CN101722001A - Composite catalyst for dimethyl ether synthesis and preparation method and application thereof - Google Patents
Composite catalyst for dimethyl ether synthesis and preparation method and application thereof Download PDFInfo
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- CN101722001A CN101722001A CN200810223935A CN200810223935A CN101722001A CN 101722001 A CN101722001 A CN 101722001A CN 200810223935 A CN200810223935 A CN 200810223935A CN 200810223935 A CN200810223935 A CN 200810223935A CN 101722001 A CN101722001 A CN 101722001A
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Abstract
The invention relates to a composite catalyst for dimethyl ether synthesis and a preparation method and an application thereof. The composite catalyst is prepared by mixing the methanol synthesis catalyst and the methanol conversion catalyst, wherein the methanol synthesis catalyst is Cu-Zn-Al composite oxide, the methanol conversion catalyst is a solid acid catalyst; and the two catalysts adopt power-mixing and granule-mixing methods to prepare the dimethyl ether synthesis catalyst. The invention has the following advantages: the CO conversion per pass is high, the selectivity of DME is good, the carbon dioxide resistance and water resistance of the catalyst are high, and the catalyst has wider application range. The composite catalyst of the invention is used for synthesizing dimethyl ether directly with synthesis gas.
Description
Technical field
The present invention relates to catalyst and method thereof, specifically, the present invention relates to synthetic used bifunctional catalyst, the preparation method and its usage of dimethyl ether (DME), the present invention relates to direct synthesis of dimethyl ether from synthesis gas high activity, high-selectivity catalyst.
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.
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.
Along with the continuous increase of national GDP, also in quick growth, so the import volume of oil constantly increases to the demand of the energy.How be high value-added product and to make full use of coal resources are problems of generally paying attention to, effectively utilize natural gas and coal to have boundless prospect, huge economic benefit and social benefit conversion of natural gas.
Utilize coal or gas production chemical products, generally needing at first coal or natural gas and water and oxygen reaction generation hydrogen and CO is the gas of main component, passes 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.
The production technology of synthesis gas is ripe at present, and is widely used in the methanol production industrial process.Being set out by synthesis gas, to produce dimethyl ether be that natural gas and coal are changed into one of feasible important technology of high value added product, is the WeiLai Technology of producing high clean environmental protection fuel.
Gas renormalizing and coal gasification are produced synthesis gas, and the synthesis gas process that is converted into fluid product is called as GTL (Gas-to-Liquids) technology then.GTL commercialization technology path and Related product have methyl alcohol, dimethyl ether and artificial oil.Though artificial oil and dimethyl ether also have the commercial off-the-shelf device, methyl alcohol product installation is that the commercial application of GTL technology is the most successful at present.
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.In the two-step method, owing to existing thermodynamics equilibrium limit to cause operating pressure height, conversion per pass low in the methyl alcohol building-up process, thereby energy consumption is bigger, operating cost is higher, cooling, separation, conveying and the consumption of operating procedure such as heating again between two courses of reaction in addition, improved product cost, unreasonable economically.The synthetic DME of one-step method from syngas is as an intermediate reaction approach of synthesis gas trans-utilization, becomes a hot issue of C1 chemical research because of the profitability on its thermodynamics and reasonability economically.
The technology of MTO (Methanol to olefine prepares alkene by methyl alcohol) and MTG (methanol to gasoline prepares gasoline by methyl alcohol) all needs at first synthesizing methanol, be alkene or gasoline by methanol conversion then, thereby process route is long.Different with above-mentioned route, the synthetic of dimethyl ether directly obtains by synthesis gas.Under the effect of composite catalyst, synthesis gas is dimethyl ether synthesis directly.
Japan Patent JP2001070793 has introduced a kind of Preparation of catalysts method.This catalyst is made up of methanol synthesis catalyst (A) and methanol dehydration catalyst (B).A contains Cu/Al/Zn/Ga or alkaline-earth metal and rare earth metal.B contains Al and Zr.Catalyst A is mixed with 50: 50 with B, form (molar fraction) H at synthesis gas
2Be 77%, C0
2Be 17% and CO be 6%, air speed 1000h
-1, under 270 ℃ of conditions of temperature, yield of dimethyl ether reaches 12%.
Zheng Xiaoming [Chin.J Chem, 2001,19 (1), 67-72] has developed new catalyst Cu-Mn-(M)/γ-Al
2O
3, prepare and tested different Cu/Mn than and this catalyst of promoter.The result shows: this catalyst has high CO conversion ratio and dimethyl ether selectivity.At 210MPa, 275 ℃, 1500h
-1Down, the CO conversion ratio is 63.27% on this catalyst, and yield of dimethyl ether reaches 46.10%.Up to today, be badly in need of a kind of method for preparing dimethyl ether of development, improve CO conversion ratio and yield of dimethyl ether, become the task of top priority.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art part, and a kind of method that is used for producing dimethyl ether by synthesis gas is provided, under the effect of composite catalyst, synthesis gas can dimethyl ether synthesis.
One-step method by the equation of producing dimethyl ether by synthesis gas is:
The methyl alcohol synthetic reaction
2H
2+CO→CH
3OH+90.4kJ/mol (1)
Dehydration of methanol
2CH
3OH→CH
3OCH
3+H
2O+23.4kJ/mol (2)
Water-gas shift reaction
CO+H
2O→CO
2+H
2+41.9kJ/mol (3)
Reaction (1) and (2) net reaction is
2CO+4H
2→CH
3OCH
3+H
2O+204.2kJ/mol (4)
Reaction (1), (2) and (3) net reaction are
3CO+3H
2→CH
3OCH
3+CO
2+246.1kJ/mol (5)
Because the CH that generates in the reaction (1)
3OH is consumed very soon, and dehydration generates dimethyl ether DME, has broken thermodynamical equilibrium, and (4) are easier carries out than reacting in reaction (5), because the H that takes off in the reaction (2)
2O is consumed by CO again, the H that generates in the reaction equation (3)
2Participate in the reaction equation (1) as raw material again, promote balance constantly to generating CH
3OH and CH
3OCh
3Direction moves, thereby the conversion per pass of CO is improved, and can significantly reduce equipment investment and operating cost, so more reasonable economically.
The method for preparing catalyst that has adopted at present, roughly be to prepare catalst for synthesis of methanol and dehydration catalyst respectively earlier, and then mix two kinds of catalyst, this method is simple to operate, avoid two kinds of components because of the mutual interference of treatment conditions difference phase, and can regulate the power of two kinds of functions arbitrarily.But methanol synthesis catalyst 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 direct synthesis of dimethyl ether from synthesis gas.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.
In addition, the precipitation sedimentation, to support method (dipping or ion-exchange) also very common.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 research 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 the repetition methods of preparation catalyst.
So, 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 synthesizing dimethyl ether by synthetic gas.
In order to achieve the above object, the inventor has carried out intensive research.As a result, find to adopt the catalyst of method for preparing catalyst preparation provided by the invention, adopt the composite catalyst of powder preparation, the selectivity height of DME, CO
2Low with the selectivity of hydrocarbon, 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 method dimethyl ether synthesis.
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 1: 2～10: 1.
Preparation of catalysts step of the present invention comprises catalyst for methanol preparation, methanol conversion catalyst preparation and synthetic
The dimethyl ether catalyst preparation:
The methanol synthesis catalyst preparation
Preparing carriers 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.
Methanol synthesis catalyst can adopt the preparation of coprecipitation method.Concrete grammar is: with required metal with nitrate or the nitrate hydrate forms is pro rata is dissolved in the deionized water, precipitating reagent can adopt sodium carbonate liquor, this mixed nitrate solution and aqueous sodium carbonate is added drop-wise to simultaneously carries out co-precipitation in the beaker that fills small amount of deionized water.Constantly stir in the coprecipitation process,, keep the ph value of precipitated liquid to remain on about 6～8 in the condition (50～80 ℃) of constant temperature.After finishing, co-precipitation wears out about 30min again.Sediment is filtered, spend deionised water then 3～5 times.With the sediment cleaned in baking oven in about 100 ℃ of baking 12h, again in Muffle furnace in 350 ℃ of calcining 4h down, promptly obtain the methanol synthesis catalyst of not moulding.
The methanol conversion catalyst preparation
Aluminium oxide or proton type molecular sieve that methanol conversion catalyst adopts usual method to produce.Because dehydration is an acid catalyzed reaction, methanol dehydration active component used in catalyst is generally solid acid catalyst.
Aluminium oxide adopts a diaspore to make aluminium oxide through roasting usually.In a specific embodiments of the present invention, can adopt following method aluminium oxide: adopt sodium metaaluminate and nitric acid to prepare the boehmite aluminum hydroxide solid elastomer, make diameter 1～2mm bead through overmolding, high-temperature roasting obtains required gama-alumina in muffle furnace.
The another kind of methanol conversion catalyst is chosen as the proton type molecular sieve, ZSM-5 molecular sieve for example, beta-molecular sieve, Y zeolite etc.Industrial goods sodium type molecular sieve is immersed in and adopts concentration is in the ammonium nitrate of 2M, stirs 8 hours under 70～80 ℃ condition, filters then, washs and drying, and last 500 ℃ of roastings 3 hours 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: 2～10: 1.Catalyst adopts the method preparation of mechanical mixture.The method of mixing has powder and particle to mix.
Catalyst mix method powder is that methanol synthesis catalyst and methanol conversion catalyst are mixed according to certain (1: 2～10: 1) mass ratio, 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).
Catalyst mix method particle mixes and to be meant respectively and methanol synthesis catalyst and methanol conversion catalyst to be prepared into to have the certain size size (1～5mm) and the particle of basic certain mechanical strength (〉=10 newton/grain), the composite catalyst that mixes according to certain mass ratio (1: 2～10: 1) then.
The catalyst activity evaluation method:
With the composite catalyst fragmentation 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.Evaluating catalyst adopts unstripped gas to consist of: CO 24%, H
265%, CO
28%, 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: catalyst of the present invention is used for the process of direct synthesis of dimethyl ether from synthesis gas, CO conversion per pass height, and the selectivity of DME is good, the anti-CO of catalyst
2And H
2The performance height of O, catalyst has the range of application of broad, can be adapted to direct synthesis of dimethyl ether from synthesis gas.
The specific embodiment
Below 6 embodiment, be to describe in further detail, but the present invention is not subjected to the restriction of these embodiment to of the present invention.
Embodiment 1
Take by weighing 9.66 gram copper nitrates, 9.39 gram zinc nitrates add deionized water after 1.88 gram aluminum nitrates mix, and are mixed with the mixed solution of 100ml; Take by weighing 10.6 gram sodium carbonate, add deionized water and be mixed with 100ml solution.Two kinds of solution is in 60 ℃ condition and flow to material, and about control pH=7 ± 0.2,30min is continued to stir in the reinforced back that finishes, and is static aging 2 hours in 70 ℃.Material in 120 ℃ times dry 12 hours, then 350 ℃ of following roastings 4 hours, cools to room temperature with the furnace in baking oven after washing, obtain 350 ℃ of roasting CuO-ZnO-Al
2O
3Catalyst obtains that quality group becomes in the catalyst for methanol: CuO 46.0%, ZnO 45.0% and Al
2O
39.0%.
Take by weighing the industrial goods boehmite aluminum hydroxide solid elastomer that 50 grams adopt nitrate method to produce, make diameter 1～2mm bead through overmolding, heat up 700 ℃ at 200 ℃/hour speed program in muffle furnace, keep roasting in 4 hours, obtain required gama-alumina, its pore volume 0.6ml/g, bulk density 0.8g/ml, specific area 179m
2/ g (BET nitrogen method).
Methanol synthesis catalyst that said method is synthetic and methanol conversion catalyst adopt the powder method to prepare dimethyl ether, be used for synthesizing dimethyl ether by synthetic gas, the mass ratio of the two mixing was respectively 1: 2,2: 1 and 10: 1, and catalyst is at reaction pressure 5MPa, air speed 1600h
-1, 275 ℃ of reaction temperatures are estimated, and product carries out on-line analysis with gas-chromatography, the results are shown in Table 1:
The evaluation result of table 1 powder mode catalyst
Annotate: X is that conversion ratio, S are that selectivity, the Y of product represents the product productive rate in the table
As can be seen from Table 1, the conversion ratio of carbon monoxide is the highest when methanol synthesis catalyst and methanol conversion catalyst ratio reach 2: 1, and the productive rate of DME is also the highest, and the productive rate of hydrocarbon is minimum, and the productive rate of carbon dioxide is also lower.
Embodiment 2
Prepare methanol synthesis catalyst and methanol conversion catalyst with the method among the embodiment 1; adopt particle to be mixed with dimethyl ether catalyst then, be used for synthesizing dimethyl ether by synthetic gas, the mass ratio of the two mixing was respectively 1: 2,2: 1 and 10: 1; all the other conditions are the same, result such as table 2.
The evaluation result of table 2 particle hybrid mode catalyst
As can be seen from Table 2, the conversion ratio of carbon monoxide is the highest when methanol synthesis catalyst and methanol conversion catalyst ratio reach 2: 1, and the selectivity of DME is also the highest, and the selectivity of carbon dioxide and hydrocarbon is also minimum.Contrast table 1 and table 2 can find that the catalyst activity of composite catalyst choice of powder hybrid mode preparation is higher, and the selectivity of DME is better.
Embodiment 3
Get industrial goods ZSM-5 molecular sieve (silica alumina ratio 50) 20 grams, put into the triangular flask of the ammonium nitrate that fills 200 milliliters of 2M, keep stirring 8 hours under 70～80 ℃ the condition, filter then, wash and dry, 500 ℃ of roastings are 3 hours in the last Muffle furnace, obtain corresponding proton type molecular sieve.
Adopting synthetic methanol synthesis catalyst of embodiment 1 method and said method to obtain methanol conversion catalyst adopts powder to prepare dimethyl ether catalyst, be used for synthesizing dimethyl ether by synthetic gas, the mass ratio of the two mixing was respectively 1: 2,2: 1 and 10: 1, and all the other conditions are the same, result such as table 3.
The evaluation result of table 3 molecular sieve powder hybrid mode catalyst
As can be seen from Table 3, the conversion ratio of carbon monoxide is higher when methanol synthesis catalyst and methanol conversion catalyst ratio reach 2: 1, and the selectivity of DME is the highest, and the selectivity of carbon dioxide and hydrocarbon is minimum.
Embodiment 4
Methanol synthesis catalyst that embodiment 1 method is synthetic and the synthetic methanol conversion catalyst of embodiment 3 methods; adopt particle to be mixed with dimethyl ether synthetic catalyst; be used for synthesizing dimethyl ether by synthetic gas; the mass ratio of the two mixing was respectively 1: 2,2: 1 and 10: 1; all the other conditions are the same, result such as table 4.
The evaluation result of table 4 sieve particle hybrid mode catalyst
As can be seen from Table 4, the conversion ratio of carbon monoxide is higher when methanol synthesis catalyst and methanol conversion catalyst ratio reach 2: 1, and the selectivity of DME is the highest, and the selectivity of carbon dioxide and hydrocarbon is minimum.Contrast table 3 and table 4 can find that the catalyst activity of composite catalyst choice of powder hybrid mode preparation is higher, and the selectivity of DME is better.
Embodiment 5
Get industrial goods beta-molecular sieve (silica alumina ratio 47) 20 grams, put into the triangular flask of the ammonium nitrate that fills 200 milliliters of 2M, keep stirring 8 hours under 70～80 ℃ the condition, filter then, wash and dry, 500 ℃ of roastings are 3 hours in the last Muffle furnace, obtain corresponding proton type molecular sieve.
Adopting synthetic methanol synthesis catalyst of embodiment 1 method and said method to obtain methanol conversion catalyst adopts powder to prepare dimethyl ether catalyst, adopt powder to prepare dimethyl ether catalyst, be used for synthesizing dimethyl ether by synthetic gas, wherein methanol conversion catalyst adopts beta-molecular sieve, the mass ratio of the two mixing was respectively 1: 2,2: 1 and 10: 1, all the other conditions are the same, result such as table 5.
The evaluation result of table 5 beta-molecular sieve powder mode catalyst
As can be seen from Table 5, the conversion ratio of carbon monoxide is higher when methanol synthesis catalyst and methanol conversion catalyst ratio reach 2: 1, and the selectivity of DME is the highest, and the selectivity of carbon dioxide and hydrocarbon is minimum.
Embodiment 6
Methanol synthesis catalyst that embodiment 1 method is synthetic and the synthetic methanol conversion catalyst of embodiment 5 methods; adopt particle to be mixed with dimethyl ether catalyst; be used for synthesizing dimethyl ether by synthetic gas; the mass ratio of its two mixing was respectively 1: 2,2: 1 and 10: 1; all the other conditions are the same, result such as table 6.
The evaluation result of table 6 beta-molecular sieve particle hybrid mode catalyst
As can be seen from Table 6, the conversion ratio of carbon monoxide is higher when methanol synthesis catalyst and methanol conversion catalyst ratio reach 2: 1, and the selectivity of DME is the highest, and the selectivity of carbon dioxide and hydrocarbon is minimum.
Contrast table 5 and table 6 can find that the catalyst activity of composite catalyst choice of powder hybrid mode preparation is higher, and the selectivity of DME is better.
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: 2～10: 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-Al composite oxide catalysts.
4. the composite catalyst of dimethyl ether synthesis according to claim 3, it is characterized in that: the preparation method of described catalyst for methanol adopts coprecipitation to prepare CuO-ZnO-Al
2O
3Catalyst consists of: CuO 46.0%, ZnO 45.0% and Al
2O
39.0%.
5. the composite catalyst of dimethyl ether synthesis as claimed in claim 1, it is characterized in that: described 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: described 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: described powder catalyst is that methanol synthesis catalyst and methanol conversion catalyst are mixed according to 1: 2～10: 1 mass ratios, 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: described 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 mixed in 1: 2～10: 1 according to the certain mass ratio then.
9. the composite catalyst of dimethyl ether synthesis as claimed in claim 5, it is characterized in that: described 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 synthesizing dimethyl ether by synthetic gas.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102125854A (en) * | 2010-12-16 | 2011-07-20 | 神华集团有限责任公司 | Method for preparation of dimethyl ether |
| CN102600852A (en) * | 2012-02-10 | 2012-07-25 | 中国科学院青岛生物能源与过程研究所 | Catalyst for preparing dimethyl ether as well as preparation method and application thereof |
| CN103223344A (en) * | 2013-04-17 | 2013-07-31 | 太原理工大学 | Copper-based catalyst for synthesis of methanol in slurry bed, preparation method and application thereof |
| CN104114274A (en) * | 2012-02-15 | 2014-10-22 | 巴斯夫欧洲公司 | Catalytically active body for the synthesis of dimethyl ether from synthesis gas |
| CN104588106A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Catalyst used for producing dimethyl ether through methanol dehydration, and preparation method thereof |
| CN106861750A (en) * | 2017-02-16 | 2017-06-20 | 浙江科技学院 | The preparation method of the nucleocapsid catalyst of modified H beta-molecular sieves cladding and product and application |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102125854A (en) * | 2010-12-16 | 2011-07-20 | 神华集团有限责任公司 | Method for preparation of dimethyl ether |
| CN102125854B (en) * | 2010-12-16 | 2013-03-27 | 神华集团有限责任公司 | Method for preparation of dimethyl ether |
| CN102600852A (en) * | 2012-02-10 | 2012-07-25 | 中国科学院青岛生物能源与过程研究所 | Catalyst for preparing dimethyl ether as well as preparation method and application thereof |
| CN102600852B (en) * | 2012-02-10 | 2013-11-20 | 中国科学院青岛生物能源与过程研究所 | Catalyst for preparing dimethyl ether as well as preparation method and application thereof |
| CN104114274A (en) * | 2012-02-15 | 2014-10-22 | 巴斯夫欧洲公司 | Catalytically active body for the synthesis of dimethyl ether from synthesis gas |
| CN104114274B (en) * | 2012-02-15 | 2016-11-09 | 巴斯夫欧洲公司 | For from the catalysis active body of synthesizing dimethyl ether by synthetic gas |
| CN103223344A (en) * | 2013-04-17 | 2013-07-31 | 太原理工大学 | Copper-based catalyst for synthesis of methanol in slurry bed, preparation method and application thereof |
| CN104588106A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Catalyst used for producing dimethyl ether through methanol dehydration, and preparation method thereof |
| CN104588106B (en) * | 2013-11-03 | 2017-01-18 | 中国石油化工股份有限公司 | Catalyst used for producing dimethyl ether through methanol dehydration, and preparation method thereof |
| CN106861750A (en) * | 2017-02-16 | 2017-06-20 | 浙江科技学院 | The preparation method of the nucleocapsid catalyst of modified H beta-molecular sieves cladding and product and application |
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Application publication date: 20100609 |