CN102500381A - Preparation method of catalyst of carbon dioxide hydrogenation methanol synthesis - Google Patents
Preparation method of catalyst of carbon dioxide hydrogenation methanol synthesis Download PDFInfo
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- CN102500381A CN102500381A CN2011103397480A CN201110339748A CN102500381A CN 102500381 A CN102500381 A CN 102500381A CN 2011103397480 A CN2011103397480 A CN 2011103397480A CN 201110339748 A CN201110339748 A CN 201110339748A CN 102500381 A CN102500381 A CN 102500381A
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 25
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000003786 synthesis reaction Methods 0.000 title abstract description 10
- 230000015572 biosynthetic process Effects 0.000 title abstract description 9
- 238000005984 hydrogenation reaction Methods 0.000 title abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000007787 solid Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000002270 dispersing agent Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 38
- 239000013049 sediment Substances 0.000 claims description 27
- 239000011259 mixed solution Substances 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 17
- 230000002194 synthesizing effect Effects 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 10
- 206010013786 Dry skin Diseases 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000004448 titration Methods 0.000 claims description 9
- 238000000975 co-precipitation Methods 0.000 abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 239000002244 precipitate Substances 0.000 abstract 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 abstract 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract 1
- 235000017550 sodium carbonate Nutrition 0.000 abstract 1
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 abstract 1
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Inorganic materials [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 abstract 1
- LBVWQMVSUSYKGQ-UHFFFAOYSA-J zirconium(4+) tetranitrite Chemical compound [Zr+4].[O-]N=O.[O-]N=O.[O-]N=O.[O-]N=O LBVWQMVSUSYKGQ-UHFFFAOYSA-J 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 11
- 239000011701 zinc Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000005469 granulation Methods 0.000 description 8
- 230000003179 granulation Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 102000040350 B family Human genes 0.000 description 4
- 108091072128 B family Proteins 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- -1 copper zinc-aluminium Chemical compound 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000001147 anti-toxic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000003407 synthetizing effect Effects 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003752 zinc compounds Chemical class 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of catalyst of carbon dioxide hydrogenation methanol synthesis, which belongs to the technical field of preparation of catalyst. The preparation method includes adding dispersing agent in Cu(NO3)2, Zn(NO3)2 and Zr(NO3)4 so as to prepare mixed liquor, then titrating the mixed liquor into Na2CO3 liquor, adjusting the pH (potential of hydrogen) of the liquor to range from 7 to 8, allowing the liquor to stand after sufficient reaction so that the liquor is aged to obtain solid precipitate, and roasting the solid precipitate to obtain methanol catalyst after the roasted solid precipitate is cooled naturally. On the basis of preparing catalyst by a coprecipitation method, the dispersing agent is added so as to prepare the methanol catalyst. The preparation method has the advantages that the preparation method is simple in technological process and easy to realize industrialization, carbon dioxide conversion rate and methanol selectivity of products are high, and the like. The obtained catalyst is applicable to carbon dioxide hydrogenation catalytic reaction under medium and low pressure.
Description
Technical field
The present invention relates to a kind of method of catalst for synthesis of methanol, especially the preparation method of used catalyst for methanol in the hydrogenation of carbon dioxide low pressure methanol synthesis belongs to catalyst preparation technical field.
Background technology
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 change of energy resource structure, methyl alcohol will brought into play very important effect in Future Society.
The low pressure methanol synthesis copper-based catalysts that the sixties in 20th century, the development of Britain ICI company was released has promoted developing rapidly of methanol industry.In, the low-pressure vapor phase methanol synthetizing technology is the general technology that at present prepares methyl alcohol in the world and adopted, the catalyst that it adopted be copper zinc-aluminium mixed oxide basically, owing to the composition of catalyst is different with the preparation method, activity of such catalysts differs greatly.At present methanol synthesis catalyst have that antitoxin performance is bad, heat endurance and problem such as the bad mechanical strength activity is low, hear resistance is not high, each active component is disperseed inhomogeneous, easy sintering and service life is short.
In order to overcome the above problems, further improve catalyst activity, the improvement research to methanol synthesis catalyst at present mainly concentrates on two aspects: the one, add other compositions beyond the copper zinc-aluminium; The 2nd, the preparation method and the technology of improvement catalst for synthesis of methanol.As; Patent CN1329938 has proposed a kind of preparation process of catalyst for methanol: prepare the coprecipitate of a part of cupric zinc-aluminium compound and the coprecipitate of another part cupric zinc compound through coprecipitation, then this two parts coprecipitate mixing, washing, drying, roasting, moulding are made a kind of catalyst.Patent CN101219382 has proposed a kind of catalst for synthesis of methanol of coprecipitation preparation, and it consists of Cu/Zn/Al/M
,/ M
,,, M
,Be the metal oxide of III B family, M
,,Be IV B family or V B family or VI B family metal oxide.
Although some technology improve to some extent to improving catalyst activity, but still problem such as ubiquity complex technical process, production cost are high, active component is disperseed inadequately evenly in the gained catalyst prod, methyl alcohol selectivity and carbon dioxide conversion are not high.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing catalyst based on synthesizing methanol by hydrogenating carbon dioxide; Prepare in traditional co-precipitation method on the basis of catalyst and add dispersant; Problem such as solve in the catalyst for methanol product that active component is disperseed inadequately evenly, methyl alcohol selectivity and carbon dioxide conversion are not high improves the activity of catalyst for methanol product.
The method for preparing catalyst of synthesizing methanol by hydrogenating carbon dioxide of the present invention is: with Cu (NO
3)
2, Zn (NO
3)
2And Zr (NO
3)
4Be raw material, on the basis of coprecipitation preparation, add an amount of dispersant, the preparation catalyst for methanol.Concrete preparation method is following:
(1) be that the ratio of 8～4:1～5:0～2 takes by weighing Cu (NO in molar ratio
3)
2, Zn (NO
3)
2And Zr (NO
3)
4, add deionized water, be configured to the mixed solution that concentration is 0.1～2.0mol/L, add the dispersant of mixed liquor gross mass 2%～50% then, make it dissolve mixing fully;
(2) under reaction temperature is 50～80 ℃ condition, 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 maintained under the reaction temperature continued stirring reaction 1～2 hour, under reaction temperature, leave standstill then and made solution aging in 0.5～2 hour, obtain solid sediment;
(3) solid sediment is filtered and spends deionised water 5～8 times, then with solid sediment in 100～120 ℃ of dryings 10～24 hours, again 300～500 ℃ of following roastings 3～8 hours, cooling granulation afterwards makes 20～40 purpose catalyst naturally.
Said dispersant is polyvinylpyrrolidone (PVP) or polyethylene glycol common commercial surfactant such as (PEG).
Na in the said step (2)
2CO
3The concentration of solution is 0.1～1.5mol/L.
Adaptive adjustment can selected or do to each material proportion and technological parameter in this method according to actual needs in given range.
The method for preparing catalyst process of synthesizing methanol by hydrogenating carbon dioxide of the present invention is simple; Be easy to realize industrialization; And carbon dioxide conversion, methyl alcohol selectivity all are higher than the catalyst that common coprecipitation prepares, and the gained catalyst is applicable to the reaction of mesolow carbon dioxide hydrogenation catalyst.
The specific embodiment:
Below in conjunction with embodiment the present invention is done further elaboration, but protection scope of the present invention is not limited to said content.
Embodiment 1: synthesizing methanol by hydrogenating carbon dioxide Preparation of catalysts method step of the present invention is following:
(1) takes by weighing Cu (NO for the ratio of 5:4:1 in molar ratio
3)
2, Zn (NO
3)
2And Zr (NO
3)
4, add deionized water, be configured to the mixed solution that concentration is 1.0mol/L;
(2) under reaction temperature is 70 ℃ condition, above-mentioned drips of solution is incorporated into the Na that concentration is 0.1mol/L
2CO
3In the solution, the pH of adjustment solution is 7, after titration finishes, mixed solution is maintained under the reaction temperature continued stirring reaction 1 hour, under reaction temperature, leaves standstill then to make solution aging in 1 hour, obtains solid sediment;
(3) solid sediment is filtered and spends deionised water 5 times, then with solid sediment in 110 ℃ of dryings 12 hours, again 500 ℃ of following roastings 5 hours, cooling granulation afterwards makes 20～40 purpose catalyst Cat0 naturally.
Embodiment 2: synthesizing methanol by hydrogenating carbon dioxide Preparation of catalysts method step of the present invention is following:
(1) takes by weighing Cu (NO for the ratio of 4:5:1 in molar ratio
3)
2, Zn (NO
3)
2And Zr (NO
3)
4, add deionized water, be configured to the mixed solution that concentration is 0.1mol/L, add the polyvinylpyrrolidone (PVP) of mixed liquor gross mass 2% then, make it dissolve mixing fully;
(2) under reaction temperature was 50 ℃ condition, it was 1.0mol/L Na that above-mentioned drips of solution is incorporated into concentration
2CO
3In the solution, the pH of adjustment solution is 7.5, after titration finishes, mixed solution is maintained under the reaction temperature continued stirring reaction 1.5 hours, under reaction temperature, leaves standstill then to make solution aging in 0.5 hour, obtains solid sediment;
(3) solid sediment is filtered and spends deionised water 6 times, then with solid sediment in 100 ℃ of dryings 18 hours, again 300 ℃ of following roastings 8 hours, cooling granulation afterwards makes 20～40 purpose catalyst P P-2 naturally.
Embodiment 3: synthesizing methanol by hydrogenating carbon dioxide Preparation of catalysts method step of the present invention is following:
(1) takes by weighing Cu (NO for the ratio of 8:5:2 in molar ratio
3)
2, Zn (NO
3)
2And Zr (NO
3)
4, add deionized water, be configured to the mixed solution that concentration is 0.8mol/L, add the polyvinylpyrrolidone (PVP) of mixed liquor gross mass 25% then, make it dissolve mixing fully;
(2) under reaction temperature was 60 ℃ condition, it was 1.2mol/L Na that above-mentioned drips of solution is incorporated into concentration
2CO
3In the solution, the pH of adjustment solution is 8, after titration finishes, mixed solution is maintained under the reaction temperature continued stirring reaction 2 hours, under reaction temperature, leaves standstill then to make solution aging in 1.5 hours, obtains solid sediment;
(3) solid sediment is filtered and spends deionised water 7 times, then with solid sediment in 120 ℃ of dryings 10 hours, again 400 ℃ of following roastings 3 hours, cooling granulation afterwards makes 20～40 purpose catalyst P P-25 naturally.
Embodiment 4: synthesizing methanol by hydrogenating carbon dioxide Preparation of catalysts method step of the present invention is following:
(1) takes by weighing Cu (NO for the ratio of 6:1 in molar ratio
3)
2, Zn (NO
3)
2, add deionized water, be configured to the mixed solution that concentration is 1.5mol/L, add the polyvinylpyrrolidone (PVP) of mixed liquor gross mass 50% then, make it dissolve mixing fully;
(2) under reaction temperature was 80 ℃ condition, it was 1.5mol/L Na that above-mentioned drips of solution is incorporated into concentration
2CO
3In the solution, the pH of adjustment solution is 8, after titration finishes, mixed solution is maintained under the reaction temperature continued stirring reaction 1.7 hours, under reaction temperature, leaves standstill then to make solution aging in 0.8 hour, obtains solid sediment;
(3) solid sediment is filtered and spends deionised water 8 times, then with solid sediment in 115 ℃ of dryings 24 hours, again 350 ℃ of following roastings 6 hours, cooling granulation afterwards makes 20～40 purpose catalyst P P-50 naturally.
Embodiment 5: synthesizing methanol by hydrogenating carbon dioxide Preparation of catalysts method step of the present invention is following:
(1) takes by weighing Cu (NO for the ratio of 7:2:1.5 in molar ratio
3)
2, Zn (NO
3)
2And Zr (NO
3)
4, add deionized water, be configured to the mixed solution that concentration is 1.0mol/L, add the polyethylene glycol (PEG) of mixed liquor gross mass 2% then, make it dissolve mixing fully;
(2) under reaction temperature was 75 ℃ condition, it was 1.3mol/L Na that above-mentioned drips of solution is incorporated into concentration
2CO
3In the solution, the pH of adjustment solution is 7, after titration finishes, mixed solution is maintained under the reaction temperature continued stirring reaction 1.8 hours, under reaction temperature, leaves standstill then to make solution aging in 1 hour, obtains solid sediment;
(3) solid sediment is filtered and spends deionised water 7 times, then with solid sediment in 118 ℃ of dryings 20 hours, again 450 ℃ of following roastings 4 hours, cooling granulation afterwards makes 20～40 purpose catalyst P E-2 naturally.
Embodiment 6: synthesizing methanol by hydrogenating carbon dioxide Preparation of catalysts method step of the present invention is following:
(1) takes by weighing Cu (NO for the ratio of 8:5:2 in molar ratio
3)
2, Zn (NO
3)
2And Zr (NO
3)
4, add deionized water, be configured to the mixed solution that concentration is 2.0mol/L, add the polyethylene glycol (PEG) of mixed liquor gross mass 25% then, make it dissolve mixing fully;
(2) under reaction temperature was 65 ℃ condition, it was 1.4mol/L Na that above-mentioned drips of solution is incorporated into concentration
2CO
3In the solution, the pH of adjustment solution is 7, after titration finishes, mixed solution is maintained under the reaction temperature continued stirring reaction 1.9 hours, under reaction temperature, leaves standstill then to make solution aging in 2 hours, obtains solid sediment;
(3) solid sediment is filtered and spends deionised water 7 times, then with solid sediment in 120 ℃ of dryings 14 hours, again 500 ℃ of following roastings 7 hours, cooling granulation afterwards makes 20～40 purpose catalyst P E-25 naturally.
Embodiment 7: synthesizing methanol by hydrogenating carbon dioxide Preparation of catalysts method step of the present invention is following:
(1) takes by weighing Cu (NO for the ratio of 5:4:1 in molar ratio
3)
2, Zn (NO
3)
2And Zr (NO
3)
4, add deionized water, be configured to the mixed solution that concentration is 0.2mol/L, add the polyethylene glycol (PEG) of mixed liquor gross mass 50% then, make it dissolve mixing fully;
(2) under reaction temperature was 55 ℃ condition, it was 1.4mol/L Na that above-mentioned drips of solution is incorporated into concentration
2CO
3In the solution, the pH of adjustment solution is 7, after titration finishes, mixed solution is maintained under the reaction temperature continued stirring reaction 1.7 hours, under reaction temperature, leaves standstill then to make solution aging in 0.7 hour, obtains solid sediment;
(3) solid sediment is filtered and spends deionised water 7 times, then with solid sediment in 118 ℃ of dryings 19 hours, again 380 ℃ of following roastings 3 hours, cooling granulation afterwards makes 20～40 purpose catalyst P E-50 naturally.
Be that the catalyst for preparing among the embodiment is carried out CO at the little reactor of urging of fixed bed in the table 1
2The synthesizing methanol by hydrogenating activity rating is loaded on the 2g catalyst in the reaction tube, and logical hydrogen temperature programming to 300 ℃ is reduced, and heating rate is 1 ℃/min, and the reducing gases flow velocity is 10mL/min, and whole reduction process continues 5h.Catalyst reduction switches to reaction gas with reducing gases after finishing, and carries out activity rating.The evaluating catalyst condition is 250 ℃, 3.0MPa, and air speed is 3000h
-1, reaction gas consists of V (H
2): V (CO
2)=3:1, reaction end gas use the gas chromatograph analysis, and TCD, FID detect.Product liquid is used gas chromatographic detection after condensation and collection.
Wherein Cat0 does not add dispersant, is control group.
Table 1 catalyst activity evaluation result
| Catalyst | CO 2Conversion ratio (﹪) | Methyl alcohol selectivity (﹪) | Methanol yield (﹪) |
| Cat0 | 22.32 | 12.12 | 2.71 |
| PVP-2 | 21.79 | 19.21 | 4.18 |
| PVP-25 | 21.67 | 27.24 | 5.90 |
| PVP-50 | 20.97 | 20.61 | 4.32 |
| PE-2 | 21.15 | 25.82 | 5.46 |
| PE-25 | 22.12 | 21.48 | 4.75 |
| PE-50 | 22.34 | 17.48 | 3.91 |
Reaction condition: T=250 ℃, P=3.0MPa, air speed is 3000h
-1, V (H
2): V (CO
2)=3:1, the reaction procatalyst is with hydrogen temperature programming to 300 ℃ reduction 5h.
Claims (5)
1. the Preparation of catalysts method of a synthesizing methanol by hydrogenating carbon dioxide is characterized in that concrete preparation process is following:
(1) configuration Cu (NO
3)
2, Zn (NO
3)
2And Zr (NO
3)
4Concentration is 0.1～2.0mol/L mixed solution, adds dispersant then, 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 maintained under the reaction temperature continued stirring reaction 1～2 hour, under reaction temperature, leave standstill then and made solution aging in 0.5～2 hour, obtain solid sediment;
(3) solid sediment is filtered and spends deionised water 5～8 times, then with solid sediment in 100～120 ℃ of dryings 10～24 hours, again 300～500 ℃ of following roastings 3～8 hours, obtain catalyst sample after cooling off naturally.
2. according to the Preparation of catalysts method of claims 1 described synthesizing methanol by hydrogenating carbon dioxide, 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.
3. according to the method for preparing catalyst of claims 1 described synthesizing methanol by hydrogenating carbon dioxide, it is characterized in that: dispersant is polyvinylpyrrolidone or polyethylene glycol in the said step (1).
4. according to the method for preparing catalyst of claims 1 or 3 described synthesizing methanol by hydrogenating carbon dioxide, it is characterized in that: the addition of dispersant is 2%～50% of a mixed liquor gross mass in the said step (1).
5. according to the method for preparing catalyst of claims 1 described synthesizing methanol by hydrogenating carbon dioxide, it is characterized in that: the Na in the said step (2)
2CO
3The concentration of solution is 0.1～1.5mol/L.
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| CN104084204A (en) * | 2014-07-15 | 2014-10-08 | 厦门大学 | Carbon nano tube (CNT) promoted Cu based p-hydroxyphenethyl alcohol synthetic catalyst and preparation method thereof |
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| CN106622252A (en) * | 2016-11-28 | 2017-05-10 | 宁夏大学 | Catalyst for production of methanol by CO2 hydrogenation |
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| 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 |
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| 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 |
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| CN113368861A (en) * | 2021-06-09 | 2021-09-10 | 上海应用技术大学 | Catalyst for synthesizing methanol by carbon dioxide hydrogenation, preparation method and application thereof |
| CN114192149A (en) * | 2021-12-29 | 2022-03-18 | 上海方民科技有限公司 | Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof |
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| CN113368861A (en) * | 2021-06-09 | 2021-09-10 | 上海应用技术大学 | Catalyst for synthesizing methanol by carbon dioxide hydrogenation, preparation method and application thereof |
| CN113368861B (en) * | 2021-06-09 | 2022-12-16 | 上海应用技术大学 | Catalyst for synthesizing methanol by carbon dioxide hydrogenation and preparation method and application thereof |
| CN114192149A (en) * | 2021-12-29 | 2022-03-18 | 上海方民科技有限公司 | Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof |
| CN114192149B (en) * | 2021-12-29 | 2024-05-10 | 上海方民科技有限公司 | Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof |
| CN114669303A (en) * | 2022-03-24 | 2022-06-28 | 山东亮剑环保新材料有限公司 | Alkaline earth metal modified CO2Preparation method of hydrogenation catalyst |
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