CN102000578A - Catalyst for preparing methyl alcohol by carbon dioxide catalytic hydrogenation and preparing method thereof - Google Patents
Catalyst for preparing methyl alcohol by carbon dioxide catalytic hydrogenation and preparing method thereof Download PDFInfo
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- CN102000578A CN102000578A CN2010105021523A CN201010502152A CN102000578A CN 102000578 A CN102000578 A CN 102000578A CN 2010105021523 A CN2010105021523 A CN 2010105021523A CN 201010502152 A CN201010502152 A CN 201010502152A CN 102000578 A CN102000578 A CN 102000578A
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- carbon dioxide
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
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- 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 provides a catalyst for preparing methyl alcohol by carbon dioxide catalytic hydrogenation and a preparing method thereof, belonging to the technical field of catalysts. The catalyst is characterized in that: the catalyst for preparing the methyl alcohol by the carbon dioxide catalytic hydrogenation comprises components in mass ratio of CuO: ZnO: Al2O3: MgO being 3: 6: 1:X (wherein X is in the range of 0.001-0.2) and is prepared by a coprecipitation method. The preparing method comprises the following steps of: (1) dissolving weighed nitrate solutions of copper, zinc, aluminum and magnesium in absolute ethyl alcohol or water, dropping oxalic acid ethanol solution or oxalic acid water solution into the mixed solution, heating, and stirring to obtain the precursor of the catalyst; (2) drying the precursor of the catalyst, roasting for a period of time at certain temperature, cooling and then grinding, tabletting, crushing and sieving the precursor of the catalyst to obtain the catalyst for preparing the methyl alcohol by the carbon dioxide catalytic hydrogenation. Compared with the MgO-free catalyst with the same component mass ratio of CuO to ZnO to Al2O3, the catalyst has better activity, stability and methyl alcohol selectivity; the preparing method is simple, and has low cost and less pollution; and the catalyst is an effective catalyst for preparing the methyl alcohol by the carbon dioxide catalytic hydrogenation.
Description
Technical field
The invention belongs to catalyst technical field, relate to a kind of catalytic hydrogenation of carbon dioxide system catalyst for methanol and preparation method.
Background technology
Quickening along with industrialization development speed, the particularly fast development of petroleum chemical industry, the overproof discharging of carbon dioxide greenhouse gas, caused " greenhouse effects " and " ozone cavity " influence getting along amiably and peacefully of human and the Nature day by day, caused mondial extensive concern, Copenhagen meeting in 2009 converges to common people's sight in the discharging of greenhouse gases again.The random discharging of carbon dioxide not only causes serious environmental problem, and causes the serious waste of carbon resource.Catalytic hydrogenation of carbon dioxide, then can generate the chemical products of high added value such as methyl alcohol, methane, formic acid, dimethyl ether, ethanol etc., these products further transform, can produce gasoline and other organic polymer etc., can alleviate the situation of present resource scarcity, have chemical industry, environmental protection, the multiple meaning of economic dispatch.
Catalytic hydrogenation of carbon dioxide system methyl alcohol is the present focus of research, nineteen twenty-three in the world first methanol plant set up in BASF AG, catalyst system therefor is ZnO/Cr
2O
3, reaction condition is 300 ℃, 20MPa.That employing is maximum at present is the CuO-ZnO-Al of high activity, high selectivity
2O
3Catalyst, this catalyst just has active preferably and methyl alcohol selectivity at 200 ℃.But along with further going deep into of research, new effective catalyst and the reaction condition that more relaxes constantly present.CuO-ZnO-Al
2O
3The Preparation of catalysts technology is constantly weeded out the old and bring forth the new, the ultra-fine grain catalyst has characteristics such as higher specific surface area, high degree of dispersion, Heat stability is good, high surface energy and surface-active point are many, show the unique catalytic performance that is different from conventional material, simultaneously superfine catalyst has characteristics such as the few and methyl alcohol selectivity height of accessory substance.Carrier is selected noveltyization more, and common carrier has ZrO
2, Al
2O
3, TiO
2, active carbon (AC) etc., occurred at present with CNT (CNTs) showing higher activity, methyl alcohol selectivity and heat endurance as carrier with the catalyst of complex carrier.Research to catalytic hydrogenation of carbon dioxide system methyl alcohol copper-based catalysts at present mainly concentrates in preparation method's the further optimization and improvement, purpose is to improve activity of such catalysts, methyl alcohol selectivity and stability, is one of target of pursuing of researcher by adding performance that auxiliary agent improves catalyst.
The methanol synthesis catalyst that Chinese patent CN1660490 is related is by CuO/ZnO/Al
2O
3, mol ratio is 6/3/1, and adds the certain amount of surfactant composition, adopts coprecipitation or step-by-step precipitation method to make.
The methanol synthesis catalyst that Chinese patent CN1329938 is related, CuO/ZnO/Al
2O
3Form according to a certain ratio, different with other method on the preparation method, catalyst masterbatch preparation is divided into two parts, the one, make the co-precipitation presoma of cupric, zinc, aluminium with coprecipitation, the 2nd, adopt the coprecipitation preparation not contain copper, the zinc co-precipitation presoma of aluminium.
Surfactant that patent CN1660490 adds can not improve the absorption to carbon dioxide, the methyl alcohol selectivity improves little, patent CN1329938 is comparatively complicated on the preparation method, the present invention compares with above two kinds of patents, has not both added surfactant, needn't prepare catalyst precursor for two parts again, only needing to add co-catalyst MgO gets final product, preparation technology is simple, and environmental pollution is little, and cost is low.
Summary of the invention
The invention provides a kind of catalytic hydrogenation of carbon dioxide system catalyst for methanol and preparation method, improve the performance of catalyst by adding a kind of co-catalyst MgO, the technical problem of solution is to improve the stability of activity of such catalysts, methyl alcohol selectivity and catalyst.
Technical scheme of the present invention is:
Catalytic hydrogenation of carbon dioxide system catalyst for methanol of the present invention comprises the component of following mass fraction: CuO: ZnO: Al
2O
3: MgO=A: B: C: D, the scope of its A: B between 1/5～5/1, the scope of C between 1～10%, the scope of D between 0.1～20%, CuO:20～70% (W/W%), ZnO:20～70% (W/W%), Al
2O
3: 5～10% (W/W%), MgO:0.1～20% (W/W%).
Preparation of catalysts of the present invention adopts coprecipitation, may further comprise the steps:
Step (1): the nitrate of copper, zinc, aluminium, magnesium is dissolved in absolute ethyl alcohol or the water, obtains the mixed solution that concentration is 0.1～5mol/L, wherein the magnesia addition is controlled between 0.1～20%;
Step (2): configuration oxalic acid ethanolic solution or oxalic acid aqueous solution 0.1～3mol/L, its mesoxalic acid can be used sodium carbonate, urea, potash, wherein a kind of replacement of carbonic acid ammonia.
Step (3): with the oxalic acid ethanolic solution of step (2) or oxalic acid aqueous solution under heating and stirring condition, splash in the mixed solution of step (1), temperature is controlled at 50～80 ℃, heating, stir, reaction is evaporated fully until ethanol, if solvent is a water, reacted 4 hours, aging 1 hour, then the sediment presoma is filtered, washing, control filtrate pH value is between 7～8, with catalyst precursor 110 ℃ of following dried overnight, with temperature programming to the 350 ℃ roasting of 3.0 ℃/min 4 hours, reduce to room temperature then, grind, compressing tablet, broken, screening promptly obtains the catalyst of catalytic hydrogenation of carbon dioxide system methyl alcohol.
Effect of the present invention and benefit are the catalytic hydrogenation of carbon dioxide system catalyst for methanol of described method preparation, and activity, methyl alcohol selectivity and stability all are better than not adding the CuO-ZnO-Al in proportion of MgO auxiliary agent
2O
3Catalyst meets energy-saving and cost-reducing and environmental requirement, is applicable to that carbon dioxide and hydrogen react under lower temperature and pressure.
The specific embodiment
Be described in detail the specific embodiment of the present invention below in conjunction with technical scheme.
Embodiment 1
Take by weighing 4.55gCu (NO
3)
23H
2O, 10.95gZn (NO
3)
26H
2O, 3.68gAl (NO
3)
39H
2O, 0.64gMg (NO
3)
26H
2O is dissolved in the 100ml ethanol, and solution is designated as A liquid, takes by weighing 8.91gH
2C
2O
4H
2O is dissolved in the 50ml ethanol, solution is designated as B liquid, under 70 ℃ and stirring condition, the B drop is gone into coprecipitation reaction in the A liquid, obtain precipitated liquid (1), under 70 ℃ and stirring condition, evaporate fully until ethanol, then the catalyst precursor that obtains 110 ℃ of down oven dry 12 hours, with temperature programming to the 350 ℃ roasting of 3.0 ℃/min 4 hours, reduce to room temperature, grinding, compressing tablet, fragmentation, sieve certain particle diameter particle, promptly obtain catalytic hydrogenation of carbon dioxide system catalyst for methanol.
Embodiment 2
Take by weighing 4.55gCu (NO
3)
23H
2O, 10.95gZn (NO
3)
26H
2O, 3.68gAl (NO
3)
39H
2O, 0.64gMg (NO
3)
26H
2O is dissolved in the 100ml water, and solution is designated as A liquid, takes by weighing 8.91gH
2C
2O
4H
2O is dissolved in the 50ml water, solution is designated as B liquid, under 70 ℃ and stirring condition, the B drop is gone into coprecipitation reaction in the A liquid, obtain precipitated liquid (1), reaction is 4 hours under 70 ℃ and stirring condition, aging 1 hour, the catalyst precursor sedimentation and filtration, the washing that obtain, control filtrate pH value is dried filter cake 12 hours down at 110 ℃ between 7～8 then, with temperature programming to the 350 ℃ roasting of 3.0 ℃/min 4 hours, reduce to room temperature, grinding, compressing tablet, fragmentation, sieve certain particle diameter particle, promptly obtain catalytic hydrogenation of carbon dioxide system catalyst for methanol.
Embodiment 3
Take by weighing 4.55gCu (NO
3)
23H
2O, 10.95gZn (NO
3)
26H
2O, 3.68gAl (NO
3)
39H
2O, 0.64gMg (NO
3)
26H
2O is dissolved in the 100ml water, and solution is designated as A liquid, takes by weighing 8.22gNa
2C0
3Be dissolved in the 50ml water, solution is designated as B liquid, under 70 ℃ and stirring condition, the B drop is gone into coprecipitation reaction in the A liquid, obtain precipitated liquid (1), reaction is 4 hours under 70 ℃ and stirring condition, aging 1 hour, the catalyst precursor sedimentation and filtration, the washing that obtain, control filtrate pH value is dried filter cake 12 hours down at 110 ℃ between 7～8 then, with temperature programming to the 350 ℃ roasting of 3.0 ℃/min 4 hours, reduce to room temperature, grinding, compressing tablet, fragmentation, sieve certain particle diameter particle, promptly obtain catalytic hydrogenation of carbon dioxide system catalyst for methanol.
Embodiment 4
Take by weighing 4.55gCu (NO
3)
23H
2O, 10.95gZn (NO
3)
26H
2O, 3.68gAl (NO
3)
39H
2O, 0.64gMg (NO
3)
26H
2O is dissolved in the 100ml water, and solution is designated as A liquid, takes by weighing 11.12gK
2CO
3Be dissolved in the 50ml water, solution is designated as B liquid, under 70 ℃ and stirring condition, the B drop is gone into coprecipitation reaction in the A liquid, obtain precipitated liquid (1), reaction is 4 hours under 70 ℃ and stirring condition, aging 1 hour, the catalyst precursor sedimentation and filtration, the washing that obtain, control filtrate pH value is dried filter cake 12 hours down at 110 ℃ between 7～8 then, with temperature programming to the 350 ℃ roasting of 3.0 ℃/min 4 hours, reduce to room temperature, grinding, compressing tablet, fragmentation, sieve certain particle diameter particle, promptly obtain catalytic hydrogenation of carbon dioxide system catalyst for methanol.
Subordinate list: catalyst catalytic performance (gcat)
Catalyst: CuO-ZnO-Al
2O
3/ MgO, CuO/ZnO/Al
2O
3/ MgO=3/6/1/X (mass ratio, wherein X=0.001～0.2)
Reaction condition: T=195 ℃, P=3.2MPa, SV=3600h
-1, H
2/ CO
2=3: 1 (volume ratio) used 10%H before the reaction
2/ N
2Temperature programming to 250 ℃ reductase 12 hour.
Claims (6)
1. the catalyst of a catalytic hydrogenation of carbon dioxide system methyl alcohol and preparation method is characterized in that: the constituent mass of described catalytic hydrogenation of carbon dioxide system catalyst for methanol is than being CuO: ZnO: Al
2O
3: MgO=A: B: C: D, the scope of its A: B is between 1/5～5/1, and the scope of C is between 1～10%, and the scope of D adopts coprecipitation to make between 0.1～20%.
2. the Preparation of catalysts method of a kind of catalytic hydrogenation of carbon dioxide system methyl alcohol according to claim 1 is characterized in that Preparation of Catalyst may further comprise the steps:
Step (1): the nitrate of copper, zinc, aluminium, magnesium is dissolved in absolute ethyl alcohol or the water, obtains the mixed solution that concentration is 0.1～5mol/L, wherein the addition of MgO is controlled between 0.1～20%;
Step (2): configuration oxalic acid ethanolic solution or oxalic acid aqueous solution 0.1～3mol/L, its mesoxalic acid can be used sodium carbonate, urea, potash, wherein a kind of replacement of carbonic acid ammonia;
Step (3): with the oxalic acid ethanolic solution of step (2) or oxalic acid aqueous solution under heating and stirring condition, splash in the mixed solution of step (1), temperature is controlled at 50～80 ℃, reaction is evaporated fully until ethanol, if solvent is a water, reacted 4 hours, aging 1 hour, then the sediment presoma is filtered, washing, control filtrate pH value is between 7～8, afterwards with the residual catalyst presoma or filter catalyst precursor put into oven drying and spend the night, with temperature programming to the 350 ℃ roasting of 3.0 ℃/min 4 hours, reduce to room temperature then, grind, compressing tablet, broken, screening promptly obtains catalytic hydrogenation of carbon dioxide system catalyst for methanol.
3. the catalyst of a kind of catalytic hydrogenation of carbon dioxide system methyl alcohol according to claim 1 is characterized in that described catalytic hydrogenation of carbon dioxide catalst for synthesis of methanol also comprises co-catalyst MgO, and its quality percentage composition is 0.1～20%.
4. the Preparation of catalysts method of a kind of catalytic hydrogenation of carbon dioxide system methyl alcohol according to claim 2 is characterized in that described carrier precipitation agent is aluminum nitrate/magnesium nitrate mixed solution 0.1～0.2mol/L.
5. the Preparation of catalysts method of a kind of catalytic hydrogenation of carbon dioxide system methyl alcohol according to claim 2 is characterized in that described precipitating reagent is that oxalic acid or sodium carbonate, potash, urea, carbonic acid ammonia are wherein a kind of.
6. the Preparation of catalysts method of a kind of catalytic hydrogenation of carbon dioxide system methyl alcohol according to claim 2, it is characterized in that 50～80 ℃ of co-precipitation, it is intact to continue to be stirred to ethanol evaporation after titration finishes, catalyst precursor 110 ℃ dry 12 hours down, with temperature programming to the 350 ℃ roasting of 3.0 ℃/min 4 hours.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105021523A CN102000578A (en) | 2010-09-29 | 2010-09-29 | Catalyst for preparing methyl alcohol by carbon dioxide catalytic hydrogenation and preparing method thereof |
| PCT/CN2010/079556 WO2012040977A1 (en) | 2010-09-29 | 2010-12-08 | Catalyst for catalytically hydrogenating co2 to methanol and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105021523A CN102000578A (en) | 2010-09-29 | 2010-09-29 | Catalyst for preparing methyl alcohol by carbon dioxide catalytic hydrogenation and preparing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102000578A true CN102000578A (en) | 2011-04-06 |
Family
ID=43808430
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105021523A Pending CN102000578A (en) | 2010-09-29 | 2010-09-29 | Catalyst for preparing methyl alcohol by carbon dioxide catalytic hydrogenation and preparing method thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN102000578A (en) |
| WO (1) | WO2012040977A1 (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102489340A (en) * | 2011-12-02 | 2012-06-13 | 北京化工大学 | Method for preparing catalyst used for one-carbon chemical reactions through coprecipitation |
| WO2012151776A1 (en) * | 2011-05-12 | 2012-11-15 | 大连理工大学 | Modified catalyst for producing methanol by catalytic hydrogenation of carbon dioxide and method for preparing same |
| CN103769158A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN106179356A (en) * | 2015-05-07 | 2016-12-07 | 中国石油化工股份有限公司 | A kind of for CO2cuZnAl catalyst of preparing methanol by hydrogenation and preparation method thereof |
| WO2017182893A1 (en) * | 2016-04-21 | 2017-10-26 | Sabic Global Technologies B.V. | Catalysts and methods for methanol synthesis from direct hydrogenation of syngas and/or carbon dioxide |
| CN109289854A (en) * | 2018-11-01 | 2019-02-01 | 四川天科技股份有限公司 | A kind of high stability high intensity catalst for synthesis of methanol and preparation method thereof |
| CN109529851A (en) * | 2018-12-26 | 2019-03-29 | 大连海事大学 | A kind of Supported Nickel Catalyst and utilize its plasma-catalytic CO2Preparing methanol by hydrogenation method |
| CN110681383A (en) * | 2018-07-06 | 2020-01-14 | 中国石油化工股份有限公司 | Multi-component methanol synthesis catalyst and preparation method thereof |
| CN111054324A (en) * | 2020-02-25 | 2020-04-24 | 贵州大学 | MnZnOx solid solution structure catalyst and preparation method thereof |
| CN111167518A (en) * | 2020-01-06 | 2020-05-19 | 上海应用技术大学 | Catalyst CuZn/UiO-66 for synthesizing methanol by carbon dioxide hydrogenation and preparation method thereof |
| CN112430472A (en) * | 2020-11-06 | 2021-03-02 | 武汉大学 | CO (carbon monoxide)2Method for directly preparing low-carbon alcohol and co-producing gasoline by hydrogenation |
| CN114029063A (en) * | 2021-12-16 | 2022-02-11 | 厦门大学 | Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof |
| EP4159710A2 (en) | 2021-10-01 | 2023-04-05 | Indian Oil Corporation Limited | Integrated process and cu/zn-based catalyst for synthesizing methanol utilizing co2, generating electricity from hydrocarbon feedstock |
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|---|---|---|---|---|
| CN110327933B (en) * | 2019-07-25 | 2022-09-20 | 甄崇礼 | Catalyst for preparing methanol by carbon dioxide hydrogenation, preparation method and application thereof |
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Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012151776A1 (en) * | 2011-05-12 | 2012-11-15 | 大连理工大学 | Modified catalyst for producing methanol by catalytic hydrogenation of carbon dioxide and method for preparing same |
| CN102489340A (en) * | 2011-12-02 | 2012-06-13 | 北京化工大学 | Method for preparing catalyst used for one-carbon chemical reactions through coprecipitation |
| WO2013078872A1 (en) * | 2011-12-02 | 2013-06-06 | 北京化工大学 | Method for preparing a catalyst used for one-carbon chemical reactions through coprecipitation |
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| CN103769158A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN103769158B (en) * | 2012-10-24 | 2015-10-21 | 中国石油化工股份有限公司 | The preparation method of hydrogenation catalyst |
| CN106179356B (en) * | 2015-05-07 | 2019-02-22 | 中国石油化工股份有限公司 | One kind being used for CO2CuZnAl catalyst of preparing methanol by hydrogenation and preparation method thereof |
| CN106179356A (en) * | 2015-05-07 | 2016-12-07 | 中国石油化工股份有限公司 | A kind of for CO2cuZnAl catalyst of preparing methanol by hydrogenation and preparation method thereof |
| CN109310995A (en) * | 2016-04-21 | 2019-02-05 | 沙特基础全球技术有限公司 | For the Catalyst And Method by synthesis gas and/or synthesizing methanol by direct hydrogenation of carbon dioxide |
| WO2017182893A1 (en) * | 2016-04-21 | 2017-10-26 | Sabic Global Technologies B.V. | Catalysts and methods for methanol synthesis from direct hydrogenation of syngas and/or carbon dioxide |
| CN110681383A (en) * | 2018-07-06 | 2020-01-14 | 中国石油化工股份有限公司 | Multi-component methanol synthesis catalyst and preparation method thereof |
| CN109289854A (en) * | 2018-11-01 | 2019-02-01 | 四川天科技股份有限公司 | A kind of high stability high intensity catalst for synthesis of methanol and preparation method thereof |
| CN109289854B (en) * | 2018-11-01 | 2020-10-27 | 西南化工研究设计院有限公司 | High-stability high-strength methanol synthesis catalyst and preparation method thereof |
| CN109529851B (en) * | 2018-12-26 | 2021-10-01 | 大连海事大学 | Nickel-based supported catalyst and method for catalyzing CO by using plasma of nickel-based supported catalyst2Method for preparing methanol by hydrogenation |
| CN109529851A (en) * | 2018-12-26 | 2019-03-29 | 大连海事大学 | A kind of Supported Nickel Catalyst and utilize its plasma-catalytic CO2Preparing methanol by hydrogenation method |
| CN111167518A (en) * | 2020-01-06 | 2020-05-19 | 上海应用技术大学 | Catalyst CuZn/UiO-66 for synthesizing methanol by carbon dioxide hydrogenation and preparation method thereof |
| CN111054324A (en) * | 2020-02-25 | 2020-04-24 | 贵州大学 | MnZnOx solid solution structure catalyst and preparation method thereof |
| CN112430472A (en) * | 2020-11-06 | 2021-03-02 | 武汉大学 | CO (carbon monoxide)2Method for directly preparing low-carbon alcohol and co-producing gasoline by hydrogenation |
| EP4159710A2 (en) | 2021-10-01 | 2023-04-05 | Indian Oil Corporation Limited | Integrated process and cu/zn-based catalyst for synthesizing methanol utilizing co2, generating electricity from hydrocarbon feedstock |
| US11773039B2 (en) | 2021-10-01 | 2023-10-03 | Indian Oil Corporation Limited | Integrated process and Cu/Zn-based catalyst for synthesizing methanol utilizing CO2, generating electricity from hydrocarbon feedstock |
| CN114029063A (en) * | 2021-12-16 | 2022-02-11 | 厦门大学 | Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof |
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