CN101722002A - Composite catalyst used for synthesizing dimethyl ether with carbon dioxide and preparation method and application thereof - Google Patents
Composite catalyst used for synthesizing dimethyl ether with carbon dioxide and preparation method and application thereof Download PDFInfo
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- CN101722002A CN101722002A CN200810223936A CN200810223936A CN101722002A CN 101722002 A CN101722002 A CN 101722002A CN 200810223936 A CN200810223936 A CN 200810223936A CN 200810223936 A CN200810223936 A CN 200810223936A CN 101722002 A CN101722002 A CN 101722002A
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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 relates to a composite catalyst used for synthesizing dimethyl ether with carbon dioxide and a preparation method and an application thereof. The composite catalyst is a mixed granular catalyst which is prepared by mixing the methanol synthesis catalyst and the methanol conversion catalyst, wherein the methanol synthesis catalyst is a CuO-ZnO-ZrO2 composite oxide catalyst, and the methanol conversion catalyst is a solid acid catalyst, namely molecular sieve or alumina. The invention has the advantages that the preparation method of the catalyst is easy, the selectivity of the catalyst to DME is high (76.2%), the selectivity of the catalyst to carbon monoxide and methanol is low (23.7% and 0.1%), and the carbon dioxide resistance and water resistance are high. The composite catalyst of the invention is used for synthesizing dimethyl ether with carbon dioxide and hydrogen.
Description
Technical field
The present invention relates to a kind of organic compound and preparation method thereof, specifically, relate to a kind of catalyst, preparation method and application thereof that is used for by coal, carbon dioxide and Hydrogen Preparation dimethyl ether (DME).
Background technology
As everyone knows, dimethyl ether claims wooden ether, methyl ether again, is a kind of colourless gas with slight ether flavor at normal temperatures and pressures, has similar physical property to oil liquefied gas.Dimethyl ether is the important intermediate of carbon one chemical industry, simultaneously as a kind of emerging basic chemical raw materials, because good characteristics such as easy compression, condensation and vaporization are arranged, makes dimethyl ether in every field such as chemical industry, daily use chemicals, pharmacy and agricultural chemicals its unique purposes be arranged all.Dimethyl ether is mainly used in fuel (domestic fuel, industrial fuel and vehicle fuel), aerosol, cold-producing medium, blowing agent and produces aspects such as low-carbon alkene.
Occurring in nature CO
2, phosphorus content is about 10
16Ton is much larger than the phosphorus content of coal, oil and natural gas.Along with the development of modern economy, human more dependence fossil energy, so whole world combustion of fossil fuel is discharged into the CO in the atmosphere
2Amount reaches 185～24,200,000,000 tons/year, and total release is above 50,000,000,000 tons/year.A large amount of dischargings of carbon dioxide cause that the content of carbon dioxide continues to increase in the atmosphere, and greenhouse effects are very significant to climatic influences, so the utilization of the industry reduction of discharging of carbon dioxide and carbon dioxide reaches global extensive concern.CO
2Hydrogenation system DME has the important strategic meaning, both can solve CO
2Pollution problem, can utilize CO again
2Produce useful product (clean fuel).
Reduce carbon dioxide in the atmosphere, two kinds of methods are arranged usually: the first is with CO
2Pressurized liquefied and solidify, seal up for safekeeping in buried then underground or seabed; It two is that the reaction of carbon dioxide and other compound is formed new stable compound.
Utilize carbon dioxide to produce other products in the chemical industry carbonic hydroammonium, urea, soda ash and other carbonic acid compounds are arranged as raw material.Utilize carbon dioxide production fuel, both can reduce the consumption of fossil energy, can reduce the increase of carbon dioxide in the atmosphere again, thereby have good social benefit.Though hydrogenation of carbon dioxide can get methyl alcohol, CO
2Preparing methanol by hydrogenation is because of being subjected to the restriction of balance, CO
2Conversion ratio is low, and the yield of methyl alcohol is very low.
CO
2Hydrogenation system DME has not only broken CO
2Hydrogenation generates the thermodynamical equilibrium of methyl alcohol reaction, can also suppress the carrying out of water-gas inverse conversion reaction.Therefore, methanol synthesis catalyst and methanol dehydration catalyst are combined, can give CO
2Transform a strong driving force.Help the carrying out that react, can obtain higher yield of dimethyl ether.
The fuel and the required raw material of Chemical Manufacture of world's consumption at present mainly rely on oil.Because the atrophy of petroleum reserves and rising steadily of oil price are sought the alternative energy source of oil and can't be avoided, caused the particularly generally attention of developed country of countries in the world in recent years.
Dimethyl ether normally utilizes coal or gas production.At first with coal or natural gas and water with oxygen reaction generates hydrogen and CO is the gas of main component, pass through CO conversion and acid gas removal then.Wherein sulphur, nitrogen oxide and carbon dioxide etc. are removed, adjust the ratio of hydrogen and CO, the preparation synthesis gas.
By the synthesis gas preparing dimethy ether two approach are arranged: one is a two-step method, generates methyl alcohol by synthesis gas earlier, again by dimethyl ether preparation by dehydrating methyl alcohol; It two is an one-step method, under the effect of composite catalyst, directly produces dimethyl ether by synthesis gas.
Along with expanding economy, the increase of energy resource consumption, because fuel oil and the coal-fired sulphur that produces, nitrogen and CO discharging, the atmosphere pollution that causes increases the weight of day by day, atmospheric environment faces immense pressure.Thereby strict more to the quality standard of oil product, it is irreversible main trend that oil quality improves constantly, along with the raising of global environmental consciousness, the oil refining industry will face the heavy pressure of product quality upgrading all the time.The raising of gasoline product quality, the cost of increase oil refining process, feasible commercial applications by the carbon dioxide synthetic liquid fuel becomes possibility.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art part, and a kind of composite catalyst, preparation method and application thereof of used for synthesizing dimethyl ether with carbon dioxide are provided.
The object of the invention can realize that the present invention will pass through following process: CO by synthesizing dimethyl ether with carbon dioxide usually by following measure
2Generate CO and water with hydrogen reaction; CO and hydrogen reaction generate methyl alcohol, and methanol dehydration generates dimethyl ether.
Overall reaction is:
Side reaction:
Same CO
2Also methyl alcohol be can directly obtain with hydrogen reaction, but the restriction of thermodynamical equilibrium, CO are subjected to
2Conversion ratio very low, and the product major part is CO.
Industrial catalyst by synthesis gas preparation methyl alcohol generally adopts the Cu-Zn composite oxide catalysts, and this catalyst is at CO
2And H
2Under the atmosphere of O, catalysqt deactivation is fast, and exactly has the product of water to generate in the DME building-up process.Therefore, the Cu series catalysts of the preparation of prior art is unsuitable for CO
2With the direct dimethyl ether synthesis of hydrogen.In fact, the key of perfect synthesis technique flow process just is to improve the activity of catalyst for methanol, reduces the right CO of catalyst
2And H
2The O sensitivity.
The catalyst that adopts has the synthetic and two kinds of functions of methanol dehydration of methyl alcohol, for bifunctional catalyst, the combination cooperative effect of two kinds of functions is crucial, bifunctional catalyst be not only simply adding of two kinds of components and, also comprise the adjustment of relative position favourable in the power of near the catalyst active center oxidation-reduction quality and Acidity of Aikalinity and the local space etc.Different technologies of preparing and processing method are often brought beyond thought effect, and this also is one of key in the whole process.
At the problems referred to above, in catalyst, add and help active constituent that the performance of the catalyst of methyl alcohol is modified, the combining form of molecule is the key that influences catalyst performance.Need searching a kind of simple to operate, effective, and preparation catalyst method.
An object of the present invention is to provide a kind of catalyst that activity is high, selectivity is good for preparing.
Another object of the present invention provides a kind of method for preparing catalyst of the present invention.Adopt the inventive method, make catalytic active component be evenly distributed in the catalyst.
A further object of the present invention is that catalyst of the present invention is used for carbon dioxide and hydrogen dimethyl ether synthesis.
In order to achieve the above object, the inventor has carried out intensive research.Found that the catalyst that adopts method for preparing catalyst preparation provided by the invention, adopt the composite catalyst of powder preparation, the selectivity height of DME, the selectivity of CO and methyl alcohol is low, anti-CO
2And H
2The performance height of O.
The catalyst that adopts this method to make, synthetic activity of such catalysts and the selectivity of DME all increases significantly than the prior art catalyst, and catalyst of the present invention has the range of application of broad simultaneously, can be adapted to the direct dimethyl ether synthesis of hydrogenation of carbon dioxide.
Catalyst of the present invention can comprise following component: methanol synthesis catalyst and methanol conversion catalyst, wherein methanol synthesis catalyst and methanol conversion catalyst weight ratio are 0.1～10.
Preparation of catalysts step of the present invention comprises catalyst for methanol preparation, methanol conversion catalyst preparation and synthesizing dimethyl ether catalyst preparation:
Catalyst for methanol is synthetic
Preparation of Catalyst is to adopt the method for co-precipitation to prepare inorganic hydrate, obtains catalyst for methanol through super-dry and high-temperature roasting then, is prepared into sphere and sheet-like particle through overmolding.
In a specific embodiments of the present invention, adopt and flow two step coprecipitations to prepare CuO-ZnO-ZrO
2Catalyst, concrete grammar is as follows:
Add deionized water after taking by weighing an amount of zirconium nitrate and zinc nitrate mixing and be mixed with mixed solution; Take by weighing and add deionized water preparation mixed solution after an amount of copper nitrate zinc nitrate mixes; Taking by weighing an amount of sodium carbonate adds deionized water and is mixed with solution.With a clean beaker place uniform temperature water bath with thermostatic control, under middling speed stirs with Zr (NO
3)
4-Zn (NO
3)
2Mixed liquor and Na
2CO
3Solution and drip are gone in the beaker, and the rate of addition of regulating two solution in the dropping process is at room temperature placed a period of time after dripping to keep certain pH value, goes supernatant liquor to get white precipitate.Other gets Cu (NO
3)
2-Zn (NO
3)
2Mixed solution and Na
2CO
3Solution is added in the above-mentioned precipitation in water-bath with under stirring, and regulates rate of addition with control pH value, drips the aging certain hour in back.Suction filtration then, filter cake with deionized water dissolving after suction filtration once more, 4～6 times to clean precipitation so repeatedly.Filter cake after cleaning is placed on the drying box drying, then a period of time of roasting at a certain temperature, cools to room temperature with the furnace, get CuO-ZnO-ZrO
2Catalyst.
Methanol conversion catalyst
Because dehydration is an acid catalyzed reaction, methanol dehydration active component used in catalyst is generally solid acid catalyst.The aluminium oxide that methanol conversion catalyst adopts usual method to produce promptly adopts a diaspore to make aluminium oxide through roasting.The another kind of methanol conversion catalyst is chosen as the proton type molecular sieve, for example ZSM-5 molecular sieve and beta-molecular sieve etc.Industrial goods sodium type molecular sieve adopts the method for cation exchange to obtain corresponding proton type molecular sieve.
The preparation of composite catalyst
Dimethyl ether synthetic catalyst is a dual-function composite catalyst, and comprising methanol synthesis catalyst and methanol conversion catalyst, wherein methanol synthesis catalyst and methanol conversion catalyst weight ratio are 1: 10～10: 1.Catalyst adopts the method preparation of mechanical mixture, being about to methanol synthesis catalyst and methanol conversion catalyst mixes according to certain mass ratio (1: 10～10: 1), pass through careful ground and mixed then, be prepared into and have the certain size size (1～5mm) and the particle of basic certain mechanical strength (〉=10 newton/grain).
The catalyst activity evaluation method:
With the catalyst breakage that makes, screening, getting 20～40 order particle 1g internal diameter of packing into is the tubular reactor of 8mm, earlier with the nitrogen that contains 5% hydrogen under normal pressure, be warming up to 300 ℃ by 150 ℃/hour speed programs, the activation of catalyst was carried out in insulation in 3 hours, reduced to room temperature then.The reducing condition of catalyst is: at nitrogen flow 95ml/min, under the hydrogen flowing quantity 5ml/min condition, by 2h to 300 ℃ of room temperature temperature programming, keep 4h at 300 ℃, 2h reduces to room temperature then.
Evaluating catalyst adopts unstripped gas to consist of: CO
2: 24% (mol), H
2: 73% (mol), all the other are Ar, reaction pressure 5MPa, air speed 1600h
-1, 275 ℃ of reaction temperatures, product carries out on-line analysis with gas-chromatography.
The present invention compared with prior art has following advantage: method for preparing catalyst is simple, the selectivity height (76.2%) of DME, the selectivity of CO and methyl alcohol low (23.7% and 0.1%), anti-CO
2And H
2The performance height of O; Catalyst has the range of application of broad, can be adapted to the direct dimethyl ether synthesis of hydrogenation of carbon dioxide.
The specific embodiment
Below 4 embodiment describe in further detail of the present invention, but the present invention is not subjected to the restriction of these embodiment.
Embodiment 1
Take by weighing 6.98 gram zirconium nitrates and 16.53 gram zinc nitrates, add deionized water after the mixing, be mixed with the mixed solution of 100ml; Take by weighing 27.2 gram copper nitrates and 16.53 gram zinc nitrates, add deionized water after the mixing, be mixed with the mixed solution of 100ml; Take by weighing 42.92 gram sodium carbonate, add deionized water and be mixed with 200ml solution.
One clean beaker is placed about 60 ℃ water bath with thermostatic control, under middling speed stirs with Zr (NO
3)
4-Zn (NO
3)
2Mixed liquor 100ml Na
2CO
3Solution and drip are gone in the beaker, and the rate of addition of regulating two solution in the dropping process drips the back and placed about one hour in 20 ℃ of environment to keep about pH=8.5, goes supernatant liquor to get white precipitate.
Other gets Cu (NO
3)
2-Zn (NO
3)
2Mixed solution and remaining 100ml Na
2CO
3Solution is added in the above-mentioned precipitation in water-bath with under stirring, and regulates rate of addition with control pH=7.5～8.5, drips the back and places about 10 hours in stirred in water bath, takes out beaker, at room temperature stirs and places about 2 hours.Suction filtration then, filter cake with deionized water dissolving after suction filtration once more, 4～6 times to clean precipitation so repeatedly.Filter cake after cleaning is placed in the drying box to descend dry about 6 hours at 80 ℃, about 6 hours, cools to room temperature 400 ℃ of following roastings with the furnace then, obtain 400 ℃ of roasting CuO-ZnO-ZrO
2Catalyst.
Adopt sodium metaaluminate and nitric acid to prepare the boehmite aluminum hydroxide solid elastomer, make diameter 1～2mm bead through overmolding, in Muffle furnace with the 700 ℃ of roastings 4 hours that heat up of 200 ℃/hour speed program, obtain institute's gama-alumina, be used for methanol dehydration catalyst, its pore volume 0.6ml/g, bulk density 0.8g/ml, specific area 179m
2/ g (BET method).
Is that 2: 1 ratio is mixed with above-mentioned methanol synthesis catalyst and methanol conversion catalyst according to mass ratio, passes through careful ground and mixed then, compression molding, and broken then, screening obtain the catalyst (Cat-1) of 40～60 order sizes.Catalyst adopts fixed bed reactors to estimate through aforesaid method, reacts that on-line analysis obtains the results are shown in Table 1 after two hours.
Embodiment 2
Industrial goods sodium type beta-molecular sieve (silica alumina ratio 25) is immersed in and adopts concentration is in the ammonium nitrate of 2M, under 70～80 ℃ condition, stirred 8 hours, filter then, wash and drying, last 500 ℃ of roastings 3 hours obtain corresponding proton type beta molecular sieve as methanol conversion catalyst.
It is that 2: 1 ratio is mixed (Cat-2) according to mass ratio that embodiment 1 preparation methanol synthesis catalyst and present embodiment are prepared methanol conversion catalyst, and method is with embodiment 1, and on-line analysis the results are shown in Table 1.
Embodiment 3
Industrial goods sodium type ZSM-5 molecular sieve (silica alumina ratio 50) is immersed in and adopts concentration is in the ammonium nitrate of 2M, under 70～80 ℃ condition, stirred 8 hours, filter then, wash and drying, last 500 ℃ of roastings 3 hours obtain corresponding proton type ZSM-5 molecular sieve as methanol conversion catalyst.
It is that 2: 1 ratio is mixed (Cat-3) according to mass ratio that embodiment 1 preparation methanol synthesis catalyst and present embodiment are prepared methanol conversion catalyst, and method is with embodiment 1, and on-line analysis the results are shown in Table 1.
Table 1 evaluating catalyst result
Comparative Examples 1
Prepare methanol synthesis catalyst with coprecipitation, method is: with Cu (NO
3)
2, Zn (NO
3)
2And Al (NO
3)
3Be dissolved in the deionized water.With this mixed nitrate solution and aqueous sodium carbonate, be added drop-wise to simultaneously and carry out co-precipitation in the beaker that fills a small amount of 20ml deionized water.Constantly stir in the coprecipitation process, at 70 ℃ of following constant temperature, the pH value remains on about 7.Aging again 30min after co-precipitation finishes.Sediment is filtered, spend deionised water then.With the sediment cleaned in baking oven in 100 ℃ of baking 12h, again in Muffle furnace in 350 ℃ of calcining 4h down, promptly obtain the methanol synthesis catalyst of not moulding.Obtain wherein that quality group becomes in the catalyst for methanol: CuO 46%, ZnO 45% and Al
2O
39%.
Is that 2: 1 ratio is mixed (Cat-1D) with method for preparing methanol synthesis catalyst and embodiment 1 preparation methanol conversion catalyst according to mass ratio, and method is with embodiment 1, and on-line analysis the results are shown in Table 2.
Comparative Examples 2
Is that 2: 1 ratio is mixed (Cat-2D) with the methanol synthesis catalyst of Comparative Examples 1 preparation and embodiment 2 preparation methanol conversion catalyst according to mass ratio, and method is with embodiment 1, and on-line analysis the results are shown in Table 2.
Comparative Examples 3
Is that 2: 1 ratio is mixed (Cat-3D) with the methanol synthesis catalyst of Comparative Examples 1 preparation and embodiment 3 preparation methanol conversion catalyst according to mass ratio, and method is with embodiment 1, and on-line analysis the results are shown in Table 2.
Table 2 evaluating catalyst result
Embodiment 4
Is 1: 10 with the methanol synthesis catalyst and the methanol conversion catalyst of embodiment 1 preparation according to mass ratio, and the ratio of 2: 1 and 10: 1 mixes that (Cat-13), method is with embodiment 1 for Cat-11, Cat-12, and on-line analysis the results are shown in Table 3.
Table 3 evaluating catalyst result
As can be seen from Table 3, the selectivity all higher (≤〉=70.9%) of three kinds of synthetic DME of ratio, methyl alcohol selectivity lower (≤2.6%), CO selectivity lower (≤26.5%).
Claims (10)
1. the composite catalyst of dimethyl ether synthesis is characterized in that: composite catalyst is that methanol synthesis catalyst and methanol conversion catalyst are mixed the mixed catalyst of forming.
2. the composite catalyst of dimethyl ether synthesis as claimed in claim 1, it is characterized in that: methanol synthesis catalyst and methanol conversion catalyst weight ratio are 1: 10～10: 1.
3. the composite catalyst of dimethyl ether synthesis as claimed in claim 1, it is characterized in that: methanol synthesis catalyst is the Cu-Zn-Zr composite oxide catalysts.
4. the composite catalyst of dimethyl ether synthesis as claimed in claim 3, it is characterized in that: the preparation method of catalyst for methanol adopts coprecipitation to prepare CuO-ZnO-ZrO
2Catalyst.
5. the composite catalyst of dimethyl ether synthesis as claimed in claim 1, it is characterized in that: methanol conversion catalyst is a solid acid catalyst.
6. the composite catalyst of dimethyl ether synthesis as claimed in claim 1 is characterized in that: the preparation method is that particle mixes and powder.
7. the composite catalyst of dimethyl ether synthesis as claimed in claim 6, it is characterized in that: the powder catalyst is that methanol synthesis catalyst and methanol conversion catalyst are mixed according to 0.5～10 mass ratio, ground and mixed is prepared into size 1～5mm and the basic necessarily particle of mechanical strength (〉=10 newton/grain) then.
8. the composite catalyst of dimethyl ether synthesis as claimed in claim 6; it is characterized in that: the particle mixed catalyst is respectively with methanol synthesis catalyst and methanol conversion catalyst preparation size size 1～5mm and the basic necessarily particle of mechanical strength (〉=10 newton/grain), the composite catalyst that mixes according to certain mass ratio 0.5～10 then.
9. the composite catalyst of dimethyl ether synthesis as claimed in claim 4, it is characterized in that: solid acid catalyst is aluminium oxide, molecular sieve.
10. the purposes of the composite catalyst of dimethyl ether synthesis as claimed in claim 1 is to be used for carbon dioxide and hydrogen dimethyl ether synthesis.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101934232A (en) * | 2010-09-13 | 2011-01-05 | 浙江大学 | Method for preparing catalyst for directly synthesizing dimethyl ether by biomass gasifiable synthesis gas |
| CN102500381A (en) * | 2011-11-01 | 2012-06-20 | 昆明理工大学 | Preparation method of catalyst of carbon dioxide hydrogenation methanol synthesis |
| US9295978B2 (en) | 2012-02-15 | 2016-03-29 | Basf Corporation | Catalyst and method for the direct synthesis of dimethyl ether from synthesis gas |
| CN106955711A (en) * | 2017-03-09 | 2017-07-18 | 昆明理工大学 | One kind prepares nanometer CuO ZrO2The method of/ZnO composite catalysts |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02280836A (en) * | 1989-04-21 | 1990-11-16 | Mitsubishi Heavy Ind Ltd | Preparation of catalyst for dimethyl ether synthesis |
| CN1153080A (en) * | 1995-12-29 | 1997-07-02 | 中国科学院兰州化学物理研究所 | Catalyst for direct preparation of dimethyl ether with synthetic gas |
| CN1883804A (en) * | 2005-06-22 | 2006-12-27 | 中国石油化工股份有限公司 | Catalyst for preparation of dimethyl ether from synthesis gas |
-
2008
- 2008-10-10 CN CN200810223936A patent/CN101722002A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02280836A (en) * | 1989-04-21 | 1990-11-16 | Mitsubishi Heavy Ind Ltd | Preparation of catalyst for dimethyl ether synthesis |
| CN1153080A (en) * | 1995-12-29 | 1997-07-02 | 中国科学院兰州化学物理研究所 | Catalyst for direct preparation of dimethyl ether with synthetic gas |
| CN1883804A (en) * | 2005-06-22 | 2006-12-27 | 中国石油化工股份有限公司 | Catalyst for preparation of dimethyl ether from synthesis gas |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101934232A (en) * | 2010-09-13 | 2011-01-05 | 浙江大学 | Method for preparing catalyst for directly synthesizing dimethyl ether by biomass gasifiable synthesis gas |
| CN102500381A (en) * | 2011-11-01 | 2012-06-20 | 昆明理工大学 | Preparation method of catalyst of carbon dioxide hydrogenation methanol synthesis |
| US9295978B2 (en) | 2012-02-15 | 2016-03-29 | Basf Corporation | Catalyst and method for the direct synthesis of dimethyl ether from synthesis gas |
| CN106955711A (en) * | 2017-03-09 | 2017-07-18 | 昆明理工大学 | One kind prepares nanometer CuO ZrO2The method of/ZnO composite catalysts |
| 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 |
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Application publication date: 20100609 |