CN114471574B - 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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- CN114471574B CN114471574B CN202210110026.6A CN202210110026A CN114471574B CN 114471574 B CN114471574 B CN 114471574B CN 202210110026 A CN202210110026 A CN 202210110026A CN 114471574 B CN114471574 B CN 114471574B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- 229910017709 Ni Co Inorganic materials 0.000 title claims abstract description 68
- 229910003267 Ni-Co Inorganic materials 0.000 title claims abstract description 68
- 229910003262 Ni‐Co Inorganic materials 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 36
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002893 slag Substances 0.000 claims abstract description 17
- 238000000975 co-precipitation Methods 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 10
- 238000011084 recovery Methods 0.000 claims abstract description 10
- 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
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 239000002244 precipitate Substances 0.000 claims abstract description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 5
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 131
- 238000006555 catalytic reaction Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 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
- 230000004913 activation Effects 0.000 claims description 9
- 229910052802 copper 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
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 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
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 229910052759 nickel Inorganic materials 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
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 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
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims 1
- 239000010926 waste battery Substances 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 11
- 238000004064 recycling Methods 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000008929 regeneration Effects 0.000 abstract 1
- 238000011069 regeneration method Methods 0.000 abstract 1
- 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000003085 diluting agent Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 238000002156 mixing Methods 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
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000002699 waste material Substances 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
- 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
- 230000005540 biological transmission Effects 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 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
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram 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
- 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
- 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
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 230000001737 promoting 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
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 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
- 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
- B01J23/74—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
- 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
-
- 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)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a Cu-Al-Ni-Co based catalyst, a preparation method and application thereof. The Cu-Al-Ni-Co based catalyst comprises CuO and Al 2 O 3 、Co 3 O 4 And 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 to carry out coprecipitation reaction, separating out 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 the recycling regeneration, the value-added and the comprehensive utilization of resources 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 industry, the discharge amount of carbon dioxide in the atmosphere is continuously increasing. To address the ever-increasing concentration of carbon dioxide, new methods are needed to capture, sequester and utilize carbon dioxide. At present, recycling and regenerating technologies of carbon dioxide are receiving a great deal of attention, wherein 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 the value-added product by hydrogenation catalysis of carbon dioxide has the problems of higher preparation cost, more complex process and poorer selectivity. There is a need to develop a green, environment-friendly, simple, low cost preparation method.
The service life of the lithium ion battery is about 3-20 years, and the recovery treatment capacity of the waste battery is also increased sharply along with the increase of the demand of the lithium ion battery. However, the waste lithium ion batteries are easy to cause environmental pollution, and how to treat the waste batteries on a large scale is a very challenging problem. Meanwhile, copper-aluminum slag generated in the recovery process of waste lithium ion battery materials generally contains Cu, al, ni, co and other elements, and the recovery process of the metal elements is generally complex, has higher cost and is not beneficial to large-scale treatment and practical popularization and application.
Therefore, research and development of a green, environment-friendly and economic way for recycling waste battery materials and recycling carbon dioxide on a large scale are needed.
Disclosure of Invention
In order to research and develop a green, environment-friendly and economic way which can recycle and treat waste battery materials in a large scale and recycle carbon dioxide to solve the recycling problem of carbon dioxide and waste battery materials, one of the purposes of the invention is to provide a Cu-Al-Ni-Co-based catalyst.
The second object of the present invention is to provide a method for preparing a Cu-Al-Ni-Co based catalyst.
It is a further object of the present invention to provide a use of the above 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 comprising CuO, al 2 O 3 、Co 3 O 4 And NiO.
Preferably, the CuO contains (-1 1 1) crystal planes, and the interplanar spacing of the crystal planes is 2-3nm.
Preferably, the Cu, al, ni and Co atoms in the Cu-Al-Ni-Co based catalyst are in mass percent:
Cu：20％-24％；
Al：22％-26％；
Ni：1％-2％；
Co：13％-18％。
further preferably, the Cu, al, ni and Co atoms in the Cu-Al-Ni-Co based catalyst are in mass percent:
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 MnO 2 、Li 2 O and Fe 2 O 3 。
Specifically, the Cu-Al-Ni-Co based catalyst contains various active components, so that the catalyst has rich alkaline sites and sites for reduction reaction, is favorable for the 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 to carry out coprecipitation reaction, separating out 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 the acid solution to perform coprecipitation reaction, separating out the obtained precipitate, and roasting to obtain the Cu-Al-Ni-Co-based catalyst.
Preferably, the mass ratio of copper, aluminum, cobalt and nickel in the copper-aluminum slag is (8-30): (10-30): (5-20): 1.
Further preferably, the mass ratio of copper, aluminum, cobalt and 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 water, sodium hydroxide, potassium hydroxide, sodium bicarbonate and sodium carbonate.
Further preferably, the base 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 50-80 ℃ and a pH=5-11, and the reaction time is 1-5 h.
More preferably, the coprecipitation reaction is carried out at a temperature of 30 to 90 ℃ and a ph=6 to 8, and the reaction time is 2 to 3 hours.
Preferably, the coprecipitation reaction process further comprises a step of stirring.
Preferably, the coprecipitation reaction further comprises a standing step, wherein the standing is carried out at 15-35 ℃, and the standing time is 1-3 h.
Preferably, the specific operation of the separation is suction filtration.
Preferably, the precipitate is further washed and dried after separation.
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 temperature rise rate of the roasting is 5 ℃ min -1 ～10℃·min -1 。
In a third aspect, the present invention provides a process for the synthesis of 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 to perform activation treatment;
2) Introducing carbon dioxide and hydrogen into the reactor, and carrying out catalytic reaction to obtain methanol.
Preferably, the Cu-Al-Ni-Co-based catalyst in the step 1) is sieved, granulated, diluted and then is added into a reactor.
Preferably, the mesh number of the screen used for sieving is 10-100 mesh.
Preferably, the specific operation of the dilution is to mix the diluent with a 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 1:2-1:3.
Preferably, the mesh number of the diluent is 10-100 mesh.
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 30mL min -1 ～100mL·min -1 。
Further 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 ℃.
It is further preferred that the temperature of the activation treatment in step 1) is 320 to 350 ℃.
Preferably, the rate of temperature rise of the active treatment in step 1) is 5℃min -1 ～10℃·min -1 。
Preferably, the time of the activation treatment in step 1) is 0.5 to 5 hours.
It is further preferred that the time for the activation treatment in step 1) is 1 to 3 hours.
Preferably, the volume ratio of carbon dioxide to hydrogen in the step 2) is 1:1-1:10.
It is further preferred that the volume ratio of carbon dioxide to hydrogen in step 2) is 1:2 to 1:5.
Preferably, the volume concentration of the carbon dioxide in the catalytic reaction in the step 2) is 5-30%.
It is further preferred that the carbon dioxide in step 2) is present in a volume concentration of 10% to 20% in the catalytic reaction.
Still more preferably, the carbon dioxide in step 2) is present in a volume concentration of 15% in the catalytic reaction.
Preferably, a shielding gas is also introduced into the reactor in step 2).
Preferably, the shielding gas is one or more of helium, nitrogen, argon and neon.
Preferably, the space velocity of the catalytic reaction in step 2) is 5000h -1 -20000h -1 。
It is further preferred that the space velocity of the catalytic reaction in step 2) is 6000h -1 -15000h -1 。
Preferably, the pressure of the catalytic reaction in step 2) is 1MPa to 5MPa.
Preferably, the temperature of the catalytic reaction in step 2) is 200 ℃ to 300 ℃.
It is further preferred that the temperature of the catalytic reaction in step 2) is 240 ℃ to 280 ℃.
Still more preferably, the temperature of the catalytic reaction in step 2) is 260 ℃.
Preferably, the reactants and products of the catalytic reaction are monitored using gas chromatography.
The beneficial effects of the invention are as follows:
the Cu-Al-Ni-Co based catalyst provided by the invention contains rich active components and reaction sites (containing 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 the recycling of the waste battery materials, has the advantages of simplicity in preparation, greenness and environmental friendliness, and is suitable for practical application.
The method comprises the following steps:
(1) The invention circularly regenerates the waste battery material into a catalyst product, thereby realizing the effect of changing waste into valuables.
(2) The Cu-Al-Ni-Co based catalyst provided by the invention has rich reduction sites and alkaline sites, has good activity for converting carbon dioxide into methanol, can recycle waste battery materials, and can comprehensively utilize and resynthesize carbon dioxide into chemical value-added products (methanol fuel).
(3) The Cu-Al-Ni-Co based catalyst can catalyze the hydrogenation of carbon dioxide to prepare methanol (fuel) at the temperature of 200-300 ℃, has higher selectivity and better stability at the reaction temperature of 240-280 ℃ (namely, the selectivity of methanol is about 75 percent, and the catalyst shows good stability at the reaction condition of 260 ℃ for 60 hours).
(4) The method for synthesizing the methanol by using the carbon dioxide comprises the activation treatment, is favorable for improving the stability of the Cu-Al-Ni-Co-based catalyst in the 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 a HRTEM diagram of the Cu-Al-Ni-Co based catalyst of example 1.
FIG. 4 is a graph showing the reaction temperature-CO of the Cu-Al-Ni-Co based catalyst in example 1 2 Conversion curve.
FIG. 5 is a graph showing the reaction temperature-methanol yield of the Cu-Al-Ni-Co based catalyst in example 1.
FIG. 6 is a graph showing the results of the reaction temperature-methanol selectivity test of the Cu-Al-Ni-Co based catalyst in example 1.
FIG. 7 is a stability test result 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) 20g of copper aluminum slag is dissolved in 3 mol.L -1 Forming a mixed solution (denoted as solution A) containing Cu-Al-Ni-Co in nitric acid; then 3 mol.L is configured -1 Aqueous ammonia (noted as solution B);
2) Adopting a coprecipitation method, simultaneously dropwise adding a solution A and a solution B into a beaker at the water bath of 80 ℃ to react, controlling the dropping speed of the solution A and the solution B to ensure that the pH value of the reaction solution is kept at about 8, continuously stirring the solution in the water bath for 3 hours, and standing at room temperature for 1 hour to obtain a suspension;
3) Filtering 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 method for synthesizing methanol by carbon dioxide catalysis, comprising the following steps:
1) Preactivation of the catalyst: mixing 1.5g Cu-Al-Ni-Co based catalyst and 4.5g inert silica sand (20-40 mesh), placing into a reactor, introducing hydrogen, and treating at 300deg.C for 1 hr (heating rate of 10deg.C. Min -1 The gas flow rate was 50 mL/min -1 )；
2) Preparation of methanol: 15% CO was introduced into the reactor 2 、45％H 2 And Ar, controlling the airspeed to 12000h -1 The pressure is 5mpa and 5 ℃ min -1 And preparing the methanol under the temperature condition of 200-300 ℃.
Characterization and performance testing:
1) The element content of the Cu-Al-Ni-Co based catalyst in example 1 was obtained by ICP-MS, and the results are shown in Table 1.
As can be seen from table 1: the catalyst prepared by the copper-aluminum slag recovery treatment had more Cu (22.66%), al (24.13%), co (15.17%) and a small amount of Ni (1.4%) because of H 2 Mainly Cu and Ni are decomposed, and CO 2 Mainly on Al and Co, which indicates that the Cu-Al-Ni-Co based catalyst of the invention is advantageous for converting carbon dioxide to methanol.
TABLE 1 elemental content 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 exist mainly in the form of oxides, and diffraction peaks at 35.5 degrees, 38.75 degrees and 48.75 degrees are attributed to CuO (PDF#72-0629); diffraction peaks at 35.16 °, 58.24 ° and 68.18 ° are ascribed to Al 2 O 3 (PDF # 75-0786); at the same time, niO (PDF#87-0712) and Co can be clearly observed 3 O 4 Characteristic diffraction peaks of (PDF # 76-1802). This shows that the invention can obtain copper-aluminum slag containing CuO and Co by using waste batteries 3 O 4 、Al 2 O 3 And a Cu-Al-Ni-Co based catalyst of NiO. Wherein the CuO and NiO substances have dissociation effect on hydrogen on the catalyst after reduction of carbon dioxide, and Al 2 O 3 And Co 3 O 4 For reactant CO 2 Has adsorption effect. Further analysis, from a kinetic point of view, CO enhancement 2 The adsorption and dissociation of hydrogen are advantageous for methanol production.
3) A Transmission Electron Microscope (TEM) image and a high-magnification transmission electron microscope (HRTEM) image 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: dark color in fig. 2Part of the catalyst is mainly a CuO distribution area, so that CuO can be observed to be distributed on the Cu-Al-Ni-Co-based catalyst, the dispersion degree of the CuO on the catalyst is good, and H is facilitated 2 Thereby promoting methanol synthesis. Further enlargement of the dark area analysis revealed that the (-1 1 1) crystal plane of CuO was evident in fig. 3, and the interplanar spacing was 2.522nm, further confirming that CuO phases with good dispersibility and crystallinity were present on the cu—al—ni—co based catalyst.
4) The catalytic activity of the Cu-Al-Ni-Co-based catalyst of example 1 was measured at different reaction temperatures under the reaction conditions of the method for synthesizing methanol by carbon dioxide catalysis, which was increased from 200 ℃ to 300 ℃ (the evaluation index of activity is: CO 2 Conversion, 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 subjected to a continuous reaction at 260℃for 60 hours, to obtain the stability test result of the Cu-Al-Ni-Co based catalyst in example 1, as shown in FIG. 7.
As can be seen from fig. 4, 5 and 6: CO with the rising of the reaction temperature under the condition of 200-260 DEG C 2 The conversion and methanol yield increase rapidly; CO with the rising of the reaction temperature under the condition of 260-300 DEG C 2 The conversion showed a tendency to increase slowly (CO at 300 ℃ C.) 2 Conversion was 9.8%) and methanol yield showed a slow decrease (64.8% methanol yield at 260 ℃); under the condition of 200-300 ℃, the selectivity of the methanol is continuously reduced, and the Cu-Al-Ni-Co based catalyst is economical to synthesize the methanol at about 260 ℃ in combination (the selectivity of the methanol is about 75%). The catalyst was used under a reaction condition of 260℃although CO 2 The conversion is 9.8%, but it has a methanol yield of 64.8%, which can achieve the effect of capturing carbon dioxide and regenerating it into a methanol product of higher economic value.
As can be seen from fig. 7: the Cu-Al-Ni-Co based catalyst is tested for stability at 260 ℃ for 60 hours, and the stability of the catalyst is good, and the CO is found 2 The conversion rate is stably maintained at about 8%, and the yield of the methanol can also be stably maintained at about 75%, so that the method is suitable for 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) 20g of copper aluminum slag is dissolved in 2 mol.L -1 Forming a mixed solution (denoted as solution A) containing Cu-Al-Ni-Co in nitric acid; then 2 mol.L is configured -1 Aqueous ammonia (noted as solution B);
2) Adopting a coprecipitation method, simultaneously dropwise adding a solution A and a solution B into a beaker at a water bath of 60 ℃ to react, controlling the dropping speed of the solution A and the solution B to ensure that the pH value of the reaction solution is kept at about 7, continuously stirring the solution in the water bath for 2 hours, and standing at room temperature for 1 hour to obtain a suspension;
3) Filtering 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 method for synthesizing methanol by carbon dioxide catalysis, comprising the following steps:
1) Preactivation of the catalyst: mixing 1g of Cu-Al-Ni-Co based catalyst and 3g of inert silica sand (20-40 meshes), placing into a reactor together, introducing hydrogen, and treating at 300 ℃ for 1 hr (heating rate is 10 ℃ C. Min) -1 The gas flow rate was 50 mL/min -1 )；
2) Preparation of methanol: 15% CO was introduced into the reactor 2 、45％H 2 And Ar, controlling the airspeed to 10000h -1 The pressure is 3mpa and 5 ℃ min -1 And at a temperature of 200-300 deg.c, to produce methanol.
The phase composition and properties (63.5% methanol yield at 260 ℃) of the catalyst prepared in this example and the catalyst prepared in example 1 were very close to each other, as tested.
Example 3
A preparation method of a Cu-Al-Ni-Co based catalyst comprises the following steps:
1) 20g of copper aluminum slag is dissolved in 1 mol.L -1 Forming a mixed solution (denoted as solution A) containing Cu-Al-Ni-Co in nitric acid; then 1 mol.L is configured -1 Ammonia solutionLabeled solution B);
2) Adopting a coprecipitation method, simultaneously dropwise adding a solution A and a solution B into a beaker to react in a water bath at 50 ℃, controlling the dropping speed of the solution A and the solution B, keeping the pH of the reaction solution at about 6, continuously stirring the solution in the water bath for 3 hours, and standing at room temperature for 2 hours to obtain a suspension;
3) Filtering the suspension obtained in the step 2), washing with deionized water, drying at 80 ℃ for 12 hours, roasting at 400 ℃ for 3 hours, granulating, and sieving (20-40 meshes) to obtain the Cu-Al-Ni-Co-based catalyst.
A method for synthesizing methanol by carbon dioxide catalysis, comprising the following steps:
1) Preactivation of the catalyst: mixing 0.5g catalyst and 1.5g inert silica sand (20-40 mesh), placing into a reactor, introducing hydrogen, and treating at 300deg.C for 2 hr (heating rate of 10deg.C. Min) -1 The gas flow rate was 50 mL/min -1 )；
2) Preparation of methanol: 15% CO was introduced into the reactor 2 、45％H 2 And Ar, controlling the airspeed to be 6000h -1 The pressure is 2mpa and 10 ℃ min -1 And at a temperature of 200-300 deg.c, to produce methanol.
The phase composition and properties (yield of methanol at 260 ℃ C. 64.2%) of the Cu-Al-Ni-Co-based catalyst prepared in this example and the catalyst prepared in example 1 were all very similar.
Comparative example
The preparation method of the Cu-Al-Ni-Co-based catalyst provided by the comparative example is different from the example in that: the method only simply activates and treats the copper aluminum slag, and specifically comprises the following steps:
mixing 1.5g copper aluminum slag and 4.5g inert silica sand (20-40 mesh), placing into a reactor, introducing hydrogen, and treating at 300deg.C for 1 hr (heating rate of 10deg.C. Min) -1 The gas flow rate was 50 mL/min -1 ) The catalyst is obtained.
The catalysts of this comparative example were subjected to performance testing under the same specific conditions as the methanol preparation in the examples.
The performance test shows that: the reaction product collected was free of methanol and CO 2 The conversion was zero, indicating 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 CO 2 The waste battery material (copper aluminum slag) cannot be regenerated as resources, and a catalyst capable of converting carbon dioxide into methanol fuel cannot be obtained.
The amounts of reactants (hydrogen and carbon dioxide) and products (methanol) in the performance test of examples 1 to 3 using carbon dioxide catalyzed synthesis of methanol and comparative examples were all tested and analyzed using a gas chromatograph (Agilent Technologies 6890 USA) with TCD (thermal conductivity detector) and FID (hydrogen flame detector), unless otherwise specified.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (6)
1. A Cu-Al-Ni-Co based catalyst is characterized by comprising CuO and Al 2 O 3 、Co 3 O 4 、NiO、MnO 2 、Li 2 O and Fe 2 O 3 ；
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％；
the Cu-Al-Ni-Co based catalyst is prepared by the following method, and comprises the following steps:
dissolving copper aluminum slag generated in the recovery process of the lithium ion battery in acid, adding alkali to carry out coprecipitation reaction, separating out obtained precipitate, and roasting to obtain the Cu-Al-Ni-Co-based catalyst.
2. The preparation method of the Cu-Al-Ni-Co based catalyst is characterized by comprising the following steps of:
dissolving copper aluminum slag generated in the recovery process of the lithium ion battery in acid, adding alkali to perform coprecipitation reaction, separating out obtained precipitate, and roasting to obtain the Cu-Al-Ni-Co-based catalyst as claimed in claim 1;
wherein the mass ratio of copper, aluminum, cobalt and nickel in the copper-aluminum slag is (8-30): (10-30): (5-20): 1;
the coprecipitation reaction is carried out at the temperature of 30-90 ℃ and the pH=5-11, and the reaction time is 1-5 h.
3. The method for producing a Cu-Al-Ni-Co based catalyst according to claim 2, characterized in that: 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.
4. A method for producing a Cu-Al-Ni-Co based catalyst as in claim 2 or 3, characterized in that: the roasting temperature is 300-700 ℃ and the roasting time is 0.5-5 h.
5. A method for synthesizing methanol from carbon dioxide, comprising the steps of:
1) Loading the Cu-Al-Ni-Co-based catalyst in claim 1 into a reactor, and introducing reducing gas to perform activation treatment;
2) Introducing carbon dioxide and hydrogen into the reactor, and carrying out catalytic reaction to obtain methanol;
wherein the temperature of the catalytic reaction in the step 2) is 240-280 ℃; the pressure of the catalytic reaction in the step 2) is 1MPa-5MPa; the space velocity of the catalytic reaction in step 2) was 5000h -1 -20000h -1 。
6. The method for synthesizing methanol from carbon dioxide as claimed in claim 5, wherein: the temperature of the activation treatment in the step 1) is 300-400 ℃.
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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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| Publication number | Priority date | Publication date | Assignee | Title |
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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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