CN115283008A - Preparation method and application of catalyst for preparing low-carbon alcohol by carbon dioxide hydrogenation - Google Patents
Preparation method and application of catalyst for preparing low-carbon alcohol by carbon dioxide hydrogenation Download PDFInfo
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- CN115283008A CN115283008A CN202211125348.4A CN202211125348A CN115283008A CN 115283008 A CN115283008 A CN 115283008A CN 202211125348 A CN202211125348 A CN 202211125348A CN 115283008 A CN115283008 A CN 115283008A
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- catalyst
- cobalt
- carbon dioxide
- ball milling
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 42
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 30
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 11
- 238000000498 ball milling Methods 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 25
- 239000010941 cobalt Substances 0.000 claims abstract description 25
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002808 molecular sieve Substances 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 21
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 239000010431 corundum Substances 0.000 claims description 4
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 3
- IUYLTEAJCNAMJK-UHFFFAOYSA-N cobalt(2+);oxygen(2-) Chemical compound [O-2].[Co+2] IUYLTEAJCNAMJK-UHFFFAOYSA-N 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 3
- 239000004677 Nylon Substances 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004576 sand Substances 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 11
- 239000007788 liquid Substances 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 37
- 238000003801 milling Methods 0.000 description 17
- 239000000047 product Substances 0.000 description 16
- 238000011056 performance test Methods 0.000 description 9
- 239000002002 slurry Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- 238000005457 optimization Methods 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 241000531116 Blitum bonus-henricus Species 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 235000008645 Chenopodium bonus henricus Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 241000282414 Homo sapiens Species 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
- 230000032683 aging Effects 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
- 235000010233 benzoic acid Nutrition 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
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/072—Iron group metals or copper
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/146—Y-type faujasite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- 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)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (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 the technical field of carbon dioxide resource utilization. The preparation method comprises the following steps: uniformly mixing a cobalt precursor I and a cobalt precursor IIAnd carrying out mechanical ball milling and heat treatment on the molecular sieve to obtain a catalyst product. The invention provides a preparation method for preparing a low carbon alcohol catalyst by carbon dioxide conversion, which takes a cobalt precursor I, a cobalt precursor II and a molecular sieve as raw materials, and Co single atomic sites (Co) are subjected to mechanical ball milling x+ ) And Co nanocluster sites (Co) 0 ) Introduction into molecular sieves to create 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, the selectivity of the low-carbon alcohol is higher than 85%, and the selectivity of C3+ alcohol is higher than 40%; 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 greenhouse effect is more serious, the temperature rises to melt glaciers, the sea level rises, and the development of human beings is seriously threatened. Reducing the emission of carbon dioxide and reducing the carbon dioxide content in the atmosphere is of great significance in achieving carbon neutralization. The conversion of carbon dioxide into high value-added lower alcohols is one of the important means for achieving carbon neutralization. The low carbon alcohol has wide market demand, and can be used in the fields of chemical industry, energy, medicine, daily chemicals and the like. However, the lack of efficient catalysts has prevented the industrial application of the reaction. The key to improving the selectivity of the low-carbon alcohol is to optimize the composition and the preparation method of the catalyst.
CN113559934B discloses a preparation method of a catalyst for preparing ethanol by carbon dioxide hydrogenation, which comprises the following steps: adding meso-tetra (4-carboxyphenyl) porphyrin into a reaction container, and dropwise adding N, N-dimethylformamide to obtain a purple mixed solution; adding CuCl into the purple mixed solution 2 ·2H 2 O, until a red precipitate is generated; cooling the mixed solution to room temperature to completely generate red precipitate; centrifuging the solution at a high speed to remove impurities to obtain a precursor; grinding the precursor, adding the ground precursor into a container containing N, N-dimethylformamide, and carrying out ultrasonic treatment to obtain a solution containing the precursor; then ZrOCl is added 2 ·8H 2 Performing ultrasonic treatment after O, adding benzoic acid, and performing ultrasonic treatment to obtain reaction liquid; cooling the reaction liquid to room temperature, and filtering to obtain a filter cake; adding the filter cake into dichloromethane, soaking, filtering, and drying to obtain the catalyst for preparing ethanol by carbon dioxide hydrogenation. The method has the disadvantages of complicated preparation process and high yieldOrganic sewage and the like.
CN110947386A discloses a preparation method of a catalyst for synthesizing low-carbon alcohol by carbon dioxide hydrogenation, which comprises the following steps: taking a mixed solution of ethanol and butyl titanate as a solvent, directly adding copper nitrate, ferric nitrate and cobalt nitrate, taking ethylene glycol as a complexing agent, then dropwise adding a KOH aqueous solution, finally performing water bath magnetic stirring at 50 ℃ to hydrolyze butyl titanate to form colloid, aging for 5-15d, drying at 80-90 ℃, roasting at 200-500 ℃, and granulating to obtain the 40-60-mesh catalyst. The catalyst can be used for directly preparing alcohol fuels with high added values such as ethanol, propanol, butanol and the like by carbon dioxide hydrogenation, and the distribution of low-carbon alcohol can be adjusted by regulating the proportion of copper, cobalt and iron. The preparation method takes 5-15 days and has low efficiency.
CN111434382A discloses a carrier-supported vanadium oxide promoted Rh-based catalyst, a preparation method and an application thereof, wherein a molecular sieve is used as a carrier, a loaded 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 hydrogenation of 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.
In summary, the existing catalyst for preparing ethanol by carbon dioxide hydrogenation has the defects of low selectivity, 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.
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 mechanically ball-milling the uniformly mixed cobalt precursor I, cobalt precursor II and molecular sieve, and carrying out heat treatment to obtain the catalyst product.
As a further preferred aspect of the technical solution of the present invention, the cobalt precursor one is selected from one or more of elemental cobalt, cobalt oxide, cobaltous oxide, cobaltosic oxide, and cobalt hydroxide.
As a further preferred aspect of the technical solution of the present invention, the cobalt precursor two is one or more selected from cobalt nitrate, cobalt acetate, cobalt chloride, cobalt oxalate, and cobalt phthalocyanine.
As a further optimization of the technical scheme of the invention, the molecular sieve is selected from one or more of BEA, MFI, FAU and MOR.
As further optimization of the technical scheme of the invention, the mass and dosage ratio of the cobalt precursor I/the cobalt precursor II/the molecular sieve is 1-30: 70-98.
As a further preferred aspect of the technical solution of the present invention, in the preparation method of the catalyst, the ball mill used for mechanical ball milling is one of a planetary ball mill, a canned ball mill, a vibratory ore mill, a stirred ball mill, a pin mill, a roller ball mill and a sand mill; the ball milling tank is one of a stainless steel ball milling tank, a polytetrafluoroethylene ball milling tank, an agate ball milling tank, a nylon ball milling tank, a corundum ball milling tank and a zirconium dioxide ball milling tank; the grinding balls are one or more of stainless steel grinding balls, aluminum oxide grinding balls, agate grinding balls or zirconium oxide grinding balls; 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.
As a further optimization of the technical scheme of the invention, a solvent can be added in the mechanical ball milling process; the water content of the solvent is 10-100%, the pH value is 5-8, and the mass ratio of the solvent to the solid is 2-0: 1.
In a further preferred embodiment of the present invention, in the above catalyst preparation method, the heat treatment atmosphere is air, hydrogen, or nitrogen, the heat treatment temperature is 20 to 800 ℃, and the heat treatment time is 0.5 to 48 hours.
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 takes different cobalt precursors and molecular sieves as raw materials, and introduces cobalt monoatomic sites (Co) into the molecular sieves under the action of mechanical ball milling x+ ) And cobalt nanocluster sites (Co) 0 ) Formation of Co x+ -Co 0 A pair of dibit points. Wherein, co x+ To form an intermediate of HCOO, co 0 At the site of which CH may be formed x An intermediate. Co x+ -Co 0 Double-point pair synergistic effect for promoting HCOO-CH x Coupling and reinforcing the growth of carbon chains, thereby greatly improving the selectivity of low-carbon alcohol, and the selectivity is as high as 90%.
(2) The catalyst prepared by the invention is prepared by mixing Co x+ And Co 0 The locus is encapsulated in the molecular sieve, and the pore canal of the molecular sieve is beneficial to enriching the reactant CO 2 And H 2 Prolongation of the intermediate species HCOO and CH x The retention time in the pore channels is improved to improve HCOO-CH x Probability of coupling, which contributes to the formation of lower alcohols, C 3+ The selectivity to alcohol is higher than 40%.
(3) The preparation method provided by the invention does not need a solvent or only needs a small amount of solvent, so that no waste liquid is generated or the waste liquid is generated little, and the cost caused by waste liquid treatment is avoided.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with 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 1.0g of simple substance cobalt, 1.0g of cobalt acetate and 9.0g of beta molecular sieve to obtain a mixture;
(2) Placing the mixture obtained in the step (1) and 250g of zirconium dioxide grinding balls into 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: alternately rotating clockwise and anticlockwise every 1h at the rotating speed of 800r/min, and performing ball milling for 2h; 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 600 ℃ for heat treatment for 3h; 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 2
A preparation method of a catalyst for preparing low carbon alcohol by carbon dioxide conversion comprises the following steps:
(1) Mixing 0.1g of cobalt oxide, 0.1g of cobalt nitrate and 10g of silicalite-1 molecular sieve to obtain a mixture;
(2) Placing the mixture obtained in the step (1), 5g of water (pH = 8) and 500g of agate milling balls in a 1000mL agate milling pot, and introducing nitrogen into the milling pot to replace air; putting the grinding tank into a roller ball mill for grinding; setting the ball milling conditions as follows: alternately rotating clockwise and anticlockwise every 1h at the rotating speed of 100r/min, and performing ball milling for 72h; taking out the mixture after the ball milling is finished;
(3) Separating the mixture subjected to ball milling in the step (2), and placing the obtained solid in hydrogen at 600 ℃ for heat treatment for 1h; 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 3
A preparation method of a catalyst for preparing low-carbon alcohol by carbon dioxide conversion comprises the following steps:
(1) Mixing 2.0g of cobaltous oxide, 1.0g of cobalt oxalate and 7.0g of ZSM-5 molecular sieve to obtain a mixture;
(2) Placing the mixture obtained in the step (1), 10g of water (pH = 5) and 500g of agate milling balls in a 1000mL agate milling pot, and introducing nitrogen into the milling pot to replace air; putting the grinding tank into a roller type grinder for grinding; setting the ball milling conditions as follows: alternately rotating clockwise and anticlockwise every 1h at a rotating speed of 30r/min, and performing ball milling for 72h; taking out the mixture after the ball milling is finished;
(3) Separating the mixture subjected to ball milling in the step (2), placing the obtained solid in hydrogen at 600 ℃ for heat treatment for 3h, and then performing heat treatment in hydrogen at 600 ℃ for 2h; 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 4
A preparation method of a catalyst for preparing low-carbon alcohol by carbon dioxide conversion comprises the following steps:
(1) Mixing 0.2g of cobalt hydroxide, 0.5g of cobalt chloride and 9.0g of Y-mordenite molecular sieve to obtain a mixture;
(2) Placing the mixture obtained in step (1), 19.4g of water (pH = 7) and 500g of stainless steel milling balls in a 1000mL stainless steel tank, and introducing nitrogen gas into the milling tank to displace 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 600r/min, and carrying out ball milling for 24h; taking out the mixture after the ball milling is finished;
(3) Separating the mixture subjected to ball milling in the step (2), and placing the obtained solid in hydrogen at 250 ℃ for heat treatment for 48 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 5
A preparation method of a catalyst for preparing low carbon alcohol by carbon dioxide conversion comprises the following steps:
(1) Mixing 0.5g of cobaltosic oxide, 1.5g of cobalt phthalocyanine and 8.0g of ZSM-5 molecular sieve to obtain a mixture;
(2) Placing the mixture obtained in the step (1), 5g of water (pH = 7) and 500g of corundum grinding balls in a 1000mL 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: alternately rotating clockwise and anticlockwise every 1h at the rotating speed of 900r/min, and performing ball milling for 10h; taking out the mixture after the ball milling is finished;
(3) Separating the mixture subjected to ball milling in the step (2), and placing the obtained solid in hydrogen at 400 ℃ for heat treatment for 10h; and (5) after the heat treatment is finished, obtaining the catalyst product.
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 0.9g of simple substance cobalt, 0.3g of cobalt phthalocyanine and 9.0g of silicalite-1 molecular sieve to obtain a mixture;
(2) Placing the mixture obtained in the step (1), 3g of water (pH = 7) and 500g of agate milling balls in a 1000mL polytetrafluoroethylene milling tank, and introducing nitrogen into the milling 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 600r/min, and ball-milling for 5h; taking out the mixture after the ball milling is finished;
(3) Separating the mixture subjected to ball milling in the step (2), and placing the obtained solid in nitrogen at 600 ℃ for heat treatment for 3h; and (5) after the heat treatment is finished, obtaining the catalyst product.
The catalyst performance test was carried out in a slurry 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) 0.4g of cobalt phthalocyanine and 9.0g of SiO 2 Mixing to obtain a mixture;
(2) Placing the mixture obtained in the step (1), 1g of water (pH = 7) and 500g of agate milling balls in a 1000mL polytetrafluoroethylene milling pot, and introducing nitrogen into the milling pot 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 600r/min, and ball-milling for 5h; taking out the mixture after the ball milling is finished;
(3) Separating the mixture subjected to ball milling in the step (2), and placing the obtained solid in nitrogen at 600 ℃ for heat treatment for 3h; and (5) obtaining a catalyst product after the heat treatment is finished.
The catalyst performance test was carried out in a slurry bed reactor.
Comparative example 2
A preparation method of a catalyst for preparing low-carbon alcohol by carbon dioxide conversion comprises the following steps:
(1) Mixing 0.4g of simple substance cobalt and 9.0g of Silicate-1 molecular sieve to obtain a mixture;
(2) Placing the mixture obtained in the step (1), 3g of water (pH = 7) and 500g of agate milling balls in a 1000mL polytetrafluoroethylene milling tank, and introducing nitrogen into the milling 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 600r/min, and ball-milling for 5h; taking out the mixture after the ball milling is finished;
(3) Separating the mixture subjected to ball milling in the step (2), and placing the obtained solid in nitrogen at 600 ℃ for heat treatment for 3h; and (5) after the heat treatment is finished, obtaining the catalyst product.
The catalyst performance test was carried out in a slurry 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, allowing feed gas (a mixture of 20v% carbon dioxide, 70v% hydrogen and 10v% nitrogen) to flow through a catalyst bed layer at a certain flow rate, adopting an airspeed of 2 liters/g catalyst/hour, gradually increasing the reaction pressure to 5MPa, gradually increasing the reaction temperature to 250 ℃ to start reaction, performing performance test for 100 hours, keeping the temperature of the product at the outlet of the reactor at 150 ℃, and introducing a chromatograph to perform 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 20v% carbon dioxide, 70v% hydrogen and 10v% 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 = (moles of inlet carbon dioxide-moles of outlet carbon dioxide)/moles of inlet carbon dioxide 100%; product selectivity = moles of product at outlet number of carbon atoms in 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 catalytic 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 21%, and the total alcohol selectivity is as high as 93%; wherein ethanol and C 3 + The selectivity of the alcohol is as high as 91 percent.
The technical idea of the present invention is explained 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 be implemented depending on the above embodiments. 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 of a catalyst for preparing low-carbon alcohol by carbon dioxide conversion is characterized in that a catalyst product is obtained by mechanically ball-milling a cobalt precursor I, a cobalt precursor II and a molecular sieve which are uniformly mixed and carrying out heat treatment.
2. The method of claim 1, wherein the cobalt precursor is selected from one or more of elemental cobalt, cobalt oxide, cobaltous oxide, cobaltosic oxide, and cobalt hydroxide.
3. The method for preparing a catalyst for converting carbon dioxide to prepare lower alcohols according to claim 1, wherein the cobalt precursor II is one or more selected from cobalt nitrate, cobalt acetate, cobalt chloride, cobalt oxalate and cobalt phthalocyanine.
4. The method for preparing the catalyst for preparing the lower alcohol by the conversion of the carbon dioxide according to claim 1, wherein the molecular sieve is one or more selected from BEA, MFI, FAU and MOR.
5. The method for preparing the catalyst for preparing the lower alcohol by converting the carbon dioxide as claimed in claim 1, wherein the mass and dosage ratio of the cobalt precursor I/the cobalt precursor II/the molecular sieve is 1-30: 70-98.
6. The method of claim 1, wherein the mechanical ball mill is one of a planetary ball mill, a canned ball mill, a vibratory ore mill, a stirred ball mill, a pin mill, a roller ball mill, and a sand mill; the ball milling tank is one of a stainless steel ball milling tank, a polytetrafluoroethylene ball milling tank, an agate ball milling tank, a nylon ball milling tank, a corundum ball milling tank and a zirconium dioxide ball milling tank; the grinding balls are one or more of stainless steel grinding balls, aluminum oxide grinding balls, agate grinding balls or zirconium oxide grinding balls; the rotating speed of the mechanical ball milling is 10-1500 r/min, and the time of the mechanical ball milling is 0.5-72 h.
7. The method for preparing the catalyst for converting carbon dioxide to prepare the low carbon alcohol according to claim 1, wherein a solvent can be added during the mechanical ball milling process; the water content of the solvent is 10-100%, the pH value is 5-8, and the mass ratio of the solvent to the solid is 2-0: 1.
8. The method for preparing the catalyst for preparing the lower alcohol by converting the carbon dioxide as claimed in claim 1, wherein the heat treatment atmosphere is air, hydrogen or nitrogen, the heat treatment temperature is 20-800 ℃, and the heat treatment time is 0.5-48 h.
9. A catalyst prepared by the process of any one of claims 1 to 8.
10. Use of the catalyst according to claim 9 for the catalytic preparation of lower alcohols by hydrogenation of carbon dioxide.
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