CN113877613A - CO (carbon monoxide)2Hydrogenated biomass charcoal-based transition metal catalyst and preparation method thereof - Google Patents
CO (carbon monoxide)2Hydrogenated biomass charcoal-based transition metal catalyst and preparation method thereof Download PDFInfo
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- CN113877613A CN113877613A CN202110828877.XA CN202110828877A CN113877613A CN 113877613 A CN113877613 A CN 113877613A CN 202110828877 A CN202110828877 A CN 202110828877A CN 113877613 A CN113877613 A CN 113877613A
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- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 114
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 94
- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 239000002028 Biomass Substances 0.000 title claims abstract description 47
- 239000003610 charcoal Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000002994 raw material Substances 0.000 claims abstract description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 172
- 239000004202 carbamide Substances 0.000 claims description 87
- 238000003756 stirring Methods 0.000 claims description 64
- 239000000463 material Substances 0.000 claims description 61
- 239000002114 nanocomposite Substances 0.000 claims description 60
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 44
- 239000008103 glucose Substances 0.000 claims description 44
- 238000000227 grinding Methods 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 39
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 32
- 229940010552 ammonium molybdate Drugs 0.000 claims description 32
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 32
- 239000011609 ammonium molybdate Substances 0.000 claims description 32
- 238000002844 melting Methods 0.000 claims description 31
- 230000008018 melting Effects 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- 229910052799 carbon Inorganic materials 0.000 claims description 29
- 239000000843 powder Substances 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 25
- 239000012298 atmosphere Substances 0.000 claims description 24
- 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 claims description 22
- -1 transition metal salt Chemical class 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 15
- 229910052755 nonmetal Inorganic materials 0.000 claims description 14
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 13
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000007790 solid phase Substances 0.000 claims description 10
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 10
- 229920002472 Starch Polymers 0.000 claims description 9
- 238000010000 carbonizing Methods 0.000 claims description 9
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 9
- 239000008107 starch Substances 0.000 claims description 9
- 235000019698 starch Nutrition 0.000 claims description 9
- 239000010902 straw Substances 0.000 claims description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 9
- 239000002023 wood Substances 0.000 claims description 9
- 229920001661 Chitosan Polymers 0.000 claims description 8
- 229920002488 Hemicellulose Polymers 0.000 claims description 7
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 7
- 229930006000 Sucrose Natural products 0.000 claims description 7
- 239000001913 cellulose Substances 0.000 claims description 7
- 229920002678 cellulose Polymers 0.000 claims description 7
- 150000002843 nonmetals Chemical group 0.000 claims description 7
- 239000005720 sucrose Substances 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229920005610 lignin Polymers 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 90
- 230000008569 process Effects 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 239000000446 fuel Substances 0.000 abstract description 3
- 150000001298 alcohols Chemical class 0.000 abstract description 2
- 229930195733 hydrocarbon Natural products 0.000 abstract description 2
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 229920000742 Cotton Polymers 0.000 abstract 1
- 238000000197 pyrolysis Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 126
- 239000007789 gas Substances 0.000 description 58
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 36
- 239000000243 solution Substances 0.000 description 27
- 239000000047 product Substances 0.000 description 23
- 238000005485 electric heating Methods 0.000 description 21
- 239000011521 glass Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 238000005303 weighing Methods 0.000 description 19
- 238000004458 analytical method Methods 0.000 description 18
- 239000000919 ceramic Substances 0.000 description 18
- 239000007791 liquid phase Substances 0.000 description 18
- 238000002156 mixing Methods 0.000 description 17
- 239000012299 nitrogen atmosphere Substances 0.000 description 17
- 239000000080 wetting agent Substances 0.000 description 12
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012072 active phase Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 239000012071 phase Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
-
- 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
Abstract
The invention provides a CO2A hydrogenated biomass charcoal-based transition metal catalyst and a preparation method thereof belong to the technical field of biomass catalytic conversion. The invention utilizes biomass charcoal-based transition metal catalyst to grow cotton stalks and the likeCO in tail gas from pyrolysis of substances2Hydrogenation for preparing fuels and chemicals such as alcohols and hydrocarbons to promote CO2And feasible strategies are provided for emission reduction and sustainable resource utilization. Meanwhile, the invention takes renewable biomass with wide source and low price as raw material, which is green and environment-friendly and has simple process. As CO2When the catalyst is hydrogenated, the reaction can be carried out under the condition of lower reaction temperature; in addition, the catalyst shows the catalytic performance of a palladium-like catalyst and a platinum-like catalyst, has strong practicability, can relieve the problems of environment and energy, has good market prospect, and is suitable for industrial large-scale production.
Description
Technical Field
The invention belongs to a catalyst preparation technology, and particularly relates to CO2Hydrogenated biomass charcoal-based transition metal and a preparation method thereof.
Background
CO rising constantly in the atmosphere2Concentrations are seriously threatening human survival, including severe climate change, glacier melting, ocean acidification, etc. Thus, control of global CO2Emissions, stabilizing atmospheric concentrations of greenhouse gases at a low level, is an urgent task to be placed on the front of all mankind. In recent years, as non-renewable fossil resources on earth are gradually exhausted, people are interested in producing energy or chemicals by using renewable resources to meet the requirements of human society. CO generation by catalytic process using renewable energy2Conversion into methanol can not only realize CO2The emission reduction and utilization of the fuel can store renewable energy sources in liquid fuel, and further zero carbon emission is realized.
Methanol is a raw material that is used very widely in global industries, and with the increasing depletion of fossil fuels, methanol is considered as an ideal clean alternative energy source. In the chemical industry, methanol is used to synthesize chemicals such as formaldehyde, aromatic hydrocarbons, ethylene, methyl tert-butyl ether, acetic acid, etc. In addition, the demand of methanol for the production of dimethyl carbonate and biodiesel is gradually rising.
CO2The preparation of methanol by hydrogenation mainly comprises 3 reactions: (1) CO 22Preparing methanol by hydrogenation; (2) CO 22Hydrogenation to produce CO, namely reverse water-gas shift reaction; (3) and (3) preparing methanol by CO hydrogenation. Wherein (1) and (2) are in a competitive reaction with each other, resulting in methanolThe main cause of the decrease in selectivity. Therefore, from a thermodynamic point of view, due to CO2The reaction for producing methanol by hydrogenation is an exothermic reaction in which the number of gas molecules is reduced, so that the methanol is more favorably produced at a high pressure and a low temperature. And CO2As inert gas, higher reaction temperatures (e.g. above 240 ℃ C.) can activate CO2While too high a reaction temperature will promote the reverse water gas shift reaction to produce CO by-products, a suitable reaction temperature is important. In addition, the by-products of the reaction include, in addition to CO, hydrocarbons and higher alcohols. In conclusion, the efficient catalyst is developed to solve the problem of CO2In addition to the activation problem, it is necessary to increase the selectivity of methanol to reduce the formation of by-products.
The catalyst widely used for preparing methanol at present is mainly a Cu-based catalyst, but the Cu-based catalyst has the defects of easy agglomeration and easy inactivation at high temperature; while the noble metal catalyst has excellent CO2The hydrogenation reaction activity can realize high methanol selectivity at a lower reaction temperature, but the price is high, the resources are scarce, the industrial large-scale production cannot be realized, the methanol yield is low, and the methanol selectivity also depends on the type of a carrier, a metal precursor and a preparation method.
Transition metal catalysts have attracted great attention as a new class of catalytic materials. Among them, the transition metal carbide shows excellent 'palladium-like and platinum-like' catalytic activity and good selectivity in the aspects of catalytic hydrogenation, alkane isomerization, dehydrogenation, desulfurization, denitrification, reforming, namely oxidation reaction and the like. However, transition metal catalysts are not typical of CO2The catalyst for preparing methanol by hydrogenation also has the problems of small specific surface area and the like, and the application of the catalyst in the field of catalysis is limited. And metal ions or non-metal atoms are doped and modified on the transition metal catalyst, so that the specific surface area of the catalyst can be increased, and the selectivity of the transition metal carbide catalyst on methanol can be enhanced.
Therefore, a catalyst having excellent methanol selectivity and CO was selected2Catalytically active catalyst, of CO2Efficient directional conversion to methanol is key to the existing problem. To solve the above problems, the method is selectedDifferent metal ions are used for loading or doping the transition metal carbide, which is beneficial to improving the selectivity of the target product methanol and reducing the production of byproducts such as CO and the like.
Disclosure of Invention
The invention aims to provide CO2The catalyst preparation method has the advantages of high conversion rate, good selectivity of the target product methanol, low cost, strong process operability and good industrial application prospect.
The technical scheme of the invention is as follows: CO (carbon monoxide)2The hydrogenated biomass charcoal-based transition metal catalyst is obtained by the following method, firstly, reacting a biomass carbon source with a transition metal salt through a melting method to prepare a transition metal carbide nano composite material, carbonizing the composite material, doping non-metal atoms through a solid phase grinding method, and finally roasting the composite material through air to prepare the biomass charcoal-based transition metal catalyst;
or reacting a biomass carbon source with transition metal salt by a melting method to prepare a transition metal carbide nano composite material, carbonizing the transition metal carbide nano composite material, carrying out metal ion loading by a solid phase grinding method or an impregnation method, and finally roasting the transition metal carbide nano composite material by air to prepare the biomass carbon-based transition metal catalyst.
The biomass charcoal source is as follows: cellulose, hemicellulose, lignin, glucose, chitosan, sucrose, starch, wood powder, straw and corncob.
In the transition metal salt, the transition metal is one of iron, cobalt, molybdenum, tungsten, titanium or vanadium; and/or the transition metal salt is one of ferric nitrate, cobalt nitrate, ammonium molybdate, ammonium tungstate, titanium tetrachloride or sodium metavanadate; the mass ratio of the carbon source to the transition metal salt is 1: 0.1 to 0.6.
The non-metal atom source is one of urea, melamine or p-phenylenediamine; the mass ratio of the carbon source to the non-metal atom source is 1:1 to 3.
The doped metal atom is one of copper, iron, cobalt, nickel, cerium or zirconium; and/or the doped metal salt is one of copper nitrate, ferric nitrate, cobalt nitrate, cerium nitrate or zirconium nitrate; the mass ratio of the carbon source to the metal salt is 1: 0.3 to 0.6.
Said CO2The preparation method of the hydrogenated biomass charcoal-based transition metal catalyst comprises the steps of firstly reacting a biomass carbon source with a transition metal salt by a melting method to prepare a transition metal carbide nano composite material, carbonizing the transition metal carbide nano composite material, doping non-metal atoms by a solid phase grinding method, and finally roasting the carbonized biomass charcoal-based transition metal catalyst by air;
or reacting a biomass carbon source with transition metal salt by a melting method to prepare a transition metal carbide nano composite material, carbonizing the transition metal carbide nano composite material, carrying out metal ion loading by a solid phase grinding method or an impregnation method, and finally roasting the transition metal carbide nano composite material by air to prepare the biomass carbon-based transition metal catalyst.
Heating and melting the biomass raw material and the urea, stirring until the solution is clarified, and stopping heating and stirring.
And drying the molten mixture in an oven for 12-24 hours.
The carbonization condition is 500-900 ℃ in inert atmosphere; the air roasting condition is 300-500 ℃.
Has the advantages that:
1. the method takes biomass as a raw material, and the unique constraint structure of the graphene layer can inhibit the formation of an amorphous carbon layer, so that unstable subphase is converted into other transition metal carbide phases with lower activity. The catalyst is modified by nonmetal/metal doping, so that the selectivity of the catalyst to a target product methanol is enhanced. The results and conclusions of the present invention help to rationally design promising active phases in industrial hydrogenation catalysts. The biomass raw material has wide source, low cost, simple process and strong feasibility. The prepared catalyst has good selectivity of a target product methanol.
2. The method of the invention has no special requirements on biomass raw materials, and can be suitable for biomass from various raw material sources, such as: cellulose, hemicellulose, lignin, glucose, chitosan, sucrose, starch, wood flour, straw, corncob and the like. The raw material source is wide, and the industrial cost of catalyst synthesis is greatly reduced.
3. The method has simple process and strong operability, and the prepared catalyst has excellent sulfur poisoning resistance and good selectivity on the target product methanol.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The reaction process is described below by way of example.
CO (carbon monoxide)2The preparation method of the hydrogenated biomass charcoal-based transition metal catalyst comprises the steps of preparing a transition metal carbide nano composite material by using a biomass resource as a carbon source and a transition metal salt through a melting method, carbonizing, and carrying out non-metal atom doping or metal ion loading through a solid phase grinding method to finally prepare the biomass charcoal-based transition metal catalyst.
CO (carbon monoxide)2The hydrogenated biomass charcoal-based transition metal catalyst and the preparation method thereof comprise the following steps: respectively weighing a carbon source and urea, putting the carbon source and the urea into a beaker, fully stirring the carbon source and the urea to uniformly mix the carbon source and the urea, then putting the beaker into an electric heating jacket with a set temperature, melting the carbon source and the urea into a viscous state after a period of time, starting to stir the solution violently by using a glass rod until the solution is clarified, slowly adding a transition metal salt, stirring the solution until the transition metal salt is completely dissolved, and then quickly transferring the beaker into an oven with a set temperature to treat the solution for a period of time. And taking the treated object out of the oven, grinding the object into powder, roasting the powder in the atmosphere of inert gas in the tube furnace, and switching the tube furnace into low-concentration oxygen mixed gas for passivation treatment when the temperature of the tube furnace is reduced to room temperature, thereby preparing the transition metal carbide nano composite material.
The obtained transition metal carbide nano composite material is doped with non-metal atoms or loaded with metal ions by a solid phase grinding method and finally roasted in the air atmosphere to obtain the transition metal carbide nano composite material.
The biomass raw material is any one of cellulose, hemicellulose, lignin, glucose, chitosan, sucrose, starch, wood powder, straw and corncob;
in the transition metal salt, the transition metal is one of iron, cobalt, molybdenum, tungsten, titanium or vanadium;
the transition metal salt is one of ferric nitrate, cobalt nitrate, ammonium molybdate, ammonium tungstate, titanium tetrachloride or sodium metavanadate;
the mass ratio of the carbon source to the transition metal salt is 1: 0.1 to 0.6;
the heating temperature of the electric heating jacket is 120-160 ℃;
the nonmetal nitrogen source is one of urea, melamine or p-phenylenediamine;
the mass ratio of the carbon source to the non-metal atom source is 1: 1-3;
the doped metal atom is one of copper, iron, cobalt, nickel, cerium or zirconium;
the doped metal salt is one of copper nitrate, ferric nitrate, cobalt nitrate, cerium nitrate or zirconium nitrate
The mass ratio of the carbon source to the metal salt is 1: 0.3 to 0.6;
the heating temperature of the oven is 160-200 ℃, and the drying time is 12-24 h;
the carbonization condition is that the carbonization temperature is 500-900 ℃ in inert atmosphere;
the air roasting temperature is 300-500 ℃.
Example 1:
respectively weighing glucose and urea, putting the glucose and the urea into a 100ml beaker, fully stirring the mixture to uniformly mix the glucose and the urea, then putting the beaker into an electric heating jacket set to be 120 ℃, melting the glucose and the urea into a sticky state after about 10-15 min, starting to stir the mixture vigorously by using a glass rod until the solution is clarified, slowly adding ferric nitrate into the mixture to be completely dissolved, and then quickly transferring the beaker into an oven set to be 200 ℃ to treat the mixture for 12 hours. The treated article was removed from the oven, ground to a powder and placed in a tube furnace under nitrogen (10 mLmin)-1) Heat treatment at 400 ℃ for 30 minutes and finally heat treatment at a final temperature of 500 ℃ for 2 hours. Mixing and grinding the obtained transition metal carbide nano composite material and urea according to different weight ratios, adding a small amount of ethanol as a wetting agent, collecting the mixture in a ceramic crucible, and finally roasting for 2 hours at 350 ℃ in an air atmosphere to obtain the transition metal carbide nano composite material.
Application of catalyst to CO2Hydrogenation reaction: 0.2g of catalyst was directly charged into a reaction tube, and a mixed gas (CO) was introduced2：H21:3), the reactor pressure was increased to 2.0MPa at 2 ℃ for min-1The temperature rise rate of (3) raises the bed temperature to the target temperature to start the reaction. Liquid phase products are collected by a cold water bath cold trap for off-line analysis, and reaction tail gas is analyzed on line by a gas chromatograph. CO 22The conversion was 19% and the methanol selectivity was 91%.
Example 2:
respectively weighing sucrose and urea, putting the sucrose and the urea into a 100ml beaker, fully stirring the mixture to be uniformly mixed, then putting the beaker into an electric heating jacket set to be 130 ℃, after about 10-15 min, melting the sucrose and the urea to be sticky, starting to stir violently by using a glass rod until the solution is clarified, slowly adding ammonium molybdate, stirring the ammonium molybdate to be completely dissolved, and then quickly transferring the beaker into an oven set to be 180 ℃ for processing for 24 hours. Taking the treated article out of the oven, grinding into powder, and placing in a tube furnace under nitrogen atmosphere (5 mLmin)-1) Heat treatment was carried out at 900 ℃ for 3 hours. Mixing and grinding the obtained transition metal carbide nano composite material and urea according to the mass ratio of 1:2, adding a small amount of ethanol as a wetting agent, collecting the mixture in a ceramic crucible, and finally roasting for 2 hours at 300 ℃ in an air atmosphere to obtain the transition metal carbide nano composite material.
Application of catalyst to CO2Hydrogenation reaction: 0.2g of catalyst was directly charged into a reaction tube, and a mixed gas (CO) was introduced2：H21:3), the reactor pressure was increased to 2.0MPa at 2 ℃ for min-1The temperature rise rate of (3) raises the bed temperature to the target temperature to start the reaction. Liquid phase products are collected by a cold water bath cold trap for off-line analysis, and reaction tail gas is analyzed on line by a gas chromatograph. CO 22The conversion was 17% and the methanol selectivity was 80%.
Example 3:
respectively weighing starch and urea, putting the starch and the urea into a 100ml beaker, fully stirring the starch and the urea to uniformly mix the starch and the urea, then putting the beaker into an electric heating jacket set to be 140 ℃, melting the starch and the urea into a sticky state after about 10-15 min, starting to stir vigorously by using a glass rod until the solution is clarified, slowly adding cobalt nitrate, stirring the cobalt nitrate until the cobalt nitrate is completely dissolved, then quickly transferring the beaker to be 200 DEG CWas treated in an oven for 18 h. Taking the treated article out of the oven, grinding into powder, and placing in a tube furnace under nitrogen atmosphere (5 mLmin)-1) Heat treatment was carried out at 750 ℃ for 2 hours. Mixing and grinding the obtained transition metal carbide nano composite material and melamine according to the mass ratio of 1:3, adding a small amount of ethanol as a wetting agent, collecting the mixture in a ceramic crucible, and finally roasting for 2 hours at 350 ℃ in an air atmosphere to obtain the transition metal carbide nano composite material.
Application of catalyst to CO2Hydrogenation reaction: 0.2g of catalyst was directly charged into a reaction tube, and a mixed gas (CO) was introduced2：H21:3), the reactor pressure was increased to 2.0MPa at 2 ℃ for min-1The temperature rise rate of (3) raises the bed temperature to the target temperature to start the reaction. Liquid phase products are collected by a cold water bath cold trap for off-line analysis, and reaction tail gas is analyzed on line by a gas chromatograph. CO 22The conversion was 18% and the methanol selectivity was 85%.
Example 4:
weighing wood powder and urea respectively, putting the wood powder and the urea into a 100ml beaker, fully stirring the wood powder and the urea to mix the wood powder and the urea uniformly, then putting the beaker into an electric heating jacket set to be 150 ℃, melting the wood powder and the urea into a sticky state after about 10-15 min, starting to stir the beaker vigorously by using a glass rod until the solution is clarified, slowly adding ammonium tungstate, stirring the ammonium tungstate until the ammonium tungstate is completely dissolved, and then quickly transferring the beaker into an oven set to be 170 ℃ for treatment for 12 hours. Taking the treated article out of the oven, grinding into powder, and placing in a tube furnace under nitrogen atmosphere (5 mLmin)-1) Heat treatment was carried out at 550 ℃ for 3 hours. Mixing and grinding the obtained transition metal carbide nano composite material and melamine according to the mass ratio of 1:1, adding a small amount of ethanol as a wetting agent, collecting the mixture in a ceramic crucible, and finally roasting for 2 hours at 500 ℃ in an air atmosphere to obtain the transition metal carbide nano composite material.
Application of catalyst to CO2Hydrogenation reaction: 0.2g of catalyst was directly charged into a reaction tube, and a mixed gas (CO) was introduced2：H21:3), the reactor pressure was increased to 2.0MPa at 2 ℃ for min-1The temperature rise rate of (3) raises the bed temperature to the target temperature to start the reaction. Liquid phase products are collected by a cold water bath cold trap for off-line analysis, and reaction tail gas is analyzed on line by a gas chromatograph. CO 22The conversion was 12% and the methanol selectivity was 88%.
Example 5:
respectively weighing chitosan and urea, putting the chitosan and the urea into a 100ml beaker, fully stirring the mixture to uniformly mix the chitosan and the urea, then putting the beaker into an electric heating jacket set to be 120 ℃, melting the chitosan and the urea into a sticky state after about 10-15 min, starting to stir violently by using a glass rod until the solution is clarified, slowly adding titanium tetrachloride, stirring the solution until the titanium tetrachloride is completely dissolved, and then quickly transferring the beaker into an oven set to be 200 ℃ for treatment for 12 hours. Taking the treated article out of the oven, grinding into powder, and placing in a tube furnace under nitrogen atmosphere (5 mLmin)-1) Heat treatment was carried out at 650 ℃ for 2 hours. Mixing and grinding the obtained transition metal carbide nano composite material and p-phenylenediamine according to the mass ratio of 1:2, adding a small amount of ethanol as a wetting agent, collecting the mixture in a ceramic crucible, and finally roasting for 2 hours at 400 ℃ in an air atmosphere to obtain the transition metal carbide nano composite material.
Application of catalyst to CO2Hydrogenation reaction: 0.2g of catalyst was directly charged into a reaction tube, and a mixed gas (CO) was introduced2：H21:3), the reactor pressure was increased to 2.0MPa at 2 ℃ for min-1The temperature rise rate of (3) raises the bed temperature to the target temperature to start the reaction. Liquid phase products are collected by a cold water bath cold trap for off-line analysis, and reaction tail gas is analyzed on line by a gas chromatograph. CO 22The conversion was 14% and the methanol selectivity was 89%.
Example 6:
respectively weighing cellulose and urea, putting the cellulose and the urea into a 100ml beaker, fully stirring the mixture to uniformly mix the mixture, then putting the beaker into an electric heating jacket set to be 140 ℃, melting the cellulose and the urea into a sticky state after about 10-15 min, starting to stir violently by using a glass rod until the solution is clarified, slowly adding sodium metavanadate, stirring the solution until the sodium metavanadate is completely dissolved, and then quickly transferring the beaker into an oven set to be 190 ℃ for processing for 12 hours. Taking the treated article out of the oven, grinding into powder, and placing in a tube furnace under nitrogen atmosphere (5 mLmin)-1) Heat treatment was carried out at 600 ℃ for 2 hours. Mixing and grinding the obtained transition metal carbide nano composite material and urea according to the mass ratio of 1:3, adding a small amount of ethanol as a wetting agent, collecting the mixture in a ceramic crucibleFinally roasting in a crucible for 3 hours at 450 ℃ in an air atmosphere.
Application of catalyst to CO2Hydrogenation reaction: 0.2g of catalyst was directly charged into a reaction tube, and a mixed gas (CO) was introduced2：H21:3), the reactor pressure was increased to 2.0MPa at 2 ℃ for min-1The temperature rise rate of (3) raises the bed temperature to the target temperature to start the reaction. Liquid phase products are collected by a cold water bath cold trap for off-line analysis, and reaction tail gas is analyzed on line by a gas chromatograph. CO 22The conversion was 15% and the methanol selectivity was 87%.
Example 7:
respectively weighing hemicellulose and urea, putting the hemicellulose and the urea into a 100ml beaker, fully stirring the mixture to uniformly mix the mixture, then putting the beaker into an electric heating jacket set to be 120 ℃, melting the hemicellulose and the urea into a sticky state after about 10-15 min, starting to stir violently by using a glass rod until the solution is clarified, slowly adding ammonium molybdate, stirring the ammonium molybdate until the ammonium molybdate is completely dissolved, and then quickly transferring the beaker into an oven set to be 200 ℃ for treatment for 12 hours. Taking the treated article out of the oven, grinding into powder, and placing in a tube furnace under nitrogen atmosphere (5 mLmin)-1) Heat treatment was carried out at 600 ℃ for 2 hours. Mixing and grinding the obtained transition metal carbide nano composite material and copper nitrate according to the mass ratio of 1:3, adding a small amount of ethanol as a wetting agent, collecting the mixture in a ceramic crucible, and finally roasting for 3 hours at 450 ℃ in an air atmosphere to obtain the transition metal carbide nano composite material.
Application of catalyst to CO2Hydrogenation reaction: 0.2g of catalyst was directly charged into a reaction tube, and a mixed gas (CO) was introduced2：H21:3), the reactor pressure was increased to 2.0MPa at 2 ℃ for min-1The temperature rise rate of (3) raises the bed temperature to the target temperature to start the reaction. Liquid phase products are collected by a cold water bath cold trap for off-line analysis, and reaction tail gas is analyzed on line by a gas chromatograph. CO 22The conversion was 10% and the methanol selectivity was 71%.
Example 8:
respectively weighing lignin and urea, placing into a 100ml beaker, stirring thoroughly to mix them uniformly, then placing the beaker into an electric heating jacket set at 140 deg.C, melting the two into a viscous state after about 10-15 min,vigorous stirring with a glass rod was started until the solution was clear, ammonium molybdate was slowly added, stirred until completely dissolved, and then the beaker was quickly transferred to an oven set at 180 ℃ for treatment for 24 h. Taking the treated article out of the oven, grinding into powder, and placing in a tube furnace under nitrogen atmosphere (5 mLmin)-1) Heat treatment was carried out at 700 ℃ for 2 hours. Mixing and grinding the obtained transition metal carbide nano composite material and zirconium nitrate according to the mass ratio of 1:2, adding a small amount of ethanol as a wetting agent, collecting the mixture in a ceramic crucible, and finally roasting for 3 hours at 500 ℃ in an air atmosphere to obtain the transition metal carbide nano composite material.
Application of catalyst to CO2Hydrogenation reaction: 0.2g of catalyst was directly charged into a reaction tube, and a mixed gas (CO) was introduced2：H21:3), the reactor pressure was increased to 2.0MPa at 2 ℃ for min-1The temperature rise rate of (3) raises the bed temperature to the target temperature to start the reaction. Liquid phase products are collected by a cold water bath cold trap for off-line analysis, and reaction tail gas is analyzed on line by a gas chromatograph. CO 22The conversion was 12% and the methanol selectivity was 70%.
Example 9:
respectively weighing straws and urea, putting the straws and the urea into a 100ml beaker, fully stirring the straws and the urea to uniformly mix the straws and the urea, then putting the beaker into an electric heating jacket set to be 120 ℃, after about 10-15 min, melting the straws and the urea to be sticky, starting to stir vigorously by using a glass rod until the solution is clarified, slowly adding ferric nitrate, stirring the ferric nitrate until the ferric nitrate is completely dissolved, and then quickly transferring the beaker into an oven set to be 160 ℃ for treatment for 24 hours. Taking the treated article out of the oven, grinding into powder, and placing in a tube furnace under nitrogen atmosphere (5 mLmin)-1) Heat treatment was carried out at 500 ℃ for 2 hours. Mixing and grinding the obtained transition metal carbide nano composite material and cerium nitrate according to the mass ratio of 1:1, adding a small amount of ethanol as a wetting agent, collecting the mixture in a ceramic crucible, and finally roasting for 2 hours at 350 ℃ in an air atmosphere to obtain the transition metal carbide nano composite material.
Application of catalyst to CO2Hydrogenation reaction: 0.2g of catalyst was directly charged into a reaction tube, and a mixed gas (CO) was introduced2：H21:3), the reactor pressure was increased to 2.0MPa at 2 ℃ for min-1The temperature rising rate of (2) raises the bed temperature to the targetThe reaction started at the target temperature. Liquid phase products are collected by a cold water bath cold trap for off-line analysis, and reaction tail gas is analyzed on line by a gas chromatograph. CO 22The conversion was 10% and the methanol selectivity was 65%.
Example 10:
respectively weighing corncobs and urea, putting the corncobs and the urea into a 100ml beaker, fully stirring the corncobs and the urea to uniformly mix the corncobs and the urea, then putting the beaker into an electric heating jacket set to be 140 ℃, melting the corncobs and the urea into a sticky state after about 10-15 min, starting to stir violently by using a glass rod until the solution is clarified, slowly adding cobalt nitrate, stirring the solution until the cobalt nitrate is completely dissolved, and then quickly transferring the beaker into an oven set to be 150 ℃ for treatment for 18 h. Taking the treated article out of the oven, grinding into powder, and placing in a tube furnace under nitrogen atmosphere (5 mLmin)-1) Heat treatment was carried out at 550 ℃ for 2 hours. Mixing and grinding the obtained transition metal carbide nano composite material and ferric nitrate according to the mass ratio of 1:3, adding a small amount of ethanol as a wetting agent, collecting the mixture in a ceramic crucible, and finally roasting for 2 hours at 450 ℃ in an air atmosphere to obtain the transition metal carbide nano composite material.
Application of catalyst to CO2Hydrogenation reaction: 0.2g of catalyst was directly charged into a reaction tube, and a mixed gas (CO) was introduced2：H21:3), the reactor pressure was increased to 2.0MPa at 2 ℃ for min-1The temperature rise rate of (3) raises the bed temperature to the target temperature to start the reaction. Liquid phase products are collected by a cold water bath cold trap for off-line analysis, and reaction tail gas is analyzed on line by a gas chromatograph. CO 22The conversion was 11% and the methanol selectivity was 64%.
Example 11:
respectively weighing glucose and urea, putting the glucose and the urea into a 100ml beaker, fully stirring the glucose and the urea to uniformly mix the glucose and the urea, then putting the beaker into an electric heating jacket set to be 140 ℃, melting the glucose and the urea into a sticky state after about 10-15 min, starting to stir violently by using a glass rod until the solution is clarified, slowly adding ammonium molybdate, stirring the ammonium molybdate until the ammonium molybdate is completely dissolved, and then quickly transferring the beaker into an oven set to be 120 ℃ for processing for 12 hours. Taking the treated article out of the oven, grinding into powder, and placing in a tube furnace under nitrogen atmosphere (5 mLmin)-1) Heat treatment was carried out at 750 ℃ for 2 hours. The obtained transition metal carbideMixing and grinding the nano composite material and cobalt nitrate according to the mass ratio of 1:2, adding a small amount of ethanol as a wetting agent, collecting the mixture in a ceramic crucible, and finally roasting for 2 hours at 350 ℃ in an air atmosphere to obtain the nano composite material.
Application of catalyst to CO2Hydrogenation reaction: 0.2g of catalyst was directly charged into a reaction tube, and a mixed gas (CO) was introduced2：H21:3), the reactor pressure was increased to 2.0MPa at 2 ℃ for min-1The temperature rise rate of (3) raises the bed temperature to the target temperature to start the reaction. Liquid phase products are collected by a cold water bath cold trap for off-line analysis, and reaction tail gas is analyzed on line by a gas chromatograph. CO 22The conversion was 14% and the methanol selectivity was 60%.
Example 12:
respectively weighing glucose and urea, putting the glucose and the urea into a 100ml beaker, fully stirring the glucose and the urea to uniformly mix the glucose and the urea, then putting the beaker into an electric heating jacket set to be 120 ℃, melting the glucose and the urea into a sticky state after about 10-15 min, starting to stir violently by using a glass rod until the solution is clarified, slowly adding ammonium molybdate, stirring the ammonium molybdate until the ammonium molybdate is completely dissolved, and then quickly transferring the beaker into an oven set to be 200 ℃ for treatment for 12 hours. Taking the treated article out of the oven, grinding into powder, and placing in a tube furnace under nitrogen atmosphere (5 mLmin)-1) Heat treatment was carried out at 600 ℃ for 2 hours. Mixing and grinding the obtained transition metal carbide nano composite material and copper nitrate according to the mass ratio of 1:3, adding a small amount of ethanol as a wetting agent, collecting the mixture in a ceramic crucible, and finally roasting for 3 hours at 350 ℃ in an air atmosphere to obtain the transition metal carbide nano composite material.
Application of catalyst to CO2Hydrogenation reaction: 0.2g of catalyst was directly charged into a reaction tube, and a mixed gas (CO) was introduced2：H21:3), the reactor pressure was increased to 2.0MPa at 2 ℃ for min-1The temperature rise rate of (3) raises the bed temperature to the target temperature to start the reaction. Liquid phase products are collected by a cold water bath cold trap for off-line analysis, and reaction tail gas is analyzed on line by a gas chromatograph. CO 22The conversion was 21% and the methanol selectivity was 83%.
Example 13:
respectively weighing glucose and urea, placing into 100ml beaker, and fillingStirring to mix uniformly, then placing the beaker in an electric heating jacket set to 120 ℃, after about 10-15 min, melting the beaker and the electric heating jacket to be sticky, beginning to stir vigorously by using a glass rod until the solution is clear, slowly adding ammonium molybdate, stirring until the ammonium molybdate is dissolved completely, and then quickly transferring the beaker to an oven set to 200 ℃ for treatment for 12 h. Taking the treated article out of the oven, grinding into powder, and placing in a tube furnace under nitrogen atmosphere (5 mLmin)-1) Heat treatment was carried out at 600 ℃ for 2 hours. Mixing the obtained transition metal carbide nano composite material and a zirconium nitrate aqueous solution according to a mass ratio of 1:3, stirring and evaporating at 80 ℃, putting into a constant-temperature oven for drying, collecting a sample obtained after drying in a ceramic crucible, and finally roasting at 350 ℃ for 3 hours in an air atmosphere to obtain the transition metal carbide nano composite material.
Application of catalyst to CO2Hydrogenation reaction: 0.2g of catalyst was directly charged into a reaction tube, and a mixed gas (CO) was introduced2：H21:3), the reactor pressure was increased to 2.0MPa at 2 ℃ for min-1The temperature rise rate of (3) raises the bed temperature to the target temperature to start the reaction. Liquid phase products are collected by a cold water bath cold trap for off-line analysis, and reaction tail gas is analyzed on line by a gas chromatograph. CO 22The conversion was 11% and the methanol selectivity was 70%.
Example 14:
respectively weighing glucose and urea, putting the glucose and the urea into a 100ml beaker, fully stirring the glucose and the urea to uniformly mix the glucose and the urea, then putting the beaker into an electric heating jacket set to be 140 ℃, melting the glucose and the urea into a sticky state after about 10-15 min, starting to stir violently by using a glass rod until the solution is clarified, slowly adding ammonium molybdate, stirring the ammonium molybdate until the ammonium molybdate is completely dissolved, and then quickly transferring the beaker into an oven set to be 180 ℃ for treatment for 18 h. Taking the treated article out of the oven, grinding into powder, and placing in a tube furnace under nitrogen atmosphere (5 mLmin)-1) Heat treatment was carried out at 500 ℃ for 2 hours. Mixing the obtained transition metal carbide nano composite material and a cerous nitrate aqueous solution according to a mass ratio of 1:3, stirring and evaporating at 80 ℃, putting into a constant-temperature oven for drying, collecting a sample obtained after drying in a ceramic crucible, and finally roasting at 350 ℃ for 3 hours in an air atmosphere to obtain the transition metal carbide nano composite material.
Application of catalyst to CO2Hydrogenation reaction: 0.2g of catalyst was directly charged into a reaction tube, and a mixed gas (CO) was introduced2：H21:3), the reactor pressure was increased to 2.0MPa at 2 ℃ for min-1The temperature rise rate of (3) raises the bed temperature to the target temperature to start the reaction. Liquid phase products are collected by a cold water bath cold trap for off-line analysis, and reaction tail gas is analyzed on line by a gas chromatograph. CO 22The conversion was 10% and the methanol selectivity was 67%.
Example 15:
respectively weighing glucose and urea, putting the glucose and the urea into a 100ml beaker, fully stirring the glucose and the urea to uniformly mix the glucose and the urea, then putting the beaker into an electric heating jacket set to be 130 ℃, melting the glucose and the urea into a sticky state after about 10-15 min, starting to stir violently by using a glass rod until the solution is clarified, slowly adding ammonium molybdate, stirring the ammonium molybdate until the ammonium molybdate is completely dissolved, and then quickly transferring the beaker into an oven set to be 170 ℃ for processing for 12 hours. Taking the treated article out of the oven, grinding into powder, and placing in a tube furnace under nitrogen atmosphere (5 mLmin)-1) Heat treatment was carried out at 500 ℃ for 2 hours. Mixing the obtained transition metal carbide nano composite material and an iron nitrate aqueous solution according to a mass ratio of 1:3, stirring and evaporating at 80 ℃, putting into a constant-temperature oven for drying, collecting a sample obtained after drying in a ceramic crucible, and finally roasting at 400 ℃ in an air atmosphere for 3 hours to obtain the transition metal carbide nano composite material.
Application of catalyst to CO2Hydrogenation reaction: 0.2g of catalyst was directly charged into a reaction tube, and a mixed gas (CO) was introduced2：H21:3), the reactor pressure was increased to 2.0MPa at 2 ℃ for min-1The temperature rise rate of (3) raises the bed temperature to the target temperature to start the reaction. Liquid phase products are collected by a cold water bath cold trap for off-line analysis, and reaction tail gas is analyzed on line by a gas chromatograph. CO 22The conversion was 8% and the methanol selectivity was 65%.
Example 16:
respectively weighing glucose and urea, putting the glucose and the urea into a 100ml beaker, fully stirring the glucose and the urea to uniformly mix the glucose and the urea, then putting the beaker into an electric heating jacket set at 160 ℃, melting the glucose and the urea into a sticky state after about 10-15 min, beginning to stir violently by using a glass rod until the solution is clarified, slowly adding ammonium molybdate, and stirring the ammonium molybdate until the ammonium molybdate is stirred until the solution is clarifiedCompletely dissolved and then the beaker was quickly transferred to an oven set at 200 ℃ for 12 h. Taking the treated article out of the oven, grinding into powder, and placing in a tube furnace under nitrogen atmosphere (5 mLmin)-1) Heat treatment was carried out at 550 ℃ for 2 hours. Mixing the obtained transition metal carbide nano composite material and a nickel nitrate aqueous solution according to a mass ratio of 1:3, stirring and evaporating at 80 ℃, putting into a constant-temperature oven for drying, collecting a sample obtained after drying in a ceramic crucible, and finally roasting at 350 ℃ for 3 hours in an air atmosphere to obtain the transition metal carbide nano composite material.
Application of catalyst to CO2Hydrogenation reaction: 0.2g of catalyst was directly charged into a reaction tube, and a mixed gas (CO) was introduced2：H21:3), the reactor pressure was increased to 2.0MPa at 2 ℃ for min-1The temperature rise rate of (3) raises the bed temperature to the target temperature to start the reaction. Liquid phase products are collected by a cold water bath cold trap for off-line analysis, and reaction tail gas is analyzed on line by a gas chromatograph. CO 22The conversion was 12% and the methanol selectivity was 72%.
Example 17:
respectively weighing glucose and urea, putting the glucose and the urea into a 100ml beaker, fully stirring the glucose and the urea to uniformly mix the glucose and the urea, then putting the beaker into an electric heating jacket set to be 170 ℃, melting the glucose and the urea into a sticky state after about 10-15 min, starting to stir violently by using a glass rod until the solution is clarified, slowly adding ammonium molybdate, stirring the ammonium molybdate until the ammonium molybdate is completely dissolved, and then quickly transferring the beaker into an oven set to be 200 ℃ for treatment for 18 h. Taking the treated article out of the oven, grinding into powder, and placing in a tube furnace under nitrogen atmosphere (5 mLmin)-1) Heat treatment was carried out at 450 ℃ for 2 hours. Mixing the obtained transition metal carbide nano composite material and a copper nitrate aqueous solution according to a mass ratio of 1:3, stirring and evaporating at 80 ℃, putting into a constant-temperature oven for drying, collecting a sample obtained after drying in a ceramic crucible, and finally roasting at 350 ℃ for 3 hours in an air atmosphere to obtain the transition metal carbide nano composite material.
Application of catalyst to CO2Hydrogenation reaction: 0.2g of catalyst was directly charged into a reaction tube, and a mixed gas (CO) was introduced2：H21:3), the reactor pressure was increased to 2.0MPa at 2 ℃ for min-1The rate of temperature increase of (2) increases the bed temperature to the target temperatureThe reaction was started. Liquid phase products are collected by a cold water bath cold trap for off-line analysis, and reaction tail gas is analyzed on line by a gas chromatograph. CO 22The conversion was 15% and the methanol selectivity was 75%.
Example 18:
respectively weighing glucose and urea, putting the glucose and the urea into a 100ml beaker, fully stirring the glucose and the urea to uniformly mix the glucose and the urea, then putting the beaker into an electric heating jacket set to be 120 ℃, melting the glucose and the urea into a sticky state after about 10-15 min, starting to stir violently by using a glass rod until the solution is clarified, slowly adding ammonium molybdate, stirring the ammonium molybdate until the ammonium molybdate is completely dissolved, and then quickly transferring the beaker into an oven set to be 200 ℃ for treatment for 12 hours. Taking the treated article out of the oven, grinding into powder, and placing in a tube furnace under nitrogen atmosphere (5 mLmin)-1) Heat treatment was carried out at 500 ℃ for 2 hours. Mixing the obtained transition metal carbide nano composite material and a cobalt nitrate aqueous solution according to a mass ratio of 1:3, stirring and evaporating at 80 ℃, putting into a constant-temperature oven for drying, collecting a sample obtained after drying in a ceramic crucible, and finally roasting at 350 ℃ for 3 hours in an air atmosphere to obtain the transition metal carbide nano composite material.
Application of catalyst to CO2Hydrogenation reaction: 0.2g of catalyst was directly charged into a reaction tube, and a mixed gas (CO) was introduced2：H21:3), the reactor pressure was increased to 2.0MPa at 2 ℃ for min-1The temperature rise rate of (3) raises the bed temperature to the target temperature to start the reaction. Liquid phase products are collected by a cold water bath cold trap for off-line analysis, and reaction tail gas is analyzed on line by a gas chromatograph. CO 22The conversion was 13% and the methanol selectivity was 69%.
Claims (9)
1. CO (carbon monoxide)2The hydrogenated biomass charcoal-based transition metal catalyst is characterized by being obtained by the following method, firstly, reacting a biomass carbon source with a transition metal salt through a melting method to prepare a transition metal carbide nano composite material, carbonizing the transition metal carbide nano composite material, doping non-metal atoms through a solid phase grinding method, and finally roasting the transition metal carbide nano composite material through air to prepare the biomass charcoal-based transition metal catalyst;
or reacting a biomass carbon source with transition metal salt by a melting method to prepare a transition metal carbide nano composite material, carbonizing the transition metal carbide nano composite material, carrying out metal ion loading by a solid phase grinding method or an impregnation method, and finally roasting the transition metal carbide nano composite material by air to prepare the biomass carbon-based transition metal catalyst.
2. CO according to claim 12The hydrogenation biomass charcoal-based transition metal catalyst is characterized in that: the biomass charcoal source is as follows: cellulose, hemicellulose, lignin, glucose, chitosan, sucrose, starch, wood powder, straw and corncob.
3. CO according to claim 12The hydrogenation biomass charcoal-based transition metal catalyst is characterized in that: in the transition metal salt, the transition metal is one of iron, cobalt, molybdenum, tungsten, titanium or vanadium; the corresponding transition metal salt is one of ferric nitrate, cobalt nitrate, ammonium molybdate, ammonium tungstate, titanium tetrachloride or sodium metavanadate; the mass ratio of the carbon source to the transition metal salt is 1: 0.1 to 0.6.
4. CO according to claim 12The hydrogenation biomass charcoal-based transition metal catalyst is characterized in that: the non-metal atom source is one of urea, melamine or p-phenylenediamine; the mass ratio of the carbon source to the non-metal atom source is 1:1 to 3.
5. CO according to claim 12The hydrogenation biomass charcoal-based transition metal catalyst is characterized in that: the metal ion is one of copper, iron, cobalt, nickel, cerium or zirconium; the corresponding metal salt is one of copper nitrate, ferric nitrate, cobalt nitrate, cerium nitrate or zirconium nitrate; the mass ratio of the carbon source to the metal salt is 1: 0.3 to 0.6.
6. CO according to any one of claims 1 to 52The preparation method of the hydrogenation biomass charcoal-based transition metal catalyst is characterized by comprising the following steps: firstly, reacting a biomass carbon source with a transition metal salt by a melting method to prepare a transition metal carbide nano composite material, carbonizing the nano composite material and then passing the carbonized nano composite material throughCarrying out non-metal atom doping by a solid phase grinding method, and finally roasting in air to obtain the biomass carbon-based transition metal catalyst;
or reacting a biomass carbon source with transition metal salt by a melting method to prepare a transition metal carbide nano composite material, carbonizing the transition metal carbide nano composite material, carrying out metal ion loading by a solid phase grinding method or an impregnation method, and finally roasting the transition metal carbide nano composite material by air to prepare the biomass carbon-based transition metal catalyst.
7. CO according to claim 62The preparation method of the hydrogenation biomass charcoal-based transition metal catalyst is characterized by comprising the following steps: heating and melting the biomass raw material and the urea, stirring until the solution is clarified, and stopping heating and stirring.
8. CO according to claim 62The preparation method of the hydrogenation biomass charcoal-based transition metal catalyst is characterized by comprising the following steps: and drying the molten mixture in an oven for 12-24 hours.
9. CO according to claim 62The preparation method of the hydrogenation biomass charcoal-based transition metal catalyst is characterized by comprising the following steps: the carbonization temperature is 500-900 ℃ in inert atmosphere; the air roasting temperature is 300-500 ℃.
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