CN102600851A - Preparation method of catalyst for synthesizing methanol by carbon dioxide hydrogenation - Google Patents
Preparation method of catalyst for synthesizing methanol by carbon dioxide hydrogenation Download PDFInfo
- Publication number
- CN102600851A CN102600851A CN2012100541499A CN201210054149A CN102600851A CN 102600851 A CN102600851 A CN 102600851A CN 2012100541499 A CN2012100541499 A CN 2012100541499A CN 201210054149 A CN201210054149 A CN 201210054149A CN 102600851 A CN102600851 A CN 102600851A
- Authority
- CN
- China
- Prior art keywords
- carbon dioxide
- solution
- catalyst
- under
- reaction
- 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.)
- Pending
Links
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 17
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 17
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000005984 hydrogenation reaction Methods 0.000 title abstract description 5
- 238000009777 vacuum freeze-drying Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 38
- 238000001914 filtration Methods 0.000 claims description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 18
- 239000013049 sediment Substances 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 9
- 238000011049 filling Methods 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 9
- 238000004448 titration Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000010949 copper Substances 0.000 abstract description 19
- 239000000126 substance Substances 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract 2
- 229910052802 copper Inorganic materials 0.000 abstract 2
- 239000013078 crystal Substances 0.000 abstract 2
- 239000006185 dispersion Substances 0.000 abstract 2
- 239000011701 zinc Substances 0.000 abstract 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract 1
- 239000004480 active ingredient Substances 0.000 abstract 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract 1
- 230000007704 transition Effects 0.000 abstract 1
- 229910052725 zinc Inorganic materials 0.000 abstract 1
- 239000011787 zinc oxide Substances 0.000 abstract 1
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000007873 sieving Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 206010036590 Premature baby Diseases 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004177 carbon cycle Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
Classifications
-
- 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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of chemical catalysis, and discloses a preparation method of catalyst for synthesizing methanol by carbon dioxide hydrogenation. The active ingredient of the catalyst consists of copper, zinc oxide and zirconium oxide, wherein the molar ratio of Cu to Zn to Zr is equal to (8-4):(1-5):(0-2). The catalyst for synthesizing the methanol by the carbon dioxide hydrogenation is prepared by adopting a microwave hydrothermal carrying vacuum freeze drying method at a low temperature within a short period of time. The catalyst for synthesizing the methanol by the carbon dioxide hydrogenation has the advantages of nanometer scale, high specific surface area, high degree of dispersion, transition of copper and zinc components from crystals to high-dispersion non-crystal phase forms on the surface of the catalyst, high catalytic activity, high selectivity and superior catalytic performance.
Description
Technical field
The invention belongs to the chemical industry catalysis technical field, is a kind of synthesizing methanol by hydrogenating carbon dioxide Preparation of catalysts method.
Technical background
Methyl alcohol is a kind of extremely important industrial chemicals, is widely used in organic synthesis, medicine, fuel, dyestuff, and its output is only second to synthetic ammonia and ethene.Methyl alcohol is not only C
1The basic substance of chemical industry can be produced hundreds of chemical products from methyl alcohol, simultaneously is again a kind of important potential clean fuel that substitutes.
Along with the development of chemical industry technology, methyl alcohol is expected to realize fully with CO
2For raw material is produced, methyl alcohol itself can be done the energy, and this just can realize energy burning-CO
2The circulation of-methyl alcohol-energy burning fundamentally solves the CO that causes because of the fossil energy burning on the earth
2The greenhouse gases problem, the ecological balance of realization carbon cycle.The key issue of research and development synthesizing methanol by hydrogenating carbon dioxide course of reaction is to improve activity of such catalysts and methyl alcohol selectivity.
Be used for this catalyst for reaction at present and develop prematurity still; Majority is to be improved and made by CO synthesizing methanol by hydrogenating catalyst system therefor; The also laboratory research fields that are confined to of relevant both at home and abroad report, research emphasis more concentrate on mostly reaction mechanism research, active component, carrier selection and investigate different preparation methods, reaction condition influence to catalyst performance.Because CO
2Chemical inertness and the unfavorable factor on the thermodynamics, make CO
2Be difficult to activating and reducing, exist that conversion ratio is low, accessory substance reaches the not high shortcoming of methyl alcohol selectivity more with the catalyst of conventional method preparation.In order to overcome the above problems, the improvement research to methanol synthesis catalyst at present mainly concentrates on two aspects: the one, add other elemental constituents beyond the copper zinc-aluminium; The 2nd, the preparation method and the technology of improvement catalst for synthesis of methanol.Specific area is big, decentralization is high and the characteristics of Heat stability is good because of having for nano-structured calalyst, will become a kind of development trend.
Summary of the invention
The purpose of this invention is to provide that a kind of the specific surface area of catalyst that makes is big based on synthesizing methanol by hydrogenating carbon dioxide catalyst for reaction preparation method, decentralization is high, has the good characteristics of methyl alcohol selectivity in carbon dioxide conversion height, the product.
Technical scheme of the present invention is: adopt microwave hydrothermal to carry the synthesizing methanol by hydrogenating carbon dioxide catalyst that vacuum freeze-drying method prepared in lower temperature and short time.
The catalyst of synthesizing methanol by hydrogenating carbon dioxide of the present invention comprises and is prepared as follows step:
(1) configuration Cu (NO
3)
2, Zn (NO
3)
2And Zr (NO
3)
4Mixed solution makes it dissolve mixing fully;
(2) under 50～80 ℃ reaction temperature, above-mentioned drips of solution is incorporated into Na
2CO
3In the solution, the pH of adjustment solution is 7～8, after titration finishes, mixed solution is maintained continuation stirring reaction 30～60min under the reaction temperature, under reaction temperature, leaves standstill 30～120min then and makes solution aging, obtains solid sediment after the filtration;
(3) sediment after filtering in the step (2) is put into the polytetrafluoroethylsubstrate substrate agitated reactor earlier; Under microwave condition, carry out hydro-thermal reaction, after microwave hydrothermal reaction is accomplished product is carried out suction filtration, washing to neutral and carry out obtaining catalyst sample after the vacuum freeze drying.
In the step of the present invention (1), Cu (NO
3)
2, Zn (NO
3)
2And Zr (NO
3)
4The mol ratio of mixed solution is 8～4:1～5:0～2, and the concentration of mixed solution is 0.1～1mol/L.
Na in the step of the present invention (2)
2CO
3The concentration of solution is 0.1～1.5mol/L.
Polytetrafluoroethylene (PTFE) agitated reactor filling rate is 10%～30% in the step of the present invention (3), and microwave hydrothermal is reflected under 100～200 ℃ of conditions of temperature and heats 30～60min.
Advantage of the present invention and good effect are:
This method adopts microwave hydrothermal to carry vacuum freeze-drying method and prepares methanol synthesis catalyst in lower temperature and short time.Compare with conventional method, avoided the hole collapse phenomenon that caused because of the capillary effect of solid liquid interface, the institutional framework and the pore size distribution of the wet stock after the vacuum freeze drying are preserved to greatest extent at vacuum freeze-drying method; Effectively suppressed the generation of particle agglomeration; Obtained to have nanoscale, specific area is big, and decentralization is high; Catalytic activity is high; The methanol synthesis catalyst that selectivity is good is superior to the catalyst that commonsense method prepares, and is applicable to the reaction of mesolow carbon dioxide hydrogenation catalyst.
The specific embodiment
Below in conjunction with embodiment the present invention is done to further describe, but the invention is not restricted to following scope.
Embodiment 1:
(1) Cu:Zn:Zr=4:5:1 takes by weighing Cu (NO in molar ratio
3)
23H
2O, Zn (NO
3)
26H
2O, Zr (NO
3)
4Be dissolved in the deionized water, obtaining mixed liquid concentration is 0.1 mol/L;
(2) under 70 ℃ reaction temperature, above-mentioned drips of solution is incorporated into the Na that concentration is 0.1 mol/L
2CO
3In the solution, the pH of adjustment solution is 7, after titration finishes, mixed solution is maintained continuation stirring reaction 60min under the reaction temperature, under reaction temperature, leaves standstill 120min then and makes solution aging, obtains solid sediment after the filtration;
(3) sediment after filtering in the step (2) being put into filling rate earlier is 10% polytetrafluoroethylsubstrate substrate agitated reactor; Under the microwave condition of reaction, carry out hydro-thermal reaction for heating 60min under 200 ℃ of conditions of temperature, after the microwave hydrothermal reaction is accomplished with product carry out suction filtration, washing to neutral and carry out obtaining back grinding, compressing tablet after the vacuum freeze drying, sieving makes 20～40 order catalyst sample CZZ1.
Embodiment 2:
(1) Cu:Zn:Zr=8:4:2 takes by weighing Cu (NO in molar ratio
3)
23H
2O, Zn (NO
3)
26H
2O, Zr (NO
3)
4Be dissolved in the deionized water, obtaining mixed liquid concentration is 0.8 mol/L;
(2) under 50 ℃ reaction temperature, above-mentioned drips of solution is incorporated into the Na that concentration is 1 mol/L
2CO
3In the solution, the pH of adjustment solution is 7.5, after titration finishes, mixed solution is maintained continuation stirring reaction 30min under the reaction temperature, under reaction temperature, leaves standstill 100min then and makes solution aging, obtains solid sediment after the filtration;
(3) sediment after filtering in the step (2) being put into filling rate earlier is 20% polytetrafluoroethylsubstrate substrate agitated reactor; Under the microwave condition of reaction, carry out hydro-thermal reaction for heating 50min under 160 ℃ of conditions of temperature, after the microwave hydrothermal reaction is accomplished with product carry out suction filtration, washing to neutral and carry out obtaining back grinding, compressing tablet after the vacuum freeze drying, sieving makes 20～40 order catalyst sample CZZ2.
Embodiment 3
(1) Cu:Zn:Zr=5:4:1 takes by weighing Cu (NO in molar ratio
3)
23H
2O, Zn (NO
3)
26H
2O, Zr (NO
3)
4Be dissolved in the deionized water, obtaining mixed liquid concentration is 1 mol/L;
(2) under 80 ℃ reaction temperature, above-mentioned drips of solution is incorporated into the Na that concentration is 1.5 mol/L
2CO
3In the solution, the pH of adjustment solution is 8, after titration finishes, mixed solution is maintained continuation stirring reaction 40min under the reaction temperature, under reaction temperature, leaves standstill 30min then and makes solution aging, obtains solid sediment after the filtration;
(3) sediment after filtering in the step (2) being put into filling rate earlier is 30% polytetrafluoroethylsubstrate substrate agitated reactor; Under the microwave condition of reaction, carry out hydro-thermal reaction for heating 30min under 100 ℃ of conditions of temperature, after the microwave hydrothermal reaction is accomplished with product carry out suction filtration, washing to neutral and carry out obtaining back grinding, compressing tablet after the vacuum freeze drying, sieving makes 20～40 order catalyst sample CZZ3.
Embodiment 4
(1) Cu:Zn:Zr=4:5:1 takes by weighing Cu (NO in molar ratio
3)
23H
2O, Zn (NO
3)
26H
2O, Zr (NO
3)
4Be dissolved in the deionized water, obtaining mixed liquid concentration is 0.6 mol/L;
(2) under 60 ℃ reaction temperature, above-mentioned drips of solution is incorporated into the Na that concentration is 1.3 mol/L
2CO
3In the solution, the pH of adjustment solution is 7, after titration finishes, mixed solution is maintained continuation stirring reaction 50min under the reaction temperature, under reaction temperature, leaves standstill 50min then and makes solution aging, obtains solid sediment after the filtration;
(3) sediment after filtering in the step (2) being put into filling rate earlier is 15% polytetrafluoroethylsubstrate substrate agitated reactor; Under the microwave condition of reaction, carry out hydro-thermal reaction for heating 40min under 180 ℃ of conditions of temperature, after the microwave hydrothermal reaction is accomplished with product carry out suction filtration, washing to neutral and carry out obtaining back grinding, compressing tablet after the vacuum freeze drying, sieving makes 20～40 order catalyst sample CZZ4.
Embodiment 5:
(1) Cu:Zn:Zr=8:1:2 takes by weighing Cu (NO in molar ratio
3)
23H
2O, Zn (NO
3)
26H
2O, Zr (NO
3)
4Be dissolved in the deionized water, obtaining mixed liquid concentration is 0.4 mol/L;
(2) under 70 ℃ reaction temperature, above-mentioned drips of solution is incorporated into the Na that concentration is 1.1 mol/L
2CO
3In the solution, the pH of adjustment solution is 8, after titration finishes, mixed solution is maintained continuation stirring reaction 35min under the reaction temperature, under reaction temperature, leaves standstill 110min then and makes solution aging, obtains solid sediment after the filtration;
(3) sediment after filtering in the step (2) being put into filling rate earlier is 25% polytetrafluoroethylsubstrate substrate agitated reactor; Under the microwave condition of reaction, carry out hydro-thermal reaction for heating 45min under 190 ℃ of conditions of temperature, after the microwave hydrothermal reaction is accomplished with product carry out suction filtration, washing to neutral and carry out obtaining back grinding, compressing tablet after the vacuum freeze drying, sieving makes 20～40 order catalyst sample CZZ5.
Embodiment 6:
(1) Cu:Zn=7:3 takes by weighing Cu (NO in molar ratio
3)
23H
2O, Zn (NO
3)
26H
2O is dissolved in the deionized water, and obtaining mixed liquid concentration is 1 mol/L;
(2) under 75 ℃ reaction temperature, above-mentioned drips of solution is incorporated into the Na that concentration is 1.4 mol/L
2CO
3In the solution, the pH of adjustment solution is 7, after titration finishes, mixed solution is maintained continuation stirring reaction 55min under the reaction temperature, under reaction temperature, leaves standstill 120min then and makes solution aging, obtains solid sediment after the filtration;
(3) sediment after filtering in the step (2) being put into filling rate earlier is 30% polytetrafluoroethylsubstrate substrate agitated reactor; Under the microwave condition of reaction, carry out hydro-thermal reaction for heating 45min under 190 ℃ of conditions of temperature, after the microwave hydrothermal reaction is accomplished with product carry out suction filtration, washing to neutral and carry out obtaining back grinding, compressing tablet after the vacuum freeze drying, sieving makes 20～40 order catalyst sample CZZ6.
Embodiment 7:
(1) Cu:Zn:Zr=4:5:1 takes by weighing Cu (NO in molar ratio
3)
23H
2O, Zn (NO
3)
26H
2O, Zr (NO
3)
4Be dissolved in the deionized water, obtaining mixed liquid concentration is 0.1 mol/L;
(2) under 80 ℃ reaction temperature, above-mentioned drips of solution is incorporated into the Na that concentration is 1 mol/L
2CO
3In the solution, the pH of adjustment solution is 8, after titration finishes, mixed solution is maintained continuation stirring reaction 55min under the reaction temperature, under reaction temperature, leaves standstill 120min then and makes solution aging, obtains solid sediment after the filtration;
(3) sediment after filtering in the step (2) being put into filling rate earlier is 30% polytetrafluoroethylsubstrate substrate agitated reactor; Under the microwave condition of reaction, carry out hydro-thermal reaction for heating 45min under 190 ℃ of conditions of temperature, after the microwave hydrothermal reaction is accomplished with product carry out suction filtration, washing to neutral and carry out obtaining back grinding, compressing tablet after the vacuum freeze drying, sieving makes 20～40 order catalyst sample CZZ7.
The activity of such catalysts of above-mentioned preparation detects carries out (stainless steel, tube inner diameter 9mm, long 340mm) on continuous fixed bed reactor.Before each reaction, catalyst all will be at 10% H
2/ N
2In the atmosphere of (volume ratio), normal pressure is reduction 8h down.Activity rating carries out under 250 ℃ the condition at 3Mpa.Loaded catalyst is 1.5g, after 150 ℃ of insulations of reacted product utilization insulating box, carries out online check and analysis with the DGC-6890 gas chromatograph, and TCD, FID detect.Utilize each components contents in the external standard method quantitative analysis tail gas.Evaluation result is seen table 1.
Table 1 catalyst activity evaluation result
| Catalyst | CO 2Conversion ratio (﹪) | Methyl alcohol selectivity (﹪) | Methanol yield (﹪) |
| CZZ1 | 22.32 | 25.24 | 5.6 |
| CZZ2 | 21.79 | 23.47 | 5.1 |
| CZZ3 | 20.64 | 22.83 | 4.7 |
| CZZ4 | 20.35 | 21.61 | 4.4 |
| CZZ5 | 21.16 | 23.82 | 5.0 |
| CZZ6 | 22.13 | 24.79 | 5.4 |
| CZZ7 | 18.94 | 19.48 | 3.7 |
Reaction condition: T=250 ℃, p=3MPa, GHSV=3000h
-1, H
2/ C=3/1 (volume ratio)
Claims (5)
1. synthesizing methanol by hydrogenating carbon dioxide Preparation of catalysts method is characterized in that preparation process comprises:
(1) configuration Cu (NO
3)
2, Zn (NO
3)
2And Zr (NO
3)
4Mixed solution makes it dissolve mixing fully;
(2) under 50～80 ℃ reaction temperature, above-mentioned drips of solution is incorporated into Na
2CO
3In the solution, the pH of adjustment solution is 7～8, after titration finishes, mixed solution is maintained continuation stirring reaction 30～60min under the reaction temperature, under reaction temperature, leaves standstill 30～120min then and makes solution aging, obtains solid sediment after the filtration;
(3) sediment after filtering in the step (2) is put into the polytetrafluoroethylsubstrate substrate agitated reactor earlier; Under microwave condition, carry out hydro-thermal reaction, after microwave hydrothermal reaction is accomplished product is carried out suction filtration, washing to neutral and carry out obtaining catalyst sample after the vacuum freeze drying.
2. according to claims 1 described synthesizing methanol by hydrogenating carbon dioxide Preparation of catalysts method, it is characterized in that: Cu (NO in the said step (1)
3)
2, Zn (NO
3)
2And Zr (NO
3)
4The mol ratio of mixed solution is 8～4:1～5:0～2, and the concentration of mixed solution is 0.1～1mol/L.
3. according to claims 1 described synthesizing methanol by hydrogenating carbon dioxide Preparation of catalysts method, it is characterized in that: the Na in the said step (2)
2CO
3The concentration of solution is 0.1～1.5mol/L.
4. according to claims 1 described synthesizing methanol by hydrogenating carbon dioxide Preparation of catalysts method, it is characterized in that: polytetrafluoroethylene (PTFE) agitated reactor filling rate is 10%～30%.
5. according to claims 1 described synthesizing methanol by hydrogenating carbon dioxide Preparation of catalysts method, it is characterized in that: microwave hydrothermal is reflected under 100～200 ℃ of conditions of temperature and heats 30～60min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100541499A CN102600851A (en) | 2012-03-05 | 2012-03-05 | Preparation method of catalyst for synthesizing methanol by carbon dioxide hydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100541499A CN102600851A (en) | 2012-03-05 | 2012-03-05 | Preparation method of catalyst for synthesizing methanol by carbon dioxide hydrogenation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102600851A true CN102600851A (en) | 2012-07-25 |
Family
ID=46518838
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100541499A Pending CN102600851A (en) | 2012-03-05 | 2012-03-05 | Preparation method of catalyst for synthesizing methanol by carbon dioxide hydrogenation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102600851A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105363436A (en) * | 2014-08-27 | 2016-03-02 | 中国石油化工股份有限公司 | Carbon monoxide gas phase coupling oxalate synthesis catalyst and preparation method and application thereof |
| CN106622252A (en) * | 2016-11-28 | 2017-05-10 | 宁夏大学 | Catalyst for production of methanol by CO2 hydrogenation |
| CN109092312A (en) * | 2018-09-19 | 2018-12-28 | 昆明理工大学 | A kind of hydro-thermal method prepares the method and application of copper-based catalysts |
| CN109621965A (en) * | 2018-12-07 | 2019-04-16 | 盐城工学院 | A kind of ZnO-ZrO of Copper-cladding Aluminum Bar2Solid solution catalyst and its preparation method and application |
| CN112121805A (en) * | 2020-09-28 | 2020-12-25 | 上海应用技术大学 | Catalyst for synthesizing methanol by carbon dioxide hydrogenation and preparation and application thereof |
| CN115722222A (en) * | 2021-08-31 | 2023-03-03 | 赤壁市高质量发展研究院有限公司 | High-surface-area amorphous zirconium oxide catalytic material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101474563A (en) * | 2009-01-13 | 2009-07-08 | 上海应用技术学院 | Preparation method of catalyst for hydrogen production from methanol-steam reforming |
| CN101584986A (en) * | 2009-07-04 | 2009-11-25 | 太原理工大学 | Method for preparing methanol synthesizing catalyst |
| CN101757943A (en) * | 2009-12-25 | 2010-06-30 | 昆明理工大学 | Catalyst for synthesizing methanol by hydrogenating carbon dioxide, preparation method and application thereof |
| CN101786001A (en) * | 2010-03-12 | 2010-07-28 | 厦门大学 | Catalyst for hydrogenation of carbon dioxide to generate methanol and preparation method thereof |
| CN102145287A (en) * | 2011-02-18 | 2011-08-10 | 哈尔滨工业大学 | Catalyst for synthesizing methanol from hydrogenated carbon dioxide and preparation method of catalyst |
-
2012
- 2012-03-05 CN CN2012100541499A patent/CN102600851A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101474563A (en) * | 2009-01-13 | 2009-07-08 | 上海应用技术学院 | Preparation method of catalyst for hydrogen production from methanol-steam reforming |
| CN101584986A (en) * | 2009-07-04 | 2009-11-25 | 太原理工大学 | Method for preparing methanol synthesizing catalyst |
| CN101757943A (en) * | 2009-12-25 | 2010-06-30 | 昆明理工大学 | Catalyst for synthesizing methanol by hydrogenating carbon dioxide, preparation method and application thereof |
| CN101786001A (en) * | 2010-03-12 | 2010-07-28 | 厦门大学 | Catalyst for hydrogenation of carbon dioxide to generate methanol and preparation method thereof |
| CN102145287A (en) * | 2011-02-18 | 2011-08-10 | 哈尔滨工业大学 | Catalyst for synthesizing methanol from hydrogenated carbon dioxide and preparation method of catalyst |
Non-Patent Citations (6)
| Title |
|---|
| 刘学铭等: "水热反应及其应用", 《化学通报》, no. 04, 30 April 1982 (1982-04-30), pages 39 - 43 * |
| 张玉龙，王欢，邓景发: "真空冷冻干燥法制备CuO－ZnO－Al_2O_3合成甲醇催化剂", 《燃料化学学报》, vol. 22, no. 03, 30 September 1994 (1994-09-30), pages 258 - 263 * |
| 徐三魁等: "低压合成甲醇CuO-ZnO-ZrO_2催化剂的活性测定和红外光谱研究", 《化学世界》, no. 04, 30 April 1999 (1999-04-30), pages 207 - 210 * |
| 施尔畏等: "《水热结晶学》", 30 September 2004, article "微波水热合成技术", pages: 64-65 * |
| 李云鹏等: "《超微粒子制造与应用技术》", 30 June 1989, article "水热反应" * |
| 赵云鹏等: "CO_2加氢合成甲醇催化剂CuO-ZnO/ZrO_2的制备", 《齐齐哈尔大学学报》, vol. 22, no. 03, 31 May 2006 (2006-05-31), pages 1 - 3 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105363436A (en) * | 2014-08-27 | 2016-03-02 | 中国石油化工股份有限公司 | Carbon monoxide gas phase coupling oxalate synthesis catalyst and preparation method and application thereof |
| CN105363436B (en) * | 2014-08-27 | 2018-02-09 | 中国石油化工股份有限公司 | Carbon monoxide gas phase coupling catalyst for synthesizing oxalic ester, preparation method and its usage |
| CN106622252A (en) * | 2016-11-28 | 2017-05-10 | 宁夏大学 | Catalyst for production of methanol by CO2 hydrogenation |
| CN109092312A (en) * | 2018-09-19 | 2018-12-28 | 昆明理工大学 | A kind of hydro-thermal method prepares the method and application of copper-based catalysts |
| CN109621965A (en) * | 2018-12-07 | 2019-04-16 | 盐城工学院 | A kind of ZnO-ZrO of Copper-cladding Aluminum Bar2Solid solution catalyst and its preparation method and application |
| CN112121805A (en) * | 2020-09-28 | 2020-12-25 | 上海应用技术大学 | Catalyst for synthesizing methanol by carbon dioxide hydrogenation and preparation and application thereof |
| CN115722222A (en) * | 2021-08-31 | 2023-03-03 | 赤壁市高质量发展研究院有限公司 | High-surface-area amorphous zirconium oxide catalytic material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102600851A (en) | Preparation method of catalyst for synthesizing methanol by carbon dioxide hydrogenation | |
| CN105218289B (en) | A kind of method that unrighted acid original position hydrogenation decarboxylation prepares long chain alkane | |
| CN106179421A (en) | The preparation of sulfide catalyst and the application in lignin conversion thereof | |
| CN102746117B (en) | Method for catalytic conversion preparation of hexahydric alcohol from jerusalem artichoke as raw material | |
| CN114031480B (en) | Method for preparing amyl alcohol by hydrogenation of 2-methylfuran through platinum-based catalyst | |
| CN101579637A (en) | Method for preparing molecular sieve solid acid catalyst used for preparing ethylene by ethanol dehydration | |
| CN106824188A (en) | A kind of preparation of tungsten-based catalyst of carrying transition metal and application process | |
| CN102731258A (en) | Method for preparing low carbon polyol by internal circulating catalysis and conversion of carbohydrate | |
| CN107159217A (en) | A kind of Cu ZnO/SiO2Aeroge bimetallic catalyst and its production and use | |
| CN103962132A (en) | Activated carbon nanogold catalyst as well as preparation and application methods thereof | |
| CN105771974A (en) | Catalyst for producing hydrogen by catalyzing decomposition of formate at room temperature | |
| CN108187745A (en) | A kind of preparation method of methanation catalyst prepared by synthetic gas | |
| CN103145545B (en) | A kind of method preparing hydroxymalonic acid for glycerol catalysis oxidation | |
| CN110407779A (en) | The method for preparing 5 hydroxymethyl furfural as raw material using biomass | |
| CN106166499A (en) | A kind of method that in green solvent system, catalysis fibre element converts preparation 5 Hydroxymethylfurfural | |
| CN104119207A (en) | Method for preparation of ethylene glycol by catalytic conversion of carbohydrate | |
| CN103357427B (en) | Nano-metal/solid alkali composite catalyst, preparation method and applications | |
| CN103420788B (en) | Method of preparing small molecule alcohol from carbohydrate in two-phase solvent | |
| CN106632370B (en) | A kind of method that glucose prepares isobide | |
| CN102173977A (en) | Cu/Al2O3 catalyst and preparation method thereof as well as method for catalyzing hydrolysis of glycerol | |
| CN109734722A (en) | A kind of method that sorb dehydration of alcohols prepares isobide | |
| CN103073420A (en) | Method for catalytic esterification of -SO3H-containing metal-organic framework compound | |
| CN110252309B (en) | CuNi/SiO2Composite bimetal supported catalyst and preparation method and application thereof | |
| CN106831367A (en) | A kind of method that oxygen catalytic oxidation biomass prepare oxide-containing chemical product | |
| CN103586029B (en) | Catalyst for hydrogen production by water-phase reforming of biomass depolymerization product and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120725 |