1st process sequence (Figure 1)

• DeC3 overhead in a DeC3-1st process sequence (Figure 2)
• Raw Gas: within the process gas compressor circuit, downstream of the caustic
tower (Figure 3)

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A subset for types of front-end hydrogenation units deals with the type of catalyst. The
dominant catalyst is Pd-based, with the "modem" catalyst being bimetallic, palladium
promoted with a second metal; e.g., with silver.

Another type of catalyst is sulfided NiCo. This catalyst was introduced 40+ years ago for
front-end hydrogenation units. This catalyst operates with inlet temperatures that range
from about 350 F (~175 C) to 450 F (~230 C). Sud Chemic still offers this catalyst,
C-36, as a replacement catalyst for the "high temperature" units still in operation. This
paper will not cover this type of selective hydrogenation unit. Major debits for this
process are"

• The NiCo catalyst must be presulfided and maintained in a sulfided state via
continuous injection of sulfur, in form of H2S, ethyl or n-butyl mercaptan, or
DMDS,
• Typically, this hydrogenation unit operates with an ethylene loss.

The Tail-end or Back-end hydrogenation unit is associated with a demethanizer-first

(DeC 1-1 st) ethylene recovery sequence. This unit is located upstream of the
ethylene/ethane splitter, on the net D e C 2 0 / H . (Figure 4) At the tail-end location,
hydrogen is injected into the reactor feed; whereas, with front-end hydrogenation units,
all the hydrogen produced in the cracking furnaces is in the reactor feed.

Comments about Acetylene Hydrogenation at V a r i o u s L o c a t i o n s w i t h i n

Ethylene Plant Process Sequences

Front-End: Overhead of a Front-end DeC2

The feed to this hydrogenation unit contains the C2 and lighter material. The feed is very
rich in hydrogen and ethylene, particularly if the furnace feed is ethane. The only
unsaturated reactants in the feed to this reactor are acetylene and ethylene. Some pros and
cons about this location include the following:

Pros:

• Clean stream; i.e., no traces of BD to cause catalyst fouling

• Do not need a spare reactor
• High concentration of H2 suppresses green oil formation
• Reactors are smaller, relative to the front-end D e C 3 0 / H system

534
Cons"

• High concentration of H2 may result in the operation being sensitive to initiation

of ethylene hydrogenation; this may result in exothermic runaways
• Stability of operation is sensitive to CO fluctuations. This is because there is no
MAPD in the feed to provide additional moderation.

Front-End: Overhead of a Front-end DeC3

The feed to this acetylene hydrogenation unit contains the C3 and lighter material. The
feed is somewhat rich in hydrogen and ethylene. The primary difference between an
acetylene hydrogenation unit in this location and one located in the front-end D e C 2 0 / H
is the presence of MAPD in the feed. Some pros and cons about this location include the
following"

Pros"

• Clean stream; however, there is the potential for the feed to contain traces of BD
• Moderately high concentration of H2; this suppresses green oil formation
• Presence of MAPD provides additional moderation that inhibits hydrogenation of
ethylene, and hence, mitigates against exothermic runaways
• About 50 % of the MAPD is hydrogenated; essentially all of this is converted to
propylene. This also means that any downstream C3 hydrogenation facilities will
be smaller.

Cons"

• Acetylene plus MAPD impose a higher "load" on the reactor. This translates to
higher overall heat rise, increasing the rate of catalyst fouling.
• Traces of BD may be in the converter feed; this will bring about additional
catalyst fouling.
• May be difficult to operate without a spare reactor for continuous operation of 5+
years.
• Reactors are larger than for front-end D e C 2 0 / H units

535
Front-End" Raw Gas Location:

This reactor is placed within the process gas compressor circuit, downstream of the
caustic tower, but upstream of the main driers. Hence, the feed to this acetylene
hydrogenation unit is wet C5 and lighter, containing some C6's. Historically~ this unit
was designed for operation with sulfided NiCo catalysts. This type acetylene
hydrogenation unit was installed in many ethane crackers designed/built in the mid
60' s/early 70's.

For many years, Pd or Pd/promoter catalysts were not considered for this service. Some
reasons for this include concerns that Pd-based catalysts were not "sufficiently rugged"
for this severe service. In addition, it is known that water inhibits the activity of Pd
catalysts, and it is known that water tends to increase the formation of green oil across Pd
catalysts. However, our industry know-how is now such that ethylene plants are being
designed and/or retrofitted with Pd/promoter catalysts in raw gas acetylene hydrogenation
units. Hence, there have been some recent grass-roots designs with Pd/promoter catalysts
in raw gas units, and there have been some conversions from sulfided NiCo to
Pd/promoter.

Pros:

• This operation will result in hydrogenation of C4 acetylenes and BD, hence

minimizing the potential for fouling at bottom of downstream DeC2 and/or DEC3.
• Converts the majority of C3 and C4 acetylenes and diolefins into olefins, making
the final C3 and C4 streams more attractive for fuel gas, and/or for recycle
cracking.
• Contributes to other cost savings within the ethylene plant; for illustration, this
allows for the elimination of a set of guard driers.

Cons:

• Catalyst deactivation can be relatively rapid, especially for the first bed° This is
primarily due to the presence of C4 and C5+ acetylene and diolefins. Hence, even
with Pd/promoter catalysts, a spare reactor system is needed for continuous
operation of 5+ years.
• May be difficult to maintain operation with an ethylene gain, especially if catalyst
is sulfided NiCo
• Some acid species may be formed across the reactor. This may result in having to
deal with downstream corrosion concerns.
• For sulfided NiCo catalyst, it is necessary to have a spare reactor system, along
with facilities for insitu regeneration, reduction, and presulfiding. There are
environmental concerns with handling sulfiding agents such as n-butyl mercaptan,
ethyl mercaptan, DMDS, etc.

536
Tail-End Location

The primary characteristics that differentiate this system from front-end systems are:

• The feed is C2's, the O/H of a backend DEC2.

• Hydrogen is controllably injected to each bed; typically at molar H2/C2H2 ratios
between 1.2 to 2.2.
• Green Oil, oligomers of acetylene, causes fairly rapid catalyst deactivation.
• There will be spare reactors with facilities for insitu catalyst regeneration and
reduction. (Figure 5) Each reactor may be regenerated about 1-4 times a year.

Tail-end acetylene hydrogenation is one of the final steps in the recovery and purification
of ethylene to produce polymer grade ethylene. This C2-stream may contain 0.5 to 2.5%
acetylene. Some concerns/considerations with tail-end acetylene hydrogenation include:

Acetylene will be upgraded to ethylene and downgraded to ethane and green oil
(oligomers of acetylene, mostly C4's with small amounts of C6 to C20+ material)

• Tail-end units have downstream green oil (C6+) removal facilities

Unreacted H2 in the reactor effluent must be removed via a pasteurization section

at the top of the ethylene/ethane splitter or via a downstream secondary
demethanizer

The character of the catalyst changes throughout the cycle. This change is
primarily due to heavy green oil lay down on the catalytic sites. This change is
temporary. The catalyst is "rejuvenated" via insitu steam/air regeneration
followed by reduction with hydrogen.

The character of the catalyst undergoes slow "permanent" changes through online
operation and on being subjected to repeated regeneration. Catalyst life is 5+
years; perhaps, even 20+ years.

Economic considerations drive operators toward optimizing tail-end

hydrogenation units to maximize ethylene gain; however, this can make the
operations vulnerable to acetylene breakthrough. An acetylene off-spec incident
may result in an substantial production loss of ethylene; e.g., perhaps 1000+ Tons°
This is because it takes several hours to eliminate acetylene from the
ethylene/ethane splitter inventory.

A presentation to the 1999 EPC (Ref 34) is a good source for more information on the
advantages and/or concerns with locations for the acetylene hydrogenation unit within
ethylene plant sequences.

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Operating Strategy
The operating strategy for acetylene hydrogenation units is primarily based on staying
within the operating window for selective stable performance. (Ref. 5, 6, 34, 35, 36) This
means that acetylene will be hydrogenated, completely, and the hydrogenation of
ethylene will be minimized. If the catalyst activity is too low, then acetylene leakage will
occur. If the catalyst activity is too high, excessive ethylene hydrogenation will occur.
The "location and size" of the operating window are affected by several parameters.
These include"

• Inlet temperature
• Amount of hydrogen
,/ For front-end units, this parameter is the hydrogen partial pressure.
¢" For tail-end units, this parameter is the H2/C2H2 ratio.
• Inlet acetylene, ---and inlet MAPD for front-end units located in D e C 3 0 / H
• Level of CO
• Space velocity .... more of a problem for front-end units
• Trace catalyst poisons
• Catalyst type, e.g., promoted catalysts have larger operating window
• Condition of catalyst; e.g., new, old, history of runaways, amount of time online,
etc.

Front-end Acetylene Hydrogenation:

For front-end units, the only control parameter is the inlet temperature for each bed. Bed
outlet acetylene level is used for feedback control of the inlet temperature. CO
fluctuations in the feed present a control problem for these units. In addition, the
operation becomes unstable at low space velocities; hence, the flow through the reactors
must be maintained above a specified minimum.

Tail-end Acetylene Hydrogenation:

There are two primary control parameters for the reactors at this location: Inlet
temperature and the H2/C2H2 ratio. Occasional changes may be made to the amount of
CO being injected into the reactor feed. Movement "above" the operating window can be
effected not only by increasing inlet temperature, but also by injecting too much
hydrogen. High temperatures and/or high hydrogen injection rates will lead to non-
selective performance, and consequently, acetylene leakage.

More information on modeling and control of acetylene hydrogenation units can be found
in References 21 to 26.

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General Design Comments"
For front-end adiabatic units, the following provides illustrative design parameters"

Space velocity for each bed: 8000-12000 V/V/Hr--Gas Volumetric Hourly Rate
@ Std Cond./Cat. Vol.
No.of beds in series, with intercooling:
¢" Feed acetylene at/below 5000-6000 ppm: two beds
¢" Feed acetylene between about 6000-7500 ppm: three beds
¢" Feed acetylene between 7500-10,000 ppm: four beds

For tail-end adiabatic units, the following design parameters may apply"

Space velocity for each bed: about 4000 V/V/Hr

No. of Beds in series, with intercooling:
¢" Feed acetylene at/below 5000 ppm: one bed
¢" Feed acetylene between 0.5 and 1.7%: two beds
¢" Feed acetylene between 1.7-2.5 %: three beds

More information on design/operating parameters for acetylene hydrogenation

parameters can be obtained from the catalyst vendors and/or from References 34 through
36.

Promoted or Bimetallic Acetylene Hydrogenation Catalysts

The "modem" or current generation of selective hydrogenation catalysts are often
referred to as being promoted or bimetallic. (Ref. 8) Dow first reported the use of
palladium/silver bimetallic catalysts for acetylene hydrogenation in 1957. (Ref. 1)
However, Chevron Phillips and Sud Chemie gave the commercial impetus to bimetallic
catalysts for acetylene hydrogenation by introducing a Pd/Ag catalyst into commercial
service on the O/H from a front-end DEC2. (Refs. 2, 5, 6) This was done in the early
'80's. This work was aimed at achieving more stable, selective catalyst performance in
service on a front-end DeC20/H stream.

Chevron Phillips continued research on acetylene hydrogenation catalysts such

that they now offer proprietary catalysts, designated "E Series" catalysts. (Ref. 5,
10, 34) These catalysts have been commercialized in several services; e.g., front-
end DeC2 O/H, front-end DeC3 O/H, and raw gas.

Sud Chemie offer a "family" of Pd/Ag catalysts for all front-end services and for
tail-end acetylene hydrogenation. (Ref. 6, 35, 36) Sud Chemie's front-end
catalyst is designated G-83C. Their tail-end catalysts are" G-58C, G-58D, G-58E,
G-58H, and G-58I.

539
 Kataleuna offer a from-end Pd/promoter catalyst designated 7741R. Their
catalyst for tail-end service is 7741 A/F. Kataleuna do not provide information
about the type of promoter used in formulating these catalysts. (Ref.34)

Axens offer LT-279 for front-end and tail-end applications. Axens do not provide
details on the promoter used in formulating this catalyst. (Ref. 3, 8)

BASF offer HO-21 for tail-end acetylene hydrogenation. This catalyst is Pd,
promoted with Ag. The support is silica oxide.

Details on the physical and chemical properties for these catalysts can be obtained from
the vendors.

Here are some points on catalyst design taken from a paper by Chevron Phillips at the
1993 Ethylene Producers Conference: (Ref 5)

The most active and selective catalysts occur when almost all of the Pd is within
300 microns of the surface.

The addition of silver to the "Pd skin" catalyst offers a trade of a small loss in
catalyst activity for a large increase in selectivity activity.

There is an optimum silver loading" too much silver, while increasing selectivity
reduces the activity to unacceptable low levels.

Silver reduces the impact of variability in Pd distribution within the catalyst

pellet.

Comments on the Theory of Acetylene Hydrogenation

From the standpoint of an industrial operation, the theory of acetylene hydrogenation is,
at best, imprecise. It is not possible to draw upon a well-formulated, well-understood
body of science and apply such information to the industrial environment. There are a
number of reasons for this:

The primary one being the conversion of acetylene to green oil. This causes a
change in the performance of the catalyst throughout a cycle. The change is much
more rapid for a tail-end hydrogenation unit.

540
 Another reason is that most reported scientific information is for academic
conditions; that is, with "new" catalysts, operating at low pressures, for short
periods of time on synthetic feeds.

The concentration of palladium deposited on the support is so small, e.g., 150-500

ppm; hence, it is very difficult to characterize these catalysts.

The catalysts undergo changes time onstream and through successive

regenerations.

Reactions

The reactions that can occur in tail-end acetylene hydrogenation units and acetylene
hydrogenation units located in the O/H of a front-end DeC2 are listed below:

C2H2 + H2 ~ C2H4 ®

C2H4 + H2 ~ C2H6 ®

2C2H2 + H2 ~ C4H6 ®

C4H6 +H2 ~ C4H8 ®

nC2H2 +nil2 --+ Green Oil (Oligomers of C2H2 ) (~)

Reaction O is desirable whereas reactions ® thru ®, are undesirable.

The amount of C2H2 converted to C6+ in a front-end D e C 2 0 / H acetylene

hydrogenation unit is much, much less than is the case for hydrogenation of C2H2 across
a tail-end unit.

In addition to reactions 1 through 5, the following reactions occur in an acetylene

hydrogenation unit located on the O/H of a front-end DEC3.

C3H4 + H2 ~ C3H6 ®

C3H6 + H2 ~ C3H8 ®

nC3H4 +nil2 --+ Green Oil (Oligomers of C3H4) ®

541
Reaction ® is desirable whereas reactions ® thru ® are undesirable.

Reactions ® and ® may not occur to a level of commercial significance in acetylene

hydrogenation units located on the O/H of a front-end DEC3.

Reactions ®, ®, and ® also occur in C3 hydrogenation reactors.

Relative Adsorption

According to literature the rate of hydrogenation of ethylene in an ethylene-hydrogen

mixture is 10-100 times faster than the rate of acetylene hydrogenation under identical
conditions of temperature, pressure and catalyst. Thus the selectivity of acetylene
hydrogenation can only be explained by the preferential adsorption of acetylene
molecules on the surface of the palladium.

The rate of adsorption of hydrocarbons can be classified in the following decreasing

order:

CO > Acetylenes >> Diolefins >> Olefins

Hence, kinetics is controlled by relative adsorption rates. The preferential adsorption of

acetylene over ethylene means that provided there are sufficient acetylene molecules to
cover all the active sites then ethylene hydrogenation to ethane is minimized. However,
in an industrial operation, near the bottom of the final bed, where the acetylene
concentration is reduced to about 1-5 ppm, a point is reached in the reactor bed where
there is an insufficient number of acetylene molecules to maintain total active site
coverage. Fortunately, carbon monoxide provides a means for blocking or inhibiting the
adsorption of ethylene, since it has a higher rate of adsorption than that of ethylene. The
CO molecules tend to occupy the active sites in the acetylene deficient regions.

For front-end acetylene hydrogenation units, CO will be in the reactor feed at a level of
about 200-2000 ppm. For tail-end units, trace amounts of CO (0.1-5 ppm) can be injected
into the reactor feed. Usually, this CO comes from bypassing a small stream of untreated
hydrogen around the PSA unit or methanator.

542
Oligomers (Green Oil) Formation

The following discussion pertains, primarily, to tail-end acetylene hydrogenation.

There is unanimous agreement in the literature that oligomers (green oil), C4's and
higher, are derived from acetylene and not ethylene. The subject of oligomers formation
is one of high commercial importance but which is only discussed in patent literature and
few published articles. The amount of green oil formation is primarily a function of the
concentration of acetylene being converted. Hence, the rate of formation of green oil is
higher on the lead bed where higher acetylene concentrations exist.

Discussion of fundamental causes of green oil formation engenders a lot of speculation.

It doesn't form without the presence of hydrogen, and the amount formed decreases as the
hydrogen partial pressure increases. Most researches agree that the precursor to all types
of green oil produced in the selective hydrogenation of acetylene is 1,3-butadiene. This
molecule is produced from hydrogenation of an acetylene dimer.

Catalyst deactivation by green oil becomes a major problem at very low hydrogen to
acetylene ratios. Furthermore, the amount of green oil formation has been reported to be
related to: surface acidity of the support, palladium crystallite size, mean pore size and
pore size distribution, feed water content, and higher operating temperatures.

The net result of heavy green oil formation is a shortening of the catalyst cycle length and
decrease in the catalyst selectivity.

About 10-20 % of the acetylene is converted to C4 and heavier green oil. (Ref 3) The
overwhelming majority is C4's. The next major constituent is C6's. A major
improvement from the promoted catalysts is that the amount of heavy green oil polymers
is substantially reduced. Hence, the rate of deactivation of the catalyst reduced.

Two industrial studies were found that dealt with green oil formation with Pd-only
catalysts in industrial units. These studies were done using slipstream test units in
ethylene plants in China and Russia (Ref. 11, 12). The Russian study reported that the
green oils were composed of 23 wt % olefins, 2.5 wt % diolefins and 74.5 wt % aromatic
compounds (Ref. 12).

The study carried out in China described the green oils as being long chained olefinic
compounds with a general formula corresponding to CnH(1.8-1.9)n where n=14-17. These
authors found that the quantity of aromatic compounds was negligible and that one
quarter of the olefins was alpha olefins (Ref. 11).

Most of the published science on selective hydrogenation is based on studies with Pd-
only catalysts. However, the latest generations of industrial acetylene converter catalysts
are promoted with another metal; in many cases this is Ag. The following information
comes from limited published information on the effect of Ag moderation on the Pd
catalytic sites.

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Axens(formerly Procatalyse) reported at the 1995 Spring AIChE Meeting that Ag
moderation reduces C6+ formation but has no effect on formation of C4's. (Ref. 3) Axens
compared the formation of green oil across a Pd-only catalyst with a Pd/Ag catalyst. Both
catalysts were on an alumina support. The feed acetylene was 2.6 %. Here are some
highlights from that paper.

Oligomerization occurs via a first step of dimerization of acetylene on palladium

sites and goes further through polymerization mechanisms to high molecular
weight compounds. The C4s remain gaseous; the C6+ compounds are liquids and
remain on the catalyst surface, reacting further to make even heavier
hydrocarbons.

The conversion of acetylene over a Pd-on-alumina catalyst showed that aboutl 5%

of the converted acetylene went to C4's and about 30 % of the converted
acetylene went to C6+.

The conversion of acetylene over the Pd/Ag catalyst showed that about 15% of
the converted acetylene went to C4's and the amount of acetylene converted to
C6+ was substantially reduced.

The amount and type of C4' s formed was independent of the addition of silver to
the catalyst.

The amount of acetylene converted to ethylene was increased on addition of the

silver.

An excerpt from a Sud Chemie brochure on the effect of Ag on green oil formation is as
follows: (Ref 35)

"This decrease in the production of green oil is accomplished by the use of Ag in

conjunction with the palladium hydrogenation metal. In essence, Ag acts like an atomic
spacer to increase the distance between the active palladium sites. This lessens the chance
for two molecules of acetylene to combine to form the 1,3-butadiene precursor, leading
directly to less potential polymer formation."

Sud Chemie has reported laboratory data to illustrate the effect of Ag on reducing the
amount of heavy green oil formed during hydrogenation of acetylene. This illustration is
provided in Figure 6. The amount of polymer formation with the promoted catalyst is
only about 40% of the amount produced with the Pd-only catalyst.

Catalyst Poisons and Inhibitors of Pd Catalysts"

Typical ethylene plant contaminants that can cause problems for acetylene and C3
selective hydrogenation catalysts are CO, H20, H2S, and mercaptans. Methanol also
causes problems. Other Pd catalyst poisons frequently encountered include COS, arsine,

544
and Hg. A thorough discussion on catalyst poisoning is beyond the scope of this paper.
For more information on this subject, see Reference articles 10 and 13 through 20.

Some comments on these poisons are as follows:

CO is a temporary inhibitor. It is important in providing selectivity/stability to the

front-end operations. However, it can cause problems for front-end operations if
the concentration fluctuates widely. It is injected, on-purpose, to control
selectivity of tail-end acetylene hydrogenation catalysts.

The effects from H20 and methanol are similar. H20 is considered to be a green
oil promoter.

H2S and COS are severe poisons at <1 ppm. COS is not removed via caustic. It
causes problems for acetylene converters in the raw gas and front-end D e C 3 0 / H
positions. It is also a poison for C3 hydrogenation catalysts

Arsenic, in the form of arsine, can poison catalysts in any of the acetylene and C3
hydrogenation units. Arsine, mostly, tracks along with propylene; however,
traces of arsine will track ethane.

If arsine and COS are present in the ethylene plant process gas, then adsorption
bed(s) will have to be installed to prevent catalyst poisoning. (Refs. 17 and 18)

Comments on Catalyst Regeneration

Typically, front-end catalysts are regenerated exsitu. Special diligence must be exercised
in getting Pd/promoter catalysts regenerated. This is especially the case if expectations
are for the regenerated catalyst to operate for 3-5+ years. The regeneration company
should have experience with regenerating Pd/promoter catalysts. In addition, the
performance of the regenerated catalysts should be confirmed via laboratory or bench
scale activity/selectivity testing.

Tail-end Pd/promoter catalysts are "rejuvenated" by an insitu steam/air bum, followed by

H2 reduction. This is a very important operation. A well executed regeneration and
reduction returns the catalyst to essentially same SOR performance as was achieved
during the previous cycle. Conversely, an incorrectly executed regeneration/reduction
can result in placing back in service a catalyst that performs worse than it did when it was
taken offiine. Some comments on insitu regeneration is as follows"

545
 Many times the regeneration step is "short-changed". This could mean any or all
of the following:

¢" Inadequate facilities

¢" Inadequate procedures
¢" Inadequate training of the operators and process engineers
¢" Insufficient operator attention

Typically, it is recommended that the catalyst be subjected to temperatures

between 850-900 F (about 450-480 C). The bum is "controlled" by limiting the
amount of air (02) in a steam/air mixture. Typical vendor guidelines call for
maintaining air between 1-5% (02 between 0.2-1.0%) during the steam/air bum.

Regeneration and the subsequent reduction is usually carried out counter current
to the process flow.

The operators must be provided with explicit guidelines so that they can achieve a
good bum at about 850 F (about 450 C), yet not getting into excessively high
temperatures, by "building upon" the exotherm as it progresses through the
catalyst bed.

Problems with the steam/air step can occur if the console operator's attention gets
diverted in the midst of a bum. For example:

¢" High exotherms if air is left in unattended

,/ Unable to restart a bum if air is cut out and bed allowed to cool

• Having more green oil fuel on the bed helps in attaining a good bum. Longer
cycle lengths help with this. Promoted catalysts mitigate against this.

C3 Hydrogenation
Typically, this unit is located on the O/H stream from a backend DEC3. (Figure 4) Most
units installed prior to the mid-70's were vapor phase reactors.

A vapor phase unit is very similar to a tail-end acetylene hydrogenation unit. The
catalyst is similar, but the Pd catalyst may not be promoted. Usually, the facilities
include a spare reactor with the capability for insitu regeneration. If the inlet MAPD is
below about 1%, the removal of MAPD may be carried out in a single reactor. Above 1
% MAPD, the reactor will be two beds with intercooling. A two-bed reactor system may
be able to completely hydrogenate inlet MAPD up to about 3.5%, without any recycle°
The operating/control strategy and safety facilities/procedures are analogous to those for
a two-bed tail-end acetylene hydrogenation unit.

546
A vapor phase C3 hydrogenation unit is easier to operate than a tail-end acetylene
hydrogenation unit. The reason for this is that the "operating window" is much larger for
C3's. That is, it's much easier to selectively hydrogenate MAPD in the presence of
propylene than to selectively hydrogenate acetylene in the presence of ethylene.

Liquid phase units can handle higher levels of MAPD in the C3 fraction by recycling
reactor product to dilute the MAPD in the DeC30/H.

This paper cannot go into the details of liquid phase C3 hydrogenation because this
technology is licensed technology. Some overview comments that can be made include
the following"

Liquid phase reactors and associated equipment is smaller, relative to the reactors
and associated equipment required for vapor phase units.

• Liquid phase units require less energy.

The dominant liquid phase C3 hydrogenation process is licensed by IFP.( Ref. 33)
Typically, this is a two-stage process. (Figure 7) Adiabatic, fixed bed reactors are
used. Effluent from the first stage is recycled to reduce the concentration of
MAPD in the reactor feed.

ABB Lummus offer a proprietary C3 liquid phase selective hydrogenation process

and catalyst. This process is designated LB Fining. This process was developed
jointly by ABB Lummus and the Beijing Research Institute for the Chemical
Industry (BRICI). This is a single stage hydrogenation process. A paper on this
process was presented to the 1992 Ethylene Producers Conference (Ref. 31).

Several ethylene plants still operate Lurgi-Bayer's isothermal liquid phase C3

hydrogenation process. This process employed only one isothermal tubular
reactor. (Ref. 37)

CD Tech offers a CDHydro process for selective hydrogenation of C3. This is a

catalytic distillation process whereby the catalyst bed is located within a backend
DEC3. A paper on this concept was presented at the 1995 Ethylene Producers
Conference. (Ref. 32)

The catalysts used in liquid phase hydrogenation contain about 10 times more Pd
than is the case for vapor phase C3 hydrogenation.

Two catalysts offered by Axens are designated LD-265 (Pd-only) and LD-273 (Pd
plus a promoter).

Other companies that offer C3 liquid phase hydrogenation catalysts include" Sud
Chemie, Englehard, Kataleuna, and BASF.

547
Safety Consideratons
The following is not intended to provide precise guidance on the safety facilities and
procedures required for acetylene and C3 hydrogenation units. The following provides
an overview on safety considerations. This may serve as background information for
some of succeeding papers in this session. For more information, see reference articles
27 through 30.

The primary safety concern with acetylene and C3 Hydrogenation is to prevent situations
that get the reactor(s) into a runaway exothermic reaction, leading to excessive
temperatures and pressures such that there is a loss of containment. It's possible to reach
conditions where uncontrollable reactions can begin to occur. The reactions include,
hydrocracking, polymerization, and ethylene decomposition.

Front-end Acetylene Hydrogenation Units:

A major consideration is that the feed to these reactors is very rich in hydrogen (20-50%)
and ethylene (30-50%); hence, the safety facilities and procedures are aimed at
preventing and/or mitigating against the consequences from the initiation of ethylene
hydrogenation in the presence of high concentrations of hydrogen. An overview on the
safety considerations is as follows"

Maintain the feed above a minimum rate: Long contact times will initiate
ethylene hydrogenation. This is usually handled by having the reactors in a
recycle loop. The catalysts suppliers and ethylene contractors provide guidelines
for the minimumallowable feed rate.

• Install multiple thermocouples in the catalyst beds.

Have these T/C's, along with bed outlet T/C's, alarm the operators when
temperatures have exceeded the upper limit for normal operating conditions. This
alerts the operator to take corrective action, such as reducing inlet temperature to
the reactor.

As the temperatures increase, the heating medium going to the reactor preheater
should be tripped.

Safety facilities and procedures should be able to handle the need to isolate and
depressure, and purge the reactor with an inert gas.

The ethylene producer has responsibility for safety facilities and procedures.
Input should come from catalyst suppliers and ethylene contractors.

548
Tail-end Acetylene Hydrogenation Units:

For tail-end hydrogenation units, the primary consideration is to avoid high ratios of
hydrogen to reactants. The normal control scheme addresses this by maintaining a
specified H2/feed ratio for each bed. However, there are a few abnormal situations that
could lead to excess hydrogen getting into one or more of the catalyst beds. These
abnormal situations would include: instrument failure, operator error, and flawed
procedures for dealing unsteady state operations. Safety facilities and procedures may
include the following"

Multiple thermocouples within each catalyst bed. These T/C's, along with bed
outlet T/C's would provide high temperature alarms. The lowest level alarm will
alert the operator of temperatures that are above the normal operating range. This
gives the operator an opportunity to take corrective action.

If the temperatures continue to climb, then the hydrogen valves will be tripped.
The main consideration is to prevent any additional hydrogen from entering the
reactor when there are high temperatures at any point(s) within the catalyst beds.

The reactor feed inlet temperature should be reduced when high catalyst bed and
outlet temperatures are detected.

If temperatures continue to increase, the reactor will have to be isolated,

depressured, and purged/cooled with an inert gas.

C3 Hydrogenation

The safety facilities and procedures for a vapor phase C3 hydrogenation unit are
analogous to those for a backend acetylene converter.

For a liquid phase C3 hydrogenation unit, the safety facilities and procedures have
to take into account auto-refrigeration concerns from depressuring equipment
containing liquid propylene.

The liquid phase system is inherently safer than the vapor phase system due to the
heat sink of the liquid, which can absorb considerable amounts of heat by
vaporization. However, the liquid phase operation, introduces another concern
over localized overheating or "hot spots" caused by flow maldistribution. This
concem has been mentioned in two EPC papers: (Ref. 29 and 30)

549
 List of References

Promoted Acetylene Hydrogenation Catalysts

1. Dow Chemical Company, US 2.802.889, (1957)

2. M.M. Johnson, D. W. Walker, G. P. Nowack, US patent 4,404,124, (1983)

o B. Didillion, P. Sarrazin, J. P. Boitiaux; "Advanced Catalyst Design for High

Ethylene Production and Maximized Cycle Lengths", AIChE Spring Meeting,
Session 43, March 1995, Houston, TX

, K. Sasaki, J. Kimble, M. Scharre, R. Callejas, "Effects of Selectivity on

Acetylene Removal Unit", AIChE(EPC), Session 33, March 1997, Houston TX

0 E. Sughrue and M. Johnson, "Highly Selective Catalysts for Acetylene

Hydrogenation", AIChE(EPC), Session 18, April 1993, Houston, TX

. R.W. Voight, J.S. Meriam, S.A. Blankenship, "Evolution of Catalyst for Selective
Hydrogenation of Acetylene", AIChE(EPC), Session 19, February 1996, New
Orleans LA

0 M. P. Kaminsky, V.J. Kwasniewski, and P. Lysenko, "Acetylene Hydrogenation

Catalysis using Pd/A1203, Finding the Optimum Pd Dispersion/Loading and
Space Velocity", AIChE(EPC), Session 68, March 1999, Houston TX

, J-P Boitiaux, J. Cosyns, M. Derrien, and G. Leger, Hydrocarbon Processing,

March 1985

0 F.E. Hancock, and J.K. Smith, "Design and Performance of Acetylene

Hydrogenation Catalysts" AIChE(EPC), Session 86, April, 1992, New Orleans,
LA

10. D. B. Tiedtke, T. T. P. Cheung, J. Leger, S. A. Zisman, J. J. Bergmeister, Go Ao

Delzer, "Chemicals Influencing the Activity of Palladium-Based Catalyst for the
Hydrogenation of Acetylene to Ethylene in Acetylene Converters" AIChE (EPC),
Session 80, March 2001, Houston, TX.

550
Green Oil Formation

11. L. Yajun, Z. Jing and M. Xueru, "Study on the Formation of Polymers During the
Hydrogenation of Acetylene in Ethylene-Ethane Fractions", Chem. Ind. Eng. Soc.
China Am. Inst. Chem. Eng. 82, (2) 688, (1982).

12. Z. E. Gandman, M. E. Aerov, V. A. Men'shchikov and V. S. Getmantsev,

"Formation of Polymers in Hydrotreating an Ethane-Ethylene Fraction of
Pyrolysis Gas to Remove Acetylene", International Chem. Engineering, (Vol. 15,
No. 1), Page 183, January 1975.

Catalyst Poisons and Ethylene Plant Contaminants

13. M.P. Kaminsky, "Deactivation Mechanisms for Pd/A1203 Acetylene

Hydrogenation Catalyts", AIChE(EPC), Session 26, March 1994, Atlanta GA

14. S. Bailey, F.E. Hancock, J.S.,Booth "The Application of EPR to the Study of
Acetylene Removal and Deactivation Reactions", AIChE(EPC), Session 65,
February 1996, New Orleans LA

15. F.E. Hancock and J.S. Booth, "A Mechanistic Study of the Deactivation by
Hydrocarbon Fouling of Front End Acetylene Hydrogenation Catalysts and the
Effect of Carbon Monoxide Incorporation", AIChE(EPC), Session 26, April 1994,
Atlanta GA

16. K.J. Enqvist, "Experience on Arsine Contaminant in Ethylene Unit Feed Stock
and Disposal of Arsine Contaminated Catalyst/Adsorbent", AIChE(EPC), Session
23, March 1995, Houston, TX

17. D.R. McPhaul and J. A. Reid, "Ethylene Plant Feedstock Contaminants

Treatment", AIChE(EPC), Session 20, March 1995, Houston TX

18. D.R. McPhaul and J. A. Reid, "Contaminant Rejection Technology Update",

AIChE(EPC), Session 21, February 1996, New Orleans LA

19. Baumgartner and S. Coleman, "Principal Feedstock Contaminants in Ethylene

Plants", AIChE(EPC), Session 19, February 1996, New Orleans LA

20. J. Reid, "An Overview of Hydrogenation Catalyst Poisons in Olefin Units"

AIChE(EPC), Session 80, March 2001, Houston, TX

551
Control and Modeling of Acetylene Hydrogenation Units

21. E.L. Sughrue, R.L. Hair. R.J. Callejas, "The use of Models in the Operation of
Acetylene Hydrogenation" AIChE(EPC), Session 21, April 1995, Houston, TX

22. A.N.R. Bos, and K.R. Westertrep, "The Behaviour of an Adiabatic Packed Bed
Reactor: The Selective Hydrogenation of Acetylene/Ethylene", Proceedings of
the International Conference of Unsteady State Processes in Catalysis, June 990,
Novosibirsk

23. M. W. Brown, A. Penlidis, and G.R. Sullivan, "Control Policies for an Industrial
Acetylene Hydrogenation Reactor", Canadian Journal of Chemical Rngineering,
Vol. 69, February 1991

24. W.K. Lam, S.C.K. Cua, K.F. McNulty, " Benefit of Acetylene Reactor
Modeling",AIChE(EPC) Session 20, March 1990.

25. M. Szukiewicz, K. Kaczmarski, R. Petrus, "Modelling of Fixed Bed Reactor:

Two Models of Industrial Reactor for Selective Hydrogenation of Acetylene",
12th International Congress of Chemical and Process Engineering, August, 1996,
Prague.

26. M. Nasi, M. Alikoski, and C White, " Advanced Control of Acetylene

Hydrogenation Reactors", Hydrocarbon Processing, June 1985.

Safety Considerations in C2 and C3 Hydrogenation Operations

27. M. Edison, "Runaway Reactor Survey", AIChE(EPC), Session 35, March 1997,
Houston TX

28. K.J. Enqvist, "The Operating Errors and the Deficiencies in the Design or in the
Safety Systems that Lead to the Acetylene Converter Temperature Runaway",
AIChE(EPC), Session 65, March 1999, Houston TX

29. J.L. Bancroft, "Temperature Monitoring Systems for Detecting Hot Spots in
Exothermic Reactors", AIChE(EPC), Session 65, March 1999, Houston TX

30. J. A Reid, "An Overview of Olefin Unit Accidents and Safety Lessons Learned",
AIChE(EPC), Session 65, March 1999, Houston TX

552
C3 Hydrogenation

31. A.E. Krumins, H.L.leung, AND L.X.Xiang, "LB Fining for Liquid Phase MAPD
Hydrogenation", AIChE(EPC), Session 86, April 1992, New Orleans, LA

32. G. Gildert, W. Groten, K. Rock, D. Weidert, "Combining Hydrogenation with

Distillation in Ethylene Plants", AIChE(EPC), Session 20, March 1995, Houston
TX

33. M.L. Derrien, J.W. Andrews, P. Bonnifay, and J. Leonard, "The IFP Selective
Hydrogenation Process", Chemical Engineering Progress, Vol. 70, No. 1, January
1974

Overview on Acetylene Hydrogenation

34. V. Kaiser, JP. Laugier, R. DiCinto, M. Picciotti, "Acetylene Removal from

Cracked Gas: A Technology Overview", AIChE(EPC), Session 68, March 1999,
Houston TX

35. Sud Chemie Technical Bulletin on C2-Tailend Hydrogenation

36. Sud Chemie Operating Instructions Bulletin for G-83C

37. M.L. Derrien, "Selective Hydrogen Applied to the refining of Petrochemical Raw
Materials Produced by Steam Cracking", Studies in Surface Science, Vol. 27,
Catalytic Hydrogenation, Elsevier.

553
 Figure 1

H2/CH4

Demethanizer

Front-End Ethylene
Acetylene Ethane/Ethylene
Hydrogenation Splitter
O1
O1
4:=

""F

Ethane
Deethanizer

"--~ C3+
HC
Depropanizer
Feed Cool/Scrub

Cracking
I "-" Heavies
Furnaces

Drawing Courtesy of Sud Chemie

 Fi_qure 2
Acetylene Hydroqenation on OIH of Front End DeC3

H2/CH4 .__=

Demethanizer

• C2

Front-End
O1
Acetylene
O1
O1
Hydrogenation
Deethanizer

• C3
Depropanizer

--~ C4+

Cracking I CoollS_.~crub
Furnaces Heavies
Drawing Courtesy of Sud Chemie
 Figure 3

H21CH4

Demethanizer

• C2=
C2 Purification

O1
O1
03
Raw Gas
Acetylene
Hydrogenation
Iii i ' i i i Deethanizer

" C3+

iii!iiiiiiiiiiiiiii!~.~..... Cool/Scrub
HC ,---,r
Feed I -
Cracking
Furnaces Heavies

Drawing Courtesy of Sud Chemie

 Figure 4
Tail-End Acetylene Hydrogenation Unit

CH4, CO, H2

Demethanizer

C2
T
C2 Selective
Hydrogenation
O1
O1
~J
= $ c2
C3
Deethanizer

C 3 Selective
Hydrogenation

Depropanizer c3

HC "F
Feed
Cracking I CoollScru~b
"'-F

Furnace Heavies C4+

Drawing Courtesy of Sud Chemie

 Figure 5
2 - B e d Tail-end A c e t y l e n e H y d r o g e n a t i o n R e a c t o r S y s t e m
ii~iiiiiiiiiiiiilili-iiiiiiiiii
i~]iii i~i i:~

ii~iiiiiiiiiiii~iiiii~iiiiiiiiiiiiiiiiiiii

l':i Cataly=!iiiiii
Bed ......i~T,l~,~, i!i!ii Bed !ii!!iiiii!!ii.......
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
Lead
Reactor
iiiiiiiiiiiiiii . . . . . . . i,,:~,,,~::~,~!~:==~:~,~,:~,,:~=
ii:i;ii;i;ii~i:iii;i;i~i;?iii;ii;i:i:i~i;i~i;i;i5

. . . . . . i~!~,~.~.~
:.!:i'.i:.!:!:::::.:.!:.:.!'):?):.:.'i!)).)::.:. :)).]:.:i?i!:.!:. '..:::.:.
....................................................................

..............................
..........................................
01
01 ~ ' ~ ! ~IG~
I

.. >........~.~. ....

~ ~ . ~ I ~ ~ ........................................

ii ~atalys~ iii !?[iiiiii}ii~ata lY~ iiiiiiiii

I ~J
Guard =e. i!i"iliiii!!......,i
Reactor ii i!iliilii ......! ~i ii iii!iiiii.:.......
:i i~i

~
iiiii !iii.i.i.iii ~ i~ii:ii(ii!i:iiiii!!iii:!!i!iiii:ii.i!ii:.]ii::i.~
~
. . . . . .

......i ~::i:=:!!!i
:i:i:.!i!

| Steam
Drawing
Courtesy of Normal < 1 ppmv C2H2 Regeneration ~ .....
Sud Chemie Operation ii!iii!i~ii~Q~ii!i!iii!i!!i!
 Figure 6
Green Oil Formation: Sud Chemie Comparison Between Standard and
Promoted Tail-end Pd Catalysts
(Ref. 35)

Graph No 1

GREEN OIL and POLYMER FORMATION

200 hours Laboratory Tests
Grams

24. I

0~ ~
Standard Catalysts Promoted Catalysts

Test conditions: 1% C2H2; 1.5 % H2

SV = 5000 Nm3/m3/h
T = 50 "C

559
 Figure 7
!FP C3 Hydrogenation Unit
to

Hydrogen steam c r a c k e r

r
......... i-i-- 7 2\~L;.L .... ill

MAIN
REACTOR FINISHING
REACTOR

01
03
O

,L I d~u~-~

-.

C3 F e e d s t o c k