CA2531922A1 - Feed gas contaminant removal in ion transport membrane systems - Google Patents

Feed gas contaminant removal in ion transport membrane systems Download PDF

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CA2531922A1
CA2531922A1 CA002531922A CA2531922A CA2531922A1 CA 2531922 A1 CA2531922 A1 CA 2531922A1 CA 002531922 A CA002531922 A CA 002531922A CA 2531922 A CA2531922 A CA 2531922A CA 2531922 A1 CA2531922 A1 CA 2531922A1
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pressure vessel
interior
oxide
oxygen
guard bed
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CA2531922C (en
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Michael Francis Carolan
Christopher Francis Miller
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Air Products and Chemicals Inc
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Air Products and Chemicals Inc
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    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • C01B13/0229—Purification or separation processes
    • C01B13/0248—Physical processing only
    • C01B13/0251—Physical processing only by making use of membranes
    • C01B13/0255—Physical processing only by making use of membranes characterised by the type of membrane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
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    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/229—Integrated processes (Diffusion and at least one other process, e.g. adsorption, absorption)
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    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/64—Heavy metals or compounds thereof, e.g. mercury
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/08—Flat membrane modules
    • B01D63/082—Flat membrane modules comprising a stack of flat membranes
    • B01D63/084—Flat membrane modules comprising a stack of flat membranes at least one flow duct intersecting the membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
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    • 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
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
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    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/384—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts the catalyst being continuously externally heated
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708—Volatile organic compounds V.O.C.'s
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2313/00—Details relating to membrane modules or apparatus
    • B01D2313/42—Catalysts within the flow path
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2319/00—Membrane assemblies within one housing
    • B01D2319/04—Elements in parallel
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    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0211—Processes for making hydrogen or synthesis gas containing a reforming step containing a non-catalytic reforming step
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    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0211—Processes for making hydrogen or synthesis gas containing a reforming step containing a non-catalytic reforming step
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    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
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    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
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    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0838—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
    • C01B2203/0844—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
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    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
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    • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
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    • C01B2203/16—Controlling the process
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    • 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
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    • C01B2210/00—Purification or separation of specific gases
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    • C01B2210/0046—Nitrogen
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    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0043—Impurity removed
    • C01B2210/0062—Water
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • 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

Abstract

Method for gas purification comprising (a) obtaining a feed gas stream containing one or more contaminants selected from the group consisting of volatile metal oxy-hydroxides, volatile metal oxides, and volatile silicon hydroxide; (b) contacting the feed gas stream with a reactive solid material in a guard bed and reacting at least a portion of the contaminants with the reactive solid material to form a solid reaction product in the guard bed; and (c) withdrawing from the guard bed a purified gas stream.

Claims (29)

1. A method for gas purification comprising (a) obtaining a feed gas stream containing one or more contaminants selected from the group consisting of volatile metal oxy-hydroxides, volatile metal oxides, and volatile silicon hydroxide;
(b) contacting the feed gas stream with a reactive solid material in a guard bed and reacting at least a portion of the contaminants with the reactive solid material to form a solid reaction product in the guard bed; and (c) withdrawing from the guard bed a purified gas stream.
2. The method of Claim 1 wherein the reactive solid material comprises one or more compounds selected from the group consisting of magnesium oxide, calcium oxide, copper oxide, calcium carbonate, sodium carbonate, strontium carbonate, zinc oxide, strontium oxide, and alkaline-earth-containing perovskites.
3. The method of Claim 2 wherein the reactive solid material comprises magnesium oxide.
4. The method of Claim 1 wherein the one or more contaminants comprise any of CrO2(OH)2, Si(OH)4, WO2(OH)2, CrO3, and oxy-hydroxides of molybdenum.
5. The method of Claim 1 wherein the feed gas stream comprises one or more components selected from the group consisting of nitrogen, oxygen, water, and carbon dioxide.
6. The method of Claim 1 wherein the feed gas stream comprises one or more components selected from the group consisting of hydrogen, carbon monoxide, carbon dioxide, methane, and water.
7. The method of Claim 1 wherein the feed gas stream is contacted with the reactive solid material at a temperature in the range of 600°C to 1100°C.
8. A method for the production of oxygen comprising (a) heating an oxygen-containing gas to form a hot oxygen-containing gas;
(b) contacting the hot oxygen-containing gas with a reactive solid material in a guard bed and withdrawing therefrom a purified hot oxygen-containing gas;
and (c) contacting the purified hot oxygen-containing gas with a first surface of a membrane comprising mixed metal oxide ceramic material, permeating oxygen through the membrane to a second surface of the membrane, and withdrawing therefrom a high purity oxygen product.
9. The method of Claim 8 wherein the hot oxygen-containing gas is obtained by the direct combustion of a gaseous fuel with air and comprises oxygen, nitrogen, carbon dioxide, and water.
10. The method of Claim 9 wherein the hot oxygen-containing gas further comprises one or more contaminant compounds selected from the group consisting of CrO2(OH)2,~
Si(OH)4, WO2(OH)2, CrO3, and oxy-hydroxides of molybdenum.
11. The method of Claim 8 wherein the reactive solid material comprises one or more compounds selected from the group consisting of magnesium oxide, calcium oxide, copper oxide, calcium carbonate, sodium carbonate, strontium carbonate, zinc oxide,~
strontium oxide, and alkaline-earth-containing perovskites.
12. The method of Claim 11 wherein the. reactive solid material comprises magnesium oxide.
13. An oxidation process comprising (a) contacting a hot oxygen-containing feed gas with a first surface of a membrane comprising mixed metal oxide ceramic material and permeating oxygen through the membrane to a second surface of the membrane to provide permeated oxygen;
(b) reacting a hot hydrocarbon-containing feed gas with the permeated oxygen to form an oxidation product; and (d) either or both of (1) providing the hot oxygen-containing feed gas by contacting a~~~
hot oxygen-containing gas stream with a reactive solid material in a guard bed and withdrawing therefrom the hot oxygen-containing feed gas and (2) providing the hot hydrocarbon-containing feed gas by contacting a hot hydrocarbon gas stream with a reactive solid material in a guard bed and withdrawing therefrom the hot hydrocarbon-containing feed gas.
14. ~The process of Claim 13 wherein the reactive solid material in the guard bed in either or both of (1) and (2) comprises one or more compounds selected from the group consisting of magnesium oxide, calcium oxide, copper oxide, calcium carbonate, sodium carbonate, strontium carbonate, zinc oxide, strontium oxide, and alkaline-earth-containing perovskites.
15. ~The process of Claim 13 wherein either or both of the hot oxygen-containing gas stream and the hot hydrocarbon gas stream comprise one or more volatile contaminant compounds selected from the group consisting of CrO2(OH)2, Si(OH)4, WO2(OH)2, CrO3, and oxy-hydroxides of molybdenum.
16. ~The process of Claim 13 wherein the hot oxygen-containing gas stream is obtained by the direct combustion of a gaseous fuel with air and comprises oxygen, nitrogen, carbon dioxide, and water.
17. ~The process of Claim 13 wherein the oxidation product is synthesis gas comprising hydrogen, carbon monoxide, and water.
18. An ion transport membrane system comprising (a) a pressure vessel having an interior, an exterior, an inlet, and an outlet;
(b) a plurality of planar ion transport membrane modules disposed in the interior of the pressure vessel and arranged in series, each membrane module comprising mixed metal oxide ceramic material and having an interior region and an exterior region, wherein any inlet and any outlet of the pressure vessel are in flow communication with exterior regions of the membrane modules;
(c) one or more gas manifolds in flow communication with interior regions of the membrane modules and with the exterior of the pressure vessel; and (d) either or both of (1) a guard bed in flow communication with the inlet of the pressure vessel and (2) a guard bed in flow communication with at least one of the one or more gas manifolds.
19. The system of Claim 18 wherein the guard bed in either or both of (1) and (2) contains a reactive solid material comprising one or more compounds selected from the group consisting of magnesium oxide, calcium oxide, copper oxide, calcium carbonate, sodium carbonate, strontium carbonate, zinc oxide, strontium oxide, and alkaline-earth-containing perovskites.
20. The system of Claim 18 wherein the guard bed in (1) is disposed exterior to the pressure vessel.
21. The system of Claim 18 wherein the guard bed in (1) is disposed in the interior of the pressure vessel.
22. The system of Claim 18 wherein the guard bed in (2) is disposed exterior to the pressure vessel.
23. The system of Claim 18 wherein the guard bed in (2) is disposed in the interior of the pressure vessel.
24. An ion transport membrane system comprising (a) a pressure vessel having an interior, an exterior, an inlet, and an outlet;
(b) a plurality of planar ion transport membrane modules disposed in the interior of the pressure vessel and arranged in series, each membrane module comprising mixed metal oxide ceramic material and having an interior region and an exterior region, wherein any inlet and any outlet of the pressure vessel are in flow communication with exterior regions of the membrane modules;
(c) one or more gas manifolds in flow communication with interior regions of the membrane modules and with the exterior of the pressure vessel; and (d) one or more guard beds, wherein each guard bed is disposed between any two adjacent planar ion transport membrane modules in the interior of the pressure vessel.
25. The system of Claim 24 that further comprises a flow containment duct disposed in the interior of the pressure vessel, wherein the flow containment duct (1) surrounds the plurality of planar ion transport membrane modules and the one or more guard beds and (2) is in flow communication with any inlet and any outlet of the pressure vessel.
26. An ion transport membrane system comprising (a) a pressure vessel having an interior, an exterior, an inlet, and an outlet;
(b) a membrane stack or module assembly disposed in the interior of the pressure vessel, the assembly having a plurality of planar wafers comprising mixed metal oxide ceramic material, each wafer having an interior region and an exterior region, and a plurality of hollow ceramic spacers, wherein the stack or module assembly is formed by alternating wafers and spacers such that the interiors of the wafers are in flow communication via the hollow spacers, the wafers are oriented parallel to one another, and the alternating spacers and wafers are oriented coaxially to form the stack or module such that the wafers are perpendicular to the stack or module axis;
(c) a gas manifold shroud assembly disposed around the membrane stack or module assembly within the interior of the pressure vessel, wherein the shroud assembly separates the stack or module into at least a first wafer zone and a second wafer zone, places any inlet of the pressure vessel in flow communication with exterior regions of the wafers in the first wafer zone, and places exterior regions of the wafers in the first wafer zone in series flow communication with exterior regions of the wafers of the second wafer zone; and (d) one or more guard beds disposed in either or both of the inlet of the pressure vessel and the gas manifold shroud assembly.
27. An ion transport membrane reactor system comprising (a) a pressure vessel having an interior, an exterior, an inlet, and an outlet;
(b) a plurality of ion transport membrane modules disposed in the interior of the pressure vessel, wherein at least a portion of the modules are arranged in series;
(c) catalyst disposed between any two adjacent membrane modules; and (d) one or more guard beds, wherein each guard bed is disposed between any two adjacent ion transport membrane modules in the interior of the pressure vessel.
28. The reactor system of Claim 27 wherein the catalyst comprises one or more metals or compounds containing metals selected from the group consisting of nickel, cobalt, platinum, gold, palladium, rhodium, ruthenium, and iron.
29. The reactor system of Claim 27 wherein each guard bed contains a reactive solid material comprising one or more compounds selected from the group consisting of magnesium oxide, calcium oxide, copper oxide, calcium carbonate, sodium carbonate, strontium carbonate, zinc oxide, strontium oxide, and alkaline-earth-containing perovskites.
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