CN113830734A - System and method for purifying hydrogen for fuel cell - Google Patents
System and method for purifying hydrogen for fuel cell Download PDFInfo
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- CN113830734A CN113830734A CN202010514667.9A CN202010514667A CN113830734A CN 113830734 A CN113830734 A CN 113830734A CN 202010514667 A CN202010514667 A CN 202010514667A CN 113830734 A CN113830734 A CN 113830734A
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000001257 hydrogen Substances 0.000 title claims abstract description 80
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000000446 fuel Substances 0.000 title claims abstract description 37
- 239000007789 gas Substances 0.000 claims abstract description 230
- 230000003197 catalytic effect Effects 0.000 claims abstract description 152
- 238000001179 sorption measurement Methods 0.000 claims abstract description 99
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 64
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000001301 oxygen Substances 0.000 claims abstract description 56
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 56
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 48
- 239000002994 raw material Substances 0.000 claims abstract description 47
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000746 purification Methods 0.000 claims abstract description 25
- 239000012535 impurity Substances 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims description 47
- 239000000047 product Substances 0.000 claims description 45
- 239000010949 copper Substances 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 239000003463 adsorbent Substances 0.000 claims description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 18
- 229910052802 copper Inorganic materials 0.000 claims description 18
- 239000002912 waste gas Substances 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- 239000002808 molecular sieve Substances 0.000 claims description 13
- 230000008929 regeneration Effects 0.000 claims description 13
- 238000011069 regeneration method Methods 0.000 claims description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000010926 purge Methods 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 229910000510 noble metal Inorganic materials 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 239000013067 intermediate product Substances 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 abstract description 5
- 229910052593 corundum Inorganic materials 0.000 description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 9
- 239000000292 calcium oxide Substances 0.000 description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 8
- 229910052681 coesite Inorganic materials 0.000 description 8
- 229910052906 cristobalite Inorganic materials 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 229910052682 stishovite Inorganic materials 0.000 description 8
- 229910052905 tridymite Inorganic materials 0.000 description 8
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- -1 meanwhile Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 239000011865 Pt-based catalyst Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 208000014342 histiocytosis-lymphadenopathy plus syndrome Diseases 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000311 lanthanide oxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
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Classifications
-
- 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
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
-
- 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
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
-
- 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
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
- C01B3/58—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
-
- 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
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/042—Purification by adsorption on solids
-
- 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
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0435—Catalytic purification
-
- 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
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/047—Composition of the impurity the impurity being carbon monoxide
-
- 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
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
-
- 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
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0495—Composition of the impurity the impurity being water
Abstract
The invention relates to the technical field of hydrogen purification, and discloses a system and a method for purifying hydrogen for a fuel cell, wherein the system comprises: pressure swing adsorption unit, catalytic unit, CO2And/or H2An O removal unit; inlet of the pressure swing adsorption unit, the CO2And/or H2The inlet of the O removal unit and the outlet of the catalytic unit are respectively communicated with a raw material gas pipeline through pipelines with valves; the outlet of the pressure swing adsorption unit, the CO2And/or H2The outlet of the O removal unit and the inlet of the catalytic unit are respectively communicated with a product gas pipeline through pipelines with valves; wherein the pressure swing adsorption unit is used for removing impurity gases in the raw material gas; the catalytic unit is used for removing carbon monoxide and/or oxygen; the CO is2And/or H2O removingThe removal unit is used for removing carbon dioxide and/or water vapor. The hydrogen purification system for the fuel cell provided by the invention purifies the hydrogen, can ensure that the yield of the hydrogen reaches 100% on the premise of keeping the purity of the hydrogen to be more than or equal to 99.97%, and completely meets the quality of the hydrogen for the fuel cell.
Description
Technical Field
The invention relates to the technical field of hydrogen purification, in particular to a system and a method for purifying hydrogen for a fuel cell.
Background
The principle of pressure swing adsorption is to realize the separation or purification of gas by periodic pressure change process by utilizing the difference of adsorption characteristics of gas components on a porous material and the characteristic that the adsorption quantity changes along with the pressure change. The basic process of pressure swing adsorption is as follows: adsorption, regeneration of pressure reducing adsorbent and pressure raising. The pressure swing adsorption method has the characteristics of capability of removing various impurities at one time and wide application range of raw material gas. For the production of high purity gas, the purity of the product gas is inversely related to the recovery rate of the product, and the recovery rate of hydrogen is necessarily reduced while high purity of the product hydrogen is sought.
At present, in the fuel cell hydrogen adding station which is operated in our country in a demonstration way, even if high-purity hydrogen with the volume fraction of more than or equal to 99.999 percent is adopted, the volume fraction of carbon monoxide can not ensure the requirement of less than or equal to 0.2 mu mol/mol. If CO is purified to be below 0.2ppm by pressure swing adsorption, the problems of low product hydrogen yield and high purification cost still exist.
Therefore, it is important to provide a new system and method for purifying hydrogen for fuel cells.
Disclosure of Invention
The invention aims to solve the problems of high hydrogen purity, low yield and high purification cost in the prior art, and provides a system and a method for purifying hydrogen for a fuel cell, wherein the system can ensure that the yield of the hydrogen reaches 100% on the premise of keeping the hydrogen purity to be more than or equal to 99.97%, and the quality of the hydrogen for the fuel cell is met.
In order to achieve the above object, a first aspect of the present invention provides hydrogen for a fuel cellA system for purifying a gas, the system comprising: pressure swing adsorption unit, catalytic unit, CO2And/or H2An O removal unit; inlet of the pressure swing adsorption unit, the CO2And/or H2The inlet of the O removal unit and the outlet of the catalytic unit are respectively communicated with a raw material gas pipeline through pipelines with valves; the outlet of the pressure swing adsorption unit, the CO2And/or H2The outlet of the O removal unit and the inlet of the catalytic unit are respectively communicated with a product gas pipeline through pipelines with valves; the inlet of the catalytic unit is also communicated with a feed gas pipeline through a pipeline with a valve; the CO is2And/or H2The inlet of the O removing unit is also communicated with a waste gas pipeline through a pipeline with a valve;
wherein the pressure swing adsorption unit is used for removing impurity gases in the raw material gas; the catalytic unit is used for removing carbon monoxide and/or oxygen; the CO is2And/or H2The O removal unit is used to remove carbon dioxide and/or water vapor.
The second aspect of the invention provides a method for purifying hydrogen for a fuel cell, comprising the steps of sequentially carrying out adsorption impurity removal, catalytic carbon monoxide and/or oxygen removal, and adsorption carbon dioxide and/or water vapor removal on raw material gas to obtain purified hydrogen; or the raw material gas is sequentially subjected to catalytic removal of carbon monoxide and/or oxygen, and adsorption removal of carbon dioxide and/or water vapor to obtain purified hydrogen;
wherein the feed gas is selected from gases having a hydrogen content of from 50 to 99.999 wt.%.
In a third aspect of the present invention, there is provided a method for purifying hydrogen gas for a fuel cell, wherein the method comprises introducing a raw material gas into the system of the first aspect of the present invention by one of the following two methods:
the first method is as follows: the raw gas enters the pressure swing adsorption unit through the raw gas pipeline and the inlet of the pressure swing adsorption unit to remove impurity gas, and the obtained impurity-removed gas enters the catalytic unit to remove carbon monoxide and/or oxygen; the resulting purified gas is fed to CO2And/or H2Carbon dioxide and/or steam removal in an O removal unitObtaining product gas; or
The second method comprises the following steps: the raw gas enters the catalytic unit through a raw gas pipeline and an inlet of the catalytic unit to remove carbon monoxide and/or oxygen; the resulting purified gas is fed to CO2And/or H2And removing carbon dioxide and/or water vapor in the O removing unit to obtain product gas.
By adopting the technical scheme, the hydrogen purification system for the fuel cell is used for purifying the hydrogen, so that the yield of the hydrogen can reach 100% on the premise of keeping the purity of the hydrogen to be more than or equal to 99.97%, and the quality of the hydrogen for the fuel cell is completely met; the hydrogen purification method provided by the invention has the advantages of simple process flow, low cost and high reliability.
Drawings
Fig. 1 is a schematic structural diagram of a hydrogen purification system for a fuel cell according to a preferred embodiment of the present invention.
Fig. 2 is a schematic structural view of a hydrogen purification system for a fuel cell according to another preferred embodiment of the present invention.
Description of the reference numerals
A pressure swing adsorption unit B gas buffer tank C1 first catalytic tower
C2 second catalytic column C3 third catalytic column D Trace oxygen introduction Unit
E CO2And/or H2O removing unit A-1-1 first valve A-1-2 second valve unit
A-1-3, A-1-4, B-1-1, and B-1
B-1-2 sixth valve C-1-1 seventh valve C-1-2 eighth valve
Ninth valve C-2-1 tenth valve C-2-2 eleventh valve C-2-3
Twelfth valve C-2-4, thirteenth valve C-3-1, thirteenth valve C-3-2, fourteenth valve
C-3-3 fifteenth valve C-3-4 sixteenth valve D-1-1 seventeenth valve
Eighteenth valve E-1-2 nineteenth valve E-1-3 twentieth valve
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides a system for purifying hydrogen gas for a fuel cell, the system comprising: pressure swing adsorption unit, catalytic unit, CO2And/or H2An O removal unit; inlet of the pressure swing adsorption unit, the CO2And/or H2The inlet of the O removal unit and the outlet of the catalytic unit are respectively communicated with a raw material gas pipeline through pipelines with valves; the outlet of the pressure swing adsorption unit, the CO2And/or H2The outlet of the O removal unit and the inlet of the catalytic unit are respectively communicated with a product gas pipeline through pipelines with valves; the inlet of the catalytic unit is also communicated with a feed gas pipeline through a pipeline with a valve; the CO is2And/or H2The inlet of the O removing unit is also communicated with a waste gas pipeline through a pipeline with a valve;
wherein the pressure swing adsorption unit is used for removing impurity gases in the raw material gas; the catalytic unit is used for removing carbon monoxide and/or oxygen; the CO is2And/or H2The O removal unit is used to remove carbon dioxide and/or water vapor.
In some embodiments of the present invention, preferably, the catalytic unit comprises: the device comprises a first catalytic tower, a trace oxygen introducing unit communicated with the inlet of the first catalytic tower and a valve.
In some embodiments of the present invention, preferably, the first catalytic tower is packed with a noble metal catalyst. More preferably, the noble metal catalyst is selected from platinum-based catalysts or gold-based catalysts. The invention is directed to the platinumThe base catalyst or gold-based catalyst is not particularly limited, and a conventional platinum-based or gold-based catalyst may be used. For example, including but not limited to Pt or Au and Fe2O3、CuO、Cr2O3、Al2O3、SiO2And the like. Further preferably, the platinum-based catalyst comprises Pt and Fe2O3、CuO、Cr2O3、Al2O3And SiO2Wherein, based on the total weight of the platinum-based catalyst, the content of Pt is 1-10 wt%, and Fe2O30.5-10 wt%, CuO 0.05-10 wt%, and Cr2O3Is contained in an amount of 0.0005 to 0.5 wt%, and Al2O3Is 30-65 wt% of SiO2The content of (B) is 30-60 wt%.
The catalytic unit includes: the system comprises a second catalytic tower and a third catalytic tower which are arranged in parallel, wherein the inlet and the outlet of the second catalytic tower and the outlet of the third catalytic tower are respectively provided with a valve; and the inlets of the second catalytic tower and the third catalytic tower are respectively communicated with an air pipeline through pipelines with valves, and the outlets of the second catalytic tower and the third catalytic tower are respectively communicated with an exhaust gas pipeline through pipelines with valves.
In some embodiments of the present invention, it is preferable that the second catalytic tower and the third catalytic tower are respectively packed with a copper-based catalyst and/or a manganese-based catalyst. The copper-based catalyst and the manganese-based catalyst are not particularly limited in the present invention, and conventional copper-based catalysts and manganese-based catalysts may be used, including, but not limited to, CuO or MnO with ZnO or SiO2、Al2O3Or any combination of lanthanide oxides. Preferably, the second catalytic tower and the third catalytic tower are respectively filled with copper-based catalysts, and the copper-based catalysts comprise CuO, MnO, ZnO, NiO, CaO and SiO2And Al2O3Wherein, based on the total weight of the copper-based catalyst, the content of CuO is 5-80 wt%, the content of MnO is 5-80 wt%, the content of NiO is 0.0005-30 wt%, the content of ZnO is 5-50 wt%, the content of CaO is 0.001-50 wt%, and SiO2The content of (B) is 0.1-50 wt%,Al2O3the content of (B) is 0.5-50 wt%.
In some embodiments of the present invention, preferably, the system further comprises: and the gas buffer tank is arranged on an inlet pipeline of the catalytic unit and is communicated with the product gas pipeline and an outlet of the pressure swing adsorption unit through an intermediate product gas pipeline with a valve and a purge gas pipeline for adsorption and regeneration respectively.
In some embodiments of the present invention, preferably, the pressure swing adsorption unit is packed with at least one selected from the group consisting of activated carbon, alumina, silica gel, and molecular sieve adsorbent, depending on the composition of the gas. The packing order of the adsorbent is not particularly limited, and the existing packing order, namely silica gel, alumina, activated carbon and molecular sieve are adopted. The adsorbents filled in the pressure swing adsorption unit can be combined according to the composition of the raw material gas, so that the pressure swing adsorption unit can remove the hydrocarbon gas such as methane, nitrogen, argon, hydrogen sulfide or organic sulfide, formaldehyde, formic acid and other impurity gases in the raw material gas by changing the pressure so as to meet the hydrogen standard for the fuel cell.
In some embodiments of the present invention, it is preferable that the pressure swing adsorption unit is filled with activated carbon and molecular sieve adsorbent, and the mass ratio of the activated carbon to the molecular sieve is (1: 10) - (10: 1), so that impurity gas can be removed better.
In some embodiments of the invention, preferably, the CO2And/or H2The O removing unit is filled with alkali metal oxide or molecular sieve adsorbent. The alkali metal oxide includes, but is not limited to, calcium oxide, sodium oxide. CO according to the invention2And/or H2The O removal unit may remove carbon dioxide and/or water vapor by pressure swing adsorption or chemical adsorption.
In some embodiments of the present invention, preferably, the waste gas pipeline is communicated with the inlet of the pressure swing adsorption unit a through a pipeline with a valve, and is used for recycling part of gas in the waste gas pipeline.
As a preferred embodiment of the present invention, as shown in fig. 1,the system comprises: a pressure swing adsorption unit A, a gas buffer tank B, a first catalytic tower C1, a trace oxygen introduction unit D and CO2And/or H2An O removal unit E; the inlet of the pressure swing adsorption unit A is communicated with a feed gas pipeline through a pipeline with a first valve A-1-1, and the CO is2And/or H2An inlet of the O removal unit E is communicated with a raw material gas pipeline through a pipeline with an eighteenth valve E-1-1, and an outlet of the first catalytic tower C1 is communicated with the raw material gas pipeline through pipelines (with an eighth valve C-1-2 and an eighteenth valve E-1-1); the outlet of the pressure swing adsorption unit A is communicated with a product gas pipeline through a pipeline with a third valve A-1-3, and the CO is2And/or H2The outlet of the O removal unit E is communicated with the product gas pipeline through a pipeline with a twentieth valve E-1-3, and the inlet of the first catalytic tower C1 is communicated with the product gas pipeline through a pipeline with a seventh valve C-1-1; the trace oxygen introducing unit D is communicated with the inlet of the first catalytic tower C1 through a pipeline with a seventeenth valve D-1-1; the gas buffer tank B is arranged on an inlet pipeline of the first catalytic tower C1 and is respectively communicated with a product gas pipeline and an outlet of the pressure swing adsorption unit A through an intermediate product gas pipeline with a sixth valve B-1-2 and an adsorption and regeneration purge gas pipeline with a fourth valve A-1-4; the waste gas pipeline is communicated with the inlet of the pressure swing adsorption unit A through a pipeline with a second valve A-1-2; the inlet of the first catalytic tower C1 is also communicated with a feed gas pipeline through a pipeline (provided with a seventh valve C-1-1, a sixth valve B-1-2 and a fifth valve B-1-1); the CO is2And/or H2The inlet of the O removal unit E is also communicated with an exhaust gas pipeline through a pipeline with a nineteenth valve E-1-2;
the pressure swing adsorption unit A is used for removing impurity gases in raw material gases; the first catalytic tower C1 is used for removing carbon monoxide and/or oxygen; the CO is2And/or H2The O removal unit E serves for removing carbon dioxide and/or water vapor.
As another preferred embodiment of the present invention, as shown in fig. 2, the system includes: a pressure swing adsorption unit A, a gas buffer tank B, a second catalytic tower C2, a third catalytic tower C3 and CO2And/or H2An O removal unit E; the inlet of the pressure swing adsorption unit A is communicated with a feed gas pipeline through a pipeline with a first valve A-1-1, and the CO is2And/or H2An inlet of the O removal unit E is communicated with a raw material gas pipeline through a pipeline with an eighteenth valve E-1-1, an outlet of the second catalytic tower C2 is communicated with the raw material gas pipeline through pipelines (provided with a tenth valve C-2-2, an eighth valve C-1-2 and an eighteenth valve E-1-1), and an outlet of the third catalytic tower C3 is communicated with the raw material gas pipeline through pipelines (provided with a fourteen valve C-3-2, an eighth valve C-1-2 and an eighteenth valve E-1-1); the outlet of the pressure swing adsorption unit A is communicated with a product gas pipeline through a pipeline with a third valve A-1-3, and the CO is2And/or H2The outlet of the O removal unit E is communicated with the product gas pipeline through a pipeline with a twentieth valve E-1-3, the inlet of the second catalytic tower C2 is communicated with the product gas pipeline through a pipeline (with a ninth valve C-2-1 and a seventh valve C-1-1), and the inlet of the third catalytic tower C3 is communicated with the product gas pipeline through a pipeline (with a thirteenth valve C-3-1 and a seventh valve C-1-1); the inlets of the second catalytic tower C2 and the third catalytic tower C3 are respectively communicated with an air pipeline through pipelines with an eleventh valve C-2-3 and a fifteenth valve C-3-3; the outlets of the second catalytic tower C2 and the third catalytic tower C3 are respectively communicated with an exhaust gas pipeline through pipelines with a twelfth valve C-2-4 and a sixteenth valve C-3-4; the gas buffer tank B is arranged on inlet pipelines of a second catalytic tower C2 and a third catalytic tower C3 and is respectively communicated with a product gas pipeline and an outlet of the pressure swing adsorption unit through an intermediate product gas pipeline with a sixth valve B-1-2 and an adsorption and regeneration purge gas pipeline with a fourth valve A-1-4; the waste gas pipeline is communicated with the inlet of the pressure swing adsorption unit A through a pipeline with a second valve A-1-2; the inlet of the second catalytic tower C2 is also communicated with a feed gas pipeline through a pipeline (provided with a ninth valve C-2-1, a seventh valve C-1-1, a sixth valve B-1-2 and a fifth valve B-1-1), and the inlet of the third catalytic tower C3 is also communicated with the feed gas pipeline through a pipeline (provided with a thirteenth valve C-3-1, a seventh valve C-1-1, a sixth valve B-1-2 and a fifth valve B-1-1); the CO is2And/or H2The inlet of the O removal unit E is also passed through a beltThe line with the nineteenth valve E-1-2 communicates with the exhaust line;
the pressure swing adsorption unit A is used for removing impurity gases in raw material gases; the second catalytic tower C2 and the third catalytic tower C3 are used for removing carbon monoxide and/or oxygen; the CO is2And/or H2The O removal unit E serves for removing carbon dioxide and/or water vapor.
By adopting the purification system provided by the invention, different raw material gases can be purified by controlling the opening and closing states of the valves, so that the hydrogen for the fuel cell is prepared.
The second aspect of the invention provides a method for purifying hydrogen for a fuel cell, comprising the steps of sequentially carrying out adsorption impurity removal, catalytic carbon monoxide and/or oxygen removal, and adsorption carbon dioxide and/or water vapor removal on raw material gas to obtain purified hydrogen; or the raw material gas is sequentially subjected to catalytic removal of carbon monoxide and/or oxygen, and adsorption removal of carbon dioxide and/or water vapor to obtain purified hydrogen;
wherein the feed gas is selected from gases having a hydrogen content of from 50 to 99.999 wt.%.
In a third aspect of the present invention, there is provided a method for purifying hydrogen gas for a fuel cell, wherein the method comprises introducing a raw material gas into the system of the first aspect of the present invention by one of the following two methods:
the first method is as follows: the raw gas enters the pressure swing adsorption unit through the raw gas pipeline and the inlet of the pressure swing adsorption unit to remove impurity gas, and the obtained impurity-removed gas enters the catalytic unit to remove carbon monoxide and/or oxygen; the resulting purified gas is fed to CO2And/or H2Removing carbon dioxide and/or water vapor in the O removing unit to obtain product gas; or
The second method comprises the following steps: the raw gas enters the catalytic unit through a raw gas pipeline and an inlet of the catalytic unit to remove carbon monoxide and/or oxygen; the resulting purified gas is fed to CO2And/or H2And removing carbon dioxide and/or water vapor in the O removing unit to obtain product gas.
The source of the raw material gas is not particularly limited in the present invention, and examples thereof include, but are not limited to, industrially pure hydrogen, hydrogen-rich gas concentrated by membrane separation of methanol purge gas, and the like.
In some embodiments of the invention, it is preferred that the temperature at which carbon monoxide and/or oxygen removal is carried out in the catalytic unit is in the range of from 0 to 200 ℃, more preferably from 25 to 90 ℃. The removal temperature of the catalytic units provided in the art is lower than the removal temperature of existing catalytic units.
In some embodiments of the invention, preferably, the purification of hydrogen is performed by introducing a feed gas into the system according to the first aspect of the invention in one of two ways:
the first method is as follows: the raw material gas enters the pressure swing adsorption unit through the raw material gas pipeline and an inlet of the pressure swing adsorption unit to remove impurity gas, so that impurity-removed gas is obtained, and the impurity-removed gas and trace oxygen enter the first catalytic tower to remove carbon monoxide and/or oxygen; or
The impurity-removed gas alternately enters a second catalytic tower and a third catalytic tower to remove carbon monoxide and/or oxygen; the resulting purified gas is fed to CO2And/or H2Removing carbon dioxide and/or water vapor in the O removing unit to obtain product gas; or
The second method comprises the following steps: the raw material gas enters the first catalytic tower through a raw material gas pipeline and an inlet of the first catalytic tower, and simultaneously trace oxygen enters the first catalytic tower to remove carbon monoxide and/or oxygen; or
The feed gas alternately enters the second catalytic tower and the third catalytic tower through a feed gas pipeline, an inlet of the second catalytic tower or an inlet of the third catalytic tower to remove carbon monoxide and/or oxygen; the resulting purified gas is fed to CO2And/or H2And removing carbon dioxide and/or water vapor in the O removing unit to obtain product gas.
In some embodiments of the present invention, it is preferred that the volume ratio of the oxygen to the carbon monoxide in the degassing gas or feed gas is not greater than 10, more preferably 0.1 to 1, so that better removal of carbon monoxide and/or oxygen is possible.
In some embodiments of the present invention, preferably, the pressure swing adsorption unit performs the following steps in sequence during one cycle: pressure boosting, adsorption, sequential discharge, reverse discharge, flushing and pressure boosting.
In some embodiments of the present invention, preferably, the method further comprises: in the first mode, part of the impurity-removed gas is introduced into the gas buffer tank for storage, and is used for entering the pressure swing adsorption unit for purging when the pressure swing adsorption unit stops working.
In the first mode of the invention, the gas buffer tank is used for storing part of the impurity-removed gas so as to purge the adsorbent in the pressure swing adsorption unit and realize the regeneration of the adsorbent. In the second aspect of the present invention, the gas buffer tank functions as a pipeline passage.
As a preferred embodiment of the present invention, the purification of hydrogen is performed by introducing a raw material gas into a hydrogen purification system for a fuel cell as shown in fig. 1 by one of two ways:
(1) raw material gas enters a pressure swing adsorption unit A through a raw material gas pipeline and a pipeline with a first valve A-1-1 to remove impurity gas to obtain impurity-removed gas, the impurity-removed gas enters a first catalytic tower C1 through a pipeline (with a third valve A-1-3 and a seventh valve C-1-1), and meanwhile, trace oxygen in a trace oxygen introduction unit D enters a first catalytic tower C1 through a pipeline with a seventeenth valve D-1-1 to remove carbon monoxide and/or oxygen; the resulting purified gas is fed to CO via a line with an eighth valve C-1-22And/or H2Removing carbon dioxide and/or water vapor in the O removing unit E, and enabling the obtained product gas to enter a product gas pipeline through a pipeline with a twentieth valve E-1-3;
(2) the feed gas enters a first catalytic tower C1 through a feed gas pipeline and a pipeline (provided with a fifth valve B-1-1, a sixth valve B-1-2 and a seventh valve C-1-1), and meanwhile, the trace oxygen in the trace oxygen introduction unit D enters a first catalytic tower C1 through a pipeline provided with a seventeenth valve D-1-1 to carry out carbon monoxide and/or oxygen removal; the resulting purified gas is fed to CO via a line with an eighth valve C-1-22And/or H2Removing carbon dioxide and/or water vapor in an O removal unit E to obtainThe product gas enters the product gas line through a line having a twentieth valve E-1-3.
As another preferred embodiment of the present invention, the purification of hydrogen is performed by introducing a raw material gas into a hydrogen purification system for a fuel cell as shown in fig. 2 by one of two ways:
(I) raw material gas enters a pressure swing adsorption unit A through a raw material gas pipeline and a pipeline with a first valve A-1-1 to remove impurity gas to obtain impurity-removed gas, the impurity-removed gas enters a second catalytic tower C2 through a pipeline (provided with a third valve A-1-3, a seventh valve C-1-1 and a ninth valve C-2-1) to remove carbon monoxide and/or oxygen, when a copper-based catalyst in the second catalytic tower C2 is in an inactivated state, the impurity-removed gas enters a third catalytic tower C3 through a pipeline (provided with a third valve A-1-3, a seventh valve C-1-1 and a thirteenth valve C-3-1) to remove carbon monoxide and/or oxygen, and simultaneously air enters a second catalytic tower C2 through a pipeline with an eleventh valve C-2-3 to oxidize and regenerate the copper-based catalyst, the generated waste gas enters a waste gas pipeline through a pipeline with a twelfth valve C-2-4; when the copper-based catalyst in the third catalytic tower C3 is in an inactivated state, the impurity-removing gas enters the second catalytic tower C2 through a pipeline (provided with a third valve A-1-3, a seventh valve C-1-1 and a ninth valve C-2-1) to remove carbon monoxide and/or oxygen, meanwhile, air enters the third catalytic tower C3 through a pipeline with a fifteenth valve C-3-3 to perform oxidation regeneration on the copper-based catalyst, and generated waste gas enters a waste gas pipeline through a pipeline with a sixteenth valve C-3-4; repeating the operation, so that the copper-based catalysts filled in the second catalytic tower C2 and the third catalytic tower C3 are alternately used and regenerated to realize continuous purification; the obtained purified gas enters CO through a pipeline (provided with a tenth valve C-2-2 and an eighth valve C-1-2) or a pipeline (provided with a fourteenth valve C-3-2 and an eighth valve C-1-2)2And/or H2Removing carbon dioxide and/or water vapor in the O removing unit E, and enabling the obtained product gas to enter a product gas pipeline through a pipeline with a twentieth valve E-1-3;
(II) the feed gas passes through a feed gas pipeline and a pipeline (provided with a fifth valve B-1-1, a sixth valve B-1-2 and a seventh valve)The gate C-1-1 and the ninth valve C-2-1) enter a second catalytic tower C2 for removing carbon monoxide and/or oxygen; when the copper-based catalyst in the second catalytic tower C2 is in an inactivated state, the feed gas enters a third catalytic tower C3 through a pipeline (provided with a fifth valve B-1-1, a sixth valve B-1-2, a seventh valve C-1-1 and a thirteenth valve C-3-1) to remove carbon monoxide and/or oxygen, meanwhile, air enters a second catalytic tower C2 through a pipeline provided with an eleventh valve C-2-3 to carry out oxidation regeneration on the copper-based catalyst, and the generated waste gas enters an exhaust gas pipeline through a pipeline provided with a twelfth valve C-2-4; when the copper-based catalyst in the third catalytic tower C3 is in an inactivated state, the feed gas enters the second catalytic tower C2 through a pipeline (provided with a fifth valve B-1-1, a sixth valve B-1-2, a seventh valve C-1-1 and a ninth valve C-2-1) to remove carbon monoxide and/or oxygen, meanwhile, air enters the third catalytic tower C3 through a pipeline provided with a fifteenth valve C-3-3 to carry out oxidation regeneration on the copper-based catalyst, and the generated waste gas enters an exhaust gas pipeline through a pipeline provided with a sixteenth valve C-3-4; repeating the above operations, so that the noble metal catalysts filled in the second catalytic tower C2 and the third catalytic tower C3 are alternately used and regenerated, thereby realizing continuous purification; the obtained purified gas enters CO through a pipeline (provided with a tenth valve C-2-2 and an eighth valve C-1-2) or a pipeline (provided with a fourteenth valve C-3-2 and an eighth valve C-1-2)2And/or H2The O removal unit E is operated for carbon dioxide and/or water vapor removal and the resulting product gas is passed via a line with a twentieth valve E-1-3 into the product gas line.
The present invention will be described in detail below by way of examples. In the following examples, various raw materials used were commercially available unless otherwise specified.
Purity of product gas (including H)2、CO2、CO、CH4、O2、H2O、N2) The measurement was carried out by means of Fourier transform infrared spectroscopy (FTIR) and gas chromatography (GC-PHID).
The yield of hydrogen gas was ═ 100% (molar amount of hydrogen in product gas/molar amount of hydrogen in raw material gas).
Example 1
By adopting the hydrogen purification system for the fuel cell shown in fig. 1, hydrogen-rich gas obtained by separating and concentrating methanol purge gas through a membrane is taken as a raw material gas and enters a pressure swing adsorption unit a through a raw material gas pipeline and a pipeline with a first valve a-1-1, an activated carbon adsorbent (purchased from shikong carbon industry limited company) and a 5A molecular sieve adsorbent (purchased from shanghai jiyu chemical company limited company) filled in the pressure swing adsorption unit a are subjected to pressure swing adsorption process to remove impurity gases such as methane, nitrogen, carbon monoxide, carbon dioxide, water vapor and the like through a cyclic adsorption and desorption process of pressure rise-adsorption-forward release-reverse release-flushing-pressure rise, wherein the weight ratio of the activated carbon adsorbent to the 5A molecular sieve adsorbent is 1: 2, the obtained impurity-removed gas enters a first catalytic tower C1 through a pipeline (provided with a third valve A-1-3 and a seventh valve C-1-1), and simultaneously, a trace amount of oxygen in the oxygen introducing unit D enters a first catalytic tower C1 through a pipeline provided with a seventeenth valve D-1-1, wherein the volume ratio of the oxygen to the carbon monoxide in the impurity-removed gas is 0.5, and the first catalytic tower C1 is filled with a Pt-based catalyst (based on the total weight of the platinum-based catalyst, the content of Pt is 1 wt%, and Fe is used as the basis)2O35 wt% of (B), 5 wt% of CuO, and Cr2O3Is 0.5 wt% of Al2O3Is 50 wt% SiO240 wt%) at 25 ℃ to convert carbon monoxide to carbon dioxide; the resulting purified gas is fed to CO via a line with an eighth valve C-1-22And/or H2In an O removal unit E, CO2And/or H2Calcium oxide adsorbent (purchased from national pharmaceutical group chemical reagent company) filled in the O removal unit E is used for removing carbon dioxide through chemical adsorption, and the obtained product gas enters a product gas pipeline through a pipeline with a twentieth valve E-1-3;
and the obtained part of the impurity-removed gas is also introduced into a gas buffer tank B for standby through a pipeline (a pipeline with a third valve A-1-3 and a sixth valve B-1-2) and is used for entering the pressure swing adsorption unit A through a pipeline with a fourth valve A-1-4 when the adsorbent in the pressure swing adsorption unit A stops working so as to provide purge gas for adsorption regeneration for the pressure swing adsorption unit A.
Example 2
By adopting the hydrogen purification system for the fuel cell shown in fig. 2, hydrogen-rich gas obtained by separating and concentrating methanol purge gas through a membrane is taken as a raw material gas and enters a pressure swing adsorption unit a through a raw material gas pipeline and a pipeline with a first valve a-1-1, and an activated carbon adsorbent (purchased from shikong carbon industry limited company) and a 5A molecular sieve adsorbent (purchased from shanghai jiyu chemical company limited company)) filled in the pressure swing adsorption unit a are subjected to pressure swing adsorption process to remove impurity gases such as methane, nitrogen, carbon monoxide, carbon dioxide, water vapor and the like through a cyclic adsorption and desorption process of pressure rise-adsorption-forward release-reverse release-flushing-pressure rise, wherein the weight ratio of the activated carbon adsorbent to the 5A molecular sieve adsorbent is 1: 2, the obtained impurity-removed gas enters a second catalytic tower C2 through a pipeline (provided with a third valve A-1-3, a seventh valve C-1-1 and a ninth valve C-2-1), and a Cu-based catalyst (based on the total weight of the copper-based catalyst, the content of CuO is 20 wt%, the content of MnO is 50 wt%, the content of NiO is 0.05 wt%, the content of ZnO is 5 wt%, the content of CaO is 0.001 wt%, and the content of SiO is 5 wt% in the second catalytic tower C22Is 5 wt% of Al2O3In an amount of 15 wt.%) converting carbon monoxide to carbon dioxide at 25 deg.c; when the Cu-based catalyst in the second catalytic column C2 was in a deactivated state, the sweep gas was introduced into the third catalytic column C3 through a line (having a third valve A-1-3, a seventh valve C-1-1, and a thirteenth valve C-3-1), and the Cu-based catalyst (CuO content of 20 wt%, MnO content of 50 wt%, NiO content of 0.05 wt%, ZnO content of 5 wt%, CaO content of 0.001 wt%, SiO content of 0.05 wt%, based on the total weight of the copper-based catalyst) was packed in the third catalytic column C32Is 5 wt% of Al2O315 wt%) at 25C, while air is introduced into the second catalytic tower C2 through a line having an eleventh valve C-2-3 to perform oxidative regeneration of the Cu-based catalyst, and the generated exhaust gas is introduced into the exhaust gas line through a line having a twelfth valve C-2-4; when the Cu-based catalyst in the third catalytic column C3 is in a deactivated state, the impurity-removed gas is brought into the second catalyst through a line (provided with a third valve A-1-3, a seventh valve C-1-1 and a ninth valve C-2-1)In the tower C2, the regenerated Cu-based catalyst filled in the second catalytic tower C2 converts carbon monoxide into carbon dioxide, meanwhile, air enters the third catalytic tower C3 through a pipeline with a fifteenth valve C-3-3 to carry out oxidation regeneration on the Cu catalyst, and generated waste gas enters an exhaust gas pipeline through a pipeline with a sixteen valve C-3-4; repeating the operation, so that the Cu catalysts filled in the second catalytic tower C2 and the third catalytic tower C3 are alternately used and regenerated to realize continuous purification; the obtained purified gas enters CO through a pipeline (provided with a tenth valve C-2-2 and an eighth valve C-1-2) or a pipeline (provided with a fourteenth valve C-3-2 and an eighth valve C-1-2)2And/or H2In an O removal unit E, CO2And/or H2Calcium oxide adsorbent (purchased from national pharmaceutical group chemical reagent company) filled in the O removal unit E is used for removing carbon dioxide through chemical adsorption, and the obtained product gas enters a product gas pipeline through a pipeline with a twentieth valve E-1-3;
and the obtained impurity-removed gas is also introduced into a gas buffer tank B for standby through a pipeline (provided with a third valve A-1-3 and a sixth valve B-1-2), and when the adsorbent in the pressure swing adsorption unit A stops working, the impurity-removed gas enters the pressure swing adsorption unit A through the pipeline with a fourth valve A-1-4 to provide purge gas for adsorption regeneration for the pressure swing adsorption unit A.
Example 3
The system for purifying hydrogen gas for a fuel cell shown in fig. 1 uses industrial pure hydrogen as a raw material gas, and only CO and CO are used as compared with hydrogen gas for a fuel cell vehicle2And H2O is over-standard, and the hydrogen purification process does not need to start the A unit and only needs B, C1 and D, E units. The specific process comprises the following steps:
the first valve to the fourth valve (A-1-1 to A-1-4) of the pressure swing adsorption unit A are in a full-closed state, industrial pure hydrogen is taken as raw material gas and enters a first catalytic tower C1 through a pipeline (provided with a fifth valve B-1-1, a sixth valve B-1-2 and a seventh valve C-1-1), meanwhile, trace oxygen introduced into a unit D enters a first catalytic tower C1 through a pipeline of a seventeenth valve D-1-1, wherein the volume ratio of the oxygen to carbon monoxide in the raw material gas is 0.5, and at the moment, a Pt-based catalyst (the platinum-based catalyst is used as the Pt-based catalyst) filled in the first catalytic tower C1Based on the total weight of (1 wt.%), Pt, Fe2O35 wt% of (B), 5 wt% of CuO, and Cr2O3Is 0.5 wt% of Al2O3Is 50 wt% SiO240 wt%) at 25 ℃ to convert carbon monoxide to carbon dioxide; the resulting purified gas is fed to CO via a line with an eighth valve C-1-22And/or H2In an O removal unit E, CO2And/or H2Calcium oxide adsorbent (purchased from national pharmaceutical group chemical reagent company) filled in the O removal unit E removes carbon dioxide by pressure swing adsorption process through a cyclic absorption and desorption process of pressure rise-adsorption-forward release-reverse release-flushing-pressure rise, and the obtained product gas enters a product gas pipeline through a pipeline with a twentieth valve E-1-3.
Comparative example
Hydrogen was purified in a similar manner to example 1, except that a conventional two-column pressure swing adsorption apparatus was used to purify the hydrogen.
The purity of the product gas obtained in the above example was measured by FTIR and GC-PHID, respectively, and the yield of hydrogen was calculated, and the results are shown in Table 1.
TABLE 1
As can be seen from the results in Table 1, the hydrogen standard (H) for fuel cells is satisfied2≥99.97％、CO2≤2ppm、CO≤0.2ppm、CH4≤2ppm、O2≤5ppm、H2O≤5ppm、N2Less than or equal to 100ppm), purifying the hydrogen by adopting the hydrogen purification system for the fuel cell provided by the invention, and obtaining the product gas H2、CO2、CO、CH4、O2、H2O and N2The purity of the product meets the quality of hydrogen used by fuel cells, and the yield of the hydrogen can reach 100 percent.
When the traditional two-tower pressure swing adsorption device is used for purifying the hydrogen, when the CO is purified to 0.2ppm which meets the quality requirement of the hydrogen for the fuel cell, the yield of the hydrogen is only 60.02 percent, or when the yield of the hydrogen reaches 69.56 percent, the purity of the CO is 39.5ppm which does not meet the quality of the hydrogen for the fuel cell.
Therefore, compared with the prior art, the hydrogen purification system for the fuel cell provided by the invention can be used for purifying the hydrogen, so that the hydrogen purity is improved, and the hydrogen yield is obviously improved.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A system for purifying hydrogen gas for a fuel cell, characterized in that: the system comprises: pressure swing adsorption unit, catalytic unit, CO2And/or H2An O removal unit; inlet of the pressure swing adsorption unit, the CO2And/or H2The inlet of the O removal unit and the outlet of the catalytic unit are respectively communicated with a raw material gas pipeline through pipelines with valves; the outlet of the pressure swing adsorption unit, the CO2And/or H2The outlet of the O removal unit and the inlet of the catalytic unit are respectively communicated with a product gas pipeline through pipelines with valves; the inlet of the catalytic unit is also communicated with a feed gas pipeline through a pipeline with a valve; the CO is2And/or H2The inlet of the O removing unit is also communicated with a waste gas pipeline through a pipeline with a valve;
wherein the pressure swing adsorption unit is used for removing impurity gases in the raw material gas; the catalytic unit is used for removing carbon monoxide and/or oxygen; the CO is2And/or H2The O removal unit is used to remove carbon dioxide and/or water vapor.
2. The system of claim 1, wherein the catalytic unit comprises: the device comprises a first catalytic tower, a trace oxygen introducing unit communicated with an inlet of the first catalytic tower, and a valve;
preferably, the first catalytic tower is filled with a noble metal catalyst; more preferably, the noble metal catalyst is selected from platinum-based catalysts or gold-based catalysts.
3. The system of claim 1, wherein the catalytic unit comprises: the system comprises a second catalytic tower and a third catalytic tower which are arranged in parallel, wherein the inlet and the outlet of the second catalytic tower and the outlet of the third catalytic tower are respectively provided with a valve; the inlets of the second catalytic tower and the third catalytic tower are respectively communicated with an air pipeline through pipelines with valves, and the outlets of the second catalytic tower and the third catalytic tower are respectively communicated with an exhaust gas pipeline through pipelines with valves;
preferably, the second catalytic tower and the third catalytic tower are respectively filled with a copper-based catalyst and/or a manganese-based catalyst.
4. The system of any one of claims 1-3, wherein the system further comprises: and the gas buffer tank is arranged on an inlet pipeline of the catalytic unit and is communicated with the product gas pipeline and an outlet of the pressure swing adsorption unit through an intermediate product gas pipeline with a valve and a purge gas pipeline for adsorption and regeneration respectively.
5. The system of any one of claims 1-4, wherein the pressure swing adsorption unit is packed with at least one selected from the group consisting of activated carbon, alumina, silica gel, and molecular sieve adsorbent;
preferably, the pressure swing adsorption unit is filled with activated carbon and a molecular sieve adsorbent, and the mass ratio of the activated carbon to the molecular sieve is (1: 10) - (10: 1);
preferably, the CO is2And/or H2The O removing unit is filled with alkali metal oxide or molecular sieve adsorbent.
6. A method of purifying hydrogen for a fuel cell, characterized by: sequentially carrying out adsorption impurity removal, catalytic removal of carbon monoxide and/or oxygen, adsorption removal of carbon dioxide and/or water vapor on the raw material gas to obtain purified hydrogen; or the raw material gas is sequentially subjected to catalytic removal of carbon monoxide and/or oxygen, and adsorption removal of carbon dioxide and/or water vapor to obtain purified hydrogen;
wherein the feed gas is selected from gases having a hydrogen content of from 50 to 99.999 wt.%.
7. A method of purifying hydrogen for a fuel cell, characterized by: the purification of hydrogen is carried out by introducing a feed gas into the system of any one of claims 1 to 5 by one of two means:
the first method is as follows: the raw gas enters the pressure swing adsorption unit through the raw gas pipeline and the inlet of the pressure swing adsorption unit to remove impurity gas, and the obtained impurity-removed gas enters the catalytic unit to remove carbon monoxide and/or oxygen; the resulting purified gas is fed to CO2And/or H2Removing carbon dioxide and/or water vapor in the O removing unit to obtain product gas; or
The second method comprises the following steps: the raw gas enters the catalytic unit through a raw gas pipeline and an inlet of the catalytic unit to remove carbon monoxide and/or oxygen; the resulting purified gas is fed to CO2And/or H2And removing carbon dioxide and/or water vapor in the O removing unit to obtain product gas.
8. The method according to claim 7, wherein the temperature at which carbon monoxide and/or oxygen removal is carried out in the catalytic unit is between 0 and 200 ℃, preferably between 25 and 90 ℃.
9. The process according to claim 7 or 8, wherein when the lean gas obtained in the first mode is fed to a catalytic unit comprising a first catalytic column and a trace oxygen introduction unit for carbon monoxide and/or oxygen removal, or when the feed gas is fed to a catalytic unit comprising a first catalytic column and a trace oxygen introduction unit for carbon monoxide and/or oxygen removal via a feed gas line and an inlet of the catalytic unit in the second mode, the volume ratio of oxygen provided by the trace oxygen introduction unit to carbon monoxide in the lean gas or feed gas is not more than 10, preferably 0.1 to 1.
10. The method of any of claims 7-9, wherein the method further comprises: in the first mode, part of the impurity-removed gas is introduced into the gas buffer tank for storage, and is used for entering the pressure swing adsorption unit for purging when the pressure swing adsorption unit stops working.
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| WO2023184935A1 (en) * | 2022-03-29 | 2023-10-05 | 国家能源投资集团有限责任公司 | Removal agent for co in refined hydrogen, and preparation method therefor and use thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5110569A (en) * | 1990-01-19 | 1992-05-05 | The Boc Group, Inc. | Low temperature purification of gases |
| US5202096A (en) * | 1990-01-19 | 1993-04-13 | The Boc Group, Inc. | Apparatus for low temperature purification of gases |
| US6074621A (en) * | 1998-12-04 | 2000-06-13 | Air Products And Chemicals, Inc. | Purification of gases |
| JP2010143778A (en) * | 2008-12-17 | 2010-07-01 | Kobe Steel Ltd | High purity hydrogen production apparatus |
| CN106698343A (en) * | 2016-12-20 | 2017-05-24 | 杨皓 | Technology for producing hydrogen from coke oven gas through deep deoxygenation and dehydration |
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5110569A (en) * | 1990-01-19 | 1992-05-05 | The Boc Group, Inc. | Low temperature purification of gases |
| US5202096A (en) * | 1990-01-19 | 1993-04-13 | The Boc Group, Inc. | Apparatus for low temperature purification of gases |
| US6074621A (en) * | 1998-12-04 | 2000-06-13 | Air Products And Chemicals, Inc. | Purification of gases |
| JP2010143778A (en) * | 2008-12-17 | 2010-07-01 | Kobe Steel Ltd | High purity hydrogen production apparatus |
| CN106698343A (en) * | 2016-12-20 | 2017-05-24 | 杨皓 | Technology for producing hydrogen from coke oven gas through deep deoxygenation and dehydration |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023184935A1 (en) * | 2022-03-29 | 2023-10-05 | 国家能源投资集团有限责任公司 | Removal agent for co in refined hydrogen, and preparation method therefor and use thereof |
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