CN114471574A - Cu-Al-Ni-Co based catalyst and preparation method and application thereof - Google Patents
Cu-Al-Ni-Co based catalyst and preparation method and application thereof Download PDFInfo
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- CN114471574A CN114471574A CN202210110026.6A CN202210110026A CN114471574A CN 114471574 A CN114471574 A CN 114471574A CN 202210110026 A CN202210110026 A CN 202210110026A CN 114471574 A CN114471574 A CN 114471574A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 93
- 229910017709 Ni Co Inorganic materials 0.000 title claims abstract description 73
- 229910003267 Ni-Co Inorganic materials 0.000 title claims abstract description 73
- 229910003262 Ni‐Co Inorganic materials 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 42
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002893 slag Substances 0.000 claims abstract description 16
- 238000000975 co-precipitation Methods 0.000 claims abstract description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 9
- 238000011084 recovery Methods 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 6
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002244 precipitate Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 131
- 238000000034 method Methods 0.000 claims description 24
- 238000006555 catalytic reaction Methods 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 230000004913 activation Effects 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims 1
- 235000017550 sodium carbonate Nutrition 0.000 claims 1
- 235000011121 sodium hydroxide Nutrition 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 11
- 239000010926 waste battery Substances 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000008929 regeneration Effects 0.000 abstract description 3
- 238000011069 regeneration method Methods 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 239000003085 diluting agent Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000007036 catalytic synthesis reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Images
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- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J23/80—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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/02—Monohydroxylic acyclic alcohols
- C07C31/04—Methanol
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- 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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a Cu-Al-Ni-Co based catalyst and a preparation method and application thereof. The Cu-Al-Ni-Co based catalyst comprises CuO and Al2O3、Co3O4And NiO. The preparation method of the catalyst comprises the following steps: dissolving copper-aluminum slag generated in the recovery process of the lithium ion battery in acid, adding alkali for coprecipitation reaction, separating the obtained precipitate, and roasting to obtain the Cu-Al-Ni-Co-based catalyst. The catalyst contains abundant alkaline sites and active sites, is simple and environment-friendly to prepare, has good catalytic activity and stability, can realize cyclic regeneration, value increase and comprehensive utilization of waste battery materials and carbon dioxide, and is suitable for practical popularization and application.
Description
Technical Field
The invention relates to the technical field of battery material recovery, in particular to a Cu-Al-Ni-Co based catalyst and a preparation method and application thereof.
Background
Due to the rapid development of the industry, the emission of carbon dioxide in the atmosphere is increasing. To address the increasing concentration of carbon dioxide, new methods are needed to capture, sequester and utilize the carbon dioxide. At present, a recycling and regenerating treatment technology of carbon dioxide is receiving wide attention, and the production of value-added products such as methane, synthesis gas, methanol and dimethyl ether by hydrogenation catalysis of carbon dioxide is considered as a way to effectively utilize carbon dioxide. However, the catalyst for producing value-added products by carbon dioxide hydrogenation catalysis has the problems of higher preparation cost, more complex process and poorer selectivity. The development of a preparation method which is green, environment-friendly, simple and low in cost is urgently needed.
The service life of the lithium ion battery is about 3-20 years, and the recycling treatment capacity of the waste battery is increased sharply along with the increase of the demand of the lithium ion battery. However, the waste lithium ion battery is easy to cause environmental pollution, and how to treat the waste lithium ion battery on a large scale is a very challenging problem. Meanwhile, copper-aluminum slag generated in the recovery process of waste lithium ion battery materials usually contains elements such as Cu, Al, Ni and Co, and the recovery process of the metal elements is generally complex and high in cost, so that the large-scale treatment and practical popularization and application are not facilitated.
Therefore, research and development of a green, environment-friendly and economical way which can recover and treat waste battery materials on a large scale and recycle carbon dioxide are urgently needed.
Disclosure of Invention
In order to research and develop a green, environment-friendly and economic way which can recover and treat waste battery materials on a large scale and recycle carbon dioxide so as to solve the problem of recovery and treatment of carbon dioxide and waste battery materials, the invention aims to provide the Cu-Al-Ni-Co based catalyst.
The second purpose of the invention is to provide a preparation method of the Cu-Al-Ni-Co based catalyst.
The invention also aims to provide application of the catalyst.
The technical scheme adopted by the invention is as follows:
in a first aspect, the present invention provides a Cu-Al-Ni-Co based catalyst, the composition of which comprises CuO and Al2O3、Co3O4And NiO.
Preferably, the CuO contains a (-111) crystal plane, and the interplanar distance of the crystal plane is 2-3 nm.
Preferably, the Cu-Al-Ni-Co based catalyst comprises the following Cu, Al, Ni and Co atoms in percentage by mass:
Cu：20％-24％；
Al：22％-26％；
Ni：1％-2％；
Co：13％-18％。
further preferably, the mass percentages of Cu, Al, Ni and Co atoms in the Cu-Al-Ni-Co base catalyst are as follows:
Cu：21％-23％；
Al：24％-25％；
Ni：1.2％-1.6％；
Co：15％-16％。
preferably, the Cu-Al-Ni-Co based catalyst composition further comprises MnO2、Li2O and Fe2O3。
Specifically, the Cu-Al-Ni-Co based catalyst contains a plurality of active components, so that the Cu-Al-Ni-Co based catalyst has abundant alkaline sites and sites for reduction reaction, is favorable for adsorption and desorption of hydrogen, and is further suitable for a catalytic hydrogenation reaction system.
In a second aspect, the present invention provides a method for preparing the Cu-Al-Ni-Co based catalyst, comprising the steps of:
dissolving copper-aluminum slag generated in the recovery process of the lithium ion battery in acid, adding alkali for coprecipitation reaction, separating the obtained precipitate, and roasting to obtain the Cu-Al-Ni-Co-based catalyst.
Preferably, the preparation method of the Cu-Al-Ni-Co based catalyst comprises the following steps:
dissolving copper-aluminum slag generated in the recovery process of the lithium ion battery in an acid solution, adding an alkali solution for coprecipitation reaction, separating the obtained precipitate, and roasting to obtain the Cu-Al-Ni-Co based catalyst.
Preferably, the mass ratio of copper to aluminum to cobalt to nickel in the copper-aluminum slag is (8-30): 10-30): 5-20): 1.
Further preferably, the mass ratio of copper to aluminum to cobalt to nickel in the copper-aluminum slag is (10-25): 15-26): 6-18): 1.
Preferably, the acid is one or more of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid and hydrofluoric acid.
Further preferably, the acid is one or more of nitric acid, hydrochloric acid and sulfuric acid.
Preferably, the alkali is one or more of ammonia, sodium hydroxide, potassium hydroxide, sodium bicarbonate and sodium carbonate.
Further preferably, the alkali is one or more of ammonia, sodium hydroxide and potassium hydroxide.
Preferably, the concentration of the acid solution is 1-3 mol/L, and the concentration of the alkali solution is 1-3 mol/L.
Preferably, the coprecipitation reaction is carried out at a temperature of 50 ℃ to 80 ℃ and a pH of 5 to 11 for 1 to 5 hours.
More preferably, the coprecipitation reaction is carried out at a temperature of 30 to 90 ℃ and a pH of 6 to 8, and the reaction time is 2 to 3 hours.
Preferably, the coprecipitation reaction process further comprises a stirring step.
Preferably, the method further comprises a standing step after the coprecipitation reaction, wherein the standing is carried out at the temperature of 15-35 ℃, and the standing time is 1-3 h.
Preferably, the specific operation of the separation is suction filtration.
Preferably, the separation of the precipitate further comprises washing and drying.
Preferably, the drying temperature is 50 ℃ to 100 ℃.
Preferably, the roasting temperature is 300-700 ℃, and the roasting time is 0.5-5 h.
Further preferably, the roasting temperature is 400-600 ℃, and the roasting time is 1-3 h.
Preferably, the heating rate of the roasting is 5 ℃ min-1～10℃·min-1。
In a third aspect, the present invention provides a method for synthesizing methanol from carbon dioxide, comprising the steps of:
1) loading the Cu-Al-Ni-Co-based catalyst in the first aspect into a reactor, and introducing reducing gas for activation treatment;
2) and introducing carbon dioxide and hydrogen into the reactor to perform catalytic reaction to obtain the methanol.
Preferably, the Cu-Al-Ni-Co based catalyst in the step 1) needs to be screened, granulated, diluted and then loaded into a reactor.
Preferably, the sieve used for sieving has a mesh number of 10-100 meshes.
Preferably, the specific operation of the dilution is to mix a diluent with the Cu-Al-Ni-Co based catalyst.
Preferably, the mass ratio of the diluent to the Cu-Al-Ni-Co based catalyst is 1: 1-1: 5.
Further preferably, the mass ratio of the diluent to the Cu-Al-Ni-Co based catalyst is 1:2 to 1: 3.
Preferably, the mesh number of the diluent is 10-100 meshes.
Preferably, the diluent is at least one of quartz sand, molecular sieve and activated carbon.
Further preferably, the diluent is quartz sand.
Preferably, the flow rate of the reducing gas in the step 1) is 30 mL-min-1～100mL·min-1。
More preferably, the flow rate of the reducing gas in the step 1) is 40 mL-min-1～60mL·min-1。
Preferably, the reducing gas in step 1) is hydrogen and/or carbon monoxide.
Further preferably, the reducing gas in step 1) is hydrogen.
Preferably, the temperature of the activation treatment in step 1) is 300 ℃ to 400 ℃.
Further preferably, the temperature of the activation treatment in the step 1) is 320 to 350 ℃.
Preferably, the temperature increase rate of the activation treatment in the step 1) is 5 ℃ min-1～10℃·min-1。
Preferably, the time of the activation treatment in the step 1) is 0.5h to 5 h.
Further preferably, the time of the activation treatment in the step 1) is 1-3 h.
Preferably, the volume ratio of the carbon dioxide to the hydrogen in the step 2) is 1: 1-1: 10.
Further preferably, the volume ratio of the carbon dioxide to the hydrogen in the step 2) is 1: 2-1: 5.
Preferably, the volume concentration of the carbon dioxide in the catalytic reaction in the step 2) is 5-30%.
Further preferably, the volume concentration of the carbon dioxide in the catalytic reaction in the step 2) is 10-20%.
Still more preferably, the concentration of carbon dioxide in the catalytic reaction in step 2) is 15% by volume.
Preferably, the reactor in the step 2) is also filled with protective gas.
Preferably, the shielding gas is one or more of helium, nitrogen, argon and neon.
Preferably, the space velocity of the catalytic reaction in the step 2) is 5000h-1-20000h-1。
Further preferably, the space velocity of the catalytic reaction in the step 2) is 6000h-1-15000h-1。
Preferably, the pressure of the catalytic reaction in the step 2) is 1MPa-5 MPa.
Preferably, the temperature of the catalytic reaction in the step 2) is 200-300 ℃.
Further preferably, the temperature of the catalytic reaction in step 2) is 240 ℃ to 280 ℃.
Even more preferably, the temperature of the catalytic reaction in step 2) is 260 ℃.
Preferably, the reactants and products of the catalytic reaction are monitored by gas chromatography.
The invention has the beneficial effects that:
the Cu-Al-Ni-Co-based catalyst disclosed by the invention contains abundant active components and reaction sites (including various alkaline sites), has a good catalytic effect when being used as a catalyst for carbon dioxide hydrogenation, is prepared from waste battery materials, realizes cyclic regeneration and utilization of the waste battery materials, has the advantages of simplicity in preparation, greenness and environmental friendliness, and is suitable for practical application.
The method specifically comprises the following steps:
(1) the invention recycles the waste battery material into the catalyst product, thereby realizing the effect of changing waste into valuable.
(2) The Cu-Al-Ni-Co-based catalyst provided by the invention is rich in reduction sites and alkaline sites, has good activity for converting carbon dioxide into methanol, can be used for recycling waste battery materials, comprehensively utilizing the carbon dioxide and synthesizing a chemical value-added product (methanol fuel).
(3) The Cu-Al-Ni-Co-based catalyst can catalyze carbon dioxide to hydrogenate to prepare methanol (fuel) at the temperature of 200-300 ℃, and has higher selectivity and better stability at the reaction temperature of 240-280 ℃ (namely the selectivity of the methanol is about 75%, and the good stability is shown under the reaction conditions of 260 ℃ and 60 hours).
(4) The method for synthesizing the methanol by using the carbon dioxide comprises activation treatment, which is beneficial to improving the stability of the Cu-Al-Ni-Co-based catalyst in catalytic reaction, and further can improve the service life of the catalyst.
Drawings
FIG. 1 is an XRD pattern of a Cu-Al-Ni-Co based catalyst in example 1.
FIG. 2 is a TEM image of the Cu-Al-Ni-Co based catalyst in example 1.
FIG. 3 is an HRTEM image of the Cu-Al-Ni-Co based catalyst in example 1.
FIG. 4 is a graph showing the reaction temperature-CO of the Cu-Al-Ni-Co based catalyst in example 12Conversion curve.
FIG. 5 is a reaction temperature-methanol yield curve of the Cu-Al-Ni-Co based catalyst in example 1.
FIG. 6 is a result of a reaction temperature-methanol selectivity test of the Cu-Al-Ni-Co based catalyst in example 1.
FIG. 7 is a result of a stability test of the Cu-Al-Ni-Co based catalyst in example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
A preparation method of a Cu-Al-Ni-Co based catalyst comprises the following steps:
1) dissolving 20g of copper-aluminum slag in 3 mol.L-1Forming a mixed solution containing Cu-Al-Ni-Co (denoted as solution A) in nitric acid; then 3 mol. L are prepared-1Aqueous ammonia solution (denoted as solution B);
2) dropwise adding the solution A and the solution B into a beaker for reaction at the same time in a water bath at 80 ℃ by adopting a coprecipitation method, controlling the dropwise adding speed of the solution A and the solution B to keep the pH of the reaction solution at about 8, continuously stirring the solution in the water bath for 3 hours, and standing for 1 hour at room temperature to obtain a suspension;
3) and (3) carrying out suction filtration on the suspension obtained in the step 2), washing with deionized water, drying at 90 ℃ for 12 hours, roasting at 600 ℃ for 3 hours, granulating, and sieving (20-40 meshes) to obtain the Cu-Al-Ni-Co based catalyst.
A process for the catalytic synthesis of methanol with carbon dioxide comprising the steps of:
1) preparation of catalystAnd (3) activation: 1.5g of Cu-Al-Ni-Co based catalyst and 4.5g of inert silica sand (20-40 meshes) are uniformly mixed, put into a reactor together, introduced with hydrogen and treated at 300 ℃ for 1 hour (the heating rate is 10 ℃ C. min)-1Gas flow rate of 50 mL/min-1)；
2) Preparation of methanol: 15% CO was introduced into the reactor2、45％H2Mixed gas of Ar and the air speed is controlled to be 12000h-1Pressure of 5MPa, 5 deg.C, min-1At a temperature of 200-300 ℃ to prepare the methanol.
Characterization and performance testing:
1) the Cu-Al-Ni-Co based catalyst of example 1 was subjected to ICP-MS to obtain the element contents, and the results are shown in Table 1.
As can be seen from Table 1: the catalyst prepared by copper aluminum slag recovery treatment has more Cu (22.66%), Al (24.13%), Co (15.17%) and a small amount of Ni (1.4%) because of H2Mainly in Cu and Ni, and CO2Activation was mainly on Al and Co, indicating that the Cu-Al-Ni-Co based catalyst of the invention favours the conversion of carbon dioxide to methanol.
TABLE 1 elemental contents of Cu-Al-Ni-Co based catalyst in example 1
2) The X-ray diffraction pattern (XRD pattern) of the Cu-Al-Ni-Co based catalyst in example 1 is shown in fig. 1.
As can be seen from fig. 1: the components in the Cu-Al-Ni-Co based catalyst are mainly present in the form of oxides, and the diffraction peaks appearing at 35.5 °, 38.75 ° and 48.75 ° are assigned to CuO (PDF # 72-0629); diffraction peaks at 35.16 °, 58.24 ° and 68.18 ° ascribed to Al2O3(PDF # 75-0786); NiO (PDF #87-0712) and Co can be clearly observed3O4(PDF # 76-1802). The invention shows that the copper-aluminum slag of the waste battery can be used for obtaining the alloy containing CuO and Co3O4、Al2O3Cu-doped with NiOAl-Ni-Co based catalysts. Wherein the CuO and NiO species dissociate the hydrogen on the catalyst after reduction with carbon dioxide, and Al2O3And Co3O4For reactant CO2Has adsorption effect. Further analysis, from the kinetic point of view, enhances CO2The adsorption and dissociation of hydrogen of (a) favours the formation of methanol.
3) Transmission Electron Microscopy (TEM) images and high magnification transmission electron microscopy (HRTEM) images of the Cu-Al-Ni-Co based catalyst in example 1 are shown in fig. 2 and 3, respectively.
As can be seen from fig. 2 and 3: in FIG. 2, the dark portion is mainly the CuO distribution region, and it can be observed that CuO is distributed on the Cu-Al-Ni-Co based catalyst, and the dispersion degree of CuO in the catalyst is better, which is helpful for H2Thereby promoting methanol synthesis. Further amplification is carried out on analysis of a dark region, a clear (-111) crystal face of CuO can be observed in FIG. 3, and the distance between the crystal faces is 2.522nm, so that the CuO phase with good dispersity and crystallinity on the Cu-Al-Ni-Co based catalyst is further verified.
4) The catalytic activity of the Cu-Al-Ni-Co based catalyst in example 1 under different reaction temperature conditions was measured by raising the temperature from 200 ℃ to 300 ℃ under the reaction conditions of the method for synthesizing methanol by carbon dioxide catalysis (evaluation indexes of activity are: CO 22Conversion, methanol yield, and methanol selectivity), the results of which are shown in fig. 4, 5, and 6. The Cu-Al-Ni-Co based catalyst was left to react at 260 ℃ for 60 hours continuously to obtain the stability test results of the Cu-Al-Ni-Co based catalyst of example 1, as shown in FIG. 7.
As can be seen from fig. 4, 5 and 6: under the condition of 200-260 ℃, CO increases along with the reaction temperature2The conversion rate and the methanol yield are increased rapidly; at the temperature of 260-300 ℃, CO increases along with the reaction temperature2The conversion rate showed a tendency to increase slowly (CO at 300 ℃ C.)2Conversion was 9.8%), methanol yield showed a slow decline (64.8% methanol yield at 260 ℃); the selectivity of the methanol is continuously reduced under the condition of 200-300 ℃, and in sum, the Cu-Al-Ni-Co based catalyst carries out the methanol at the temperature of about 260 DEG CThe synthesis of (2) is economical (selectivity of methanol is about 75%). The catalyst is under the reaction condition of 260 ℃ although CO2The conversion was 9.8%, but it had a methanol yield of 64.8%, and the effect of capturing carbon dioxide and regenerating it to a methanol product of higher economic value could be achieved.
As can be seen from fig. 7: the stability test of the Cu-Al-Ni-Co based catalyst is carried out for 60 hours at the temperature of 260 ℃, and the stability of the catalyst is found to be good, and the CO of the catalyst is found to be2The conversion rate is stably maintained at about 8 percent, the yield of the methanol can also be stably maintained at about 75 percent, and the method is suitable for the actual production and application of the methanol.
Example 2
A preparation method of a Cu-Al-Ni-Co based catalyst comprises the following steps:
1) dissolving 20g of copper-aluminum slag in 2 mol.L-1Forming a mixed solution containing Cu-Al-Ni-Co (referred to as solution A) in nitric acid; then 2 mol. L is prepared-1Aqueous ammonia solution (denoted as solution B);
2) dropwise adding the solution A and the solution B into a beaker for reaction at the same time in a water bath at 60 ℃ by adopting a coprecipitation method, controlling the dropwise adding speed of the solution A and the solution B to keep the pH of the reaction solution at about 7, continuously stirring the solution in the water bath for 2 hours, and standing for 1 hour at room temperature to obtain a suspension;
3) and (3) carrying out suction filtration on the suspension obtained in the step 2), washing with deionized water, drying at 100 ℃ for 12 hours, roasting at 500 ℃ for 3 hours, granulating, and sieving (20-40 meshes) to obtain the Cu-Al-Ni-Co based catalyst.
A process for the catalytic synthesis of methanol with carbon dioxide comprising the steps of:
1) pre-activation of the catalyst: 1g of Cu-Al-Ni-Co based catalyst and 3g of inert silica sand (20-40 meshes) are uniformly mixed, put into a reactor together, introduced with hydrogen and treated at 300 ℃ for 1 hour (the heating rate is 10 ℃ per minute)-1Gas flow rate of 50 mL/min-1)；
2) Preparation of methanol: 15% CO was introduced into the reactor2、45％H2And Ar mixed gas, and the space velocity is controlled to be 10000h-1Pressure of 3MPa, 5 deg.C, min-1And preparing the methanol at the temperature of 200-300 ℃.
The phase composition and performance of the catalyst prepared in this example was tested to be very similar to that of the catalyst prepared in example 1 (yield of 63.5% methanol at 260 ℃).
Example 3
A preparation method of a Cu-Al-Ni-Co based catalyst comprises the following steps:
1) dissolving 20g of copper-aluminum slag in 1 mol.L-1Forming a mixed solution containing Cu-Al-Ni-Co (denoted as solution A) in nitric acid; then 1 mol. L is prepared-1Aqueous ammonia solution (denoted as solution B);
2) dropwise adding the solution A and the solution B into a beaker for reaction at the same time in a water bath at 50 ℃ by adopting a coprecipitation method, controlling the dropwise adding speed of the solution A and the solution B to keep the pH of the reaction solution at about 6, continuously stirring the solution in the water bath for 3 hours, and standing for 2 hours at room temperature to obtain a suspension;
3) and (3) carrying out suction filtration on the suspension obtained in the step 2), washing with deionized water, drying at 80 ℃ for 12 hours, roasting at 400 ℃ for 3 hours, and then granulating and sieving (20-40 meshes) to obtain the Cu-Al-Ni-Co based catalyst.
A process for the catalytic synthesis of methanol with carbon dioxide comprising the steps of:
1) pre-activation of the catalyst: 0.5g of catalyst and 1.5g of inert silica sand (20-40 meshes) are uniformly mixed, then the mixture is put into a reactor, hydrogen is introduced, and the mixture is treated for 2 hours at 300 ℃ (the heating rate is 10 ℃ per minute)-1Gas flow rate of 50 mL/min-1)；
2) Preparation of methanol: 15% CO was introduced into the reactor2、45％H2Mixed gas of Ar and the air speed is controlled to be 6000h-1Pressure of 2MPa, 10 deg.C, min-1And preparing the methanol at the temperature of 200-300 ℃.
The phase compositions and performances (64.2% methanol yield at 260 ℃) of the Cu-Al-Ni-Co-based catalyst prepared in the example are very similar to those of the catalyst prepared in the example 1.
Comparative example
The comparative example provides a preparation method of a Cu-Al-Ni-Co based catalyst, which is different from the examples in that: only the copper-aluminum slag is simply activated and treated, and the method specifically comprises the following steps:
1.5g of copper-aluminum slag and 4.5g of inert silica sand (20-40 meshes) are uniformly mixed, put into a reactor together, introduced with hydrogen and treated at 300 ℃ for 1 hour (the heating rate is 10 ℃ per minute)-1Gas flow rate of 50 mL/min-1) And obtaining the catalyst.
The catalyst in this comparative example was subjected to performance test under the same conditions as those for methanol preparation in the examples.
The performance test shows that: the reaction product collected was free of methanol and CO2The conversion was zero, which indicates that the catalyst obtained in the comparative example using only a simple activation treatment did not have the ability to capture, collect, store and convert CO2The capacity of the method is further incapable of carrying out resource regeneration on waste battery materials (copper-aluminum slag) and obtaining a catalyst capable of converting carbon dioxide into methanol fuel.
Unless otherwise specified, the amounts of the reactants (hydrogen and carbon dioxide) and the product (methanol) in the performance tests of the method for catalytically synthesizing methanol using carbon dioxide and the comparative example in examples 1 to 3 were measured and analyzed by using a gas chromatograph (Agilent Technologies 6890USA) equipped with TCD (thermal conductivity detector) and FID (hydrogen flame detector).
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A Cu-Al-Ni-Co based catalyst is characterized in that the composition comprises CuO and Al2O3、Co3O4And NiO.
2. The Cu-Al-Ni-Co based catalyst of claim 1, wherein: the Cu-Al-Ni-Co based catalyst comprises the following Cu, Al, Ni and Co atoms in percentage by mass:
Cu：20％-24％；
Al：22％-26％；
Ni：1％-2％；
Co：13％-18％。
3. the Cu-Al-Ni-Co based catalyst according to claim 1 or 2, characterized in that: the composition of the Cu-Al-Ni-Co based catalyst also comprises MnO2、Li2O and Fe2O3。
4. A preparation method of a Cu-Al-Ni-Co based catalyst is characterized by comprising the following steps:
dissolving copper-aluminum slag generated in the recovery process of the lithium ion battery in acid, adding alkali for coprecipitation reaction, separating the obtained precipitate, and roasting to obtain the Cu-Al-Ni-Co-based catalyst.
5. The method for preparing a Cu-Al-Ni-Co based catalyst according to claim 4, wherein: the mass ratio of copper, aluminum, cobalt and nickel in the copper-aluminum slag is (8-30): 10-30): 5-20): 1.
6. The method for preparing a Cu-Al-Ni-Co based catalyst according to claim 4, wherein: the acid is one or more of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid and hydrofluoric acid; the alkali is one or more of ammonia water, sodium hydroxide, potassium hydroxide, sodium bicarbonate and sodium carbonate.
7. The method for preparing a Cu-Al-Ni-Co based catalyst according to any one of claims 4 to 6, wherein: the coprecipitation reaction is carried out at the temperature of 30-90 ℃ and under the condition that the pH value is 5-11, and the reaction time is 1-5 h.
8. The method for preparing a Cu-Al-Ni-Co based catalyst according to any one of claims 4 to 6, wherein: the roasting temperature is 300-700 ℃, and the roasting time is 0.5-5 h.
9. A method for synthesizing methanol by using carbon dioxide is characterized by comprising the following steps:
1) loading the Cu-Al-Ni-Co-based catalyst according to any one of claims 1 to 3 into a reactor, and introducing a reducing gas for activation treatment;
2) and introducing carbon dioxide and hydrogen into the reactor to perform catalytic reaction to obtain the methanol.
10. The method for synthesizing methanol using carbon dioxide according to claim 9, characterized in that: the temperature of the activation treatment in the step 1) is 300-400 ℃; the temperature of the catalytic reaction in the step 2) is 200-300 ℃.
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| WO2023142671A1 (en) * | 2022-01-29 | 2023-08-03 | 广东邦普循环科技有限公司 | Cu-al-ni-co-based catalyst, and preparation method therefor and use thereof |
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| US4659742A (en) * | 1982-03-26 | 1987-04-21 | Institut Francais Du Petrol | Process for manufacturing a mixture of methanol and higher alcohols from synthesis gas |
| CA2635312A1 (en) * | 2008-06-19 | 2009-12-19 | University Of Saskatchewan | Catalyst for production of synthesis gas |
| CN104645991A (en) * | 2015-02-09 | 2015-05-27 | 天津大学 | Preparation method and application of mixed oxide-doped nano copper-cobalt alloy catalyst |
| WO2021262922A1 (en) * | 2020-06-25 | 2021-12-30 | Air Company Holdings, Inc. | Modified copper-zinc catalysts and methods for alcohol production from carbon dioxide |
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| US4659742A (en) * | 1982-03-26 | 1987-04-21 | Institut Francais Du Petrol | Process for manufacturing a mixture of methanol and higher alcohols from synthesis gas |
| CA2635312A1 (en) * | 2008-06-19 | 2009-12-19 | University Of Saskatchewan | Catalyst for production of synthesis gas |
| CN104645991A (en) * | 2015-02-09 | 2015-05-27 | 天津大学 | Preparation method and application of mixed oxide-doped nano copper-cobalt alloy catalyst |
| WO2021262922A1 (en) * | 2020-06-25 | 2021-12-30 | Air Company Holdings, Inc. | Modified copper-zinc catalysts and methods for alcohol production from carbon dioxide |
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| WO2023142671A1 (en) * | 2022-01-29 | 2023-08-03 | 广东邦普循环科技有限公司 | Cu-al-ni-co-based catalyst, and preparation method therefor and use thereof |
| GB2622722A (en) * | 2022-01-29 | 2024-03-27 | Guangdong Brunp Recycling Technology Co Ltd | Cu-Al-Ni-Co-based catalyst, and preparation method thereof and use thereof |
| CN115350706A (en) * | 2022-08-29 | 2022-11-18 | 南京信息工程大学 | CO (carbon monoxide) 2 Preparation method of three-element metal MOF (Metal organic framework) derivative catalyst for hydrogenation thermal catalysis |
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