CN111530467B - A kind of carbon-modified copper-based catalyst and its preparation method and application - Google Patents
A kind of carbon-modified copper-based catalyst and its preparation method and application Download PDFInfo
- Publication number
- CN111530467B CN111530467B CN201911011719.4A CN201911011719A CN111530467B CN 111530467 B CN111530467 B CN 111530467B CN 201911011719 A CN201911011719 A CN 201911011719A CN 111530467 B CN111530467 B CN 111530467B
- Authority
- CN
- China
- Prior art keywords
- carbon
- copper
- based catalyst
- independently
- active component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 136
- 150000001879 copper Chemical class 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 88
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 58
- 239000010949 copper Substances 0.000 claims abstract description 58
- 229910052751 metal Inorganic materials 0.000 claims abstract description 55
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 229910052802 copper Inorganic materials 0.000 claims abstract description 54
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 44
- 239000011787 zinc oxide Substances 0.000 claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 27
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 23
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000005751 Copper oxide Substances 0.000 claims abstract description 17
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims description 52
- -1 carbon modified copper Chemical class 0.000 claims description 36
- 150000003839 salts Chemical class 0.000 claims description 34
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 23
- 230000032683 aging Effects 0.000 claims description 22
- 238000000975 co-precipitation Methods 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 238000006722 reduction reaction Methods 0.000 claims description 14
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- 239000012716 precipitator Substances 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 7
- 239000012495 reaction gas Substances 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 229910007470 ZnO—Al2O3 Inorganic materials 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000012266 salt solution Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000003751 zinc Chemical class 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000002485 combustion reaction Methods 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
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- 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
- C07C29/154—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 copper, silver, gold, 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明提供了一种碳改性铜基催化剂及其制备方法和应用，属于催化剂技术领域。本发明提供的碳改性铜基催化剂，包括活性组分和包覆在活性组分表面的碳；所述活性组分包括氧化铜、氧化锌和氧化铝，或者包括铜、氧化锌和氧化铝；所述碳具有石墨结构。本发明采用特定金属元素配合作为活性组分，同时配合使用具有石墨结构的碳，能够避免催化剂发生团聚，保证碳改性铜基催化剂有较高的活性组分含量，不会堵塞碳改性铜基催化剂的孔隙结构，不会破坏其中的活性位点，有利于保持碳改性铜基催化剂具有较高的催化活性，用作二氧化碳加氢制甲醇的催化剂，能够显著提高二氧化碳的转化率、甲醇的收率及其选择性，且本发明提供的碳改性铜基催化剂稳定性优异。
The invention provides a carbon-modified copper-based catalyst, a preparation method and application thereof, and belongs to the technical field of catalysts. The carbon-modified copper-based catalyst provided by the present invention includes active components and carbon coated on the surface of the active components; the active components include copper oxide, zinc oxide and aluminum oxide, or copper, zinc oxide and aluminum oxide ; the carbon has a graphitic structure. The invention adopts specific metal elements as active components, and at the same time uses carbon with graphite structure, which can avoid catalyst agglomeration, ensure that the carbon-modified copper-based catalyst has a higher content of active components, and will not block the carbon-modified copper. The pore structure of the base catalyst will not destroy the active sites in it, which is beneficial to keep the carbon-modified copper-based catalyst with high catalytic activity. It can be used as a catalyst for hydrogenation of carbon dioxide to methanol, which can significantly improve the conversion rate of carbon dioxide and methanol. The yield and its selectivity are excellent, and the carbon-modified copper-based catalyst provided by the present invention has excellent stability.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a carbon modified copper-based catalyst and a preparation method and application thereof.
Background
With the rapid development of industry, a large amount of carbon dioxide is generated by the combustion of fossil fuels (coal, petroleum and natural gas), and because of the disorder of cutting and logging of forests and the establishment of cities and factories in a large number of farmlands, the vegetation coverage rate is greatly reduced, the dynamic balance of the generation and conversion of carbon dioxide is destroyed, the concentration of the carbon dioxide rises sharply, and a series of environmental problems such as global warming are caused. Therefore, how to reasonably utilize carbon dioxide is particularly important.
The methanol has wide application prospect as a basic organic chemical raw material and a power fuel, and the carbon dioxide can be changed into valuable substances by synthesizing the methanol through hydrogenation of the carbon dioxide, so that the method is one of effective ways for reasonably utilizing the carbon dioxide. At present, most of copper-based catalysts for preparing methanol by carbon dioxide hydrogenation are obtained by improvement on the basis of catalysts for preparing methanol by carbon monoxide hydrogenation, and the improvement method comprises the steps of adding an auxiliary agent, selecting different carriers, different preparation methods, optimizing reaction conditions and the like. For example, Chinese patent CN103272607A discloses a method for CO2The copper-based catalyst for synthesizing methanol by hydrogenation uses high molecular polymer as stabilizer, adopts parallel-flow coprecipitation method to prepare Cu/Zn/Al/Zr-based catalyst, and adopts H reaction at 250 deg.C and 5.0MPa2/CO2The volume ratio is 3/1, the GHSV is 4000h-1Under the reaction conditions of (3), the catalyst stability is good, but CO2The conversion rate and the methanol selectivity are low; chinese patent CN107008332A discloses a method for CO2The copper-based catalyst for synthesizing the methanol by hydrogenation adopts a method of fractional precipitation or a method of firstly precipitating an accelerant and then precipitating and pulping with an active component, can effectively improve the conversion rate of carbon dioxide, but has low selectivity of the methanol; chinese patent CN103721719A discloses a method for CO2The copper-based catalyst for synthesizing methanol by hydrogenation contains Cu, Zn, Al, X, halogen and oxygen elements, consists of oxide and halide, and can effectively improve CO2Conversion, but methanol selectivity is low.
Disclosure of Invention
The invention aims to provide a carbon modificationThe invention provides a copper-based catalyst, a preparation method and application thereof, and the carbon modified copper-based catalyst provided by the invention is used for CO2The hydrogenation for preparing the methanol can obviously improve the CO2Conversion rate, CH3The yield and selectivity of OH are excellent, and the stability of the carbon modified copper-based catalyst is excellent.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a carbon modified copper-based catalyst, which comprises an active component and carbon coated on the surface of the active component; the active component comprises copper oxide, zinc oxide and aluminum oxide, or comprises copper, zinc oxide and aluminum oxide; the carbon has a graphite structure.
Preferably, the particle size of the carbon modified copper-based catalyst is 20-40 meshes.
Preferably, the mass ratio of the active component to the carbon is 1: (0.04-0.2).
Preferably, when the active component comprises copper oxide, zinc oxide and aluminum oxide, the mass ratio of the copper oxide to the zinc oxide to the aluminum oxide in the active component is (4-6): (2.5-3.5): (2.5-3.5);
when the active component comprises copper, zinc oxide and aluminum oxide, the mass ratio of the copper to the zinc oxide to the aluminum oxide in the active component is (4-6): (2.5-3.5): (2.5-3.5).
The invention provides a preparation method of the carbon modified copper-based catalyst in the technical scheme, wherein (i) when the active component comprises copper oxide, zinc oxide and aluminum oxide, the preparation method of the carbon modified copper-based catalyst comprises the following steps:
mixing metal salt, a precipitator and water, and carrying out coprecipitation reaction to obtain a coprecipitate;
sequentially aging and first roasting the coprecipitate to obtain a copper-based catalyst;
mixing the copper-based catalyst and aromatic hydrocarbon, and carrying out second roasting to obtain a carbon-modified copper-based catalyst;
the metal salt is a metal salt corresponding to a metal element in the active component;
(ii) when the active components include copper, zinc oxide and alumina, the preparation method of the carbon-modified copper-based catalyst includes the steps of:
mixing metal salt, a precipitator and water, and carrying out coprecipitation reaction to obtain a coprecipitate;
sequentially carrying out aging, first roasting and reduction reactions on the coprecipitate to obtain a copper-based catalyst;
mixing the copper-based catalyst and aromatic hydrocarbon, and carrying out second roasting to obtain a carbon-modified copper-based catalyst;
the metal salt is a metal salt corresponding to a metal element in the active component.
Preferably, in (i) and (ii), the metal salt independently comprises a nitrate and/or an acetate;
the precipitating agent independently comprises at least one of sodium carbonate, sodium bicarbonate and sodium hydroxide;
the aromatic hydrocarbons independently comprise at least one of benzene, toluene, and xylene.
Preferably, in the (i) and the (ii), the temperature of the coprecipitation reaction is independently 60-80 ℃, the time is independently 1-5 h, and the pH value of the system during the coprecipitation reaction is independently 6-8;
the aging temperature is independently 20-50 ℃, and the aging time is independently 10-15 h;
the temperature of the first roasting is 200-400 ℃ independently, and the time is 2-6 hours independently;
the temperature of the second roasting is 200-500 ℃ independently, and the time is 2-5 hours independently.
Preferably, the reduction reaction in (ii) is in H2/N2In a mixed atmosphere, said H2/N2H in mixed atmosphere2The volume fraction of (A) is 4-7%; the temperature of the reduction reaction is 200-350 ℃, and the time is 3-10 h.
The invention also provides the application of the carbon modified copper-based catalyst in the technical scheme or the carbon modified copper-based catalyst prepared by the preparation method in the technical scheme in the preparation of methanol by carbon dioxide hydrogenation.
Preferably, the application conditions of the carbon-modified copper-based catalyst in the preparation of methanol by hydrogenation of carbon dioxide comprise:
the dosage of the carbon modified copper-based catalyst is 0.8-1.2 g;
the reaction gas is H2/CO2A mixed gas of/Ar, H in the reaction gas2、CO2And Ar in a volume ratio of (65-75): (18-28): (7-17);
the contact time W/F is 7-10 g.h/mol;
the reaction pressure is 2.95-3.05 MPa, the temperature is 180-250 ℃, and the reaction time is 30-60 h.
The invention provides a carbon modified copper-based catalyst, which comprises an active component and carbon coated on the surface of the active component; the active component comprises copper oxide, zinc oxide and aluminum oxide, or comprises copper, zinc oxide and aluminum oxide; the carbon has a graphite structure. The invention adopts the specific metal elements as active components (copper oxide, zinc oxide and aluminum oxide, or copper, zinc oxide and aluminum oxide) in combination with the carbon with the graphite structure, can avoid the catalyst agglomeration, is favorable for keeping the carbon modified copper-based catalyst with higher catalytic activity, can obviously improve the CO when being used as the catalyst for preparing the methanol by carbon dioxide hydrogenation2Conversion of (2), CH3The yield and the selectivity of OH are high, and the carbon modified copper-based catalyst provided by the invention has excellent stability. The experimental results of the examples show that when the carbon modified copper-based catalyst provided by the invention is used as a catalyst for preparing methanol by hydrogenation of carbon dioxide, CO is used2The conversion rate is improved by 66.7 percent, and CH3The OH yield is improved by 75.2%, and the copper-based catalytic activity is not obviously reduced after the catalyst is used for catalytic reaction for 100 hours, which shows that the carbon modified copper-based catalyst provided by the invention can obviously improve CO2Conversion and CH3OH selectivity and excellent stability.
The preparation method of the carbon modified copper-based catalyst provided by the invention is simple to operate, wide in raw material source, low in cost and free of secondary pollution.
Drawings
Fig. 1 is a graph of the stability of the carbon-modified copper-based catalyst prepared in example 1.
Detailed Description
The invention provides a carbon modified copper-based catalyst, which comprises an active component and carbon coated on the surface of the active component; the active component comprises copper oxide, zinc oxide and aluminum oxide, or comprises copper, zinc oxide and aluminum oxide; the carbon has a graphite structure.
In the present invention, the metal element in the active component preferably includes copper, zinc and aluminum. In the invention, when the active component comprises copper oxide, zinc oxide and aluminum oxide, the mass ratio of the copper oxide to the zinc oxide to the aluminum oxide in the active component is preferably (4-6): (2.5-3.5): (2.5-3.5), more preferably (4-6): (2.8-3.2): (2.8-3.2), most preferably (4-6): 3: 3.
in the invention, when the active component comprises copper, zinc oxide and aluminum oxide, the mass ratio of the copper to the zinc oxide to the aluminum oxide in the active component is preferably (4-6): (2.5-3.5): (2.5-3.5), more preferably (4-6): (2.8-3.2): (2.8-3.2), most preferably (4-6): 3: 3.
in the present invention, the mass ratio of the active component to carbon is preferably 1: (0.04 to 0.2), more preferably 1: (0.05 to 0.15), most preferably 1: (0.1-0.15). The invention preferably controls the mass ratio of the active component to the carbon within the range, thereby not only ensuring higher active component content, but also not blocking the pore structure of the catalyst and destroying active sites therein, and being beneficial to leading the catalyst to have higher catalytic activity.
In the invention, the particle size of the carbon modified copper-based catalyst is preferably 20-40 meshes.
The invention adopts the specific metal elements as the active components and uses the carbon with the graphite structure in a matching way, which is favorable for preventing the active components from agglomerating, improving the stability of the carbon modified copper-based catalyst and improving the CO in the process of preparing the methanol by the carbon dioxide hydrogenation2Conversion of (2), CH3The selectivity and yield of OH are improved, the inactivation time is delayed, and the carbon modified copper-based catalyst has longer service life.
The invention provides a preparation method of the carbon modified copper-based catalyst in the technical scheme, wherein (i) when the active component comprises copper oxide, zinc oxide and aluminum oxide, the preparation method of the carbon modified copper-based catalyst comprises the following steps:
mixing metal salt, a precipitator and water, and carrying out coprecipitation reaction to obtain a coprecipitate;
sequentially aging and first roasting the coprecipitate to obtain a copper-based catalyst;
mixing the copper-based catalyst and aromatic hydrocarbon, and carrying out second roasting to obtain a carbon-modified copper-based catalyst;
the metal salt is a metal salt corresponding to a metal element in the active component.
Mixing metal salt, a precipitator and water, and carrying out coprecipitation reaction to obtain a coprecipitate; the metal salt is a metal salt corresponding to a metal element in the active component.
In the invention, the metal salt is a metal salt in which the metal salt is a metal salt corresponding to a metal element in the active component, that is, a copper salt, a zinc salt and an aluminum salt, and preferably includes a nitrate and/or an acetate, the copper salt is more preferably copper nitrate and/or copper acetate, the zinc salt is more preferably zinc nitrate and/or zinc acetate, and the aluminum salt is more preferably aluminum nitrate and/or aluminum acetate.
In the present invention, the precipitant preferably includes at least one of sodium carbonate, sodium bicarbonate and sodium hydroxide, and more preferably sodium carbonate, sodium bicarbonate or sodium hydroxide.
In the present invention, the mass ratio of the copper salt, the zinc salt, the aluminum salt, and the precipitant is preferably 1: (0.5-0.9): (1.3-1.6): (1.5 to 1.9), more preferably 1: (0.6-0.8): (1.4-1.6): (1.6-1.9), most preferably 1: (0.7-0.8): (1.4-1.5): (1.7-1.8).
In the invention, the mixing is preferably stirring mixing, and the stirring mixing speed is preferably 650-900 r/min, and more preferably 700-850 r/min. In the invention, the mixing is preferably to firstly mix the metal salt and the first part of water to obtain a metal salt solution; and carrying out second mixing on the precipitant and second part of water to obtain a precipitant solution, and then enabling the metal salt solution and the precipitant solution to flow into the residual water in parallel to carry out coprecipitation reaction. In the invention, the first part of water preferably accounts for 15-25% of the total volume of water, and more preferably 17-20%. In the invention, the concentration of the precipitant solution is preferably 1.0-1.5 mol/L, and more preferably 1.0-1.3 mol/L; the second part of water preferably accounts for 25-35% of the total volume of water, and more preferably accounts for 27-30%. In the invention, the residual water preferably accounts for 40-60% of the total volume of the water, and more preferably 50-56%. In the present invention, the total volume of the first portion of water, the second portion of water and the remaining water is 100%. The water used in the present invention is not particularly limited, and water known in the art may be used, and specifically, deionized water, distilled water, or high purity water may be used.
In the invention, the temperature of the coprecipitation reaction is preferably 60-80 ℃, more preferably 65-75 ℃ and 70 ℃; the time of the coprecipitation reaction is preferably 1-5 h, more preferably 2-4 h, and most preferably 2-3 h; the pH value of the system during the coprecipitation reaction is preferably 6-8, more preferably 6.5-7.5, and most preferably 7. In the present invention, the pH value of the system is preferably measured by using a pH meter. In the invention, the monitoring of the pH value of the system is realized by controlling the addition amount of the precipitator. In the invention, in the coprecipitation reaction process, the metal salt in the system forms a coprecipitate of one or more of metal hydroxide, carbonate and bicarbonate under the action of a precipitator.
After the coprecipitate is obtained, the coprecipitate is aged and roasted for the first time in sequence to obtain the copper-based catalyst.
In the present invention, the aging is preferably carried out by standing. In the invention, the aging temperature is preferably 20-50 ℃, more preferably 25-45 ℃, and most preferably 30-40 ℃; the aging time is preferably 10-15 h, more preferably 11-14 h, and most preferably 12-13 h. In the aging process, the coprecipitate forms uniform grains under the action of the catalyst, and a small amount of amorphous precipitate can realize gradual crystallization in the aging process, so that the uniform grains are finally obtained.
After the aging is completed, the present invention preferably subjects the resulting system to solid-liquid separation, washing and drying in this order. The solid-liquid separation method of the present invention is not particularly limited, and a solid-liquid separation method known in the art may be used, specifically, filtration or centrifugal separation. The present invention is not particularly limited to the filtration and centrifugation, and may be carried out by filtration and centrifugation well known in the art. In the present invention, the solvent used for the washing is preferably deionized water. In the invention, the drying temperature is preferably 60-100 ℃, more preferably 70-90 ℃, and most preferably 80-90 ℃; the drying time is preferably 5-12 h, more preferably 8-12 h, and most preferably 10-12 h.
In the invention, the temperature of the first roasting is preferably 200-400 ℃, more preferably 250-400 ℃, and most preferably 300-400 ℃; the first roasting time is preferably 2-6 h, more preferably 3-6 h, and most preferably 5-6 h. In the present invention, the first firing is preferably performed in an air atmosphere. In the present invention, the coprecipitate undergoes a decomposition reaction during the first firing to produce a metal oxide. Performing first roasting under the conditions, decomposing the precipitate to form stable metal oxide, activating the species on the surface of the catalyst, and enabling active elements to interact at high temperature, so that the metal oxide in the copper-based catalyst plays a synergistic effect, and further the stability of the carbon-modified copper-based catalyst is improved, and CO is produced in the process of preparing methanol by carbon dioxide hydrogenation2Conversion rate of (2) and CH3Selectivity to OH.
After the completion of the calcination, the present invention preferably performs the tabletting and crushing of the obtained metal oxide in this order. In the invention, the pressure of the tabletting is preferably 5-10 MPa, more preferably 6-9 MPa, and most preferably 7-8 MPa; the tabletting time is preferably 1-5 min, more preferably 2-4 min, and most preferably 3 min. In the invention, the particle size obtained by crushing is preferably 20-40 meshes. In the present invention, as the particle size of the catalyst is reduced, the specific surface area and pore volume thereof are increased, the utilization rate of the inner surface of the catalyst is increased, the reactant is more easily diffused to the active site, and the conversion rate is increased, but when the particle size of the catalyst is reduced to a certain extent, the internal diffusion of the catalyst particles is substantially eliminated, and the conversion rate of the reactant tends to a steady state. The particle size of the catalyst is controlled within the range, so that the optimal catalytic effect of the carbon modified copper-based catalyst can be ensured.
After the copper-based catalyst is obtained, the copper-based catalyst and the aromatic hydrocarbon are mixed and subjected to second roasting to obtain the carbon modified copper-based catalyst.
In the present invention, the aromatic hydrocarbon preferably includes at least one of benzene, toluene and xylene, and more preferably includes benzene, toluene or xylene.
In the present invention, the mixing is preferably stirring mixing, and the stirring speed in the present invention is not particularly limited, and a stirring speed well known in the art may be used. In the present invention, the order of mixing is preferably such that the aromatic hydrocarbon is added dropwise to the copper-based catalyst; the dropping speed of the aromatic hydrocarbon is preferably 0.1 to 0.5mL/min, and more preferably 0.2 to 0.4 mL/min. According to the invention, the aromatic hydrocarbon is added in a dropwise manner, so that the reaction rate can be controlled, the aromatic hydrocarbon can be more uniformly distributed on the copper-based catalyst, and the catalytic effect of the carbon-modified copper-based catalyst can be further improved.
In the present invention, the second calcination is preferably performed under vacuum, and the degree of vacuum is not particularly limited in the present invention, and may be a degree of vacuum well known in the art; the second roasting temperature is preferably 200-500 ℃, more preferably 300-500 ℃, and most preferably 400-500 ℃; the second roasting time is preferably 2-5 h, more preferably 2.5-4.5 h, and most preferably 3-4 h; the second baking time is preferably counted when the temperature rises to 200 to 500 ℃. In the invention, the second roasting is carried out under the above conditions, the aromatic hydrocarbon reacts to generate carbon with a graphite structure, the carbon is coated on the surface of the active component, and the active component is modified by the carbon, so that the reduction of the agglomeration effect of the active component is facilitated, the stability of the carbon-modified copper-based catalyst is further improved, and the CO is hydrogenated to prepare the methanol in the carbon dioxide hydrogenation process2Conversion rate of (2) and CH3Selectivity to OH.
The invention provides a preparation method of the carbon modified copper-based catalyst in the technical scheme, (ii) when the active component comprises copper, zinc oxide and aluminum oxide, the preparation method of the carbon modified copper-based catalyst comprises the following steps:
mixing metal salt, a precipitator and water, and carrying out coprecipitation reaction to obtain a coprecipitate;
sequentially carrying out aging, first roasting and reduction reactions on the coprecipitate to obtain a copper-based catalyst;
mixing the copper-based catalyst and aromatic hydrocarbon, and carrying out second roasting to obtain a carbon-modified copper-based catalyst;
the metal salt is a metal salt corresponding to a metal element in the active component.
In the present invention, the reduction reaction is preferably in H2/N2In a mixed atmosphere, said H2/N2H in mixed atmosphere2The volume fraction of (a) is preferably 4 to 7%, more preferably 4 to 6%, and most preferably 5%; the temperature of the reduction reaction is preferably 200-350 ℃, more preferably 250-350 ℃, and most preferably 300-350 ℃; the time of the reduction reaction is preferably 3-10 h, more preferably 4-8 h, and most preferably 7-8 h. In the present invention, the temperature at which zinc oxide is reduced is 650 ℃ or higher, and at the above-mentioned reduction temperature, it cannot be reduced by hydrogen gas; according to the metal activity order table, alumina cannot be reduced by hydrogen; therefore, only the copper oxide is reduced into the copper simple substance in the reduction reaction process.
In the present invention, other preparation conditions of the carbon-modified copper-based catalyst in (ii) are preferably the same as the reaction conditions of the carbon-modified copper-based catalyst in the technical scheme of (i), and thus, the details are not repeated herein.
The invention also provides the application of the carbon modified copper-based catalyst in the technical scheme or the carbon modified copper-based catalyst prepared by the preparation method in the technical scheme in the preparation of methanol by carbon dioxide hydrogenation.
In the present invention, the application conditions of the carbon-modified copper-based catalyst in the preparation of methanol by hydrogenation of carbon dioxide preferably include: the reaction gas is preferably H2/CO2A mixed gas of/Ar, the reaction gasMiddle H2、CO2And Ar preferably has a volume ratio of (65-75): (18-28): (2-17), more preferably (68-72): (20-25): (3-12), most preferably 70: 23: 7; the dosage ratio of the carbon modified copper-based catalyst to the reaction gas is preferably 1g (2200-2300 mL), and more preferably 1g:1150 mL; the contact time W/F is preferably 8-12 g.h/mol, more preferably 9-11 g.h/mol, and most preferably 10 g.h/mol; the reaction pressure is preferably 2.9-3.1 MPa, more preferably 2.95-3.05 MPa, and most preferably 3.0 MPa; the reaction temperature is preferably 180-250 ℃, more preferably 190-220 ℃, and most preferably 200 ℃; the reaction time is preferably 30 to 60 hours, and more preferably 40 to 50 hours.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) 6.0g of Cu (NO)3)2·3H2O、4.4g Zn(NO3)2·6H2O and 8.8g Al (NO)3)3·9H2Dissolving O in 63mL of deionized water to obtain a metal salt solution; adding 10.6g of Na2CO3Dissolved in 100mL of deionized water to obtain Na2CO3A solution; mixing the metal salt solution and Na at 70 ℃ and 900r/min2CO3The solution is in parallel flow in 200mL of deionized water, the pH value of the system is controlled to be 7, coprecipitation reaction is carried out for 2h, standing and aging are carried out for 12h at the temperature of 30 ℃, the obtained reaction system is sequentially filtered and washed with water, and then drying is carried out for 12h at the temperature of 80 ℃ to obtain a coprecipitate;
(2) roasting the coprecipitate for 5 hours at the temperature of 350 ℃, then sequentially tabletting, crushing and screening particles with the particle size of 20-40 meshes, and then carrying out H2/N2Atmosphere (H)2The volume fraction is 5 percent) and is reduced for 7 hours at the temperature of 300 ℃ to obtain Cu-ZnO-Al2O3Copper based catalystOxidant (Cu: ZnO: Al)2O3Mass ratio 4:3:3, abbreviated CuZA);
(3) 1.1mL of benzene was added dropwise to 1.2g of Cu-ZnO-Al2O3Stirring the copper-based catalyst until the benzene solution is completely absorbed, and roasting the mixture in a tube furnace at 400 ℃ for 3 hours in vacuum to obtain the carbon modified copper-based catalyst (abbreviated as C/CuZA).
Example 2
(1) 6.0g of Cu (NO)3)2·3H2O、4.4g Zn(NO3)2·6H2O and 8.8g Al (NO)3)3·9H2Dissolving O in 63mL of deionized water to obtain a metal salt solution; adding 10.6g of Na2CO3Dissolved in 100mL of deionized water to obtain Na2CO3A solution; mixing the metal salt solution and Na at 70 ℃ and 900r/min2CO3The solution is in parallel flow in 200mL of deionized water, the pH value of the system is controlled to be 7, coprecipitation reaction is carried out for 2h, standing and aging are carried out for 12h at the temperature of 30 ℃, the obtained reaction system is sequentially filtered and washed with water, and then drying is carried out for 12h at the temperature of 80 ℃ to obtain a coprecipitate;
(2) roasting the coprecipitate for 5 hours at the temperature of 350 ℃, and then sequentially performing tabletting, crushing and screening to obtain particles with the particle size of 20-40 meshes to obtain CuO-ZnO-Al2O3Copper-based catalyst (CuO: ZnO: Al)2O3Mass ratio 5:3:3, abbreviated CuOZA);
(3) 1.1mL of benzene was added dropwise to 1.2g of CuO-ZnO-Al2O3Stirring the copper-based catalyst until the benzene solution is completely absorbed, and roasting the mixture in a tube furnace at 400 ℃ for 3 hours in vacuum to obtain the carbon modified copper-based catalyst (abbreviated as C/CuOZA).
Example 3
A carbon-modified copper-based catalyst was prepared in the same manner as in example 1, except that toluene was used instead of benzene.
Example 4
A carbon-modified copper-based catalyst was prepared in the same manner as in example 1, except that xylene was used instead of benzene.
Comparative example 1
Cu-ZnO-Al was prepared according to the method of example 12O3Copper-based catalysts (abbreviated as CuZA).
Comparative example 2
Preparation of CuO-ZnO-Al according to example 22O3Copper-based catalysts (abbreviated CuOZA).
Comparative example 3
The carbon-modified copper-based catalyst prepared by the method in example 1 is different from the method in example 1 in that particles with the particle size of 10-20 meshes are screened.
Comparative example 4
The carbon-modified copper-based catalyst prepared by the method in example 1 is different from the method in example 1 in that particles with the particle size of 60-80 meshes are screened.
Application example 1
1.0g of the carbon-modified copper-based catalysts prepared in examples 1 to 4 and comparative examples 3 to 4 and the copper-based catalysts prepared in comparative examples 1 to 2 were used independently as catalysts for preparing methanol by carbon dioxide hydrogenation, respectively, and were used for preparing methanol by carbon dioxide hydrogenation. Wherein, the reaction conditions for preparing the methanol by the hydrogenation of the carbon dioxide are as follows: reaction gas H2/CO2The catalyst effects of the carbon-modified copper-based catalysts prepared in examples 1 to 4 and comparative examples 3 to 4 and the copper-based catalysts prepared in comparative examples 1 to 2 are shown in Table 1, wherein the volume ratio of/Ar is 70/23/7, the contact time W/F is 10 g.h/mol, the reaction pressure is 3.0MPa, and the reaction temperature is 200 ℃.
TABLE 1 catalysis Effect of examples 1 to 4, comparative examples 3 to 4 for carbon-modified copper-based catalysts, and comparative examples 1 to 2 for copper-based catalysts
As can be seen from the contents of Table 1, Cu-ZnO-Al alone2O3Active component or CuO-ZnO-Al2O3Active component as catalyst, CO2The conversion rate is only 4.8-4.9%, CH3The yield of OH is only 3.31-3.77%, and the yield of the Cu-ZnO-Al2O3Active component or CuO-ZnO-Al2O3Carbon modified copper-based catalyst CO obtained by carbon modification of active component2The conversion rate is improved by 66.7 percent, and CH3The OH yield is improved by 75.2 percent, and the carbon dioxide conversion rate and the methanol yield are obviously improved.
The results of the stability experiment of the carbon-modified copper-based catalyst prepared in example 1 for preparing methanol by hydrogenation of carbon dioxide are shown in fig. 1. As can be seen from FIG. 1, when the carbon-modified copper-based catalyst prepared according to the present invention was used as a catalyst, CO was observed to increase with the increase of the reaction time2Conversion and CH3The OH selectivity is gradually increased and tends to be stable, and the catalytic activity is not obviously reduced after the catalytic reaction is carried out for 100 hours, which shows that the carbon modified copper-based catalyst provided by the invention has excellent stability.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. The carbon modified copper-based catalyst is characterized by comprising an active component and carbon coated on the surface of the active component; the active component comprises copper oxide, zinc oxide and aluminum oxide, or comprises copper, zinc oxide and aluminum oxide; the carbon has a graphite structure;
the preparation method of the carbon modified copper-based catalyst comprises the following steps: (i) when the active components include copper oxide, zinc oxide and aluminum oxide, the preparation method of the carbon-modified copper-based catalyst includes the steps of:
mixing metal salt, a precipitator and water, and carrying out coprecipitation reaction to obtain a coprecipitate;
sequentially aging and first roasting the coprecipitate to obtain a copper-based catalyst;
mixing the copper-based catalyst and aromatic hydrocarbon, and carrying out second roasting to obtain a carbon-modified copper-based catalyst;
the metal salt is a metal salt corresponding to a metal element in the active component;
(ii) when the active components include copper, zinc oxide and alumina, the preparation method of the carbon-modified copper-based catalyst includes the steps of:
sequentially carrying out aging, first roasting and reduction reactions on the coprecipitate to obtain a copper-based catalyst;
the metal salt is a metal salt corresponding to a metal element in the active component;
the metal salt independently comprises nitrate and/or acetate;
the precipitating agent independently comprises at least one of sodium carbonate, sodium bicarbonate and sodium hydroxide;
the aromatic hydrocarbons independently comprise at least one of benzene, toluene, and xylene;
the temperature of the coprecipitation reaction is independently 60-80 ℃, the time is independently 1-5 h, and the pH value of the system during the coprecipitation reaction is independently 6-8;
the aging temperature is independently 20-50 ℃, and the aging time is independently 10-15 h;
the temperature of the first roasting is 200-400 ℃ independently, and the time is 2-6 hours independently;
the temperature of the second roasting is 200-500 ℃ independently, and the time is 2-5 hours independently.
2. The carbon-modified copper-based catalyst according to claim 1, wherein the particle size of the carbon-modified copper-based catalyst is 20 to 40 mesh.
3. The carbon-modified copper-based catalyst according to claim 1 or 2, wherein the mass ratio of the active component to carbon is 1: (0.04-0.2).
4. The carbon-modified copper-based catalyst according to claim 1 or 2, wherein when the active component comprises copper oxide, zinc oxide and aluminum oxide, the mass ratio of copper oxide, zinc oxide and aluminum oxide in the active component is (4-6): (2.5-3.5): (2.5-3.5);
when the active component comprises copper, zinc oxide and aluminum oxide, the mass ratio of the copper to the zinc oxide to the aluminum oxide in the active component is (4-6): (2.5-3.5): (2.5-3.5).
5. The method for producing a carbon-modified copper-based catalyst according to any one of claims 1 to 4, wherein (i) when the active component comprises copper oxide, zinc oxide and aluminum oxide, the method for producing a carbon-modified copper-based catalyst comprises the steps of:
mixing metal salt, a precipitator and water, and carrying out coprecipitation reaction to obtain a coprecipitate;
sequentially aging and first roasting the coprecipitate to obtain a copper-based catalyst;
mixing the copper-based catalyst and aromatic hydrocarbon, and carrying out second roasting to obtain a carbon-modified copper-based catalyst;
the metal salt is a metal salt corresponding to a metal element in the active component;
(ii) when the active components include copper, zinc oxide and alumina, the preparation method of the carbon-modified copper-based catalyst includes the steps of:
sequentially carrying out aging, first roasting and reduction reactions on the coprecipitate to obtain a copper-based catalyst;
the metal salt is a metal salt corresponding to a metal element in the active component;
the metal salt independently comprises nitrate and/or acetate;
the precipitating agent independently comprises at least one of sodium carbonate, sodium bicarbonate and sodium hydroxide;
the aromatic hydrocarbons independently comprise at least one of benzene, toluene, and xylene;
the temperature of the coprecipitation reaction is independently 60-80 ℃, the time is independently 1-5 h, and the pH value of the system during the coprecipitation reaction is independently 6-8;
the aging temperature is independently 20-50 ℃, and the aging time is independently 10-15 h;
the temperature of the first roasting is 200-400 ℃ independently, and the time is 2-6 hours independently;
the temperature of the second roasting is 200-500 ℃ independently, and the time is 2-5 hours independently.
6. The method according to claim 5, wherein the reduction reaction in (ii) is carried out in H2/N2In a mixed atmosphere, said H2/N2H in mixed atmosphere2The volume fraction of (A) is 4-7%; the temperature of the reduction reaction is 200-350 ℃, and the time is 3-10 h.
7. Use of the carbon-modified copper-based catalyst according to any one of claims 1 to 4 or the carbon-modified copper-based catalyst prepared by the preparation method according to any one of claims 5 to 6 in the preparation of methanol by hydrogenation of carbon dioxide.
8. The use of claim 7, wherein the conditions for the carbon-modified copper-based catalyst used in the hydrogenation of carbon dioxide to methanol comprise:
the reaction gas is H2/CO2A mixed gas of/Ar, H in the reaction gas2、CO2And Ar in a volume ratio of (65-75): (18-28): (7-17);
the contact time W/F is 7-10 g.h/mol;
the reaction pressure is 2.95-3.05 MPa, the temperature is 180-250 ℃, and the reaction time is 30-60 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911011719.4A CN111530467B (en) | 2019-10-23 | 2019-10-23 | A kind of carbon-modified copper-based catalyst and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911011719.4A CN111530467B (en) | 2019-10-23 | 2019-10-23 | A kind of carbon-modified copper-based catalyst and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111530467A CN111530467A (en) | 2020-08-14 |
| CN111530467B true CN111530467B (en) | 2021-02-05 |
Family
ID=71969141
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911011719.4A Active CN111530467B (en) | 2019-10-23 | 2019-10-23 | A kind of carbon-modified copper-based catalyst and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111530467B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112452332A (en) * | 2020-10-27 | 2021-03-09 | 安徽华塑股份有限公司 | Micro-nano copper-based high-activity catalyst and preparation method thereof |
| CN118925732A (en) * | 2024-07-19 | 2024-11-12 | 太原理工大学 | A copper-based catalyst and its preparation method and application |
| CN119897104B (en) * | 2025-04-02 | 2025-07-11 | 安徽大学 | A sea urchin-shaped copper-based catalyst and its application in the transfer hydrodeoxygenation reaction of vanillin |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0721799B1 (en) * | 1995-01-11 | 1999-12-08 | United Catalysts, Inc. | Promoted and stabilized copper oxide and zinc oxide catalyst and preparation method |
| CN1101263C (en) * | 1999-09-29 | 2003-02-12 | 中国石油化工集团公司 | Cu-contained catalyst and preparing process thereof |
| CN1301793C (en) * | 2004-07-29 | 2007-02-28 | 复旦大学 | Nano carbon material modified copper base catalyst and its preparing method |
| CN100551535C (en) * | 2005-11-09 | 2009-10-21 | 南化集团研究院 | Catalyst for synthesizing methanol and preparation method thereof |
| CN101549289B (en) * | 2009-05-12 | 2012-08-22 | 武汉大学 | Nucleocapsid energizing agent for propelling agent and method for preparing same |
| US8822386B2 (en) * | 2010-06-28 | 2014-09-02 | Baker Hughes Incorporated | Nanofluids and methods of use for drilling and completion fluids |
| CN105498779A (en) * | 2014-10-11 | 2016-04-20 | 中国石油化工股份有限公司 | Preparation method of nano copper based catalyst for CO2 hydrogenation for producing methanol |
| CN104324757B (en) * | 2014-11-13 | 2017-06-27 | 太原理工大学 | A rapid preparation method of core-shell carbon-coated nano-copper catalyst |
| CN105536802A (en) * | 2015-12-17 | 2016-05-04 | 中国科学院上海高等研究院 | Micro-nano structure copper-based catalyst and preparation method and application thereof |
| CN106563454A (en) * | 2016-11-11 | 2017-04-19 | 宁夏大学 | A kind of catalyst for CO2 hydrogenation methanol and its preparation method and application |
| CN107042101A (en) * | 2017-06-02 | 2017-08-15 | 宁夏大学 | A kind of hydrogenation of carbon dioxide catalyst for methanol of doped graphene |
| CN109453799B (en) * | 2018-09-20 | 2022-06-14 | 上海大学 | Nitrogen-doped carbon material coated nano titanium dioxide material and application thereof |
| CN110224128A (en) * | 2019-06-21 | 2019-09-10 | 南京农业大学 | Cobalt acid zinc nano-array material of a kind of PVA pyrolysis carbon coated and preparation method thereof, application |
-
2019
- 2019-10-23 CN CN201911011719.4A patent/CN111530467B/en active Active
Non-Patent Citations (3)
| Title |
|---|
| "Enhanced Catalytic Performance for CO2 Hydrogenation to Methanol over N-doped Graphene Incorporated Cu-ZnO-Al";Qingxiang Ma等;《Chemistry Select》;20190110;第4卷(第1期);第78-83页 * |
| "Synthesis, structures and magnetic properties of carbon-encapsulated nanoparticles via thermal decomposition of metal acetylide";Junichi Nishijo等;《Carbon》;20060707;第44卷;第2943-2949页 * |
| "限域型碳包覆铜催化剂制备及其合成碳酸二甲酯性能研究";郝盼盼;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20160815(第08期);B014-554 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111530467A (en) | 2020-08-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US12203182B2 (en) | Preparation method and application of non-noble metal single atom catalyst | |
| CN111530467B (en) | A kind of carbon-modified copper-based catalyst and its preparation method and application | |
| CN103157491B (en) | Mesoporous metal oxide supported palladium catalyst for catalytic oxidation of volatile organic compounds | |
| CN107442154A (en) | A kind of cryptomelane based composite metal element catalyst and its production and use | |
| CN109126808A (en) | A kind of additive modification copper-based catalysts and preparation method and applications | |
| CN102039131B (en) | Catalyst for generating hydrogen by visible light photocatalytic reduction of water, and preparation method thereof | |
| CN115254100A (en) | Preparation and application of a metal oxide-doped single-atom catalyst for CO2 hydrogenation to ethanol | |
| CN111085218A (en) | Manganese-cobalt composite oxide catalyst for eliminating VOCs (volatile organic compounds), and preparation method and application thereof | |
| CN102302934A (en) | Novel auxiliary-modified catalyst for preparing methanol by catalytic hydrogenation of carbon dioxide and preparation method of catalyst | |
| CN102000578A (en) | Catalyst for preparing methyl alcohol by carbon dioxide catalytic hydrogenation and preparing method thereof | |
| CN114425392B (en) | Carbon-nitrogen based composite material, preparation method and application thereof | |
| CN108479762A (en) | A kind of manganese oxide catalyst and its preparation method and application | |
| CN102350355A (en) | Iron-based water gas transformation catalyst and preparation method thereof | |
| CN110433811B (en) | MgO-modified Ni/CaO bifunctional catalyst and preparation method and application | |
| KR102035714B1 (en) | Nickel catalysts for reforming hydrocarbons | |
| CN105597775A (en) | Graphene /Cu-Mn-Ce compound catalyst, and preparation method and applications thereof | |
| CN111437862A (en) | Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof | |
| CN115650829A (en) | Method for preparing cyclohexanone compounds by photocatalysis of biomass phenolic compounds | |
| CN113797935A (en) | A kind of catalyst for low temperature and high efficiency treatment of VOCs and preparation method thereof | |
| CN111036199A (en) | Application of Rutile Titanium Oxide Supported Catalyst in Carbon Dioxide Hydrogenation | |
| Šalipur et al. | Metal doped TiO2 decorated carbon nanostructured materials as an emerging photocatalysts for solar fuels production | |
| CN102218322B (en) | Catalyst for hydrogen production | |
| CN116408102A (en) | Catalyst for catalytic combustion of methane and preparation method thereof | |
| JP2016153368A (en) | Method for producing hydrogen by reforming hydrocarbon, apparatus for producing hydrogen, operation method for fuel battery, and operation device for fuel battery | |
| CN114602524A (en) | Preparation of nitrogen modified catalyst and application thereof in preparation of cyclohexanone by phenol hydrogenation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |