CN1883798A - Catalyst for direct preparation of dimethyl ether by using synthesis gas - Google Patents
Catalyst for direct preparation of dimethyl ether by using synthesis gas Download PDFInfo
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Abstract
The invention relates to a catalyst for direct preparing dimethyl ether from synthesis gas. The invention resolves the problems in existent technique that reactive temperature of catalyst is high, conversion of carbon monoxide and/or selective of dimethyl ether is low by employing CuO-ZnO-Fe2O3 molecular sieve, which is at least one of ZSM-5, ZSM-11, ZSM-48, MCM-22, MCM-49 or MCM-56, beta, Y or mordenite, as component. The catalyst can be used in industrial production for direct preparation of dimethyl ether from synthesis gas.
Description
Technical field
The present invention relates to a kind of catalyst that is used for direct preparation of dimethyl ether by using synthesis gas.
Background technology
Dimethyl ether is mainly used in the propellant of aerosol because of its distinctive physicochemical property.In addition, dimethyl ether also can be used as the industrial chemicals of synthetic sulfuric acid dimethyl ether etc., substitute diesel oil and be used for domestic fuel etc. as clean automobile fuel and replacement liquid gasification, especially in recent years the one-step method from syngas technology progressively develops, the construction of large-scale dimethyl ether process units is brought into schedule, and the development prospect of its alternative diesel oil or liquefied gas aspect is generally had an optimistic view of.
Dimethyl ether is by making after the byproduct rectifying in the high pressure methanol production the earliest.Along with the low pressure methanol synthesis broad application, side reaction significantly reduces, and the dimethylether industrial production technology develops into methanol dehydration or synthesis gas direct synthesis process very soon, promptly so-called two-step method and one-step method.Two-step method is earlier synthesis gas to be converted into methyl alcohol, then methanol dehydration is converted into dimethyl ether.The methanol dehydration method comprises two kinds of liquid phase method and vapor phase methods.The former is reflected in the liquid phase and carries out, and methyl alcohol makes through concentrated sulfuric acid dehydration.This technology has reaction condition gentleness (130～160 ℃), methyl alcohol conversion per pass height (about 90%), but can be intermittently also quantity-produced advantage.But, progressively be eliminated because of there are problems such as equipment corrosion, environmental pollution, operating condition be abominable in this method.Because the dimethyl ether demand growth is very fast, various countries develop reduced investment again in succession, operating condition is good, free of contamination methanol gas phase dehydration method new technology.Research and develop out the methanol vapor phase method dewatering preparing dimethy ether method of utilizing crystalline aluminosilicate to make catalyst as nineteen sixty-five Mobil company.Early 1980s Mobil company improves catalyst again, and dimethyl ether selectivity and methanol conversion are all improved a lot.Mitsui east pressed chemical company also to develop new catalyst in 1991.Domestic southwestern chemical research institute and Shanghai petrochemical industry research institute etc. have also all developed the catalyst of methanol gas phase dehydration, and are applied on the commercial plant of different scales.
Directly producing dimethyl ether by synthesis gas is that one-step technology is a kind of new technology of developing in recent years, exactly synthetic being reflected in the same reactor with two of methanol dehydrations of methyl alcohol there is not pilot process, because there is the synthetic and methanol dehydration two classes reaction of methyl alcohol simultaneously in reaction system, therefore broken the thermodynamics equilibrium limit that exists in the simple methyl alcohol building-up process, produce bigger forward reaction motive force, thereby can reduce the conversion per pass of operating pressure and raising CO effectively.In general, one-step method is better than two step method, so the domestic and international at present research about dimethyl ether mainly concentrates on the research to one-step method.
Reaction by directed preparing dimethyl ether by synthetic gas can be divided into following a few step:
(1)+(2)：
ΔH＝-180.58kJ/mol (4)
(1)+(2)+(3)：
ΔH＝-180.58kJ/mol (5)
By above-mentioned reaction as can be seen:
The methyl alcohol that generates in formula (1) is consumed generation dimethyl ether and water in formula (2), the water generation transformationreation that is generated generates CO
2And H
2, and the H that generates
2It is again the raw material of synthesizing methanol.The product that each step reaction is generated is the reactant of another step reaction, and this can not be subjected to the thermodynamic limitation of synthesizing methanol just for entire reaction has produced very big motive force, thereby obtains higher CO conversion rate.
The bifunctional catalyst of the catalyst that one-step method adopted for being composited by methanol synthesis catalyst and methanol dehydration catalyst.Methanol synthesis catalyst is mainly the copper base oxide catalyst, as composite oxides such as Cu-Zn-Al or Cu-Zn-Cr.Methanol dehydration catalyst is mainly solid acid catalysts such as aluminium oxide, molecular sieve or aluminum phosphate, wherein, and γ-Al
2O
3With molecular sieve be with the most use two kinds.
It is that synthetic component of methyl alcohol and aluminium oxide are the bifunctional catalyst that the methanol dehydration active component is composited that the Chinese patent CN 1233527A (1999) that is entitled as the Catalysts and its preparation method of dimethyl ether synthesis " directly " has disclosed with oxides such as copper, manganese.At H
2/ CO mol ratio is 3/2,250～270 ℃ of reaction temperatures, reaction pressure 4MPa and unstripped gas air speed 1500 hours
-1Reaction condition under,, this shows that the reactivity of above-mentioned catalyst is lower though the conversion ratio of carbon monoxide has reached 82.59%.
It is that synthetic component of methyl alcohol and aluminium oxide are the bifunctional catalyst that the methanol dehydration active component is composited that the Chinese patent CN1356163A (2002) that is entitled as the bifunctional catalyst and the preparation technology thereof of synthesis gas preparing dimethy ether " directly by " has disclosed with composite oxides such as copper, zinc.At H
2/ CO mol ratio is 3.85,300 ℃ of reaction temperatures, reaction pressure 4MPa and unstripped gas air speed 1490 hours
-1Reaction condition under, the conversion ratio of carbon monoxide is 81.75%, the dimethyl ether selectivity is 93.56%.This shows that the reaction temperature of above-mentioned catalyst is higher, the conversion ratio of carbon monoxide is lower.
Because active A l
2O
3Optimum activity temperature as methanol dehydration catalyst higher (about 300 ℃), the optimum activity temperature (about 250 ℃) of synthesizing the copper-based catalysts of component with methyl alcohol is not complementary.So, adopt active A l
2O
3Prepare bifunctional catalyst as the methanol dehydration active component and have following shortcoming: (1) is as if carrying out under the optimum activity temperature that is reflected at copper-based catalysts, because active A l
2O
3Dewatering under this temperature is relatively poor, and not only the selectivity of dimethyl ether is lower in the product, and because the advantage of one-step method can't be fully played, the conversion ratio of carbon monoxide is also lower; (2) if be reflected at active A l
2O
3The optimum activity temperature under carry out, because the reaction by preparation of dimethyl ether from synthesis gas is a course of reaction that low temperature is favourable, so, under higher reaction temperature, be difficult to obtain higher carbon monoxide conversion ratio, and higher reaction temperature helps the generation of hydro carbons accessory substance, thereby also can cause the selectivity of dimethyl ether in the product to reduce.
Because γ-Al
2O
3The optimum activity temperature and the optimum activity temperature of the copper-based catalysts of the synthetic component of methyl alcohol be not complementary, cause the performance of bifunctional catalyst to reduce.For this reason, people have carried out with the research of various molecular sieve catalysts as the methanol dehydration active component.
The Chinese patent CN 1087033A (1994) that is entitled as " being converted into the dimethyl ether metallic zeolite catalyst for reaction by synthesis gas " has disclosed with H type faujasite or modenite and the H type Y after hydrothermal treatment consists or the modenite bifunctional catalyst as the methanol dehydration active component.This catalyst is at H
2/ CO mol ratio is 2,260 ℃ of reaction temperatures, reaction pressure 3.5MPa and unstripped gas air speed 1000 hours
-1Reaction condition under, the conversion ratio of carbon monoxide can be up to 80～90%, the dimethyl ether selectivity is more than 90%.
Ge Qingjie, (gas chemical industry, 1996,21 (6): result 16) also shows Huang Youmei, replaces γ-Al with HSY or HZSM-5
2O
3Make the dehydration activity component, can make the active temperature of bifunctional catalyst be reduced to 250～260 ℃ from 280～290 ℃; And the selectivity of dimethyl ether and space-time yield all increase.
Chen Jiangang, Niu Yuqin (gas chemical industry, 1997,22 (6): 6) studied of the influence of the silica alumina ratio of HZSM-5 molecular sieve to the bifunctional catalyst reactivity worth, the result shows that the silica alumina ratio of HZSM-5 molecular sieve optionally influences very obvious to dimethyl ether, along with the increase of HZSM-5 molecular sieve silica alumina ratio, the selectivity of dimethyl ether raises.
Tan give birth to wait (Journal of Molecular Catalysis, 1999,13 (4): 246) the HZSM-5 molecular sieve of then having studied with hydrothermal treatment consists is the influence of dehydration activity component to bifunctional catalyst, the result shows the raising along with the hydrothermal treatment consists temperature, the selectivity of dimethyl ether improves thereupon.
Above-mentioned result of study shows that all the weak acid center on HZSM-5 molecular sieve surface helps the generation of dimethyl ether, the strong acid center generation hydro carbons that then methyl alcohol and dimethyl ether further dewatered, thus reduced the selectivity of dimethyl ether in the product.So if the silica alumina ratio of HZSM-5 molecular sieve is too low, because of there being more strong acid center, the selectivity of dimethyl ether reduces in the product that can induce reaction; If silica alumina ratio is too high, though the selectivity of dimethyl ether can be very high, because the acid amount is less, its dehydration activity must reduce.Though hydrothermal treatment consists can make the strong acid center on molecular sieve surface significantly reduce, also reduced the weak acid center simultaneously, thereby reduced reactivity.
Summary of the invention
Technical problem to be solved by this invention is to have reaction temperature height, carbon monoxide conversion ratio and/or the not high problem of dimethyl ether selectivity in the conventional art, and a kind of new catalyst that is used for direct preparation of dimethyl ether by using synthesis gas is provided.Use catalyst of the present invention to be used for direct preparation of dimethyl ether by using synthesis gas to have that reaction temperature is low, carbon monoxide conversion ratio height and the good characteristics of dimethyl ether selectivity.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyst that is used for direct preparation of dimethyl ether by using synthesis gas comprises following component by weight percentage:
A) 10～70% CuO;
B) 5～50% ZnO;
C) 10～60% molecular sieve;
D) 0.1～10% Fe
2O
3
At least a in ZSM-5, ZSM-11, ZSM-48, MCM-22, MCM-49, MCM-56, β, Y or modenite of molecular screening wherein.
In the technique scheme, the preferable range of CuO is 25～50% by weight percentage; The preferable range of ZnO is 10～30%; The preferable range of molecular sieve is 20～50%; Fe
2O
3Preferable range be 0.5～5%; Preferred version is also to contain 0.1～10% Al in the catalyst
2O
3, more preferably scheme is also to contain 3～7% Al in the catalyst
2O
3The preferred version of molecular sieve is for being selected from ZSM-5.
Iron modifier in the catalyst of the present invention is to add on the molecular sieve by methods such as ion-exchange, hydrothermal synthesis method or infusion processes, and drying and high-temperature roasting make then.Sintering temperature is 250～750 ℃, is preferably 350～650 ℃.The adding form of additive can be their oxide or the compound of iron content, as iron oxide, ferric nitrate, ferric sulfate and iron chloride etc.Molecular sieve with the prepared iron content of said method is formed bifunctional catalyst as methanol dehydration component and the synthetic component of copper base methyl alcohol.
Be used for bifunctional catalyst of the present invention and can adopt mechanical mixing, infusion process, co-precipitation-sedimentation or coprecipitation preparation, prepared catalyst can be used for fixed bed reactors and fluidized-bed reactor, and also can be used for gas-liquid-solid three-phase bed reactor is paste state bed reactor.
The reason that its reactivity worth of bifunctional catalyst for preparing as the methanol dehydration active component with the molecular sieve of iron content of the present invention is significantly increased mainly is because the change of its acidity.Acid characterization (NH
3-TPD) result shows, the strong acid center number of iron content molecular sieve obviously reduces, and weak acid and moderate strength acid site do not have obvious variation.Because the methanol dehydration step in the preparing dimethylether from synthetic gas by reaction is mainly carried out on weak acid position or moderate strength acid position, side reaction significantly reduces as the methanol dehydration active component with the molecular sieve of iron content like this, thereby improved the dimethyl ether selectivity and the stability of catalyst greatly, obtained better technical effect.
The catalyst that is used for the present invention preparation need reduce processing earlier before reaction.The mixture that consists of hydrogen and inert gas of reducing gases, inert gas are one or more the mixture in nitrogen, helium and the argon gas etc.The volume content of hydrogen is 0.5～20% in the reducing gases, is preferably 1～10%; Reduction temperature is 180～300 ℃, is preferably 220～280 ℃; The air speed of reducing gases is 500～5000 hours
-1, be preferably 1000～3000 hours
-1
Catalyst of the present invention is used for direct preparation of dimethyl ether by using synthesis gas, and its reaction condition that is suitable for is: the mol ratio of raw material of synthetic gas hydrogen and carbon monoxide is 0.8: 1～5: 1, is preferably 1: 1～3: 1; And preferably contain a certain amount of carbon dioxide in the gaseous mixture, its volume content is 0.5～10%, is preferably 1～5%.The volume space velocity of reaction gas is 100～10000 hours
-1, be preferably 500～3000 hours
-1Reaction temperature is 200～400 ℃, is preferably 220～300 ℃.Reaction pressure is 2.0～8.0MPa, is preferably 3.5～6.0MPa.
An example of the inventive method of using fixed bed reactors is hereinafter described.
It is 6 millimeters that a certain amount of catalyst granules (20～40 order) is loaded in internal diameter, and length is in 300 millimeters the stainless steel reactor.Adopt electrical heating, temperature adopts intelligent temperature controller to control automatically.Reactor bottom filling 20～40 purpose inert materials are as supporter, a certain amount of catalyst of filling in the reactor, and filling 20～40 purpose inert materials in catalyst top are made for the usefulness of raw material preheating.Co hydrogenation and Dehydration of methanol take place from top to bottom by beds in material synthesis gas, generate purpose product dimethyl ether and accessory substances such as methyl alcohol and a spot of alkane.Catalyst filling back reducing gases volume fraction (5%H
2/ 95%N
2) after (240 ℃) reduction that heats up, switch unstripped gas and react.The composition of unstripped gas (volume fraction) is CO:28.9%, CO
2: 3.9%, all the other are H
2Reaction pressure 4.0MPa; Reaction temperature is 260 ℃; The volume space velocity of unstripped gas is 1500 hours
-1Adopt HP 4890D type gas chromatograph to carry out on-line analysis, use thermal conductivity detector (TCD), carbon molecular sieve chromatogram column analysis carbon monoxide and carbon dioxide; Use hydrogen flame ionization detector, Porapak-N chromatogram column analysis methyl alcohol, dimethyl ether and hydro carbons accessory substance.
According to each components contents in the reaction end gas, adopt following formula to calculate the conversion ratio of carbon monoxide and the selectivity of the hydro carbons in the product, methyl alcohol and dimethyl ether in the molal quantity of carbon atom:
Carbon monoxide conversion ratio (%)=(amount of the amount+dimethyl ether of the amount+methyl alcohol of the amount+hydro carbons of carbon dioxide * 2)/(amount of the amount+dimethyl ether of the amount+methyl alcohol of the amount+hydro carbons of the amount+carbon dioxide of carbon monoxide * 2) * 100%
The amount of the selectivity=dimethyl ether of dimethyl ether * 2/ (amount of the amount+dimethyl ether of the amount+methyl alcohol of hydro carbons * 2) * 100%
The amount of the selectivity=methyl alcohol of methyl alcohol/(amount of the amount+dimethyl ether of the amount+methyl alcohol of hydro carbons * 2) * 100%
The amount of the selectivity=hydro carbons of hydro carbons/(amount of the amount+dimethyl ether of the amount+methyl alcohol of hydro carbons * 2) * 100%
The invention will be further described below by embodiment, but do not limit its scope.
The specific embodiment
[embodiment 1]
Adopt hydrothermal synthesis method to prepare the HZSM-5 molecular sieve of iron content.With 1 gram Fe (NO
3)
39H
2O is made into 22 milliliters water solution A with dissolved in distilled water, adds the NaOH of 1.2 grams at the 24 gram TPAOH aqueous solution (weight content of TPAOH is 40%), then with 22 gram Ludox (SiO
2Weight content is 40%) mix, as solution B.Under agitation solution A is slowly joined in the solution B, after aging half an hour, transfer in the high pressure-volume bullet, in 170 ℃ of following crystallization 2 days.Crystallization product 500 ℃ in air roasting 4 hours to remove the template agent.Products therefrom is through NH
4NO
3Solution obtained the Fe-ZSM-5 molecular sieve in 4 hours in 550 ℃ of roastings again in air after 80 ℃ exchange is handled 3 times, each 1 hour down.With above-mentioned resulting Fe-ZSM-5 is acidic components, carries out mechanical mixture with the synthetic component of methyl alcohol and obtains bifunctional catalyst A, and wherein the weight percentage of each component is CuO 45%, and ZnO 20%, Al
2O
37%, Fe-ZSM-5 28%, the SiO in the molecular sieve
2/ Fe
2O
3Mol ratio is 60.
[embodiment 2]
With embodiment 1 preparation Fe-ZSM-5 molecular sieve, just Fe (NO
3)
39H
2The addition of O is 2 grams.With this Fe-ZSM-5 that obtains is acidic components, carries out mechanical mixture with the synthetic component of methyl alcohol and obtains bifunctional catalyst B, and wherein the weight percentage of each component is CuO 40%, and ZnO 25%, Al
2O
34%, Fe-ZSM-5 31%, the SiO in the molecular sieve
2/ Fe
2O
3Mol ratio is 30.
[embodiment 3]
Prepare the ZSM-5 molecular sieve that contains Fe with embodiment 1, just in solution A, add the Al (NO of 0.8 gram simultaneously
3)
39H
2O.With above-mentioned resulting Fe-Al-ZSM-5 is acidic components, carries out mechanical mixture with the synthetic component of methyl alcohol and obtains bifunctional catalyst C, and wherein the weight percentage of each component is CuO 35%, and ZnO 15%, Al
2O
33%, Fe-Al-ZSM-5 47%, the SiO in the molecular sieve
2/ Al
2O
3Mol ratio is 60, SiO
2/ Fe
2O
3Mol ratio is 60.
[embodiment 4]
Adopt the solid ionic exchange process to prepare the HZSM-5 molecular sieve of iron content.With 10 gram SiO
2/ Al
2O
3Mol ratio is 60 HZSM-5 molecular sieve and 1 gram Fe (NO
3)
39H
2O fully mills in grinding alms bowl, then in air in 550 ℃ of following roastings 4 hours, obtain the ZSM-5 molecular sieve of Fe modification.ZSM-5 with above-mentioned resulting Fe modification is acidic components, carries out mechanical mixture with the synthetic component of methyl alcohol and obtains bifunctional catalyst D, and wherein the weight percentage of each component is CuO30%, and ZnO 30%, Al
2O
35%, ZSM-5 35%, the SiO in the molecular sieve
2/ Al
2O
3Mol ratio is 60, SiO
2/ Fe
2O
3Mol ratio is 60.
[embodiment 5]
With embodiment 4 preparation catalyst E, wherein the weight percentage of each component is CuO 35%, and ZnO 30%, ZSM-535%, the SiO in the molecular sieve
2/ Al
2O
3Mol ratio is 60, SiO
2/ Fe
2O
3Mol ratio is 60.
[comparative example 1]
H-ZSM-5 molecular sieve (SiO with non-modified
2/ Al
2O
3Mole=60) replacing Fe-ZSM-5 molecular sieve among the embodiment 1 and methanol synthesis catalyst to carry out mechanical mixture, compressing tablet, pulverizing and sieve gets 20～40 purpose particles and obtains bifunctional catalyst F, wherein the weight percentage of each component is CuO 45%, ZnO 20%, Al
2O
37%, H-ZSM-5 28%.
[comparative example 2]
The industrial dimethyl ether by methanol dewater CM-3-1 of southwestern chemical research institute development and industrial methanol synthesis catalyst C302 are carried out mechanical mixture, compressing tablet, pulverizing and sieve get 20～40 purpose particles and obtain bifunctional catalyst G, wherein to synthesize the ratio of component and methanol dehydration active component be 2/1 to methyl alcohol.
[embodiment 6]
With embodiment 1～5 and comparative example 1～2 prepared catalyst A, B, C, D, E, F and G, in continuous-flow fixed bed compressive reaction evaluating apparatus, carry out gas-phase reaction.The loadings of catalyst: 1g.After catalyst has loaded, at logical reducing gases volume fraction (5%H
2/ 95%N
2, flow velocity is 25 ml/min) condition under be warming up to 240 ℃, after reduction in 6 hours, under the condition that continues logical reducing gases, reaction bed temperature is reduced to 200 ℃, switch unstripped gas then and be warming up to 260 ℃ gradually and react.The composition of unstripped gas (volume fraction) is CO:28.9%, CO
2: 3.9%, all the other are H
2Reaction condition is pressure: 4MPa; Air speed: 1500 hours
-1System reaches balance after reacting 3 hours, then sample analysis.Online the carrying out of HP 4890D type gas chromatograph adopted in the analysis of product, uses thermal conductivity detector (TCD), carbon molecular sieve chromatogram column analysis carbon monoxide and carbon dioxide; Use hydrogen flame ionization detector, Porapak-N chromatogram column analysis methyl alcohol, dimethyl ether and hydro carbons accessory substance.The evaluation result of catalyst sees Table 1.
The reactivity worth of table 1 catalyst
| Catalyst | Carbon monoxide conversion ratio (%) | Dimethyl ether selectivity (%) | Methyl alcohol selectivity (%) | Hydrocarbon selective (%) |
| A | 94.1 | 94.0 | 5.9 | 0.1 |
| B | 84.8 | 89.0 | 10.8 | 0.2 |
| C | 94.6 | 94.4 | 5.5 | 0.06 |
| D | 95.5 | 95.3 | 4.7 | 0.04 |
| E | 90.5 | 95.6 | 4.3 | 0.08 |
| F | 93.1 | 84.7 | 5.2 | 10.1 |
| G | 80.0 | 75.5 | 24.0 | 0.5 |
By data in the table as seen, the H-ZSM-5 molecular sieve with iron content that adopts the present invention to make is the bifunctional catalyst of methanol dehydration active component preparation, react for directed preparing dimethyl ether by synthetic gas, the selectivity of dimethyl ether is greatly improved before than modification, and the growing amount of hydro carbons accessory substance reduces significantly.And compare the carbon monoxide conversion ratio of catalyst of the present invention be significantly improved (about 10～15%) with industrialized methanol dehydration catalyst CM-3-1; The selectivity of dimethyl ether has then improved 10～20%, has obtained satisfied effect.
Claims (8)
1, a kind of catalyst that is used for direct preparation of dimethyl ether by using synthesis gas comprises following component by weight percentage:
A) 10～70% CuO;
B) 5～50% ZnO;
C) 10～60% molecular sieve;
D) 0.1～10% Fe
2O
3
At least a in ZSM-5, ZSM-11, ZSM-48, MCM-22, MCM-49, MCM-56, β, Y or modenite of molecular screening wherein.
2,, it is characterized in that the consumption of CuO is 25～50% by weight percentage according to the described catalyst that is used for direct preparation of dimethyl ether by using synthesis gas of claim 1.
3,, it is characterized in that the consumption of ZnO is 10～30% by weight percentage according to the described catalyst that is used for direct preparation of dimethyl ether by using synthesis gas of claim 1.
4,, it is characterized in that the consumption of molecular sieve is 20～50% by weight percentage according to the described catalyst that is used for direct preparation of dimethyl ether by using synthesis gas of claim 1.
5, according to the described catalyst that is used for direct preparation of dimethyl ether by using synthesis gas of claim 1, it is characterized in that molecular screening is from ZSM-5.
6, according to the described catalyst that is used for direct preparation of dimethyl ether by using synthesis gas of claim 1, it is characterized in that Fe by weight percentage
2O
3Consumption be 0.5～5%.
7,, it is characterized in that also containing 0.1～10% Al in the catalyst by weight percentage according to the described catalyst that is used for direct preparation of dimethyl ether by using synthesis gas of claim 1
2O
3
8,, it is characterized in that by weight percentage Al in the catalyst according to the described catalyst that is used for direct preparation of dimethyl ether by using synthesis gas of claim 1
2O
3Consumption be 3～7%.
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|---|---|---|---|---|
| CN101934233A (en) * | 2010-09-13 | 2011-01-05 | 浙江大学 | Preparation method of catalyst Cu-ZnO/HZSM-5 for directly synthesizing dimethyl ether by using synthesis gas |
| CN103012062A (en) * | 2012-12-20 | 2013-04-03 | 上海戊正工程技术有限公司 | Process for indirectly producing alcohol with synthetic gas and application of process |
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|---|---|---|---|---|
| CN101934233A (en) * | 2010-09-13 | 2011-01-05 | 浙江大学 | Preparation method of catalyst Cu-ZnO/HZSM-5 for directly synthesizing dimethyl ether by using synthesis gas |
| CN103012062A (en) * | 2012-12-20 | 2013-04-03 | 上海戊正工程技术有限公司 | Process for indirectly producing alcohol with synthetic gas and application of process |
| CN103012062B (en) * | 2012-12-20 | 2015-04-22 | 上海戊正工程技术有限公司 | Process for indirectly producing alcohol with synthetic gas and application of process |
| WO2016059431A1 (en) * | 2014-10-17 | 2016-04-21 | Johnson Matthey Public Limited Company | Catalyst and process |
| GB2535567A (en) * | 2014-10-17 | 2016-08-24 | Johnson Matthey Plc | Catalyst and process |
| CN105289707A (en) * | 2015-11-06 | 2016-02-03 | 中国第一汽车股份有限公司 | Method for preparing novel Cu-Fe molecular sieve catalyst for diesel vehicle tail gas |
| CN105289708A (en) * | 2015-11-06 | 2016-02-03 | 中国第一汽车股份有限公司 | Method for preparing novel high-activity SCR catalyst |
| CN105289707B (en) * | 2015-11-06 | 2018-01-16 | 中国第一汽车股份有限公司 | A kind of preparation method of exhaust gas from diesel vehicle Cu Fe molecular sieve catalysts |
| CN107344114A (en) * | 2016-05-05 | 2017-11-14 | 中国石油化工股份有限公司 | A kind of modified Y/ZSM-48 composite molecular screens and its preparation method and application |
| CN107344114B (en) * | 2016-05-05 | 2020-02-14 | 中国石油化工股份有限公司 | Modified Y/ZSM-48 composite molecular sieve and preparation method and application thereof |
| CN106423066A (en) * | 2016-12-06 | 2017-02-22 | 中国工程物理研究院材料研究所 | Adsorbent filler and preparation method thereof |
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| CN100553771C (en) | 2009-10-28 |
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