CN113893843A - For CO2Zn for preparing methanol by catalytic hydrogenation1Zr2O3Process for preparing catalyst - Google Patents
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 230000003197 catalytic effect Effects 0.000 title abstract description 24
- 239000011701 zinc Substances 0.000 claims abstract description 48
- 229910008253 Zr2O3 Inorganic materials 0.000 claims abstract description 25
- 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 abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 239000002244 precipitate Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 abstract description 9
- 238000011068 loading method Methods 0.000 abstract description 4
- 238000013461 design Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment 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
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of 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
- 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
-
- 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
-
- 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
-
- 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 CO2Zn for preparing methanol by catalytic hydrogenation1Zr2O3A preparation method of a catalyst relates to the field of catalyst design. The invention comprises the following steps: (1) dissolving zinc nitrate and zirconium nitrate with the molar ratio of 1: 2 into deionized water at room temperature; (2) mixing ammonia and absolute ethyl alcohol with the molar ratio of 1:1 to form an alkali liquor, and slowly adding the alkali liquor into the mixed solution obtained in the step (1); (3) stirring in water bath at 70-80 deg.C for 20-30 min, filtering to obtain precipitate, and collecting the precipitateDrying the mixture in a low-temperature environment at 50-60 ℃; (4) calcining the dried solid at 300-350 ℃ for 4-6 h to obtain Zn1Zr2O3The catalyst with higher catalytic activity at lower catalytic temperature can be prepared by preparing specific alkali liquor and reducing the calcining temperature, In loading is not needed, the preparation difficulty is reduced and the production cost is reduced on the premise of improving the catalytic activity at lower catalytic temperature and normal pressure.
Description
Technical Field
The invention relates to the field of catalyst design, in particular to a catalyst for CO2Zn for preparing methanol by catalytic hydrogenation1Zr2O3A method for preparing the catalyst.
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, can be used for CO2The catalysts for preparing methanol by catalytic hydrogenation are various except TiO2The catalyst, ZnO catalyst is also CO2The common chemical catalyst for preparing high value-added chemical products such as methanol and the like by catalytic hydrogenation, namely the existing ZnO catalyst, is used for CO2The catalytic activity is shown in the chemical reaction for preparing high value-added chemical products such as methanol and the like by catalytic hydrogenation, but the highest catalytic conversion rate is less than 20 percent.
In view of the above, research on modified ZnO-based catalysts has been conducted, such as the solid catalyst with the patent name of CN110052261A for selectively preparing methanol and carbon monoxide from carbon dioxide and the application thereof, In which2O3/ZnO-ZrO2The catalyst is prepared through the reaction of the mixture of zirconium nitrate, zirconium chloride and/or zirconium oxychloride and/or zinc nitrate, zinc chloride and zinc sulfate in the alkaline system comprising ammonia carbonate, sodium hydroxide, potassium hydroxide, etc. to produce ZnO-ZrO2Reloading with In2O3Wherein the molar ratio of Zn to Zr is 1: 6-6: 1, and ZnO-ZrO is used2The amount of the substance(s) is 100%, the loading amount of In is 1 to 15 mol%, and the molar ratio of Zn to Zr is preferably 1:1 to 4:1, In terms of ZnO-ZrO2The amount of the substance(s) is 100%, the loading amount of In is 5 mol% to 10 mol%, and finally the obtained In2O3/ZnO-ZrO2Catalyst at 330 ℃ CO2The highest conversion rate is 39.68 percent, and CO is obtained at 510 DEG C2The conversion rate can reach 67.4 percent, the catalytic activity of the catalyst is improved along with the increase of the catalytic temperature, but simultaneously, the higher the reaction temperature is, the lower the selectivity of methanol is, and at the lower catalytic temperature, the catalytic activity is lower, so that the current requirements on energy conservation and emission reduction are not met, therefore, the catalyst can be used for CO2The ZnO catalyst for preparing the methanol by catalytic hydrogenation is necessarily further researched to obtain a ZnO-based catalyst with higher catalytic activity at a lower catalytic temperature, and CO is abundantly adopted2The kind of catalyst for preparing methanol by catalytic hydrogenation.
Disclosure of Invention
The invention aims to provide a method for preparing CO2Zn for preparing methanol by catalytic hydrogenation1Zr2O3Method for preparing catalyst for CO2In the chemical reaction of preparing high-added-value chemical products such as methanol by catalytic hydrogenation, the technical problem that the catalytic activity of the existing ZnO-based catalyst is not high enough at a lower catalytic temperature is solved.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
for CO2Zn for preparing methanol by catalytic hydrogenation1Zr2O3The preparation method of the catalyst comprises the following steps:
(1) dissolving zinc nitrate and zirconium nitrate with the molar ratio of 1: 2 into deionized water at room temperature;
(2) mixing ammonia and absolute ethyl alcohol with the molar ratio of 1:1 to form an alkali liquor, and slowly adding the alkali liquor into the mixed solution obtained in the step (1);
(3) stirring in a water bath at 70-80 ℃ for 20-30 min, filtering to obtain a precipitate, and drying the precipitate in a low-temperature environment at 50-60 ℃;
(4) calcining the dried solid at 300-350 ℃ for 4-6 h to obtain Zn1Zr2O3A catalyst.
Preferably, in the step (1), the zirconium nitrate is dissolved, the solution is cooled to room temperature after the zirconium nitrate is completely dissolved, and then the zinc nitrate is dissolved.
Preferably, the zirconium nitrate is Zr (NO)3)4·5H2O。
Preferably, the zinc nitrate is Zn (NO)3)2·6H2O。
Preferably, the volume ratio of the alkali liquor prepared in the step (2) to the mixed solution prepared in the step (1) is 1: 1-1.5.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the catalyst with higher catalytic activity at lower catalytic temperature can be prepared by preparing the specific alkali liquor and reducing the calcining temperature, In loading is not required, the preparation difficulty is reduced and the production cost is reduced on the premise of improving the catalytic activity at lower catalytic temperature and normal pressure.
2. The catalyst provided by the invention can realize CO2The low-temperature and normal-pressure preparation of the methanol by catalytic hydrogenation.
3. Zn prepared by the invention1Zr2O3The catalyst is safe and easily available in raw material medicaments, and can be used for development and application of green and environment-friendly new energy.
Drawings
FIG. 1 shows Zn prepared in example 11Zr2O3Perspective electron microscope image of catalyst;
FIG. 2 shows Zn prepared in example 11Zr2O3Catalyst, ZnO and ZrO2And Zn prepared in comparative examples 1 to 31Zr2O3-1 to 3 pairs of catalysts to CO2The yield of each product of catalytic hydrogenation is compared with the figure.
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 Zn1Zr2O3The catalyst is prepared by heating zinc nitrate and zirconium nitrate solution with a molar ratio of 1: 2 and special ammonia and absolute ethyl alcohol alkali liquor with a molar ratio of 1:1, filtering to obtain solid substances, and then drying and calcining the solid substances. The preparation method comprises the following steps:
(1) dissolving zinc nitrate and zirconium nitrate with the molar ratio of 1: 2 into deionized water at room temperature;
(2) mixing ammonia and absolute ethyl alcohol with the molar ratio of 1:1 to form an alkali liquor, and slowly adding the alkali liquor into the mixed solution obtained in the step (1);
(3) stirring in a water bath at 70-80 ℃ for 20-30 min, filtering to obtain a precipitate, and drying the precipitate in a low-temperature environment at 50-60 ℃;
(4) calcining the dried solid at 300-350 ℃ for 4-6 h to obtain Zn1Zr2O3A catalyst.
The following examples, comparative experiments and accompanying drawings further illustrate Zn1Zr2O3The preparation process of the catalyst, the structure and the performance of the product.
Example 1
This example provides Zn1Zr2O3An example of the preparation of the catalyst comprises the following steps:
a) 3.6kg of Zr (NO)3)4·5H2Dissolving O in 18.8L of deionized water at 50-60 ℃;
b) after the solution is completely dissolved, cooling toAt room temperature, 1.28kg of Zn (NO) was added3)2·6H2O, stirring until the mixture is completely dissolved;
c) slowly adding a mixture of 18L ammonia and absolute ethyl alcohol (1:1mol/mol) into the solution;
d) stirring in a water bath at 70-80 ℃ for 20min, filtering and precipitating with deionized water, and placing the precipitate in an oven at 60 ℃ for 24 h;
e) calcining the dried solid at 300-350 ℃ for 4h to obtain the catalyst Zn1Zr2O3The structure appearance is shown in figure 1.
Comparative example 1
This example provides Zn for control experiments1Zr2O3-1 a process for the preparation of a catalyst comprising the steps of:
a) 3.6kg of Zr (NO)3)4·5H2Dissolving O in 18.8L of deionized water at 50-60 ℃;
b) after the solution was completely dissolved, it was cooled to room temperature and 1.28kg of Zn (NO) was added3)2·6H2O, stirring until the mixture is completely dissolved;
c) slowly adding an ammonia carbonate solution into the solution, and controlling the pH value of the system to be 6-8;
d) stirring in a water bath at 70-80 ℃ for 20min, filtering and precipitating with deionized water, and placing the precipitate in an oven at 60 ℃ for 24 h;
e) calcining the dried solid at 300-350 ℃ for 4h to obtain the catalyst Zn1Zr2O3-1。
Comparative example 2
This example provides Zn for control experiments1Zr2O3-2 a process for the preparation of a catalyst comprising the steps of:
a) 3.6kg of Zr (NO)3)4·5H2Dissolving O in 18.8L of deionized water at 50-60 ℃;
b) after the solution was completely dissolved, it was cooled to room temperature and 1.28kg of Zn (NO) was added3)2·6H2O, stirring until the mixture is completely dissolved;
c) slowly adding a sodium hydroxide solution into the solution, and controlling the pH value of the system to be 6-8;
d) stirring in a water bath at 70-80 ℃ for 20min, filtering and precipitating with deionized water, and placing the precipitate in an oven at 60 ℃ for 24 h;
e) calcining the dried solid at 300-350 ℃ for 4h to obtain the catalyst Zn1Zr2O3-2。
Comparative example 3
This example provides Zn for control experiments1Zr2O3-3 a process for the preparation of a catalyst comprising the steps of:
a) 3.6kg of Zr (NO)3)4·5H2Dissolving O in 18.8L of deionized water at 50-60 ℃;
b) after the solution was completely dissolved, it was cooled to room temperature and 1.28kg of Zn (NO) was added3)2·6H2O, stirring until the mixture is completely dissolved;
c) slowly adding a mixture of 18L ammonia and absolute ethyl alcohol (1:1mol/mol) into the solution;
d) stirring in a water bath at 70-80 ℃ for 20min, filtering and precipitating with deionized water, and placing the precipitate in an oven at 60 ℃ for 24 h;
e) calcining the dried solid at 450-550 ℃ for 4h to obtain the catalyst Zn1Zr2O3-3。
Control experiment
Zn prepared as in example 11Zr2O3Catalyst is experimental group, Zn is used1Zr2O3-1 to 3, ZnO and ZrO2As a control, 20mg of the catalyst was charged in a straight tube quartz reactor having a diameter of 1cm, and heated to 240 ℃ for 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.
From the second diagram, Zn1Zr2O3The synergistic effect of Zn and Zr in the catalyst weakens C-O bondTo make H easier to combine with it, gradually hydrogenating to form CH3OH, thus compared to pure ZnO and ZrO2，Zn1Zr2O3Zn of catalyst or even control1Zr2O31-3 all show good catalytic performance; however, Zn prepared by different preparation methods1Zr2O3The catalysts show different catalytic performances and compare Zn prepared by different preparation methods1Zr2O3Catalyst, Zn1Zr2O3-1 catalyst, Zn1Zr2O3-2 catalyst and Zn1Zr2O3-3 catalyst, Zn1Zr2O3Under the catalytic action of CO2Can reach 76.3 percent, wherein CH3The yield of OH was 59.8% and the yield of CO was 12.4%. And Zn1Zr2O3-1 catalyst, Zn1Zr2O3-2 catalyst and Zn1Zr2O3-3 catalysis of the catalyst, CO2The conversion of (A) is up to 57.4%, where CH3The yield of OH was 33.4%, the yield of CO was 15.4%, and the methanol selectivity was also significantly worse, as indicated in Zn1Zr2O3Although all the catalysts can improve CO2Catalytic hydroconversion of (a), but under the same thermocatalytic conditions, Zn prepared herein1Zr2O3The catalytic activity of the catalyst is better, and the selectivity of the methanol is also improved.
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 (5)
1. For CO2Zn for preparing methanol by catalytic hydrogenation1Zr2O3The preparation method of the catalyst is characterized by comprising the following steps:
(1) dissolving zinc nitrate and zirconium nitrate with the molar ratio of 1: 2 into deionized water at room temperature;
(2) mixing ammonia and absolute ethyl alcohol with the molar ratio of 1:1 to form an alkali liquor, and slowly adding the alkali liquor into the mixed solution obtained in the step (1);
(3) stirring in a water bath at 70-80 ℃ for 20-30 min, filtering to obtain a precipitate, and drying the precipitate in a low-temperature environment at 50-60 ℃;
(4) calcining the dried solid at 300-350 ℃ for 4-6 h to obtain Zn1Zr2O3A catalyst.
2. The method according to claim 1, wherein in the step (1), the zirconium nitrate is dissolved, the solution is cooled to room temperature after the zirconium nitrate is completely dissolved, and then the zinc nitrate is dissolved.
3. The method of claim 1, wherein the zirconium nitrate is Zr (NO)3)4·5H2O。
4. The method according to claim 1, wherein the zinc nitrate is Zn (NO)3)2·6H2O。
5. The preparation method according to claim 1, wherein the volume ratio of the alkali solution prepared in the step (2) to the mixed solution prepared in the step (1) is 1: 1-1.5.
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| CN109420486A (en) * | 2017-08-29 | 2019-03-05 | 中国科学院大连化学物理研究所 | The ZnZrO of synthesizing methanol by hydrogenating carbon dioxidexSolid solution catalyst and preparation and application |
| CN111632596A (en) * | 2020-06-15 | 2020-09-08 | 华东理工大学 | High-dispersion metal-oxide bifunctional catalyst and preparation method and application thereof |
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