CN111715227A - Copper-based medium-temperature shift catalyst and preparation method thereof - Google Patents
Copper-based medium-temperature shift catalyst and preparation method thereof Download PDFInfo
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- CN111715227A CN111715227A CN201910213770.7A CN201910213770A CN111715227A CN 111715227 A CN111715227 A CN 111715227A CN 201910213770 A CN201910213770 A CN 201910213770A CN 111715227 A CN111715227 A CN 111715227A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 239000010949 copper Substances 0.000 title claims abstract description 18
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000005751 Copper oxide Substances 0.000 claims abstract description 5
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 5
- 239000011787 zinc oxide Substances 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 30
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 10
- 238000005469 granulation Methods 0.000 claims description 10
- 230000003179 granulation Effects 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 238000004537 pulping Methods 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims 1
- 150000004679 hydroxides Chemical class 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 4
- 238000000975 co-precipitation Methods 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 230000009466 transformation Effects 0.000 abstract description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 3
- 239000001569 carbon dioxide Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 39
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 35
- 229910000029 sodium carbonate Inorganic materials 0.000 description 18
- 239000007789 gas Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- -1 copper-zinc-aluminum Chemical compound 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052795 boron group element Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous 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
- C01B2203/02—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
-
- 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
- C01B2203/1076—Copper or zinc-based catalysts
-
- 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)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of catalysts, and particularly relates to a high-CO-content copper-based medium-temperature shift catalyst for generating carbon dioxide and hydrogen through the reaction of carbon monoxide and steam and a preparation method thereof. The catalyst comprises the following components in percentage by weight: 35-50% of copper oxide, 25-40% of zinc oxide, 5-15% of aluminum oxide and 5-15% of structure auxiliary agent M oxide, wherein M is one or a mixture of more of Zr, Mg and Mn. The catalyst is prepared by a coprecipitation method, has excellent performance, improves the structure of the catalyst by adding a structural auxiliary agent, enhances the performance of the catalyst, and is suitable for a transformation reaction process with high CO content (more than 10 percent by volume).
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a high-CO-content copper-based medium-temperature shift catalyst for generating carbon dioxide and hydrogen through the reaction of carbon monoxide and steam and a preparation method thereof.
Background
In 1063, copper-based low-temperature shift catalysts were used for producing synthesis gas, and were widely used in ammonia synthesis plants and hydrogen production plants with the development of gas purification technology.
The shift reaction carried out industrially usually comprises one-step or two-step processes, namely iron-based high-temperature shift reaction and copper-based low-temperature shift reaction, the copper-based low-temperature shift reaction can only be adapted to the shift reaction of gas with lower content of CO (less than 5 volume percent), the traditional copper-based shift catalyst mainly refers to copper-zinc-aluminum system, and some researchers also try to add other auxiliary agents into the system to improve the performance of the catalyst, especially enhance the thermal stability performance of the catalyst, so as to adapt to the shift reaction with high content of CO.
Chinese patent CN105536803A discloses a copper-based medium temperature shift catalyst for carbon monoxide and a preparation method thereof. The catalyst takes copper salt, zinc salt and aluminum salt as active components, and a coprecipitation process and special equipment are adopted in the preparation process.
Chinese patent CN106179360A discloses a copper-zinc-aluminum catalyst and a preparation method thereof. The catalyst comprises CuO, ZnO and Al2O3Compared with the traditional precipitation method, the method is different in that an organic solvent is added in the dissolving of the precipitating agent.
Chinese patent CN103170339A discloses a Cu-based high-temperature water gas shift catalyst in a hydrogen-rich atmosphere and a preparation method thereof. The catalyst is composed of copper oxide, cerium oxide and zirconium oxide, and is prepared by a reverse coprecipitation method.
Chinese patent CN101786000A discloses a carbon monoxide shift catalyst and a preparation method thereof. The catalyst is prepared by adding boron group element compound on the basis of copper-zinc-aluminum system and adopting a coprecipitation method.
No shift catalyst suitable for high CO content exists in the market, and a novel copper-based medium-temperature shift catalyst is urgently needed to be developed to meet the requirement of medium-temperature shift reaction of high-content CO (more than 10 percent by volume).
Disclosure of Invention
The invention aims to overcome the defect that the traditional copper-based shift catalyst cannot be suitable for high CO content, and provides a copper-based medium-temperature shift catalyst which is suitable for high CO content (more than 10 vol%) and high performance.
The invention is characterized in that other structural auxiliary agents are introduced on the basis of copper, zinc and aluminum, and the aluminum and the structural auxiliary agents play the role of double carriers, thereby improving the structure of the catalyst, enhancing the performance of the catalyst and being suitable for the transformation reaction process with high CO content.
The catalyst comprises the following components in percentage by weight: 35-50% of copper oxide is preferably 40-45%, 25-40% of zinc oxide is preferably 30-35%, 5-15% of aluminum oxide is preferably 9-12%, and 5-15% of structure promoter M oxide is preferably 8-10%.
The structural auxiliary agent in the catalyst composition is one or a mixture of more of Zr, Mg and Mn.
The catalyst is prepared by a precipitation method, and comprises the following specific steps:
(1) adding the prepared alkaline precipitant into a reactor with a stirring paddle and water bath heating, adding mixed solution containing copper nitrate, zinc nitrate and an auxiliary agent M salt into the alkaline precipitant at a constant speed of 50-70ml/min for precipitation, wherein the neutralization temperature is 65-70 ℃, the end-point pH value is 7.0-7.2, and the aging is carried out for 0.3-0.5 h;
(2) settling and washing the aged material, adding alumina powder, and pulping for 0.3-0.5 h;
(3) and carrying out suction filtration, drying, grinding, granulation, roasting and tabletting on the pulped materials to obtain the catalyst.
Generally, the salt of the auxiliary agent M is one or a mixture of several corresponding nitrate, carbonate and hydroxide.
The total concentration of metal ions in the mixed solution of the auxiliary M salt is 0.2-2.0 mol/L.
The total concentration of metal ions in the mixed solution of the auxiliary M salt is 0.8-1.5 mol/L.
The mixed solution of the auxiliary agent M and the salt is added into the alkaline precipitator at a constant speed of 60-65ml/min for precipitation.
The aged material was washed by 6 sedimentation.
The catalyst of the invention is suitable for shift reaction with the CO volume content of 10-15%.
The invention has the following effects: in the preparation process of the catalyst, other structural auxiliaries are added, so that the structure of the catalyst is improved, the performance of the catalyst is enhanced, and the catalyst is suitable for a transformation reaction process with high CO content (more than 10 vol%).
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
Example 1
Putting 4.0L of prepared sodium carbonate solution with the concentration of 1mol/L into a reaction kettle with a stirring paddle and water bath heating, preparing 440mL of 3.5mol/L copper nitrate solution, 240mL of 3.5mol/L zinc nitrate solution and 175mL of 1.0mol/L auxiliary agent M salt mixed solution into 2.0L of mixed solution A with the temperature of 70 ℃, adding the mixed solution A into the sodium carbonate solution at a constant speed of 60mL/min at the temperature of 70 ℃, stirring and aging for 0.5h at the temperature of 70 ℃, settling and washing the aged material for 6 times, adding 45g of alumina powder and pulping for 0.3 h; and performing suction filtration, drying, material grinding, granulation, roasting and tabletting on the pulped materials to obtain a catalyst sample 1.
Example 2
Putting 4.0L of prepared sodium carbonate solution with the concentration of 1mol/L into a reaction kettle with a stirring paddle and water bath heating, preparing 420mL of 3.5mol/L copper nitrate solution, 260mL of 3.5mol/L zinc nitrate solution and 270mL of 0.8mol/L auxiliary agent M salt mixed solution into 2.0L of mixed solution A with the temperature of 65 ℃, adding the mixed solution A into the sodium carbonate solution at a constant speed of 63mL/min under the condition of the temperature of 65 ℃, stirring and aging for 0.4h under the condition of the temperature of 70 ℃, settling and washing the aged material for 6 times, adding 50g of alumina powder and pulping for 0.4 h; and performing suction filtration, drying, material grinding, granulation, roasting and tabletting on the pulped materials to obtain a catalyst sample 2.
Example 3
Putting 4.0L of prepared sodium carbonate solution with the concentration of 1mol/L into a reaction kettle with a stirring paddle and water bath heating, preparing 470mL of 3.5mol/L copper nitrate solution, 210mL of 3.5mol/L zinc nitrate solution and 133mL of 1.5mol/L auxiliary agent M salt mixed solution into 2.0L of mixed solution A with the temperature of 68 ℃, adding the mixed solution A into the sodium carbonate solution at a constant speed of 65mL/min under the condition of the temperature of 68 ℃, stirring and aging for 0.3h under the condition of the temperature of 70 ℃, settling and washing the aged material for 6 times, adding 55g of alumina powder and pulping for 0.5 h; and performing suction filtration, drying, material grinding, granulation, roasting and tabletting on the pulped materials to obtain a catalyst sample 3.
Example 4
Putting 4.0L of prepared sodium carbonate solution with the concentration of 1mol/L into a reaction kettle with a stirring paddle and water bath heating, preparing 440mL of 3.5mol/L copper nitrate solution, 245mL of 3.5mol/L zinc nitrate solution and 220mL of 0.5mol/L auxiliary agent M salt mixed solution into 2.0L of mixed solution A with the temperature of 70 ℃, adding the mixed solution A into the sodium carbonate solution at a constant speed of 55mL/min at the temperature of 70 ℃, stirring and aging for 0.4h at the temperature of 70 ℃, settling and washing the aged material for 6 times, adding 40g of alumina powder and pulping for 0.3h, wherein the pH value of the end point is 7.2; and performing suction filtration, drying, material grinding, granulation, roasting and tabletting on the pulped materials to obtain a catalyst sample 4.
Example 5
Putting 4.0L of prepared sodium carbonate solution with the concentration of 1mol/L into a reaction kettle with a stirring paddle and water bath heating, preparing 380mL of 3.5mol/L copper nitrate solution, 295mL of 3.5mol/L zinc nitrate solution and 165mL of 1.6mol/L auxiliary agent M salt mixed solution into 2.0L of mixed solution A with the temperature of 68 ℃, adding the mixed solution A into the sodium carbonate solution at a constant speed of 50mL/min under the condition of the temperature of 68 ℃, stirring and aging for 0.4h under the condition of the temperature of 68 ℃, settling and washing the aged material for 6 times, adding 60g of alumina powder and pulping for 0.4 h; and performing suction filtration, drying, material grinding, granulation, roasting and tabletting on the pulped materials to obtain a catalyst sample 5.
Example 6
Putting 4.0L of prepared sodium carbonate solution with the concentration of 1mol/L into a reaction kettle with a stirring paddle and water bath heating, preparing 400mL of 3.5mol/L copper nitrate solution, 280mL of 3.5mol/L zinc nitrate solution and 60mL of 2.0mol/L auxiliary agent M salt mixed solution into 2.0L of mixed solution A with the temperature of 70 ℃, adding the mixed solution A into the sodium carbonate solution at a constant speed of 70mL/min at the temperature of 70 ℃, stirring and aging for 0.4h at the temperature of 70 ℃, settling and washing the aged material for 6 times, adding 65g of alumina powder and pulping for 0.4 h; and performing suction filtration, drying, material grinding, granulation, roasting and tabletting on the pulped materials to obtain a catalyst sample 6.
Example 7
Putting 4.0L of prepared sodium carbonate solution with the concentration of 1mol/L into a reaction kettle with a stirring paddle and water bath heating, preparing 480mL of 3.5mol/L copper nitrate solution, 220mL of 3.5mol/L zinc nitrate solution and 350mL of 0.4mol/L auxiliary agent M salt mixed solution into 2.0L of mixed solution A with the temperature of 68 ℃, adding the mixed solution A into the sodium carbonate solution at a uniform speed of 58mL/min under the condition of the temperature of 68 ℃, stirring and aging for 0.4h under the condition of the temperature of 68 ℃, settling and washing the aged material for 6 times, adding 60g of alumina powder and pulping for 0.4 h; and performing suction filtration, drying, material grinding, granulation, roasting and tabletting on the pulped materials to obtain a catalyst sample 7.
Example 8
Putting 4.0L of prepared sodium carbonate solution with the concentration of 1mol/L into a reaction kettle with a stirring paddle and water bath heating, preparing 490mL of 3.5mol/L copper nitrate solution, 215mL of 3.5mol/L zinc nitrate solution and 300mL of 0.8mol/L auxiliary agent M salt mixed solution into 2.0L of mixed solution A with the temperature of 65 ℃, adding the mixed solution A into the sodium carbonate solution at a constant speed of 68mL/min under the condition of the temperature of 65 ℃, stirring and aging for 0.5h under the condition of the temperature of 70 ℃, settling and washing the aged material for 6 times, adding 55g of alumina powder and pulping for 0.3 h; and performing suction filtration, drying, material grinding, granulation, roasting and tabletting on the pulped materials to obtain a catalyst sample 8.
Comparative example 1
See patent CN106179360A, example 1.
Collecting 73.5g Na2CO3Dissolved in 800ml of water as solution I, toAdding 200ml of methanol into the solution I to obtain a solution II, and heating the solution II to 55 ℃; 72.9g of Cu (NO) are weighed out3)2∙3H2O and 73.1g Zn (NO)3)2∙6H2Dissolving O in 500ml of water, recording as a solution III, adding the solution III into the solution II, and changing the dropwise adding into stirring; after precipitation was complete, 9.2g of Al (OH) were added3Filtering, washing, drying, burning at 350 ℃ for 5h, granulating the roasted product, mixing with 3% graphite, and tabletting to obtain a comparative sample 1.
Comparative example 2
Maintaining pH at 9-11, and adding copper nitrate (Cu (NO)3)2∙3H20.05mol of O) and magnesium nitrate (Mg (NO)3)2∙6H20.05mol of O and chromium nitrate (Cr (NO)3)2∙9H2O)0.05mol in 103ml of water, and the resulting aqueous solution was slowly added with sodium carbonate (Na)2CO3) 0.1mol/L and 0.33mol/L of sodium hydroxide (NaOH) were dissolved in 102mL of an aqueous solution maintained at 65 ℃ and then aged at 65 ℃ for 18 hours to form a precipitate. The obtained crystalline precipitate was filtered, washed with water, dried, and then calcined at 400 ℃ for 2 hours to obtain a catalyst powder containing a composite oxide of Cu, Mg, and Cr, which was press-molded using an oil press to obtain comparative sample 2.
The results of the relevant performance tests on the samples prepared in 8 examples of the present invention and comparative examples are shown in table 1 below.
Catalyst performance test conditions:
the fixed bed reactor, catalyst loading 40ml, catalyst crushed particle size 0.85-2.0mm, raw material gas composition (v/v%): 5% -15% of CO, CO24%-10%、H235%-70%、CH45 to 15 percent, the steam-gas ratio (the molar ratio of water vapor to dry gas) is 0.43, the reaction pressure is 3.0MPa, and the space velocity is 2000h-1And an inlet temperature of 230 ℃. Before the catalyst is used, reduction is needed, and the activation conditions are as follows: reducing atmosphere N2/H2Mixed gas (N)25% of the total weight of the composition, and the balance of H2) (ii) a Reduction pressure: 0.4-0.5 Mpa; reduction space velocity of 1000 h-1(ii) a The temperature programming is slowly raised to 230 ℃ and stays for 2.0h (temperature rise)At a rate of 1 deg.C/3 min).
CO conversion calculation formula:
wherein: phi1: the volume fraction of CO in the intake air (raw material gas) is%
Φ2: volume fraction of CO in the gas (product gas)%.
Table 1 performance testing of samples prepared in examples and comparative examples at different CO contents
Note: the conditions 1, 2 and 3 are the same except that the volume content of CO is different.
As can be seen from the data in table 1: the catalyst prepared by the method has excellent performance, the structure of the catalyst is improved by adding the structural auxiliary agent, the performance of the catalyst is enhanced, the catalyst is suitable for a transformation reaction process with high CO content (more than 10 volume percent), and the conversion rate of CO is kept above 89.5 percent.
The present invention and the embodiments thereof have been described in an illustrative manner, and the description is not intended to be limiting, so that those skilled in the art should be able to devise similar arrangements and embodiments without inventively designing them without departing from the spirit and scope of the invention.
Claims (10)
1. A copper-based medium-temperature shift catalyst is characterized by comprising the following components in percentage by weight: 35-50% of copper oxide, 25-40% of zinc oxide, 5-15% of aluminum oxide and 5-15% of structure auxiliary agent M oxide.
2. The catalyst according to claim 1, characterized in that the catalyst consists of, in weight percent: 40-45% of copper oxide, 30-35% of zinc oxide, 9-12% of aluminum oxide and 8-10% of structure auxiliary agent M oxide.
3. The catalyst according to claim 1 or 2, characterized in that the structural assistant M in the catalyst composition is one or a mixture of Zr, Mg and Mn.
4. The method for preparing the catalyst according to claim 1, characterized by comprising the steps of: (1) adding the prepared alkaline precipitant into a reactor with a stirring paddle and water bath heating, adding mixed solution containing copper nitrate, zinc nitrate and an auxiliary agent M salt into the alkaline precipitant at a constant speed of 50-70ml/min for precipitation, wherein the neutralization temperature is 65-70 ℃, the end-point pH value is 7.0-7.2, and the aging is carried out for 0.3-0.5 h; (2) settling and washing the aged material, adding alumina powder, and pulping for 0.3-0.5 h; (3) and carrying out suction filtration, drying, grinding, granulation, roasting and tabletting on the pulped materials to obtain the catalyst.
5. The preparation method according to claim 4, characterized in that the salt of the auxiliary M is one or a mixture of several corresponding nitrates, carbonates and hydroxides.
6. The method according to claim 4, wherein the total concentration of metal ions in the mixed solution of the M salt is 0.2 to 2.0 mol/L.
7. The method according to claim 6, wherein the total concentration of metal ions in the mixed solution of the M salt is 0.8 to 1.5 mol/L.
8. The preparation method according to claim 4, wherein the mixed solution of the M salt is added to the alkaline precipitant at a constant speed of 60-65ml/min for precipitation.
9. The method according to claim 4, wherein the aged material is washed by 6 times of sedimentation.
10. Use of a catalyst according to any of claims 1 to 3, characterised in that the catalyst is suitable for shift reactions with a CO content of 10 to 15% by volume.
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