CN113398929A - For CO2Cu/TiO for preparing methanol by catalytic hydrogenation2Catalyst and preparation method thereof - Google Patents
For CO2Cu/TiO for preparing methanol by catalytic hydrogenation2Catalyst and preparation method thereof Download PDFInfo
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- CN113398929A CN113398929A CN202110773469.9A CN202110773469A CN113398929A CN 113398929 A CN113398929 A CN 113398929A CN 202110773469 A CN202110773469 A CN 202110773469A CN 113398929 A CN113398929 A CN 113398929A
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- ethanol
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 title abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 61
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 24
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 12
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 7
- 238000000975 co-precipitation Methods 0.000 claims abstract description 7
- 239000013078 crystal Substances 0.000 claims abstract description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 28
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000013461 design Methods 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 3
- 238000005470 impregnation Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000007327 hydrogenolysis reaction Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- -1 aluminum oxide compound Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229960002380 dibutyl phthalate Drugs 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
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- B01J23/72—Copper
-
- B01J35/394—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
- B01J37/088—Decomposition of a metal salt
-
- 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
-
- 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 discloses a method for preparing CO2Cu/TiO for preparing methanol by catalytic hydrogenation2A catalyst and a preparation method thereof relate to the field of catalyst design. The Cu/TiO of the invention2The catalyst is prepared by mixing isopropyl titanate and copper nitrate as raw materials and ethanol as a solution, and obtaining a catalyst with a structure that Cu atoms are embedded in TiO through a coprecipitation method and roasting in a strong ammonia water environment2Cu/TiO in the crystal lattice of2And carrying out co-carrying. The invention inlays Cu atoms in TiO by a coprecipitation method2In the crystal lattice, active centers are favoredThe dispersion of Cu improves the catalytic activity.
Description
Technical Field
The invention relates to the field of catalyst design, in particular to a catalyst for CO2Cu/TiO for preparing methanol by catalytic hydrogenation2A catalyst and a preparation method thereof.
Background
The excessive consumption of fossil fuels raises concerns about environmental issues and national energy safety, and thus, the demand for environmentally friendly and renewable alternative fuels is increasing. At present, CO2As a widely-occurring carbon source, it plays an increasingly important role in the chemical industry and is one of promising renewable energy sources. To CO2The catalytic hydrogenation is carried out to prepare high value-added chemical products such as methanol and the like, and the economic value is extremely high.
In the prior art, Cu/TiO2The catalyst being CO2Common chemical catalyst for preparing high-added-value chemical products such as methanol and the like by catalytic hydrogenation, Cu/TiO2The catalyst is prepared by impregnation method, which has two methods, one is to make TiO2Impregnated in copper nitrate, e.g. in patent application Cu/TiO, publication No. CN102225883B2Catalyst, process for preparing the same and process for the hydrogenolysis of glycerol wherein Cu/TiO is described2The preparation method of the catalyst comprises the following steps: Cu/TiO2The catalyst is prepared by an isovolumetric impregnation method, and the raw material is Cu (NO)3)2·3H2O and TiO2First, the support TiO is measured2The impregnation volume of (2) is that according to the mass ratio composition requirement of the catalyst, the raw materials with corresponding amount are weighed and mixed, the equal volume impregnation is carried out, and in the process, the stirring is needed to ensure that the copper nitrate solution and the TiO carrier are mixed2Fully and uniformly dipping; drying the sample at 120 ℃ for 12h, and roasting at 450 ℃ for 2h to prepare Cu/TiO2A catalyst precursor; Cu/TiO2Tabletting the catalyst matrix under 14MPa, and sieving to obtain 20-40 mesh particles to obtain Cu/TiO2The prepared copper-supported catalyst does not contain heavy metal chromium which pollutes the environment, has good catalytic activity and stability in the reaction process, is carried out under normal pressure, and is superior to other glycerin catalytic hydrogenolysis reactions which can show higher conversion rate under the condition of higher reaction pressure; secondly, the nano-copper is dipped in the ethanol solution of butyl phthalate or isopropyl titanate or ethyl titanate, for example, the preparation method of the black TiO2 coated metal copper nano-photocatalyst of the patent application with the publication number of CN105195146BAnd the application, the preparation method comprises two steps: firstly, preparing nano metal copper particles, including the synthesis of copper oxide and aluminum oxide compound, the removal of aluminum oxide and the reduction of nano copper oxide; secondly, under the protection of inert or hydrogen atmosphere, the titanium source is hydrolyzed and deposited on the surface of the metallic copper nano-particle, and the black titanium dioxide coated metallic copper nano-catalyst is obtained through drying and vacuum roasting2And (4) sex. And the metal copper nano particles in the catalyst are not oxidized in the process of photocatalytic reaction.
Whatever the impregnation method, the Cu/TiO produced2Catalyst, albeit in the presence of CO2The chemical reaction for preparing high value-added chemical products such as methanol and the like by catalytic hydrogenation shows high catalytic activity, but the catalytic conversion rate is only about 50 percent substantially, so that the Cu/TiO is required to be further improved2Catalytic activity of the catalyst.
Disclosure of Invention
The invention aims to provide a method for preparing CO2Cu/TiO for preparing methanol by catalytic hydrogenation2The catalyst is prepared by embedding Cu atoms in TiO by coprecipitation method2In the crystal lattice, the dispersion of active center Cu is facilitated, so as to further improve the Cu/TiO2Catalytic activity of the catalyst.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
for CO2Cu/TiO for preparing methanol by catalytic hydrogenation2Catalyst, said Cu/TiO2The catalyst is prepared by mixing isopropyl titanate and copper nitrate as raw materials and ethanol as a solution, and obtaining a catalyst with a structure that Cu atoms are embedded in TiO through a coprecipitation method and roasting in a strong ammonia water environment2Cu/TiO in the crystal lattice of2And carrying out co-carrying.
For CO2Cu/TiO for preparing methanol by catalytic hydrogenation2The preparation method of the catalyst comprises the following steps:
(1) dissolving isopropyl titanate in ethanol to prepare a solution A;
(2) dissolving copper nitrate or hydrated copper nitrate in ethanol to prepare a solution B;
(3) mixing the solution A and the solution B, and stirring and uniformly mixing;
(4) adding concentrated ammonia water into the mixed solution, controlling the pH value to be 9-11, and stirring for 5-15 h at 50-70 ℃ to obtain solid precipitate;
(5) filtering to obtain solid precipitate, washing and drying at 50-70 ℃;
(6) roasting the dried solid powder at 550-650 ℃ for 3-6 h to obtain Cu/TiO2A catalyst.
Preferably, in the step (1) and the step (2), the total amount of ethanol used in the solution A and the solution B is 40ml, and the amount of copper nitrate added is 0.046g, based on 15ml of isopropyl titanate added and having a mass content of 27.8-28.6%.
Preferably, in the step (3), the solution A and the solution B are mixed and stirred for 30-60 min.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention inlays Cu atoms in TiO by a coprecipitation method2The crystal lattice is beneficial to the dispersion of active center Cu and improves the catalytic activity;
2. Cu/TiO prepared by the invention2The catalyst is safe and easily obtained, and used for CO2The catalytic hydrogenation for preparing methanol shows higher catalytic reaction activity under the conditions of lower temperature and normal pressure, and can be used for development and application of green and environment-friendly new energy. And the cost is relatively low, the process flow is convenient and fast, the operation is simple, the energy is saved, and the engineering popularization is facilitated.
Drawings
FIG. 1 shows Cu/TiO prepared in example 12Perspective electron microscope image of catalyst;
FIG. 2 shows Cu/TiO prepared by the impregnation method2-i Cu/TiO prepared in example 12To CO2The yield of each product of catalytic hydrogenation of the catalyst is compared with the graph.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the present invention is further described below with reference to various embodiments and the accompanying drawings, and the implementation manner of the present invention includes, but is not limited to, the following embodiments.
The invention provides Cu/TiO2Catalyst, said Cu/TiO2The catalyst is prepared by mixing isopropyl titanate and copper nitrate as raw materials and ethanol as a solution, and obtaining a catalyst with a structure that Cu atoms are embedded in TiO through a coprecipitation method and roasting in a strong ammonia water environment2Cu/TiO in the crystal lattice of2A co-cargo, wherein the loading of Cu is 0.2 wt%. The following examples and experimental examples are further illustrated with reference to the accompanying drawings2The preparation process of the catalyst, the structure and the performance of the product.
Example 1
This example provides Cu/TiO2A method of preparing a catalyst comprising the steps of:
a) solution A was prepared by dissolving 15mL of isopropyl titanate (27.8-28.6%) in 20mL of ethanol.
b) 0.06g of Cu (NO)3)2·3H2O was dissolved in 20mL of ethanol to prepare a solution B.
c) Mixing solution A and solution B, and stirring for 40 min.
d) Adding concentrated ammonia water into the mixed solution, controlling the pH value at 10, and stirring at 60 ℃ for 12h to obtain solid precipitate.
e) Filtering to obtain solid precipitate, washing with deionized water and ethanol for three times, and drying at 60 deg.C for 24 hr.
g) Roasting the solid powder at 600 ℃ for 5h to obtain Cu/TiO with the loading of 0.2 wt%2The structure appearance is shown in figure 1.
Comparative example 1
Preparation of Cu/TiO by existing impregnation methods2-i catalyst: with Cu (NO)3)2·3H2O and TiO2As a raw material, firstly, the TiO carrier is measured2The impregnation volume of (A) is that according to the mass ratio composition requirement of the catalyst, the raw materials with corresponding amount are weighed and mixed, the equal volume impregnation is carried out, and the stirring is needed in the process to ensure that the copper nitrate solution and the copper nitrate solution are mixedSupport TiO2Fully and uniformly dipping; drying the sample at 120 ℃ for 12h, and roasting at 450 ℃ for 2h to prepare Cu/TiO2A catalyst precursor; Cu/TiO2Tabletting the catalyst matrix under 14MPa, and sieving to obtain 20-40 mesh particles to obtain Cu/TiO2-i catalyst.
Control experiment
20mg of the catalyst was charged in a straight tube quartz reactor having a diameter of 1cm, and heated to 240 ℃ to effect a reaction. The gas flow at the inlet of the reactor was 100mL/min and the gas composition was 30% H2，10％CO2And 60% Ar. The gas components after the reaction were analyzed at the outlet of the reactor using a mass spectrometer, the yield of each component was calculated, and a histogram as shown in fig. 2 was obtained after the summary.
It can be easily seen from the second diagram, compared to Cu/TiO prepared by the immersion method2-i Cu/TiO prepared in example 12To CO2The catalyst has further improved activity and selectivity.
The above-mentioned embodiment is only one of the preferred embodiments of the present invention, and should not be used to limit the scope of the present invention, but all the insubstantial modifications or changes made within the spirit and scope of the main design of the present invention, which still solve the technical problems consistent with the present invention, should be included in the scope of the present invention.
Claims (4)
1. For CO2Cu/TiO for preparing methanol by catalytic hydrogenation2Catalyst, characterized in that the Cu/TiO2The catalyst is prepared by mixing isopropyl titanate and copper nitrate as raw materials and ethanol as a solution, and obtaining a catalyst with a structure that Cu atoms are embedded in TiO through a coprecipitation method and roasting in a strong ammonia water environment2Cu/TiO in the crystal lattice of2And carrying out co-carrying.
2. A process for CO as claimed in claim 12Cu/TiO for preparing methanol by catalytic hydrogenation2The preparation method of the catalyst is characterized by comprising the following steps:
(1) dissolving isopropyl titanate in ethanol to prepare a solution A;
(2) dissolving copper nitrate or hydrated copper nitrate in ethanol to prepare a solution B;
(3) mixing the solution A and the solution B, and stirring and uniformly mixing;
(4) adding concentrated ammonia water into the mixed solution, controlling the pH value to be 9-11, and stirring for 5-15 h at 50-70 ℃ to obtain solid precipitate;
(5) filtering to obtain solid precipitate, washing and drying at 50-70 ℃;
(6) roasting the dried solid powder at 550-650 ℃ for 3-6 h to obtain Cu/TiO2A catalyst.
3. The production method according to claim 2, wherein in the steps (1) and (2), based on 15ml of isopropyl titanate added in an amount of 27.8 to 28.6% by mass, the total amount of ethanol used in the solution A and the solution B is 40ml, and the amount of copper nitrate added is 0.046 g.
4. The method according to claim 2, wherein in the step (3), the solution A and the solution B are mixed and stirred for 30-60 min.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110773469.9A CN113398929A (en) | 2021-07-08 | 2021-07-08 | For CO2Cu/TiO for preparing methanol by catalytic hydrogenation2Catalyst and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115715981A (en) * | 2022-11-04 | 2023-02-28 | 安徽华塑股份有限公司 | Preparation method of catalyst for preparing ethanol by carbon dioxide hydrogenation |
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|---|---|---|---|---|
| CN102658151A (en) * | 2012-04-28 | 2012-09-12 | 上海华谊（集团）公司 | Preparation method of methanol catalyst master body by carbon dioxide (CO2) hydrogenation |
| JP2012211100A (en) * | 2011-03-31 | 2012-11-01 | Nippon Steel Corp | Method and catalyst for producing methanol |
| WO2018049735A1 (en) * | 2016-09-14 | 2018-03-22 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | A metal oxide catalyst for methanol synthesis from co2 hydrogenation and preparation method of the catalyst |
| CN110563592A (en) * | 2019-09-18 | 2019-12-13 | 宁夏大学 | method for preparing dimethylamine from carbon dioxide, hydrogen and ammonia in one step |
| CN110947386A (en) * | 2019-11-21 | 2020-04-03 | 太原理工大学 | Preparation method of catalyst for synthesizing low-carbon alcohol by carbon dioxide hydrogenation |
-
2021
- 2021-07-08 CN CN202110773469.9A patent/CN113398929A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012211100A (en) * | 2011-03-31 | 2012-11-01 | Nippon Steel Corp | Method and catalyst for producing methanol |
| CN102658151A (en) * | 2012-04-28 | 2012-09-12 | 上海华谊（集团）公司 | Preparation method of methanol catalyst master body by carbon dioxide (CO2) hydrogenation |
| WO2018049735A1 (en) * | 2016-09-14 | 2018-03-22 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | A metal oxide catalyst for methanol synthesis from co2 hydrogenation and preparation method of the catalyst |
| CN110563592A (en) * | 2019-09-18 | 2019-12-13 | 宁夏大学 | method for preparing dimethylamine from carbon dioxide, hydrogen and ammonia in one step |
| CN110947386A (en) * | 2019-11-21 | 2020-04-03 | 太原理工大学 | Preparation method of catalyst for synthesizing low-carbon alcohol by carbon dioxide hydrogenation |
Non-Patent Citations (1)
| Title |
|---|
| 侯瑞君;邱瑞;孙克宁;: "Cu基CO_2合成甲醇催化剂载体的研究进展" * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115715981A (en) * | 2022-11-04 | 2023-02-28 | 安徽华塑股份有限公司 | Preparation method of catalyst for preparing ethanol by carbon dioxide hydrogenation |
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