CN102580750A - Catalyst for preparing methanol by hydrogenation of carbon dioxide and preparation method and application of catalyst - Google Patents
Catalyst for preparing methanol by hydrogenation of carbon dioxide and preparation method and application of catalyst Download PDFInfo
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- CN102580750A CN102580750A CN2012100662402A CN201210066240A CN102580750A CN 102580750 A CN102580750 A CN 102580750A CN 2012100662402 A CN2012100662402 A CN 2012100662402A CN 201210066240 A CN201210066240 A CN 201210066240A CN 102580750 A CN102580750 A CN 102580750A
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- 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 catalyst for preparing methanol by hydrogenation of carbon dioxide and a preparation method and application of the catalyst. The catalyst is prepared by adopting a parallel flow co-precipitating method, and comprises a Cu oxide and a Zn oxide which serve as main components and a Ti oxide and an Al oxide which serve as multifunctional composite carriers; and the catalyst comprises the following components in percentage by mass: 10 to 50 percent of Cu, 3 to 25 percent of Zn, 1 to 25 percent of Ti and Al, and the balance of O. The catalyst has the characteristics of high activity and stability at a low temperature under low pressure, is simple in preparation process and good in repeatability, and is an effective catalyst for preparing the methanol by hydrogenation of CO2.
Description
Technical field
The invention belongs to catalyst technical field, relate to a kind of Catalysts and its preparation method and application of hydrogenation of carbon dioxide to generate methanol.
Background technology
In organic synthesis industry, methyl alcohol is the important Organic Chemicals that is only second to alkene and aromatic hydrocarbons, can produce a series of chemical products from methyl alcohol.At present, methyl alcohol is widely used in aspects such as producing formaldehyde, acetate, methyl tertiary butyl ether(MTBE), medicine, agricultural chemicals.Simultaneously, methyl alcohol still is a kind of important clean fuel.Can directly be used for motor vehicle fuel, also can mix as vehicle fuel with gasoline, diesel oil.Along with the price of fossil fuel rises steadily and the influence of factor such as world energy sources is in short supply, methyl alcohol has very strong economy and real feasibility undoubtedly as novel alternative energy source.
On the other hand, because greenhouse effects have just progressively caused the deterioration of global climate environment, the pay attention to day by day that receives countries in the world about the reduction of discharging work and the comprehensive utilization thereof of carbon dioxide.At CO
2In the research of fully utilize, turning waste into wealth, CO
2Preparing methanol by hydrogenation is considered to fixation of C O in a short time
2One of economical and effective method of a large amount of dischargings.
CO
2The synthesizing methanol by hydrogenating catalyst is on the basis of CO synthesizing methanol by hydrogenating catalyst, to research and develop mostly.Its catalyst system comprises that mainly copper-based catalysts, noble metal are the loaded catalyst and the other types catalyst of main active component.At present, form through transformation catalyst and improve the Preparation of Catalyst mode and improve the performance of catalyst and be still the important directions that various countries' researcher is made great efforts research.
Chinese patent CN1329938A relates to a kind of preparation method of catalst for synthesis of methanol, and this catalyst is by CuO, ZnO, Al
2O
3Form, its preparation process is: catalyst masterbatch is prepared separated into two parts, and a part is processed the coprecipitate of cupric, zinc-aluminium compound with co-precipitation, and another part contains the coprecipitate of copper, zinc compound with the coprecipitation preparation.Then with the mixing of two sediments, washing, drying, roasting, moulding.
Chinese patent CN101444731A discloses a kind of CO
2The catalyst of synthesizing methanol by hydrogenating.This catalyst comprises Pd, Zn major constituent and carbon nano-tube material promoter, and each constituent mass percentage composition is Pd2%～25%, Zn55%～90%, carbon nano-tube material 6%～20%.
Chinese patent CN101513615A relates to a kind of CO
2The Catalysts and its preparation method of synthesizing methanol by hydrogenating.Each component mol ratio of this catalyst is Cu: Zn: Al: Zr: M=45: 45: 10: 5: 2 (M is MnO, CeO
2, Ag
2O, Fe
2O
3, La
2O
3).The preparation method is: 1) mixed liquor of aluminum nitrate solution and zirconium nitrate solution and carbonate solution and flow co-precipitation make the carrier precursor; 2) copper zinc M mixed nitrate and the carbonate same trade and flow co-precipitation and add 1) in, aging then, filter, dry fired catalst for synthesis of methanol.
Chinese patent CN101757943A relates to a kind of CO
2The Catalysts and its preparation method of synthesizing methanol by hydrogenating.With the HZSM-5 molecular sieve make carrier, the cerium zirconium is an auxiliary agent; Prepare the Cu-Zn-Ce-Zr-HZSM-5 catalyst, the mol ratio of Cu/Zn is 2～4: 1, and the mol ratio of Ce/Zr is 1～3: 1; The Cu-Zn mass content is 30%～70%, and the mass content of HZSM-5 is 5%～50%.
At present, the CO that has reported
2The hydrogenation preparing catalyst for methanol is mainly the Cu-Zn catalyst series, and mainly selecting carrier for use is Al
2O
3, TiO
2, SiO
2Deng, the preparation method is main with dipping or co-precipitation, the subject matter that catalyst exists is CO
2Conversion ratio low, the methyl alcohol selectivity is relatively poor, catalyst performance is not satisfactory.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of Catalysts and its preparation method and application of hydrogenation of carbon dioxide to generate methanol, and this catalyst has higher CO
2Conversion ratio and methyl alcohol selectivity.
The catalyst of described hydrogenation of carbon dioxide to generate methanol comprises principal component Cu oxide, Zn oxide and multi-functional complex carrier Ti oxide, Al oxide.In mass percent, Cu content is 10～50%, and Zn content is 3～25%, Ti and Al total content are 1%～25%, and surplus is O.Wherein, multifunctional carrier Ti oxide, Al oxide exist with nanometer particle or amorphous mode.
The catalyst of described hydrogenation of carbon dioxide to generate methanol adopts and the stream coprecipitation makes, and the preparation method is following:
1) titanium source (as: titanyl sulfate or butyl titanate) carried out preliminary treatment through heating, ultrasonic, microwave, the carrier precursor of solution state;
2) with mixture (as: copper nitrate, zinc nitrate, the aluminum nitrate of the soluble-salt solution of copper, zinc, aluminium; Copper chloride, zinc chloride, aluminium chloride) (the shallow lake agent is for making the material of copper in the solution, zinc, aluminum metal element deposition with precipitating reagent; Including but not limited to sodium carbonate, NaOH) solution is under stirring condition; Add in the carrier precursor in 30～90 ℃ and stream, control pH value of solution value is between 7～10;
3) after precipitation reaction finishes, continue to stir 2h, the deposition dope filtration that will obtain then, 80-120 ℃ of following dried overnight at 350 ℃～550 ℃ following roasting 2h, pulverized and processed 20～40 orders, promptly gets, and be subsequent use.
The above-mentioned catalyst applications that makes in hydrogenation of carbon dioxide to generate methanol, is reacted 160～250 ℃ of reaction temperatures, GHSV (Gas Hour Space Velocity, volume space velocity) 3000h on pressurization static bed continuous flow reactor
-1～10000h
-1, V (H
2): V (CO
2)=2-6: 1, reaction pressure 2-6MPa.
Reaction result shows: catalyst of the present invention is owing to adopt special preparation method, thereby makes its catalytic activity high and stable, CO
2The selectivity of conversion ratio and product methyl alcohol can be reacted under lower temperature and pressure also apparently higher than existing similar catalyst, meets energy conservation and consumption reduction effects; Catalyst preparation process is simple simultaneously, good reproducibility.
Description of drawings
Fig. 1 is the XRD figure of catalyst of the present invention, wherein 1～8 be respectively embodiment 1～8 catalyst XRD figure.
The specific embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described in further detail, but said embodiment does not limit protection scope of the present invention.
With titanyl sulfate (TiOSO
4) 3.5g pours in the 100ml deionized water, at 70 ℃ of heating 20min down, is placed on 5min in the ultrasonic wave, and it is dissolved fully; Place micro-wave oven to handle 1min this solution, give over to mother liquor.
Get copper nitrate (Cu (NO
3)
23H
2O) 7.5g, zinc nitrate (Zn (NO
3)
26H
2O) 18.9g and aluminum nitrate 17g are dissolved in the 400ml deionized water, and the mixed solution that makes is designated as A liquid.With sodium carbonate (Na
2CO
3) 26g is dissolved in the deionized water of 400ml, solution is designated as B liquid.Under 50 ℃ of control temperature and pH=7 condition, A liquid and B liquid are also flowed in the adding mother liquor, and fully stir with mechanical agitator.
Deposition finishes continued and stirs aging 2h; It is neutral that the liquid that filtration is flowed out until the Buchner funnel lower end is; Then with filter cake 120 ℃ of following dried overnight, place 350 ℃ of following roastings to obtain metal oxide powder in 2 hours at last, promptly get catalyst of the present invention; Be crushed to 20 orders～40 order particles behind the compression molding, preserve subsequent use.
With titanyl sulfate (TiOSO
4) 7g pours in the 100ml deionized water, at 70 ℃ of heating 20min down, is placed on 5min in the ultrasonic wave, and it is dissolved fully; Place micro-wave oven to handle 1min this solution, give over to mother liquor.
Get copper nitrate (Cu (NO
3)
23H
2O) 30g, zinc nitrate (Zn (NO
3)
26H
2O) 11g and aluminum nitrate 17g are dissolved in the 400ml deionized water, and the mixed solution that makes is designated as A liquid.With sodium carbonate (Na
2CO
3) 40g is dissolved in the deionized water of 400ml, solution is designated as B liquid.Under 70 ℃ of control temperature and pH=8 condition, A liquid and B liquid are also flowed in the adding mother liquor, and fully stir with mechanical agitator.
Deposition finishes continued and stirs aging 2h; It is neutral that the liquid that filtration is flowed out until the Buchner funnel lower end is; Then with filter cake 120 ℃ of following dried overnight, place 450 ℃ of following roastings to obtain metal oxide powder in 2 hours at last, promptly get catalyst of the present invention; Be crushed to 20 orders～40 order particles behind the compression molding, preserve subsequent use.
With titanyl sulfate (TiOSO
4) 3.5g pours in the 100ml deionized water, at 70 ℃ of heating 20min down, is placed on 5min in the ultrasonic wave, and it is dissolved fully; Place micro-wave oven to handle 1min this solution, give over to mother liquor.
Get copper nitrate (Cu (NO
3)
23H
2O) 30g, zinc nitrate (Zn (NO
3)
26H
2O) 18.9g and aluminum nitrate 3g are dissolved in the 400ml deionized water, and the mixed solution that makes is designated as A liquid.With sodium carbonate (Na
2CO
3) 28g is dissolved in the deionized water of 400ml, solution is designated as B liquid.Under 50 ℃ of control temperature and pH=9 condition, A liquid and B liquid are also flowed in the adding mother liquor, and fully stir with mechanical agitator.
Deposition finishes continued and stirs aging 2h; It is neutral that the liquid that filtration is flowed out until the Buchner funnel lower end is; Then with filter cake 120 ℃ of following dried overnight, place 550 ℃ of following roastings to obtain metal oxide powder in 2 hours at last, promptly get catalyst of the present invention; Be crushed to 20 orders～40 order particles behind the compression molding, preserve subsequent use.
With titanyl sulfate (TiOSO
4) 11g pours in the 100ml deionized water, at 70 ℃ of heating 20min down, is placed on 5min in the ultrasonic wave, and it is dissolved fully; Place micro-wave oven to handle 1min this solution, give over to mother liquor.
Get copper nitrate (Cu (NO
3)
23H
2O) 38g, zinc nitrate (Zn (NO
3)
26H
2O) 2.3g and aluminum nitrate 1.3g are dissolved in the 400ml deionized water, and the mixed solution that makes is designated as A liquid.With sodium carbonate (Na
2CO
3) 28g is dissolved in the deionized water of 400ml, solution is designated as B liquid.Under 30 ℃ of control temperature and pH=10 condition, A liquid and B liquid are also flowed in the adding mother liquor, and fully stir with mechanical agitator.
Deposition finishes continued and stirs aging 2h; It is neutral that the liquid that filtration is flowed out until the Buchner funnel lower end is; Then with filter cake 120 ℃ of following dried overnight, place 350 ℃ of following roastings to obtain metal oxide powder in 2 hours at last, promptly get catalyst of the present invention; Be crushed to 20 orders～40 order particles behind the compression molding, preserve subsequent use.
Butyl titanate 8.5g is poured in the 50ml absolute ethyl alcohol, stir, the solution clarification does not have muddy, in ultrasonic wave, handles 5min, gives over to mother liquor.
Get copper nitrate (Cu (NO
3)
23H
2O) 7.5g, zinc nitrate (Zn (NO
3)
26H
2O) 18.9g and aluminum nitrate 17g are dissolved in the 400ml deionized water, and the mixed solution that makes is designated as A liquid.With sodium carbonate (Na
2CO
3) 26g is dissolved in the deionized water of 400ml, solution is designated as B liquid.Under 50 ℃ of control temperature and pH=7 condition, A liquid and B liquid are also flowed in the adding mother liquor, and fully stir with mechanical agitator.
Deposition finishes continued and stirs aging 2h; It is neutral that the liquid that filtration is flowed out until the Buchner funnel lower end is; Then with filter cake 120 ℃ of following dried overnight, place 350 ℃ of following roastings to obtain metal oxide powder in 2 hours at last, promptly get catalyst of the present invention; Be crushed to 20 orders～40 order particles behind the compression molding, preserve subsequent use.
Butyl titanate 17g is poured in the 50ml absolute ethyl alcohol, stir, the solution clarification does not have muddy, in ultrasonic wave, handles 5min, gives over to mother liquor.
Get copper nitrate (Cu (NO
3)
23H
2O) 30g, zinc nitrate (Zn (NO
3)
26H
2O) 11g and aluminum nitrate 17g are dissolved in the 400ml deionized water, and the mixed solution that makes is designated as A liquid.With sodium carbonate (Na
2CO
3) 40g is dissolved in the deionized water of 400ml, solution is designated as B liquid.Under 70 ℃ of control temperature and pH=8 condition, A liquid and B liquid are also flowed in the adding mother liquor, and fully stir with mechanical agitator.
Deposition finishes continued and stirs aging 2h; It is neutral that the liquid that filtration is flowed out until the Buchner funnel lower end is; Then with filter cake 120 ℃ of following dried overnight, place 450 ℃ of following roastings to obtain metal oxide powder in 2 hours at last, promptly get catalyst of the present invention; Be crushed to 20 orders～40 order particles behind the compression molding, preserve subsequent use.
Butyl titanate 8.5g is poured in the 50ml absolute ethyl alcohol, stir, the solution clarification does not have muddy, in ultrasonic wave, handles 5min, gives over to mother liquor.
Get copper nitrate (Cu (NO
3)
23H
2O) 30g, zinc nitrate (Zn (NO
3)
26H
2O) 18.9g and aluminum nitrate 3g are dissolved in the 400ml deionized water, and the mixed solution that makes is designated as A liquid.With sodium carbonate (Na
2CO
3) 28g is dissolved in the deionized water of 400ml, solution is designated as B liquid.Under 50 ℃ of control temperature and pH=9 condition, A liquid and B liquid are also flowed in the adding mother liquor, and fully stir with mechanical agitator.
Deposition finishes continued and stirs aging 2h; It is neutral that the liquid that filtration is flowed out until the Buchner funnel lower end is; Then with filter cake 120 ℃ of following dried overnight, place 550 ℃ of following roastings to obtain metal oxide powder in 2 hours at last, promptly get catalyst of the present invention; Be crushed to 20 orders～40 order particles behind the compression molding, preserve subsequent use.
Butyl titanate 25.5g is poured in the 50ml absolute ethyl alcohol, stir, the solution clarification does not have muddy, in ultrasonic wave, handles 5min, gives over to mother liquor.
Get copper nitrate (Cu (NO
3)
23H
2O) 38g, zinc nitrate (Zn (NO
3)
26H
2O) 2.3g and aluminum nitrate 1.3g are dissolved in the 400ml deionized water, and the mixed solution that makes is designated as A liquid.With sodium carbonate (Na
2CO
3) 28g is dissolved in the deionized water of 400ml, solution is designated as B liquid.Under 30 ℃ of control temperature and pH=10 condition, A liquid and B liquid are also flowed in the adding mother liquor, and fully stir with mechanical agitator.
Deposition finishes continued and stirs aging 2h; It is neutral that the liquid that filtration is flowed out until the Buchner funnel lower end is; Then with filter cake 120 ℃ of following dried overnight, place 350 ℃ of following roastings to obtain metal oxide powder in 2 hours at last, promptly get catalyst of the present invention; Be crushed to 20 orders～40 order particles behind the compression molding, preserve subsequent use.
Catalyst XRD characterizes: referring to Fig. 1, the result shows that the oxide of no crystalline state Ti, Al in the catalyst of the present invention exists.Be that complex carrier Ti in the catalyst of the present invention, Al oxide exist with nano particle or amorphous form.
Embodiment 9
The catalyst that usefulness pressurization continuous flow fixed bed reactor evaluation the foregoing description 1～8 makes is at CO
2Catalytic performance in the preparing methanol by hydrogenation reaction.
Evaluation method: catalyst powder is broken to 20 orders～40 orders, and amount of fill is 5.0g.Use earlier content 5%-H
2And 90%-N
2Under normal pressure, carry out temperature programmed reduction, reduction temperature progressively even 230 ℃, reductase 12 hour under this temperature.Feed CO after reducing to reaction temperature then
275%, H
225% unstripped gas carries out its reactivity evaluation.With gas chromatograph analytical reactions tail gas, calculate CO
2Conversion ratio and methyl alcohol selectivity, experimental result is as shown in table 1 below.
Table 1
| Embodiment | Reaction temperature/℃ | Reaction pressure MPa | GHSV/h -1 | V(H 2/CO 2) | CO 2Conversion ratio/% | Methyl alcohol selectivity/% |
| 1 | 210 | 3 | 3000 | 3 | 15.2 | 70.9 |
| 2 | 170 | 3 | 5000 | 6 | 9.2 | 77.5 |
| 3 | 190 | 2 | 10000 | 3 | 10.1 | 69 |
| 3 | 210 | 6 | 5000 | 3 | 21 | 60.4 |
| 4 | 200 | 3 | 3000 | 3 | 18.7 | 53 |
| 5 | 230 | 3 | 3000 | 3 | 19.6 | 69.3 |
| 6 | 170 | 6 | 5000 | 6 | 6.2 | 88 |
| 6 | 210 | 3 | 3000 | 3 | 20.8 | 57.3 |
| 7 | 210 | 2 | 3000 | 3 | 22.9 | 64.8 |
| 8 | 200 | 3 | 5000 | 3 | 12.34 | 59.06 |
Should be noted that at last; Above embodiment is only unrestricted in order to technical scheme of the present invention to be described; Although with reference to preferred embodiment the present invention is specified, those of ordinary skill in the art should be appreciated that and can make amendment or be equal to replacement the technical scheme of invention; And not breaking away from the spirit and the scope of technical scheme of the present invention, it all should be encompassed in the claim scope of the present invention.
Claims (8)
1. the catalyst of a hydrogenation of carbon dioxide to generate methanol comprises principal component Cu oxide, Zn oxide and multifunctional carrier Ti oxide, Al oxide; In mass percent, Cu content is 10～50%, and Zn content is 3～25%, and Ti, Al total content are 1%～25%, and surplus is O.
2. the catalyst of carbon dioxide system methyl alcohol according to claim 1 is characterized in that, multifunctional carrier Ti oxide, Al oxide exist with nanometer particle or amorphous mode.
3. the Preparation of catalysts method of the described hydrogenation of carbon dioxide to generate methanol of claim 1 adopts and flows coprecipitation to make, and may further comprise the steps:
1) preliminary treatment is carried out through heating, ultrasonic, microwave in the titanium source, the carrier precursor of solution state;
2) with the mixture of the soluble-salt solution of copper, zinc, aluminium and precipitant solution under stirring condition, in 30-90 ℃ down and stream add in the carrier precursor, control pH value of solution value is between 7～10;
3) after reaction finishes, continue to wear out, filter the deposition slurries that obtain, dried overnight, roasting promptly gets.
4. the Preparation of catalysts method of hydrogenation of carbon dioxide to generate methanol according to claim 3 is characterized in that, said titanium source is titanyl sulfate or titanate esters.
5. the Preparation of catalysts method of hydrogenation of carbon dioxide to generate methanol according to claim 3 is characterized in that, precipitating reagent is for making the material of copper in the solution, zinc, aluminum metal element deposition.
6. the Preparation of catalysts method of hydrogenation of carbon dioxide to generate methanol according to claim 3 is characterized in that, baking temperature is 80～120 ℃.
7. the Preparation of catalysts method of hydrogenation of carbon dioxide to generate methanol according to claim 3 is characterized in that, sintering temperature is 350 ℃～550 ℃, and roasting time is 1～5h.
8. the method for a hydrogenation of carbon dioxide to generate methanol is characterized in that, adopts the described catalyst of claim 1, on pressurization static bed continuous flow reactor, reacts 160～250 ℃ of reaction temperatures, GHSV=3000h
-1～10000h
-1, V (H
2): V (CO
2)=2-6: 1, reaction pressure 2-6MPa.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102658151A (en) * | 2012-04-28 | 2012-09-12 | 上海华谊（集团）公司 | Preparation method of methanol catalyst master body by carbon dioxide (CO2) hydrogenation |
| CN106622252A (en) * | 2016-11-28 | 2017-05-10 | 宁夏大学 | Catalyst for production of methanol by CO2 hydrogenation |
| CN108794298A (en) * | 2018-06-29 | 2018-11-13 | 厦门大学 | A kind of method of low-temp synthesis of methanol |
| CN109420485A (en) * | 2017-08-29 | 2019-03-05 | 中国科学院大连化学物理研究所 | CdO-TiO for hydrogenation of carbon dioxide methanol2Catalyst and preparation and application |
| CN113842914A (en) * | 2021-10-29 | 2021-12-28 | 中国华能集团清洁能源技术研究院有限公司 | Catalyst for synthesizing methanol from carbon dioxide, and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102302934A (en) * | 2011-05-12 | 2012-01-04 | 大连理工大学 | Novel auxiliary-modified catalyst for preparing methanol by catalytic hydrogenation of carbon dioxide and preparation method of catalyst |
-
2012
- 2012-03-14 CN CN2012100662402A patent/CN102580750A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102302934A (en) * | 2011-05-12 | 2012-01-04 | 大连理工大学 | Novel auxiliary-modified catalyst for preparing methanol by catalytic hydrogenation of carbon dioxide and preparation method of catalyst |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102658151A (en) * | 2012-04-28 | 2012-09-12 | 上海华谊（集团）公司 | Preparation method of methanol catalyst master body by carbon dioxide (CO2) hydrogenation |
| CN106622252A (en) * | 2016-11-28 | 2017-05-10 | 宁夏大学 | Catalyst for production of methanol by CO2 hydrogenation |
| CN109420485A (en) * | 2017-08-29 | 2019-03-05 | 中国科学院大连化学物理研究所 | CdO-TiO for hydrogenation of carbon dioxide methanol2Catalyst and preparation and application |
| CN109420485B (en) * | 2017-08-29 | 2021-09-21 | 中国科学院大连化学物理研究所 | CdO-TiO for preparing methanol by carbon dioxide hydrogenation2Catalyst, preparation and application |
| CN108794298A (en) * | 2018-06-29 | 2018-11-13 | 厦门大学 | A kind of method of low-temp synthesis of methanol |
| CN108794298B (en) * | 2018-06-29 | 2020-12-25 | 厦门大学 | Method for synthesizing methanol at low temperature |
| CN113842914A (en) * | 2021-10-29 | 2021-12-28 | 中国华能集团清洁能源技术研究院有限公司 | Catalyst for synthesizing methanol from carbon dioxide, and preparation method and application thereof |
| WO2023071244A1 (en) * | 2021-10-29 | 2023-05-04 | 中国华能集团清洁能源技术研究院有限公司 | Catalyst for synthesizing carbon dioxide into methanol, preparation method therefor, and use thereof |
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Application publication date: 20120718 |