CN114853567A - Catalyst for preparing low-carbon alcohol by carbon dioxide conversion, and preparation method and application thereof - Google Patents
Catalyst for preparing low-carbon alcohol by carbon dioxide conversion, and preparation method and application thereof Download PDFInfo
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- CN114853567A CN114853567A CN202210686594.0A CN202210686594A CN114853567A CN 114853567 A CN114853567 A CN 114853567A CN 202210686594 A CN202210686594 A CN 202210686594A CN 114853567 A CN114853567 A CN 114853567A
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- Prior art keywords
- catalyst
- preparing
- carbon dioxide
- cobalt
- carbon
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 51
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 38
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000000498 ball milling Methods 0.000 claims abstract description 53
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000010941 cobalt Substances 0.000 claims abstract description 13
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 12
- 150000001869 cobalt compounds Chemical class 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 37
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 12
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000004576 sand Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- IUYLTEAJCNAMJK-UHFFFAOYSA-N cobalt(2+);oxygen(2-) Chemical compound [O-2].[Co+2] IUYLTEAJCNAMJK-UHFFFAOYSA-N 0.000 claims 1
- 238000005096 rolling process Methods 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000003993 interaction Effects 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- 238000000227 grinding Methods 0.000 description 46
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 238000002156 mixing Methods 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 238000011056 performance test Methods 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 4
- 239000010431 corundum Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- -1 carbon alcohols Chemical class 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 241000531116 Blitum bonus-henricus Species 0.000 description 1
- 235000008645 Chenopodium bonus henricus Nutrition 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229940063663 carbon dioxide 100 % Drugs 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000000366 colloid method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000005406 washing 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01J23/75—Cobalt
-
- 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
- B01J23/83—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 rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- 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
- B01J37/08—Heat treatment
-
- 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
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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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a catalyst for preparing low-carbon alcohol by carbon dioxide conversion, a preparation method and application thereof, and belongs to dioxygenThe technical field of carbon conversion resource utilization. The preparation method comprises the following steps: and carrying out mechanical ball milling on the uniformly mixed cobalt simple substance, cobalt compound and/or catalyst carrier, and then carrying out heat treatment, thus obtaining the catalyst product after the heat treatment is completed. The invention provides a preparation method for preparing a low-carbon alcohol catalyst by carbon dioxide conversion, which takes a cobalt simple substance and an oxide or hydroxide of cobalt as raw materials, strengthens the interaction of the simple substance cobalt and a cobalt compound under the action of mechanical ball milling, and creates Co 0 ‑Co x+ The double sites can catalyze the generation of alcohol and the growth of carbon chains, so that the selectivity of the low-carbon alcohol is greatly promoted, and is higher than 90%; the preparation method has the characteristics of less waste liquid, low cost, simple process and the like, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of carbon dioxide resource utilization, and particularly relates to a catalyst for preparing low-carbon alcohol by carbon dioxide conversion, and a preparation method and application thereof.
Background
In recent years, the large emission of carbon dioxide has caused global warming and threatened the sustainability of human development. Therefore, reducing the emission of carbon dioxide and reducing the concentration of carbon dioxide in the atmosphere to alleviate global warming are of great importance to the sustainable development of human beings. Capturing carbon dioxide and converting it into fuels and chemicals with high added value is a key means to reduce carbon dioxide emissions and to reduce the concentration of carbon dioxide in the atmosphere. Among them, low carbon alcohols, such as ethanol, propanol and butanol, are widely used as alternative fuels and solvents and raw materials in chemical processes, and have great market demands. Therefore, the conversion of the captured carbon dioxide into the lower alcohol is not only beneficial to the alleviation of global warming, but also expected to create huge thorns benefit.
However, the selectivity of the lower alcohol in the current process of preparing the lower alcohol by hydrogenating carbon dioxide is low, which hinders further industrial application. The key to solving this problem is to develop a catalyst with high selectivity by optimizing the component-based preparation method of the catalyst.
CN113751062A discloses a porous copper-based catalyst for preparing ethanol by carbon dioxide hydrogenation and a preparation method thereof, which comprises the following steps: dissolving a template agent and soluble salt of copper in a solvent, depositing on the molecular sieve by an isometric impregnation method, drying and roasting to obtain a loaded molecular sieve; reacting the loaded molecular sieve with a strong alkali solution, removing the template agent after the reaction, and drying to obtain a sample; mixing an aluminum source, a silicon source, strong base, a template agent and a sample to obtain a gel embedding body, and then aging and drying to obtain dry gel; and crystallizing the dried gel, and then washing, drying and roasting to obtain the copper-based catalyst. The catalyst is applied to the preparation of ethanol by carbon dioxide hydrogenation, and the selectivity of the ethanol is lower than 80%.
CN111434382A discloses a carrier-supported vanadium oxide promoted Rh-based catalyst, a preparation method and application thereof, wherein a molecular sieve is used as a carrier, a supported active component Rh is used, and V is used as an auxiliary agent. When the catalyst is prepared, a co-impregnation method is adopted, the carrier is immersed in oxalic acid aqueous solution of rhodium chloride and ammonium metavanadate, and the carrier is dried and roasted to obtain the catalyst. The catalyst is suitable for the reaction of preparing ethanol by hydrogenating carbon dioxide and carbon monoxide, but the selectivity of the ethanol is lower than 30 percent. In addition, the Rh-based catalyst has a high price, and the preparation process is complicated.
CN111185160A discloses a supported catalyst and a preparation method thereof, the catalyst takes noble metal Au as an active component, and is immobilized on an oxide carrier by a colloid method, so that the catalyst can improve the dispersion of the noble metal, improve the interaction between the carriers and reduce the metal agglomeration. The catalyst prepared by the method has the ethanol selectivity of 94% in the carbon dioxide hydrogenation reaction, but the gold-based catalyst has the defects of high price and the like.
In conclusion, the existing catalyst for preparing ethanol by carbon dioxide hydrogenation has the defects of low ethanol selectivity, high cost, complex preparation process and the like.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a catalyst for preparing low carbon alcohol by carbon dioxide conversion, a preparation method and application thereof, wherein the preparation method is simple and low in cost, and the catalyst has high selectivity on the low carbon alcohol in the reaction of preparing the low carbon alcohol by carbon dioxide hydrogenation catalysis.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a catalyst for preparing low-carbon alcohol by carbon dioxide conversion comprises the following steps: and carrying out mechanical ball milling on the uniformly mixed cobalt simple substance, cobalt compound and/or catalyst carrier, and then carrying out heat treatment, thus obtaining the catalyst product after the heat treatment is completed.
As a further preferred embodiment of the present invention, the cobalt compound is one or more selected from cobalt oxide and cobalt hydroxide.
In a further preferred embodiment of the present invention, the cobalt oxide is one or more selected from the group consisting of cobalt monoxide, cobaltosic oxide, and cobaltosic oxide.
As a further preferable mode of the technical solution of the present invention, the catalyst carrier is selected from one or a mixture of several of oxides or carbon materials of iron, zirconium, aluminum, cerium, zinc, manganese, titanium, copper, magnesium, silicon, nickel, molybdenum, tungsten, vanadium, and lanthanum.
As further optimization of the technical scheme of the invention, the mass and dosage ratio of the cobalt simple substance, the cobalt compound and the catalyst carrier is 0.5-95: 0.5-95: 0.5 to 95.
As a further preferred aspect of the present invention, the mechanical ball milling is performed using a ball mill selected from one or more of a planetary ball mill, a canned ball mill, a vibratory ore mill, a stirred ball mill, a pin mill, a roll mill, and a sand mill.
As a further preferred aspect of the technical solution of the present invention, the ball milling jar in the mechanical ball milling is selected from one or more of a stainless steel ball milling jar, a polytetrafluoroethylene ball milling jar, an agate ball milling jar, a nylon ball milling jar, a corundum ball milling jar, and a zirconium dioxide ball milling jar.
As a further preferred aspect of the technical solution of the present invention, the grinding balls used in the mechanical ball milling are selected from one or more of stainless steel grinding balls, alumina grinding balls, agate grinding balls, and zirconia grinding balls.
As a further optimization of the technical scheme of the invention, the mechanical ball milling speed is 10-1500 r/min, and the mechanical ball milling time is 0.5-72 h.
As a further optimization of the technical scheme of the invention, the heat treatment temperature is 20-800 ℃, and the heat treatment time is 0.5-48 h.
Meanwhile, the invention also claims the catalyst prepared by the method.
Meanwhile, the invention also discloses application of the catalyst in preparation of low-carbon alcohol by carbon dioxide hydrogenation catalysis.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides a preparation method for preparing a low-carbon alcohol catalyst by carbon dioxide conversion, which takes a cobalt simple substance and an oxide or hydroxide of cobalt as raw materials, strengthens the interaction of the simple substance cobalt and a cobalt compound under the action of mechanical ball milling, and creates Co 0 -Co x+ The double sites can catalyze the generation of alcohol and the growth of carbon chains, so that the selectivity of the low-carbon alcohol is greatly promoted, and is higher than 90%.
(2) According to the preparation method for preparing the low carbon alcohol catalyst by carbon dioxide conversion, provided by the invention, the catalyst raw material is creatively treated by mechanical ball milling, so that the particle size is reduced, a large number of defects are formed on the surface, and a large number of sites are provided for carbon dioxide adsorption, so that the conversion rate of carbon dioxide is greatly promoted and is higher than 20%.
(3) The preparation method for preparing the low-carbon alcohol catalyst by carbon dioxide conversion mainly comprises mechanical ball milling and heat treatment, wherein the heat treatment can further strengthen the interaction between simple substance cobalt and a cobalt compound and regulate and control the content of the simple substance cobalt and the compound.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Unless otherwise specified, all goods or reagents of the present invention are purchased through market channels.
Example 1
A preparation method of a catalyst for preparing low-carbon alcohol by carbon dioxide conversion comprises the following steps:
(1) mixing 0.5g Co and 0.5g Co 3 O 4 And 9g of Al 2 O 3 Mixing to obtain a mixture;
(2) placing the mixture obtained in the step (1) and 250g of corundum grinding balls in a 500mL corundum grinding tank, and introducing nitrogen into the grinding tank to replace air; putting the grinding tank into a planetary ball mill for grinding; setting the ball milling conditions as follows: rotating clockwise and anticlockwise alternately every 1h at the rotating speed of 100r/min, and ball-milling for 70 h; taking out the mixture after the ball milling is finished;
(3) placing the mixture subjected to ball milling in the step (2) in nitrogen at 500 ℃ for heat treatment for 5 hours; and (5) obtaining a catalyst product after the heat treatment is finished.
The catalyst performance test was carried out in a slurry bed reactor.
Example 2
A preparation method of a catalyst for preparing low-carbon alcohol by carbon dioxide conversion comprises the following steps:
(1) 2g of Co, 1g of Co (OH) 2 And 7g of MoO 3 Mixing to obtain a mixture;
(2) the mixture obtained in step (1) and 250g of ZrO 2 Placing the grinding balls in a 500mL zirconium dioxide grinding tank, and introducing nitrogen into the grinding tank to replace air; putting the grinding tank into a planetary ball mill for grinding; setting the ball milling conditions as follows: rotating clockwise and anticlockwise alternately at intervals of 1h at the rotating speed of 800r/min, and carrying out ball milling for 24 h; taking out the mixture after the ball milling is finished;
(3) placing the mixture subjected to ball milling in the step (2) in argon gas at 800 ℃ for heat treatment for 1 h; and (5) obtaining a catalyst product after the heat treatment is finished.
The catalyst performance test was carried out in a fixed bed reactor.
Example 3
A preparation method of a catalyst for preparing low-carbon alcohol by carbon dioxide conversion comprises the following steps:
(1) mixing 4g of Co, 4g of CoO and 2g of MnO to obtain a mixture;
(2) placing the mixture obtained in the step (1) and 250g of corundum grinding balls into a 500mL nylon grinding tank, and introducing nitrogen into the grinding tank to replace air; putting the grinding tank into a roller ball mill for grinding; setting the ball milling conditions as follows: rotating clockwise and anticlockwise alternately at intervals of 1h at the rotating speed of 200r/min, and ball-milling for 50 h; taking out the mixture after the ball milling is finished;
(3) placing the mixture subjected to ball milling in the step (2) in carbon monoxide at 500 ℃ for heat treatment for 3 h; and (5) obtaining a catalyst product after the heat treatment is finished.
The catalyst performance test was carried out in a slurry bed reactor.
Example 4
A preparation method of a catalyst for preparing low-carbon alcohol by carbon dioxide conversion comprises the following steps:
(1) 2g of Co, 6g of CoO and 2g of SiO 2 Mixing to obtain a mixture;
(2) placing the mixture obtained in the step (1) and 250g of stainless steel grinding balls in a 500mL stainless steel grinding tank, and introducing nitrogen into the grinding tank to replace air; putting the grinding tank into a planetary ball mill for grinding; setting the ball milling conditions as follows: alternately rotating clockwise and anticlockwise every 1h at the rotating speed of 800r/min, and performing ball milling for 0.5 h; taking out the mixture after the ball milling is finished;
(3) placing the mixture subjected to ball milling in the step (2) in air at 50 ℃ for heat treatment for 48 h; and (5) obtaining a catalyst product after the heat treatment is finished.
The catalyst performance test was carried out in a fixed bed reactor.
Example 5
A preparation method of a catalyst for preparing low-carbon alcohol by carbon dioxide conversion comprises the following steps:
(1) mixing 4g Co and 4g Co 3 O 4 And 4g La 2 O 3 Mixing to obtain a mixture;
(2) the mixture obtained in step (1) and 250g of ZrO 2 Placing the grinding balls in a 500mL zirconium dioxide grinding tank, and introducing nitrogen into the grinding tank to replace air; putting the grinding pot into the grinding tankGrinding in a star-type ball mill; setting the ball milling conditions as follows: rotating clockwise and anticlockwise alternately at intervals of 1h at the rotating speed of 400r/min, and ball-milling for 20 h; taking out the mixture after the ball milling is finished;
(3) placing the mixture subjected to ball milling in the step (2) in hydrogen at 250 ℃ for heat treatment for 3 h; and (5) obtaining a catalyst product after the heat treatment is finished.
The catalyst performance test was carried out in a slurry bed reactor.
Example 6
A preparation method of a catalyst for preparing low-carbon alcohol by carbon dioxide conversion comprises the following steps:
(1) mixing 5g Co and 3g Co 3 O 4 Mixing with 4g of activated carbon to obtain a mixture;
(2) the mixture obtained in step (1) and 250g of ZrO 2 Placing the grinding balls in a 500mL zirconium dioxide grinding tank, and introducing nitrogen into the grinding tank to replace air; putting the grinding tank into a planetary ball mill for grinding; setting the ball milling conditions as follows: rotating clockwise and anticlockwise alternately every 1h at the rotating speed of 300r/min, and performing ball milling for 60 h; taking out the mixture after the ball milling is finished;
(3) placing the mixture subjected to ball milling in the step (2) in nitrogen at 700 ℃ for heat treatment for 3 h; and (5) obtaining a catalyst product after the heat treatment is finished.
The catalyst performance test was carried out in a slurry bed reactor.
Example 7
A preparation method of a catalyst for preparing low-carbon alcohol by carbon dioxide conversion comprises the following steps:
(1) mixing 3g Co, 5g Co (OH) 2 And 4g of ZrO 2 Mixing to obtain a mixture;
(2) the mixture obtained in step (1) and 250g of ZrO 2 Placing the grinding balls in a 500mL zirconium dioxide grinding tank, and introducing nitrogen into the grinding tank to replace air; putting the grinding tank into a planetary ball mill for grinding; setting the ball milling conditions as follows: rotating clockwise and anticlockwise alternately at intervals of 1h at the rotating speed of 400r/min, and performing ball milling for 30 h; taking out the mixture after the ball milling is finished;
(3) placing the mixture subjected to ball milling in the step (2) in carbon monoxide at 500 ℃ for heat treatment for 3 h; and (5) obtaining a catalyst product after the heat treatment is finished.
The catalyst performance test was carried out in a fixed bed reactor.
Comparative example 1
A preparation method of a catalyst for preparing low-carbon alcohol by carbon dioxide conversion comprises the following steps:
(1) mixing 0.5g of Co and 9.5g of CoO to obtain a mixture;
(2) placing the mixture obtained in the step (1) and 250g of stainless steel grinding ball grinding balls in a 500mL polytetrafluoroethylene grinding tank, and introducing nitrogen into the grinding tank to replace air; putting the grinding tank into a planetary ball mill for grinding; setting the ball milling conditions as follows: rotating clockwise and anticlockwise alternately at intervals of 1h at the rotating speed of 400r/min, and ball-milling for 5 h; and taking out the mixture after the ball milling is finished to obtain the catalyst product.
The catalyst performance test was carried out in a fixed bed reactor.
Test example
A fixed bed reactor: mixing 0.3g of the prepared catalyst and 2g of SiC, placing the mixture in a reactor, enabling feed gas (a mixture of 20 v% of carbon dioxide, 70 v% of hydrogen and 10 v% of nitrogen) to flow through a catalyst bed layer at a certain flow, gradually increasing the reaction pressure to 5MPa at an adopted airspeed of 2 liters/g of catalyst/hour, gradually increasing the reaction temperature to 250 ℃ to start reaction, carrying out performance test for 100 hours, keeping the temperature of the product at the outlet of the reactor at 150 ℃, and introducing a chromatogram for online analysis.
Slurry bed reactor: 3g of the catalyst obtained in the preparation were mixed with 100mL of a high-boiling wax oil at room temperature, and the mixture was then transferred to a 1L continuously stirred reactor. Raw material gas (a mixture of 20 v% carbon dioxide, 70 v% hydrogen and 10 v% nitrogen) is introduced into a reactor at a certain flow rate, the space velocity adopted is 2L/g catalyst/h, the reaction pressure is gradually increased to 5.0MPa, the reaction temperature is gradually increased to 230 ℃ for starting reaction, the product at the outlet of the reactor is kept at 150 ℃, and chromatography is introduced for on-line analysis.
The carbon dioxide conversion and product selectivity were calculated according to the following formulas:
carbon dioxide conversion rate (mole of inlet carbon dioxide-mole of outlet carbon dioxide)/mole of inlet carbon dioxide 100%;
product selectivity is the moles of outlet product plus the number of carbon atoms in the product/(moles of inlet carbon dioxide-moles of outlet carbon dioxide) 100%.
The test results are shown in table 1.
TABLE 1 results of catalyst performance testing
As can be seen from table 1, the catalyst prepared by the present invention can better achieve the technical effect of preparing low carbon alcohol by carbon dioxide hydrogenation, taking example 6 as an example, the conversion rate of carbon dioxide is 22%, and the total alcohol selectivity is as high as 93%; wherein the selectivity of ethanol is up to 88 percent, and the sum of the selectivity of methanol and ethanol is up to 90 percent.
The technical idea of the present invention is illustrated by the above embodiments, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must depend on the above embodiments to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitution of individual materials for the product of the present invention and addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A preparation method for preparing a low-carbon alcohol catalyst by carbon dioxide conversion is characterized in that a cobalt simple substance, a cobalt compound and/or a catalyst carrier which are uniformly mixed are subjected to mechanical ball milling and then are subjected to heat treatment, and a catalyst product is obtained after the heat treatment is finished.
2. The method for preparing the catalyst for preparing the lower alcohol by converting the carbon dioxide as claimed in claim 1, wherein the cobalt compound is selected from one or more of cobalt oxide and cobalt hydroxide.
3. The method as claimed in claim 2, wherein the cobalt oxide is selected from one or more of cobalt monoxide, cobaltous oxide and cobaltosic oxide.
4. The method as claimed in claim 1, wherein the catalyst carrier is selected from one or more of oxides of iron, zirconium, aluminum, cerium, zinc, manganese, titanium, copper, magnesium, silicon, nickel, molybdenum, tungsten, vanadium, lanthanum, or a mixture of carbon materials.
5. The method for preparing the catalyst for preparing the low carbon alcohol through the carbon dioxide conversion according to claim 1, wherein the mass ratio of the cobalt simple substance to the cobalt compound to the catalyst carrier is 0.5-95: 0.5-95: 0.5 to 95.
6. The method for preparing the catalyst for preparing the low carbon alcohol by the conversion of the carbon dioxide, according to claim 1, wherein the mechanical ball milling is performed by using a ball mill, and the ball mill is selected from one or more of a planetary ball mill, a canned ball mill, a vibration type ore mill, a stirring type ball mill, a pin mill, a rolling mill or a sand mill.
7. The method for preparing the catalyst for preparing the low carbon alcohol through the conversion of the carbon dioxide as claimed in claim 1, wherein the rotation speed of the mechanical ball milling is 10-1500 r/min, and the time of the mechanical ball milling is 0.5-72 h.
8. The method for preparing the catalyst for preparing the lower alcohol through the carbon dioxide conversion according to claim 1, wherein the heat treatment temperature is 20-800 ℃, and the heat treatment time is 0.5-48 h.
9. A catalyst prepared by the method of any one of claims 1 to 8.
10. Use of the catalyst of claim 9 for the catalytic preparation of lower alcohols by hydrogenation of carbon dioxide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115283008A (en) * | 2022-09-15 | 2022-11-04 | 南京工业大学 | Preparation method and application of catalyst for preparing low-carbon alcohol by carbon dioxide hydrogenation |
| CN115532315A (en) * | 2022-09-30 | 2022-12-30 | 南京工业大学 | Preparation method and application of catalyst for synthesizing low-carbon alcohol by carbon dioxide hydrogenation |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060266A (en) * | 2010-11-25 | 2011-05-18 | 张文丛 | Magnesium hydride based composite powder |
| CN103801340A (en) * | 2013-07-24 | 2014-05-21 | 南昌航空大学 | Photocatalytic degradation organic matter pollutant catalyst TiO2/Co4S4.23Se3.77 as well as preparation method thereof |
| CN104549282A (en) * | 2013-10-21 | 2015-04-29 | 大连市沙河口区中小微企业服务中心 | Preparation method of low-carbon alcohol synthetic catalyst |
| CN106374101A (en) * | 2016-09-14 | 2017-02-01 | 福建师范大学 | Preparation method and application of Co<3>O<4>@Co@ carbon nanometer cage |
| CN108483394A (en) * | 2018-04-28 | 2018-09-04 | 洛阳师范学院 | A method of carbon dioxide is carried out with hydrogen storage material to add hydrogen |
| CN109950555A (en) * | 2019-03-12 | 2019-06-28 | 安徽师范大学 | Cobalt@cobaltosic oxide nanoparticles are embedded in nitrogen-doped carbon nanometer pipe material and its preparation method and application |
| CN111477840A (en) * | 2019-01-24 | 2020-07-31 | 南京大学 | Closed lithium ion battery anode based on oxyanion oxidation/reduction and preparation method thereof |
| CN112246273A (en) * | 2020-10-28 | 2021-01-22 | 南京工程学院 | Catalyst for preparing low-carbon alcohol by carbon dioxide conversion, preparation method and application |
| WO2021226172A1 (en) * | 2020-05-08 | 2021-11-11 | Air Company Holdings, Inc. | Molybdenum-based catalysts for carbon dioxide conversion |
| WO2021262922A1 (en) * | 2020-06-25 | 2021-12-30 | Air Company Holdings, Inc. | Modified copper-zinc catalysts and methods for alcohol production from carbon dioxide |
| CN114029061A (en) * | 2021-11-22 | 2022-02-11 | 北京化工大学 | Double-metal efficient catalyst, preparation method and method for preparing ethanol/acetaldehyde by co-conversion of methane and carbon dioxide |
| CN114377713A (en) * | 2021-12-28 | 2022-04-22 | 盐城工学院 | Catalyst for preparing ethanol from carbon dioxide and preparation method and application thereof |
-
2022
- 2022-06-16 CN CN202210686594.0A patent/CN114853567B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060266A (en) * | 2010-11-25 | 2011-05-18 | 张文丛 | Magnesium hydride based composite powder |
| CN103801340A (en) * | 2013-07-24 | 2014-05-21 | 南昌航空大学 | Photocatalytic degradation organic matter pollutant catalyst TiO2/Co4S4.23Se3.77 as well as preparation method thereof |
| CN104549282A (en) * | 2013-10-21 | 2015-04-29 | 大连市沙河口区中小微企业服务中心 | Preparation method of low-carbon alcohol synthetic catalyst |
| CN106374101A (en) * | 2016-09-14 | 2017-02-01 | 福建师范大学 | Preparation method and application of Co<3>O<4>@Co@ carbon nanometer cage |
| CN108483394A (en) * | 2018-04-28 | 2018-09-04 | 洛阳师范学院 | A method of carbon dioxide is carried out with hydrogen storage material to add hydrogen |
| CN111477840A (en) * | 2019-01-24 | 2020-07-31 | 南京大学 | Closed lithium ion battery anode based on oxyanion oxidation/reduction and preparation method thereof |
| CN109950555A (en) * | 2019-03-12 | 2019-06-28 | 安徽师范大学 | Cobalt@cobaltosic oxide nanoparticles are embedded in nitrogen-doped carbon nanometer pipe material and its preparation method and application |
| WO2021226172A1 (en) * | 2020-05-08 | 2021-11-11 | Air Company Holdings, Inc. | Molybdenum-based catalysts for carbon dioxide conversion |
| WO2021262922A1 (en) * | 2020-06-25 | 2021-12-30 | Air Company Holdings, Inc. | Modified copper-zinc catalysts and methods for alcohol production from carbon dioxide |
| CN112246273A (en) * | 2020-10-28 | 2021-01-22 | 南京工程学院 | Catalyst for preparing low-carbon alcohol by carbon dioxide conversion, preparation method and application |
| CN114029061A (en) * | 2021-11-22 | 2022-02-11 | 北京化工大学 | Double-metal efficient catalyst, preparation method and method for preparing ethanol/acetaldehyde by co-conversion of methane and carbon dioxide |
| CN114377713A (en) * | 2021-12-28 | 2022-04-22 | 盐城工学院 | Catalyst for preparing ethanol from carbon dioxide and preparation method and application thereof |
Non-Patent Citations (12)
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115283008A (en) * | 2022-09-15 | 2022-11-04 | 南京工业大学 | Preparation method and application of catalyst for preparing low-carbon alcohol by carbon dioxide hydrogenation |
| CN115532315A (en) * | 2022-09-30 | 2022-12-30 | 南京工业大学 | Preparation method and application of catalyst for synthesizing low-carbon alcohol by carbon dioxide hydrogenation |
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|---|---|
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