GB2423489A - Water gas shift reactor - Google Patents

Water gas shift reactor Download PDF

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Publication number
GB2423489A
GB2423489A GB0503895A GB0503895A GB2423489A GB 2423489 A GB2423489 A GB 2423489A GB 0503895 A GB0503895 A GB 0503895A GB 0503895 A GB0503895 A GB 0503895A GB 2423489 A GB2423489 A GB 2423489A
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Prior art keywords
water gas
gas shift
catalyst
section
monolith
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GB0503895D0 (en
Inventor
Janet Mary Fisher
David Thompsett
Suzanne Rose Ellis
John Paul Breen
Robert Burch
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Johnson Matthey PLC
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Johnson Matthey PLC
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Priority to GB0503895A priority Critical patent/GB2423489A/en
Publication of GB0503895D0 publication Critical patent/GB0503895D0/en
Publication of GB2423489A publication Critical patent/GB2423489A/en
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    • B01J35/19—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/248—Reactors comprising multiple separated flow channels
    • B01J19/2485—Monolithic reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/248—Reactors comprising multiple separated flow channels
    • B01J19/249—Plate-type reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0207—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly horizontal
    • B01J8/0221—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly horizontal in a cylindrical shaped bed
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/02—Processes carried out in the presence of solid particles; Reactors therefor with stationary particles
    • B01J2208/023—Details
    • B01J2208/024—Particulate material
    • B01J2208/025—Two or more types of catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24—Stationary reactors without moving elements inside
    • B01J2219/2401—Reactors comprising multiple separate flow channels
    • B01J2219/245—Plate-type reactors
    • B01J2219/2461—Heat exchange aspects
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24—Stationary reactors without moving elements inside
    • B01J2219/2401—Reactors comprising multiple separate flow channels
    • B01J2219/245—Plate-type reactors
    • B01J2219/2476—Construction materials
    • B01J2219/2477—Construction materials of the catalysts
    • B01J2219/2479—Catalysts coated on the surface of plates or inserts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • B01J35/56—
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C01B2203/0288—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step containing two CO-shift steps
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1064—Platinum group metal catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/82—Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Fluid Mechanics (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

A water gas shift reactor 1 comprises a fist water gas shift reaction zone 2 in series with a second water gas shift zone 3 comprising different catalyst material. No heat exchanger is used on gases leaving the first zone and entering the second zone therefore the temperature of the gases leaving the first zone is the same as the temperature of the gases entering the second zone. The water gas shift zones comprise different catalysts arranged such that the first zone comprises a catalyst having positive order kinetics, comprising for example gold dispersed on ceria or zirconia, and the second water gas shift zone comprises a catalyst having negative order kinetics, comprising platinum dispersed on ceria or zirconia. The catalysts may be arranged such that the first zone comprises a high temperature catalyst and the second zone comprises a low temperature catalyst or vice versa. The catalyst may be supported on a single or double monolith, foam or in a bed arrangement.

Description

Water Gas Shift Reactor The present invention relates to a water gas shift
reactor and a method of purifying hydrogen using the reactor.
The water gas shift (WGS) reaction converts water and carbon monoxide into hydrogen and carbon dioxide: H20+CO-*H2+C02 The reaction is commonly used to remove carbon monoxide from gas streams, e.g. hydrogen-rich gas streams produced by the reforming of hydrocarbon fuels. The reaction is catalysed by heterogeneous catalysts, which are usually classified as high temperature WGS catalysts (capable of catalysing the reaction at 400450 C) and low temperature WGS catalysts (capable of catalysing the reaction at 200- 400 C). State-of- the-art WGS catalysts include iron/chromiumlcopper oxide (for high temperature WGS) and copper oxide/zinc oxide (for low temperature WGS).
Typical WGS reactors contain two stages: a high temperature WGS stage (typically run at 400-450 C) followed by a low temperature WGS stage (typically run at 200-400 C). The WGS reaction is exothermic and it is necessary to cool the gas stream between the high temperature WGS stage and the low temperature WGS stage in order to reach low equilibrium levels of CO. Heat exchangers are typically used to cool the gas stream.
The present inventors have developed a WGS reactor which takes advantage of the differing activity of different WGS catalysts, but does not require cooling between the different catalytic stages.
The present invention provides a water gas shift reactor comprising: a first water gas shift reaction zone, comprising a first water gas shift catalyst; and a second water gas shift reaction zone, comprising a second water gas shift catalyst that is different to the first water gas shift catalyst, wherein the second water gas shift reaction zone is downstream of the first water gas shift reaction zone; PFC1712GB 25Feb2005 : :: , :: : PFCI712: : : : : : : S S * S characterised in that the first and second water gas shift reaction zones are located such that, in use, the temperature of gases exiting the first water gas shift reaction zone is the same as the temperature of gases entering the second water gas shift reaction zone.
Unlike prior art WGS reactors wherein the gas stream is cooled between catalytic stages, the WGS reactor of the invention has two different catalytic zones but there is no cooling between the zones. In a preferred embodiment of the invention, the first and second water gas shift reaction zones are located such that, in use, the gases exiting the first water gas shift reaction zone pass directly into the second water gas shift reaction zone, i.e. there is no intervening zone between the first and second water gas shift reaction zones. Typically, the first WGS reaction zone does not comprise the second WGS catalyst and the second WGS reaction zone does not comprise the first WGS catalyst. However, it is possible that there will be a limited region in the reactor comprising both the first and second WGS catalysts. For the purposes of this description, a region comprising both the first and second WGS catalysts will be considered as part of the first WGS reaction zone (i.e. the first WGS reaction zone may comprise the second WGS catalyst, but the second WGS reaction zone does not comprise the first WGS catalyst).
In a first embodiment of the invention, the first water gas shift catalyst has positive order kinetics with respect to carbon monoxide for the water gas shift reaction, and the second water gas shift catalyst has negative order kinetics with respect to carbon monoxide for the water gas shift reaction. This means that the rate of reaction in the first reaction zone should increase with increasing CO concentration, whereas the rate of reaction in the second reaction zone should increase with decreasing CO concentration.
This is advantageous because the CO concentration of the reactant gases entering the second WGS reaction zone will be lower than the CO concentration of the reactant gases entering the first WGS reaction zone, and the efficacy of CO removal will be increased.
Catalysts having positive order kinetics and negatives order kinetics with respect to carbon monoxide for the WGS reaction can be identified by rate studies of the catalytic reaction. A suitable catalyst having positive order kinetics with respect to CO for the WGS reaction is gold supported by ceria andlor zirconia. A suitable catalyst PFC 1712GB 25Feb2005 **
I III I I I I
PFC1712 *** *. : . . having negative order kinetics with respect to CO for the WGS reaction is platinum supported by ceria and/or zirconia.
In a second embodiment of the invention, the first water gas shift catalyst has an optimum temperature T1 wherein its activity for the water gas shift reaction is highest, and the second water gas shift catalyst has an optimum temperature T2 wherein its activity for the water gas shift reaction is highest, and T1 is less than T2. This is advantageous if the first WGS reaction zone is not cooled because the WGS reaction is exothermic and, in the absence of cooling, the gas stream will be heated as it passes through the first WGS reaction zone, and the gas stream entering the second WGS reaction zone will be hotter than the gas stream entering the first WGS reaction zone, and the efficacy of CO removal will be increased. Suitably T is in the range 200-250 C and T2 is in the range 250-300 C.
In a third embodiment of the invention, the first water gas shift catalyst has an optimum temperature 13 wherein its activity for the water gas shift reaction is highest, and the second water gas shift catalyst has an optimum temperature T4 wherein its activity for the water gas shift reaction is highest, and T3 is more than T4. This is advantageous if the WGS reaction zones are force cooled so that, despite the exothennic WGS reaction, the gas stream will be cooled as it passes through the first WGS reaction zone, and the gas stream entering the second WGS reaction zone will be cooler than the gas stream entering the first WGS reaction zone and the efficacy of CO removal will be increased. Suitably 13 is in the range 250-300 C.and 14 is in the range 200-250 C.
The WGS reactor according to the invention can take a variety of forms. The reactor may comprise a catalyst support monolith, wherein the first water gas shift catalyst is coated on a first section of the monolith and the second water gas shift catalyst is coated on a second section of the monolith, such that the first section of the monolith is proximate to the second section of the monolith. The first section and second section are proximate insofar as there is no or only a negligible distance between the first and second sections. In a particular embodiment, the first and second sections overlap, so that there is a region in the centre of the monolith comprising both catalysts. Because the first and second sections are proximate, the temperature of the gases exiting the first PFC 1712GB 25Feb2005 ** : * *S S S S S S I St PFC17I2: : * : : : : : S S * S S WGS reaction zone will be the same as the temperature of the gases entering the second WGS reaction zone.
Methods of coating catalysts onto a catalyst support monolith are known to those skilled in the art and are disclosed in e.g. EP 1 064 094. The simplest method of producing a zoned coated monolith is to coat the first WGS catalyst onto a first face of the monolith, then turn the monolith over and coat the second WGS catalyst onto the second face of the monolith. Through trial and error it is possible to control the depth of the coating and therefore it is possible to control the proximity of the first and second sections. The catalyst support monolith may be ceramic (e.g. cordierite) or metallic (e.g. Fecralloy').
The WGS reactor may alternatively comprise a first catalyst support monolith and a second catalyst support monolith, wherein the first water gas shift catalyst is coated on the first monolith and the second water gas shift catalyst is coated on the second monolith, such that the first monolith is proximate to the second monolith. The first monolith and second monolith are proximate insofar as there is no or only a negligible distance between the first and second monoliths. Because the first and second monoliths are proximate, the temperature of the gases exiting the first WGS reaction zone will be the same as the temperature of the gases entering the second WGS reaction zone.
Methods of incorporating monoliths into catalytic reactors are well known to those skilled in the art. The catalyst support monoliths may be ceramic (e.g. cordierite) or metallic (e.g. Fecralloy).
The WGS reactor may alternatively comprise a heat exchanger, wherein the first water gas shift catalyst is deposited on a first section of the heat exchanger and the second water gas shift catalyst is deposited on a second section of the heat exchanger, such that the first section of the heat exchanger is proximate to the second section of the heat exchanger. The first and second sections of the heat exchanger are proximate insofar as there is no or only a negligible distance between the first and second sections.
Because the first and second sections are proximate, the temperature of the gases exiting the first WGS reaction zone will be the same as the temperature of the gases entering the second WGS reaction zone. The catalysts are deposited on the heat exchanger and may PFC 1712GB 25Feb2005 . fr: *i, *S f I I I I II las S S * * PFCI712: : * . a I * I S either be coated onto the heat exchanger, or may be present as a catalyst bed, which is supported by the heat exchanger. Heat exchangers such as plate reactors are known to the skilled person, and methods of depositing catalysts on the heat exchangers are also known to the skilled person. In the third embodiment of the invention wherein the WGS catalysts have optimum temperature T3 and T4 it is particularly advantageous for the WGS reactor to comprise a heat exchanger, so that the WGS zones may be force cooled.
The WGS reactor may alternatively comprise a foam, wherein the first water gas shift catalyst is deposited on a first section of the foam and the second water gas shift catalyst is deposited on a second section of the foam, such that the first section of the foam is proximate to the second section of the foam. The first and second sections of the foam are proximate insofar as there is no or only a negligible distance between the first and second sections. In a particular embodiment, the first and second sections overlap, so that there is a region in foam comprising both catalysts. Because the first and second sections are proximate, the temperature of the gases exiting the first WGS reaction zone will be the same as the temperature of the gases entering the second WGS reaction zone.
Foams may be coated by similar methods to those used to coat monoliths. A zoned coated foam may be produced by coating the first WGS catalyst onto a first face of the foam, then turning the foam over and coating the second WGS catalyst onto the second face of the foam. Through trial and error it is possible to control the depth of the coating and therefore it is possible to control the proximity of the first and second sections. The foam may be ceramic or metallic.
The WGS reactor may alternatively comprise a catalyst bed, wherein the first water gas shift catalyst is present in a first section of the bed and the second water gas shift catalyst is present in a second section of the bed, such that the first section of the bed is proximate to the second section of the bed. The first and second sections of the foam are proximate insofar as there is no or only a negligible distance between the first and second sections. In a particular embodiment, the first and second sections overlap, so there is a region in the bed comprising both catalysts. Because the first and second sections are proximate, the temperature of the gases exiting the first WGS reaction zone will be the same as the temperature of the gases entering the second WGS reaction zone.
PFC17I2GB 25Feb2005 :: :: : . : PFC1712: :
I I I S S
Methods of preparing catalyst beds containing more than one catalyst in separate sections are known to the person skilled in the art.
In a further aspect the present invention provides a method of purifying hydrogen comprising steps of (a) supplying a first reactant stream comprising hydrogen, carbon monoxide and steam to a first water gas shift reaction zone comprising a first water gas shift catalyst, thereby producing a first product stream at a first temperature; and (b) supplying the first product stream at the first temperature to a second water gas shift reaction zone comprising a second water gas shift catalyst, thereby producing a second product stream.
The first product stream contains less carbon monoxide than the first reactant stream, and the second product stream contains less carbon monoxide than the first product stream. In a preferred embodiment, the first reactant stream comprises hydrogen as a main component (suitably greater than 50mo1%) and carbon monoxide as a minor component (suitably less than lmol%).
The WGS reactor of the present invention may be combined with other reactors in a system for removing carbon monoxide from a gas stream. For example, the WGS reactor of the present invention may be downstream of a high-temperature WGS reactor, operating at 400-450 C.
Figure 1 is a representation of an embodiment of the invention. The WGS reactor (1) has a first WGS reaction zone (2) and a second WGS reaction zone (3), which is downstream of the first reaction zone (2). The black arrows show the direction of the gas flow. A first WGS catalyst is deposited on the first WGS reaction zone (2) and a second WGS catalyst is deposited on the second WGS reaction zone (3). A gas stream containing hydrogen, carbon monoxide and steam is fed to the first WGS zone (2).
Within the first reaction WGS zone, at least some of the carbon monoxide and steam react to form carbon dioxide and hydrogen. The first and second WGS zones are proximate so that the gas stream passes directly from the first WGS zone (2) to the PFCI712GB 25Feb2005 * ,!* * * I. * I * I I I I * I I I I II PFC1712: :::: * I * S S second WGS zone (3) and the temperature of the gas stream exiting the first water gas shift reaction zone (2) is the same the temperature of gases entering the second water gas shift reaction zone (3). Within the second WGS reaction zone, further reaction of carbon monoxide and steam occurs such that the gas stream leaving the second WGS reaction zone is substantially depleted of carbon monoxide.
The WGS reactor of the present invention can increase the efficacy of CO removal from a hydrogen-containing gas stream. This means that effective CO removal may be achieved with a smaller reactor, with a smaller amount of catalytic metal or with a decreased use of energy.
PFC 1712GB 25Feb2005

Claims (14)

  1. * : * * I S * S S I IS : * *. * PFC17I2, *, : . . Claims 1. A water gas
    shift reactor comprising: a first water gas shift reaction zone, comprising a first water gas shift catalyst; and a second water gas shift reaction zone, comprising a second water gas shift catalyst that is different to the first water gas shift catalyst, wherein the second water gas shift reaction zone is downstream of the first water gas shift reaction zone; characterised in that the first and second water gas shift reaction zones are located such that, in use, the temperature of gases exiting the first water gas shift reaction zone is the same the temperature of gases entering the second water gas shift reaction zone.
  2. 2. A water gas shift reactor according to claim 1, wherein the first water gas shift catalyst has positive order kinetics with respect to carbon monoxide for the water gas shift reaction, and wherein the second water gas shift catalyst has negative order kinetics with respect to carbon monoxide for the water gas shift reaction.
  3. 3. A water gas shift reactor according to claim 2, wherein the first water gas shift catalyst comprises gold, and the second water gas shift catalyst comprises platinum.
  4. 4. A water gas shift reactor according to claim 3, wherein the first water gas shift catalyst comprises gold dispersed on ceria andlor zirconia and the second water gas shift catalyst comprises platinum dispersed on ceria and/or zirconia.
  5. 5. A water gas shift reactor according to claim 1, wherein the first water gas shift catalyst has an optimum temperature T1 wherein its activity for the water gas shift reaction is highest, and the second water gas shift catalyst has an optimum temperature T2 wherein its activity for the water gas shift reaction is highest, and wherein T1 is less than T2.
    PFCI 7 12GB 25Feb2005 * : Ie * I I * a a I ** * 0 ** a I I * PFC1712 a a I, * a I
  6. 6. A water gas shift reactor according to claim 6, wherein T1 is in the range 200- 250 C and T2 is in the range 250-300 C.
  7. 7. A water gas shift reactor according to claim 1, wherein the first water gas shift catalyst has an optimum temperature T3 wherein its activity for the water gas shift reaction is highest, and the second water gas shift catalyst has an optimum temperature T4 wherein its activity for the water gas shift reaction is highest, and wherein T3 is more than 14.
  8. 8. A water gas shift reactor according to claim 7, wherein T3 is in the range 250- 3 00 C and T4 is in the range 200-250 C.
  9. 9. A water gas shift reactor according to any preceding claim, comprising a catalyst support monolith, wherein the first water gas shift catalyst is coated on a first section of the monolith and the second water gas shift catalyst is coated on a second section of the monolith, such that the first section of the monolith is proximate to the second section of the monolith.
  10. 10. A water gas shift reactor according to any one of claims 1 to 8, comprising a first catalyst support monolith and a second catalyst support monolith, wherein the first water gas shift catalyst is coated on the first monolith and the second water gas shift catalyst is coated on the second monolith, such that the first monolith is proximate to the second monolith.
  11. 11. A water gas shift reactor according to any one of claims 1 to 8, comprising a heat exchanger, wherein the first water gas shift catalyst is deposited on a first section of the heat exchanger and the second water gas shift catalyst is deposited on a second section of the heat exchanger, such that the first section of the heat exchanger is proximate to the second section of the heat exchanger.
  12. 12. A water gas shift reactor according to any one of claims 1 to 8, comprising a foam, wherein the first water gas shift catalyst is deposited on a first section of the foam and the second water gas shift catalyst is deposited on a second section PFC1712GB 25Feb2005 a. a,, a P. a a a I P I I PFCI712 *- : : : : I $ I S
    I I
    of the foam, such that the first section of the foam is proximate to the second section of the foam.
  13. 13. A water gas shift reactor according to any one of claims 1 to 8, comprising a catalyst bed, wherein the first water gas shift catalyst is present in a first section of the bed and the second water gas shift catalyst is present in a second section of the bed, such that the first section of the bed is proximate to the second section of the bed.
  14. 14. A method of purifying hydrogen comprising steps of (a) supplying a first reactant stream comprising hydrogen, carbon monoxide and steam to a first water gas shift reaction zone comprising a first water gas shift catalyst, thereby producing a first product stream at a first temperature; and (b) supplying the first product stream at the first temperature to a second water gas shift reaction zone comprising a second water gas shift catalyst, thereby producing a second product stream.
    PFC1712GB 25Feb2005
GB0503895A 2005-02-25 2005-02-25 Water gas shift reactor Withdrawn GB2423489A (en)

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
EP1930292A1 (en) * 2006-12-05 2008-06-11 Air Products and Chemicals, Inc. Process and apparatus for production of hydrogen using the water gas shift reaction
FR2953149A1 (en) * 2009-12-01 2011-06-03 Air Liquide CATALYTIC REACTOR COMPRISING AT LEAST ONE CONTROLLED MACROPOROSITY ALVEOL ARCHITECTURE ZONE AND A STANDARD ARCHITECTURE-MICROSTRUCTURE AREA
CN102284259A (en) * 2010-06-18 2011-12-21 乔治洛德方法研究和开发液化空气有限公司 Catalytic reactor comprising a catalytic structure providing an improved gas flow distribution
EP2592046A1 (en) * 2010-07-06 2013-05-15 Renaissance Energy Research Corporation Apparatus and process for carbon monoxide shift conversion, and hydrogen production equipment

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US3825501A (en) * 1969-11-26 1974-07-23 Texaco Inc Exothermic reaction process
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US6524550B1 (en) * 1999-05-03 2003-02-25 Prashant S. Chintawar Process for converting carbon monoxide and water in a reformate stream
US6548029B1 (en) * 1999-11-18 2003-04-15 Uop Llc Apparatus for providing a pure hydrogen stream for use with fuel cells
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US3825501A (en) * 1969-11-26 1974-07-23 Texaco Inc Exothermic reaction process
JPH02188406A (en) * 1989-01-18 1990-07-24 Fuji Electric Co Ltd Carbon monoxide converter
DE19719997A1 (en) * 1997-05-13 1998-05-28 Daimler Benz Ag Reformer for stream reforming methanol
US6524550B1 (en) * 1999-05-03 2003-02-25 Prashant S. Chintawar Process for converting carbon monoxide and water in a reformate stream
US6548029B1 (en) * 1999-11-18 2003-04-15 Uop Llc Apparatus for providing a pure hydrogen stream for use with fuel cells
WO2002000547A1 (en) * 2000-06-19 2002-01-03 Uop Llc Apparatus for producing hydrogen
DE10041712A1 (en) * 2000-08-25 2002-03-07 Volkswagen Ag Reforming device used for producing a hydrogen-rich gas from a mixture containing hydrocarbons comprises a high temperature shift reaction unit, a low temperature shift reaction unit and a heat exchanger contained in a converter
GB2389544A (en) * 2000-12-28 2003-12-17 Ballard Power Systems Shell and tube reactor

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1930292A1 (en) * 2006-12-05 2008-06-11 Air Products and Chemicals, Inc. Process and apparatus for production of hydrogen using the water gas shift reaction
FR2953149A1 (en) * 2009-12-01 2011-06-03 Air Liquide CATALYTIC REACTOR COMPRISING AT LEAST ONE CONTROLLED MACROPOROSITY ALVEOL ARCHITECTURE ZONE AND A STANDARD ARCHITECTURE-MICROSTRUCTURE AREA
WO2011067509A1 (en) 2009-12-01 2011-06-09 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Catalytic reactor including one cellular area having controlled macroporosity and a controlled microstructure and one area having a standard microstructure
US9034282B2 (en) 2009-12-01 2015-05-19 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Catalytic reactor including one cellular area having controlled macroporosity and a controlled microstructure and one area having a standard microstructure
CN102284259A (en) * 2010-06-18 2011-12-21 乔治洛德方法研究和开发液化空气有限公司 Catalytic reactor comprising a catalytic structure providing an improved gas flow distribution
EP2592046A1 (en) * 2010-07-06 2013-05-15 Renaissance Energy Research Corporation Apparatus and process for carbon monoxide shift conversion, and hydrogen production equipment
EP2592046A4 (en) * 2010-07-06 2014-01-29 Renaissance Energy Res Corp Apparatus and process for carbon monoxide shift conversion, and hydrogen production equipment

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