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US 201403.

78725A1
(19) United States
(12) Patent Application Publication (10) Pub. No.: US 2014/0378725 A1
LUEBKE et al. (43) Pub. Date: Dec. 25, 2014
(54) PROCESS FOR HIGH TEMPERATURE Publication Classification
REMOVAL OF TRACE CHLORIDE
CONTAMINANTS IN A CATALYTC (51) Int. Cl.
DEHYDROGENATION PROCESS C07C 7/12 (2006.01)
C07C 5/327 (2006.01)
(71) Applicant: UOP LLC, DES PLAINES, IL (US) (52) U.S. Cl.
CPC. C07C 7/12 (2013.01); C07C5/327 (2013.01)
(72) Inventors: CHARLES P. LUEBKE, MT. USPC ........................................... 585/324; 585/823
PROSPECT, IL (US); JAYANT K. (57) ABSTRACT
GORAWARA, BUFFALO GROVE, IL
(US); VLADISLAV I. KANAZIREV, A process for removal of trace chloride contaminants from a
ARLINGTON HEIGHTS, IL (US) reactor effluent in a catalytic dehydrogenation process is
described. The reactor effluent is compressed in a compressor
to provide a compressed effluent. The compressed effluent is
(21) Appl. No.: 13/922,071 introduced from the compressor into a chloride treater. In the
chloride treater, trace chloride contaminants in the com
pressed effluent are adsorbed to provide a treated effluent. The
(22) Filed: Jun. 19, 2013 treated effluent is cooled in a cooler.
Patent Application Publication Dec. 25, 2014 Sheet 1 of 3 US 2014/03.78725 A1

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Patent Application Publication Dec. 25, 2014 Sheet 2 of 3 US 2014/03.78725 A1
Patent Application Publication Dec. 25, 2014 Sheet 3 of 3 US 2014/03.78725 A1

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US 2014/03.78725 A1 Dec. 25, 2014

PROCESS FOR HIGH TEMPERATURE can be a reactor effluent drier system (RED) for drying and
REMOVAL OF TRACE CHLORIDE purification, including water and hydrogen Sulfide (H2S)
CONTAMINANTS INA CATALYTC removal.
DEHYDROGENATION PROCESS 0008. An example reactor effluent dryer (RED) system
includes two or more adsorbent beds arranged in a typical
BACKGROUND OF THE INVENTION thermal swing adsorption (TSA) system. While one or more
adsorbent beds is in adsorption mode to purify and dehydrate
0001 Catalytic dehydrogenation can be used to convert the process stream, the other bed(s) are in regeneration mode.
paraffins to the corresponding olefin, e.g., propane to pro When the adsorbent bed(s) in the adsorption step starts to
pene, or butane to butene. breakthrough the contaminants, the bed(s) on adsorbent
0002 FIG. 1 shows one typical arrangement for a catalytic mode is Switched to regeneration mode and the freshly regen
dehydrogenation process 5. The process 5 includes a reactor erated bed(s) are placed in adsorption mode. The beds are
section 10, a catalyst regeneration section 15, and a product Switched between adsorption and regeneration modes to pro
recovery section 20. vide for continuous purification of the process stream. Regen
0003. The reactor section 10 includes one or more reactors eration of the adsorbents is accomplished by purging the beds
25 (four are shown in FIG. 1). A hydrocarbon feed 30 is sent with a regenerant stream Such as an inert gas, net gas, or
to a heat exchanger 35 where it exchanges heat with a reactor vaporized hydrocarbon stream, at elevated temperature to
effluent 40 to raise the feed temperature. The feed 30 is sent to desorb the impurities and water to rejuvenate the adsorbent
a preheater 45 where it is heated to the desired inlet tempera and prepare it for a fresh adsorption step. The TSA process is
ture. The preheated feed 50 is sent from the preheater 45 to the well known to those skilled in the art.
first reactor 25. Because the dehydrogenation reaction is 0009. The dried effluent is separated in separator 85. Gas
endothermic, the temperature of the effluent 55 from the first 90 is expanded in expander 95 and separated into a recycle
reactor 25 is less than the temperature of the preheated feed hydrogen stream 100 and a net separator gas stream 105. A
50. The effluent 55 is sent to interstage heaters 60 to raise the liquid stream 110, which includes the olefin product and
temperature to the desired inlet temperature for the next reac unconverted paraffin, is sent for further processing, where the
tor 25. desired olefin product is recovered and the unconverted par
0004. After the last reactor (in this example, the fourth affin is recycled to the dehydrogenation reactor 25.
reactor), the reactor effluent 40 is sent to the heat exchanger 0010. An example chloride scavenging guard bed for the
35, and heat is exchanged with the feed 30. The reactor chloride treater 130 includes a vessel having one or more
effluent 40 is then sent to the product recovery section 20. chloride scavenging adsorbents, referred to as guard beds.
Examples of adsorbents include activated alumina, promoted
0005. The catalyst 65 moves through the series of reactors aluminas, metal oxides, Zeolite-based adsorbents, and others.
25. When the catalyst 70 leaves the last reactor 25, it is sent to The cooled compressed effluent 125 passes through the ves
the catalyst regeneration section 15. The catalyst regeneration sel, and over the beds, contacting the adsorbent to remove
section 15 includes a reactor 75 where coke on the catalyst is chloride contaminants. It is possible that both physical and
burned off and the catalyst may go through a reconditioning chemical adsorption may take place.
step. A regenerated catalyst 80 is sent back to the first reactor 0011. A significant amount of heavy hydrocarbon residue
25.
that is present in the reactor effluent 40 enters the chloride
0006. As will be appreciated by those of ordinary skill in treater 130. The heavy hydrocarbon residue is a result of
the art, the organic chloride used to condition paraffin dehy undesirable side reactions occurring primarily in the reactor
drogenation catalysts results in undesirable chlorinated spe section 10 of the catalytic dehydrogenation unit. Examples of
cies (chloride) compounds, such as HCl and organic chlorides heavy hydrocarbons include polynuclear aromatics. The
(RCI), in the reactor effluent. Such compounds are referred to heavy hydrocarbon residue, a known impurity, negatively
herein as trace chloride contaminants. Example deleterious affects the performance of the chloride treater adsorbent.
effects from untreated trace chloride contaminants include While a solvent, such as para-diethylbenzene or light cycle
corrosion, poisoning of downstream catalysts, and other oil, can be provided to clean the reactor effluent 40 and the
effects. Accordingly, product recovery in typical catalytic cooler 120, hydrocarbon residue still is present in feed to the
dehydrogenation processes includes a process for removal of chloride remover 130 or the reactor effluent driers 84.
trace chloride contaminants. 0012. If a reactive adsorbent is employed in a highly reac
0007 For example, FIG. 1 shows a typical chloride tive hydrocarbon stream, Such as that present in the catalytic
removal process that is integrated into the product recovery dehydrogenation process, undesirable reactions. Such as
section 20. The reactor effluent 40 is compressed in the com polymerization, alkylation, etc. can result in formation of
pressor 82. The compressed effluent 115, which typically high molecular weight heavier hydrocarbons. These heavy
occurs at a temperature of about 110-177° C. (230-350° F.) hydrocarbons can deposit on the adsorbent Surfaces, filling up
when exiting the compressor 82 (e.g., via a discharge drum), pore Volume and creating mass transfer resistance by forming
is introduced to a cooler 120, for instance a heat exchanger. liquid film around adsorbent particles, thereby reducing
The cooler 120 lowers the temperature of the compressed capacity of the adsorbent. To compensate for Such effects, it
effluent to about 25-60° C. and in some examples 38-60° C. may be possible to increase the surface to volume ratio of the
(100-120° F.). The cooled effluent 125 (cooled product adsorbent particle by use of higher external Surface area par
stream) is then introduced into a chloride remover 130, such ticles or reducing the particle size of the adsorbent. However,
as a chloride scavenging guard bed. The chloride remover 130 Such strategies are not very effective, and may result in
includes an adsorbent, which adsorbs chlorides from the increased cost of production. In addition, reducing the adsor
cooled effluent 125 and provides a treated effluent 135. bent particle size will result in an undesirably large pressure
Treated effluent 135 is introduced to a drier 84. The drier 84 drop across the chloride remover 130.
US 2014/03.78725 A1 Dec. 25, 2014

SUMMARY OF THE INVENTION processes will be apparent to those of ordinary skill in the art.
0013. One aspect of the invention involves a process for The reactor effluent is compressed in a compressor to provide
trace chloride contaminant removal of a reactor effluent in a a compressed effluent. Compression includes increasing a
catalytic dehydrogenation process. The reactor effluent is pressure of the reactor effluent. The compressed effluent is
compressed in a compressor to provide a compressed efflu introduced from the compressor into a chloride remover. In
ent. The compressed effluent is introduced from the compres the chloride remover, chloride present in the compressed
sor into a chloride remover. Chlorides present in the com effluent is adsorbed to provide a treated effluent. The treated
effluent is then cooled in a cooler.
pressed effluent are adsorbed in the chloride remover to 0022. The compressed effluent can be introduced directly
provide a treated effluent. The treated effluent is subsequently from the compressor into the chloride remover. By “directly.”
cooled in a cooler.
0014) Another aspect of the invention involves a process it is intended that the compressed effluent be introduced with
for high temperature trace chloride contaminant removal of a out entering into an intervening process component that pro
reactor effluent in a catalytic dehydrogenation process. A vides a significant change in the composition or pressure of
hydrocarbon feedina dehydrogenation reaction Zone is dehy the compressed effluent. A suitable fluid line between the
drogenated under dehydrogenation reaction conditions in the compressor and the chloride remover can be used and still
presence of a dehydrogenation catalyst to form a reactor provide a “direct' introduction to the chloride remover. In
effluent. The reactor effluent is compressed to provide a com another example, the temperature of the compressed effluent
pressed effluent. The compressed effluent is introduced into a can be adjusted, such as by a heater or cooler disposed
chloride remover at a temperature that is above a dew point of between the compressor and the chloride remover, to a suffi
the compressed effluent. Trace chloride contaminants present ciently high level to reduce or prevent condensation or foul
in the compressed effluent are adsorbed in the chloride ing, yet low enough to reduce or prevent polymerization
remover with an adsorbent to provide a treated effluent. The reactions. This temperature can be optimized in an example
treated effluent is cooled. embodiment.
0023 The chloride adsorption can take place at a tempera
BRIEF DESCRIPTION OF THE DRAWINGS ture that is above the dew point temperature of the incoming
stream (e.g., the compressed effluent) at the particular process
0.015 FIG. 1 is an illustration of a conventional trace chlo conditions. This temperature in an example process is
ride contaminant removal process for reactor effluent in a between about 93-300° C. (about 200-572°F), more prefer
catalytic dehydrogenation process. ably between about 93-177° C. (about 200 to about 350°F),
0016 FIG. 2 is an illustration of an embodiment of a trace and most preferably between about 121-177°C. (about 250
chloride contaminant removal process for reactor effluentina 350°F), though in some processes temperatures above 200°
catalytic dehydrogenation process. C. can also increase the side reactions of the main (olefinic)
0017 FIG.3 is an illustration of a chloride remover for use stream, which can lead to adsorbent fouling.
in an example trace chloride contaminant removal process. 0024. The chloride adsorption can comprise contacting
DETAILED DESCRIPTION OF THE INVENTION
the compressed effluent with an adsorbent, wherein chloride
is adsorbed. The adsorption process can involve physical
0018. The propensity for undesirable side reactions over a adsorption, chemisorption, and chemical reaction.
chloride adsorbent, Such as acid catalyzed polymerization, 0025. The adsorbent material has a low catalytic activity
oligomerization, cyclization, and heavy residue formation by for olefinic hydrocarbons to limit side reactions and fouling
condensation, typically increases at higher temperatures. Fur events in the chloride remover. The adsorbent can comprise
ther, it was believed that higher temperatures unduly reduce activated alumina, a promoted alumina product, a highly pro
adsorbent capacity of the adsorption process. It was thought moted alumina, metal oxides or Suitable molecular sieves, or
that the best performance for the chloride remover could be a combination thereof. Activated alumina is a highly porous
achieved with a cooled product stream from the cooler down material manufactured by dehydroxylating aluminum
stream of the reactor effluent compressor in a catalytic dehy hydroxide. Promoted alumina refers to impregnating or dop
drogenation unit. Thus, conventionally, the chloride remover ing the alumina, for instance with sodium carbonate, sodium
has been located downstream of the compressor and down hydroxide, or calcium hydroxide, to cause the alumina to
stream of the cooler to enable an increased capacity of the absorb more chlorides, and highly promoted alumina refers to
adsorbent, as shown in FIG. 1. at least about 3 wt % as alkaline oxide as an amount of
0019. However, if there is an available adsorbent with impregnation or doping.
Suitable properties, such as low reactivity towards olefin poly 0026. A pressure of the compressed effluent can be
merization and high capacity at elevated temperatures of between about 345 kPa to about 2750 kPa (about 50 to about
operation, it is better to locate the chloride remover on a hotter 400 psig).
stream before the cooler. This hotter stream reduces adsor 0027. The cooled effluent can be introduced into a drier.
bent fouling caused by condensation of heavy hydrocarbons The cooling of the treated effluent takes place downstream of
and boosts the kinetics of the chloride removal process, pro the chloride remover and upstream of the drier.
viding higher chloride removal capacity and better utilization 0028. Another inventive aspect includes a process for high
of the active component of the adsorbent. temperature trace chloride contaminant removal from a reac
0020. An example embodiment of the present invention tor effluent in a catalytic dehydrogenation process. A hydro
involves a process for trace chloride contaminant removal of carbon feed is dehydrogenated in a dehydrogenation reaction
a reactor effluent in a catalytic dehydrogenation process. Zone, such as the reactor section 10. The dehydrogenation
0021. An example catalytic dehydrogenation process for takes place under dehydrogenation reaction conditions in the
which an embodiment trace chloride contaminant removal presence of a dehydrogenation catalyst to form a reactor
process can be employed is shown in FIG. 2, though other effluent. The reactor effluent is compressed to provide a com
US 2014/03.78725 A1 Dec. 25, 2014

pressed effluent. The compressed effluent is introduced into a pressure of from about 0 MPa (0 bar) to about 3.5 MPa (35
chloride remover at a temperature that is above the dew point bars) and a temperature of from about 480° C. (900°F) to
temperature of the incoming stream (e.g., the compressed about 760° C. (1400°F). The suitable hydrocarbon feed 30 is
effluent 115, either directly or via a heater or cooler). In an charged to the reactors 25 and contacted with the catalyst
example process, this temperature is between about 93-300 contained therein at an LHSV of from about 1 to about 10.
C. (about 200-572 F.), more preferably between about Hydrogen, principally recycle hydrogen, is suitably admixed
93-177° C. (about 200 to about 350°F), and most preferably with the hydrocarbon feed 30 in a mole ratio of from about 0.1
between about 121-177° C. (about 250-350° F.). This high to about 10. Preferred dehydrogenation conditions, particu
temperature can be provided by introducing a reactor effluent larly with respect to C-Cs paraffinic hydrocarbon feedstocks,
to a chloride treater either directly or after adjusting the tem include a pressure of from about 0 MPa (0 bar) to about 0.5
perature via a heater or cooler. Trace chloride contaminants MPa (5 bars) and a temperature of from about 540° C. (1000°
present in the compressed effluent are adsorbed in the chlo F.) to about 705° C. (1300 F), a hydrogen-to-hydrocarbon
ride remover with an adsorbent to provide a treated effluent. mole ratio of from about 0.1 to about 2, and an LHSV of less
The treated effluent is cooled. than 4.
0029. The cooled effluent can be introduced into a drier. 0034. The dehydrogenation may use any suitable dehy
The cooling of the treated effluent takes place downstream of drogenation catalyst. Generally, preferred Suitable catalyst
the chloride remover and upstream of the drier. comprises a Group VIII noble metal component (e.g., plati
0030. In an embodiment, an olefin product, an uncon num, iridium, rhodium, and palladium), an alkali metal com
Verted paraffin, and a recycle hydrogen stream are separated ponent, and a porous inorganic carrier material. The catalyst
from an output stream of the drier. The olefin product is may also contain promoter metals which advantageously
recovered. The recycle hydrogen stream and the unconverted improve the performance of the catalyst. The porous carrier
paraffin are recycled to the dehydrogenation reaction Zone. material should be relatively refractory to the conditions uti
0031 Referring now to FIG. 2, the hydrocarbon feed 30 is lized in the reactor section 10 and may be chosen from those
dehydrogenated in a dehydrogenation Zone provided by the carrier materials which have traditionally been utilized in
reactor section 10. The dehydrogenation of paraffinic hydro dual function hydrocarbon conversion catalysts. A preferred
carbons is well known to those skilled in the art of hydrocar porous carrier material is a refractory inorganic oxide, with
bon processing. In the dehydrogenation process, the fresh the most preferred an alumina carrier material. The particles
hydrocarbon feed 30 is combined with recycle hydrogen and are usually spheroidal and have a diameter of from about/16
unconverted hydrocarbons. Dehydrogenatable hydrocarbons to about /s inch (about 1.6 to about 3.2 mm), although they
preferably include isoalkanes having 3 or 5 carbon atoms. A may be as large as about 4 inch (about 6.4 mm).
suitable feed of dehydrogenatable hydrocarbons will often 0035. Operation of the reactor section 10 will produce a
contain light hydrocarbons (i.e., those having less carbon mixture of hydrogen and hydrocarbons. Normally, a portion
atoms than the primary feed components) which, for the of the hydrocarbons will include an equilibrium mixture of
purpose of reaction, serve as contaminants. In most cases, the desired olefin and its alkane precursor. The reactor efflu
olefins are excluded from the dehydrogenation Zone recycle ent 40 from the reactor section 10 passes to the product
in order to avoid the formation of dienes which produce recovery section 20. The product recovery section 20 removes
unwanted by-products in many of the olefin conversion pro hydrogen from the reactor effluent 40 and recovers it in high
cesses. Along with the dehydrogenatable hydrocarbons, the purity for recycle to the reactor section 10. Separation steps
feed 30 to the reactor section 10 comprises an H-rich stream, for the removal of hydrogen will normally include cooling
preferably containing at least 75 mol % H. The H acts to and compressing with Subsequent cooling and flashing in a
Suppress the formation of hydrocarbonaceous deposits on the separation vessel. Such methods for the separation of hydro
Surface of the catalyst, more typically known as coke, and can gen and light gases are well known by those skilled in the art.
act to suppress undesirable thermal cracking. Because H is 0036. A typical dehydrogenation process passes the com
generated in the dehydrogenation reaction and comprises a bined hydrocarbon and hydrogen feed through the plurality of
portion of the effluent, the H-rich stream introduced into the reactors 25 with interstage heating between the reactors pro
reactor section 10 generally comprises recycle H derived vided by the interstage heaters 60. The feed 30 including
from separation of the reactor effluent 40. Alternately, the H. hydrocarbons and hydrogen is initially heated by indirect heat
may be supplied from suitable sources other than the reactor exchange 35 with the reactor effluent 40 from the reactor
effluent 40. section 10. Following heating, the feed 30 normally passes
0032. The combined stream of hydrogen and hydrocar through the preheater 45 to further increase the temperature
bons is passed through the reactors 25, which include a suit of the feed components before it enters the reactors 25 where
able bed of dehydrogenation catalyst maintained at the proper it is contacted with the dehydrogenation catalyst. The endot
dehydrogenation conditions such as temperature, pressure hermic reaction reduces the temperature of the reactants
and space velocity. The reactor effluent 40 from the reactor which then undergo interstage heating at the interstage heat
section 10 is processed further to yield a stream of olefinic ers 60 before entering the next reactor. After the heat
hydrocarbons. exchange 35 with the feed 30, the reactor effluent 40 from the
0033. The dehydrogenation reaction is a highly endother last reactor 25 passes to the product recovery section 20.
mic reaction which is typically effected at low (near atmo 0037. In the product recovery section 20, the reactor efflu
spheric) pressure conditions. The precise dehydrogenation ent 40 is compressed in the compressor 82 to provide a com
temperature and pressure employed in the dehydrogenation pressed effluent. The compressed effluent 115 is either intro
reaction Zone will depend on a variety of factors, such as the duced directly into a chloride remover 130, as shown in FIG.
composition of the paraffinic hydrocarbon feedstock, the 2, or is passed through a cooler or heater to adjust the tem
activity of the selected catalyst, and the hydrocarbon conver perature of the compressed effluent 115, to a temperature that
sion rate. In general, dehydrogenation conditions include a is above the dew point temperature of the compressed effluent
US 2014/03.78725 A1 Dec. 25, 2014

stream 115 at the particular process conditions. In an example 200 to about 350° F.), and most preferably between about
embodiment, this temperature is between about 93-300° C. 121-177° C. (about 250-350° F.). Other temperature ranges
(about 200-572 F.), more preferably between about 93-177° are possible for the compressed effluent 115, for instance
C. (about 200 to about 350°F), and most preferably between depending on the particular catalytic dehydrogenation pro
about 121-177° C. (about 250-350° F.). In the chloride cess (e.g., C4, C5).
remover 130, chloride present in the compressed effluent 115 0044 An example pressure for the compressed effluent
is adsorbed with an adsorbent to provide a treated effluent 115 that is introduced into the chloride remover 130 is about
190. 345 kPa to 2750 kPa (about 50 psig to 400 psig), and in a
0038. In an embodiment, the adsorbent has a low hydro particular example embodiment is about 1450 kPa (about 210
carbon reactivity. “Low hydrocarbon reactivity” refers to a psig). The pressure of the reactor effluent 40 before the com
strongly reduced susceptibility of the adsorbent material to pressor 82 is typically too low (e.g., only about 7 kPa (1 psig))
catalyze side reactions of the main stream (e.g., the com and it is not practical to locate the chloride remover 130 at this
pressed effluent 115) upon formation of undesirable side location. However, it is possible that the chloride remover 130
products and fouling components which jeopardize the prod could be located before the compressor 82 if the catalytic
uct purity and adsorbent effectiveness. dehydrogenation process is performed at a higher pressure,
0039. In an example embodiment, the treated effluent 190 though this lower pressure could impact olefin conversion in
is cooled at the cooler 120, which in FIG. 2 is downstream of the catalytic dehydrogenation reactors 25.
the chloride removal. In an embodiment, cooling the treated 0045. As shown in FIG. 2, in a particular example embodi
effluent 190 cools the treated effluent to a temperature of ment, the compressed effluent 115 is directly introduced as an
between about 25-50° C. incoming stream into the chloride remover 130, without first
0040. The present inventors have observed that heavy cooling the compressed effluent. This provides both a suitable
hydrocarbons such as polynuclear aromatics condense from a temperature and pressure of the compressed effluent 115 for
process stream at lower temperatures (e.g., about 38-49 C. operation of the chloride remover 130. In another embodi
(about 100-120°F.)) and form a layer of deposit on the adsor ment, a cooler or heater (not shown) can be disposed in the
bent of the chloride remover 130, fouling the adsorbent. This process between the compressor 82 and the chloride remover
fouling reduces the capacity of the adsorbent, for instance by 130 to adjust (raise or lower) the temperature of the com
two thirds to a half of the maximum capacity. The result is pressed effluent 115 to a selected (e.g., an optimal) tempera
poor chloride capacity in the chloride remover 130. ture that is above the dew point temperature of the incoming
0041) To avoid fouling the absorbent, the chloride remover stream at the particular process conditions.
130 can be located at a higher temperature that is above the 0046. The chloride remover 130 can be configured simi
dew point temperature of the process stream at the particular larly to the chloride remover 130 in FIG. 1, or can be other
process conditions, which lowers the degree of condensation. wise configured. In an example embodiment shown in FIG.3,
An example higher temperature is between about 93-300° C. the chloride remover 130 is a non-regenerative chloride
(about 200-572 F.), more preferably between about 93-177° remover including a vessel 160 and Scavenging guard beds
C. (about 200 to about 350°F), and most preferably between 162 disposed therein that includes one or more adsorbents,
about 121-177° C. (about 250-350° F.). In a particular which are typically formed as extrudates or beads. An inlet
example, this higher temperature can be located at the dis distributor 164 is provided at a top of the vessel 160, and inert
charge of the compressor 82, as shown in FIG. 2. This higher Support media 166, 168 (e.g., ceramic Support balls) are dis
temperature reduces or prevents the condensation of heavy posed above and below the adsorbent material, respectively,
hydrocarbons. to provide for optimal flow distribution. In an example
0042. By selecting and using a high capacity chloride embodiment, the support media 1.66 above the adsorbent
adsorbent that is operable at elevated temperatures and that material guard beds 162 includes 19 mm balls 169 disposed
has a low hydrocarbon reactivity, the chloride removal per on a screen 170, and the support media 168 below the adsor
formance can be improved from that of traditional adsorbent bent material guard beds includes layers 172, 174, 176
placed downstream of the cooler 120 in FIG. 1, even at higher (higher to lower) of 3 mm balls, 6 mm balls, and 19 mm balls
temperatures. In addition, an optimum chloride adsorbent disposed on a support screen 178, which is disposed above an
will have the additional property of no or low reduction in outlet 180. The support media 166, 168 may be of other sizes,
capacity at the higher proposed operating temperature. This as will be appreciated by those of ordinary skill in the art.
provides a surprising result in that it allows the chloride 0047. An example chloride adsorbent is a shaped particle
remover 130 to be located upstream of the cooler 120 on a (such as beads or pellets) in a suitable size to allow for good
hotter stream, e.g., at the discharge of the compressor 82. This flow distribution while managing the pressure drop to a low
results in high chloride loading and better adsorbent life. level. The typical adsorbent particle size used in the catalyti
0043. The reactor effluent 40 in an example embodiment cal dehydrogenation process is of a nominal particle diameter
contains unconverted Saturated hydrocarbons, olefin hydro of 3.2 mm (/s inch), although it is contemplated for other
carbons, mononuclear aromatic compounds in an amount example processes to use a larger or Smaller size also. For
from about 100 to about 5,000 wppm, and polynuclear aro promoted alumina adsorbents, as the adsorbents pickup chlo
matic compounds in an amount from about 5 to about 500 ride, the promoter and the aluminum react with the chloride to
wppm. This reactor effluent 40 is compressed in compressor form salts.
82. The compressed effluent 115 at the discharge of the com 0048. An example adsorbent that can be used is in the class
pressor 82, e.g., from a compressor discharge drum, is intro of promoted alumina products, such as but not limited to
duced into the chloride remover 130. For a C3 catalytic dehy highly promoted alumina. Example highly promoted alumina
drogenation process, the compressed effluent 115 can be at a contains sodium (Na) from about 1-28 wt % calculated as an
temperature that is between about 93-300° C. (about 200 oxide, and in a more particular example contains Na from
572 F.), more preferably between about 93-177° C. (about about 3-18 wt %. Example highly promoted alumina adsor
US 2014/03.78725 A1 Dec. 25, 2014

bents that can be used are disclosed in U.S. Pat. No. 7,758,837 enough to reduce or prevent byproducts such as heavy hydro
and in US Patent Application Publication No. 2010/0222215. carbons from polymerizing and forming coke in the chloride
A particular example highly promoted alumina adsorbent is remover 130.
CLR-204, manufactured by UOP, of Des Plaines, Ill. CLR 0055 While at least one exemplary embodiment has been
204 has properties of low reactivity (e.g., no measurable presented in the foregoing detailed description of the inven
changes in the stream composition attemperatures of 200°C. tion, it should be appreciated that a vast number of variations
or higher), as compared to traditional adsorbent, and high exist. It should also be appreciated that the exemplary
capacity (e.g., 14%) at elevated temperatures (e.g., 200° C.). embodiment or exemplary embodiments are only examples,
0049 Other activated aluminas can also be used as the and are not intended to limit the scope, applicability, or con
chloride adsorbent, though olefin reactivity and hence fouling figuration of the invention in any way. Rather, the foregoing
effects can be a consideration. Other chloride absorbent such detailed description will provide those skilled in the art with
as metal oxide/metal carbonate products can also be used, a convenient road map for implementing an exemplary
provided a Sufficient Surface area is provided to maximize embodiment of the invention. It being understood that various
chloride capacity. Example metal oxides include ZnO, MgO, changes may be made in the function and arrangement of
CaO, and combined products. Another example of an adsor elements described in an exemplary embodiment without
bent that can be used is a molecular sieve adsorbent Such as departing from the scope of the invention as set forth in the
natural and synthetic Zeolites modified to reduce catalytic appended claims.
reactivity. An example molecular sieve adsorbent material is What is claimed is:
a sodium faujisite. 1. A process for removal of trace chloride contaminants in
0050. In an example operation of the chloride remover a reactor effluent in a catalytic dehydrogenation process, the
130, the compressed effluent 115, at a temperature between process comprising:
about 93-300° C. (about 200-572 F.), more preferably compressing the reactor effluentina compressor to provide
between about 93-177° C. (about 200 to about 350°F), and a compressed effluent;
most preferably between about 121-177° C. (about 250-350° introducing the compressed effluent into a chloride
F.), passes through the vessel 160, through the Support media remover,
166, 168, and over the adsorbent guard bed 162. Both physi adsorbing chlorides present in the compressed effluent in
cal and chemical adsorption take place in the guard bed 162 as
the adsorbent contacts the compressed effluent 115, removing the chloride remover, to provide a treated effluent; and
trace chloride contaminants from the compressed effluent. cooling the treated effluent in a cooler.
0051 Referring again to FIG. 2, operation of the chloride 2. The process of claim 1, wherein the compressed effluent
remover 130 results in the treated effluent 190. In an example is introduced directly from the compressor into the chloride
eOWe.
process, the treated effluent 190 is introduced to the cooler
120, which is located downstream of the chloride remover 3. The process of claim 1, wherein the compressed effluent
130 and upstream of the drier84. An example cooler 120 is a is cooled or heated to a temperature above a dew point of the
heat exchanger. An example operation of the cooler 120 low compressed effluent prior to the introducing the compressed
ers the temperature of the treated effluent 190 to a range of effluent into the chloride remover.
about 38-49° C. (about 100-120°F). The cooled effluent 120 4. The process of claim 1 wherein absorbing the chlorides
is then introduced to the drier84. Operation of the drier84 can takes place at a temperature between about 93 and 300° C.
be as described above, or in other ways as will be appreciated 5. The process of claim 1 wherein adsorbing the chlorides
by those of ordinary skill in the art. takes place at a temperature between about 121 and 177°C.
0052. The drier84 output stream is separated in separator 6. The process of claim 1 wherein adsorbing the chloride
85. Gas 90 is expanded in expander 95 and separated into a comprises:
recycle hydrogen stream 100 and a net separator gas stream contacting the compressed effluent with an adsorbent
105. A liquid stream 110, which includes the olefin product material.
and unconverted paraffin, is sent for further processing, where 7. The process of claim 6, wherein the chloride is physi
the desired olefin product is recovered and the unconverted cally adsorbed, chemsorbed, chemically reacted, or a combi
paraffin is recycled to the dehydrogenation reactors 25. nation.
0053. Thus, the example chloride remover 130 in FIG.3 is 8. The process of claim 6, wherein the adsorbent material
located upstream of the cooler 120 and downstream of the comprises activated alumina, a promoted alumina product,
compressor 82. Locating the chloride remover 130 upstream metal oxides, molecular sieves, or a combination.
of the cooler 120 provides the advantage that there is less 9. The process of claim 6, wherein the adsorbent material
heavy hydrocarbon deposition. This also makes the chloride comprises a highly promoted alumina.
remover 130 easier to unload. By contrast, in some conven 10. The process of claim 1, further comprising:
tional processes, agglomeration of heavy hydrocarbons
makes the chloride remover difficult to unload. Further, if introducing the cooled effluent to a drier;
adsorbents such as CLR-204 are used, the chloride remover wherein cooling the treated effluent takes place down
130 can be unloaded as non-hazardous material. stream of the chloride remover and upstream of the drier.
0054 By placing the chloride remover 130 just down 11. The process of claim 1, wherein a pressure of the
stream of the compressor 82 in the chloride removal process, compressed effluent is between about 345 kPa and 2750 kPa
the compressed effluent 115 can be hot enough to prevent or (about 50 psig and 400 psig).
minimize condensation of heavy hydrocarbons from the reac 12. A process for high temperature removal of trace chlo
tor effluent 40 which would cause absorbent fouling. Further, ride contaminants from a reactor effluent in a catalytic dehy
the temperature of the compressed effluent 115 can be cold drogenation process, the process comprising:
US 2014/03.78725 A1 Dec. 25, 2014

dehydrogenating a hydrocarbon feed in a dehydrogenation 16. The process of claim 12 wherein adsorbing the trace
reaction Zone under dehydrogenation reaction condi chloride contaminants takes place at a temperature between
tions in the presence of a dehydrogenation catalyst to about 93-300° C.
form a reactor effluent; 17. The process of claim 12 wherein adsorbing the trace
compressing the reactor effluent to provide a compressed chloride contaminants takes place at a pressure between
effluent; about 345 kPa to 2750 kPa (about 50 to 400 psig).
introducing the compressed effluent into a chloride 18. The process of claim 12, wherein the trace chloride
remover at a temperature that is above a dew point of the contaminants are physically adsorbed, chemsorbed, chemi
compressed effluent; cally reacted, or a combination.
adsorbing trace chloride contaminants present in the com 19. The process of claim 12, further comprising:
pressed effluent in the chloride remover with an adsor introducing the cooled effluent to a drier;
bent to provide a treated effluent; and wherein cooling the treated effluent takes place down
cooling the treated effluent. stream of the chloride remover and upstream of the drier.
13. The process of claim 12, wherein the adsorbent has a 20. The process of claim 19, further comprising:
low catalytic activity for olefinic hydrocarbons to limit side separating an olefin product, an unconverted paraffin, and a
reactions and fouling events in the chloride remover. recycle hydrogen stream from an output stream of the
14. The process of claim 12, wherein the adsorbent com drier;
prises an activated alumina, a promoted alumina product, recovering the olefin product; and
metal oxides, molecular sieves, or combinations thereof recycling the recycle hydrogen stream and the unconverted
15. The process of claim 12, wherein the reactor effluent paraffin to the dehydrogenation reaction Zone.
comprises heavy hydrocarbons. k k k k k