CN1153080A - Catalyst for direct preparation of dimethyl ether with synthetic gas - Google Patents
Catalyst for direct preparation of dimethyl ether with synthetic gas Download PDFInfo
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- CN1153080A CN1153080A CN 95121619 CN95121619A CN1153080A CN 1153080 A CN1153080 A CN 1153080A CN 95121619 CN95121619 CN 95121619 CN 95121619 A CN95121619 A CN 95121619A CN 1153080 A CN1153080 A CN 1153080A
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Abstract
A catalyst for one-step synthesizing dimethyl ether from synthetic gas has both the active center for methanol synthesis and the active center for methanol dewatering. The catalyst is prepared from copper, zinc oxide and zirconium oxide, as well as assistant element as components of synthesizing methanol and H-type Y or SY or ZSM-5 molecular sieve, or mordenite, or assistant element-containing H-type Y or SY or ZSM-5 molecular sieve as components of methanol dewatering by coprecipitating. It advantages are less generation of CO2, high selectivity of dimethyl ether (80-95%), catalytic activity and stability, high conversion of CO (up to 90% or more) and low reaction pressure and temp.
Description
The present invention belongs to synthesis gas one to go on foot the method for producing dimethyl ether, particularly used catalyst and preparation process thereof.
Dimethyl ether is not only from the main intermediate of synthesis gas via methanol conversion system gasoline improved method, and is the important source material of producing multiple chemical products, and the purposes of many uniquenesses is arranged in industry such as pharmacy, dyestuff, agricultural chemicals.Dimethyl ether also may be as the substitute of a kind of town gas or liquefied gas even diesel oil and is drawn attention day by day.
The process of being produced dimethyl ether by one step of synthesis gas is from existing patent of the seventies and bibliographical information.As United States Patent (USP), U.S.P.4,098,809, U.S.P.4,177,167, U.S.P.4,375,424, U.S.P.4,417,000 Japan Patent JP155496, application for a patent for invention publication number CN1087033A of the People's Republic of China (PRC) and document Ind.Eng.Chem.Res., Vol.30, No.11,1991 P2372-2378.Frankly, the various catalyst of putting down in writing in the patent documentation, its common drawback is with industrial synthesis gas H
2/ CO=2-3 is under the condition of unstripped gas, CO
2The accessory substance growing amount is too high, or lack the report of these data, the catalyst that these patents and document adopt is made by synthesizing methanol metal active component and methanol dehydration acidic components, combined method is that the synthesizing methanol industrial catalyst is ground to form fine powder, as methyl alcohol synthesizing activity component, mechanical mixture (do and mix or wet mixing) is together equably with the fine powder of methanol dehydration active constituent, it is mechanical mixing, or synthesizing methanol metal active component is immersed in (infusion process) on the methanol dehydration acidic components, and synthesizing methanol reactive metal component all concentrates on Cu, Zn, on the Cr, its auxiliary element is K.The acidic dehydration component adopts before the modification or the r-Al after the modification
2O
3, modenite, HY, HZSM-5 molecular sieve.
The purpose of this invention is to provide a kind of Catalysts and its preparation method of using by one step of synthesis gas preparing dimethy ether.Adopt this catalyst to carry out synthesis gas and transform dimethyl ether reaction, the conversion ratio height of its reactant CO, CO
2The accessory substance growing amount is few, the selectivity height of dimethyl ether, and good stability, and be reflected under the lower pressure and carry out.
The catalyst that is used for by one step of synthesis gas preparing dimethy ether of the present invention is to form with synthesizing methanol active constituent and methanol dehydration component, it is characterized in that the synthesizing methanol active constituent is Cu, zinc oxide and zirconia, wherein the atomic ratio of copper, zinc, zirconium is: Cu: (Zn+Zr)=1: 0.5-5.0, Zn: Zr=1: 0.3-3.0, the methanol dehydration component is H type Y or SY or ZSM-5 molecular sieve or modenite, and the weight ratio of synthesizing methanol component and methanol dehydration component is 1: 0.3-3.0.
Synthesizing methanol active constituent of the present invention except that Cu, zinc oxide, zirconia, also can contain Sr, Mg, Mn, B one of them as auxiliary element, the atomic ratio of auxiliary element and Cu is: 1: 10-100.
Methanol dehydration component of the present invention except that H type Y or SY or ZSM-5 molecular sieve or modenite, can also contain V, Ti, W one of them as auxiliary element, with the weight ratio of methanol dehydration component be: 1: 50-500, auxiliary element is oxide.
Preparation of catalysts method of the present invention comprises the steps:
1) adopts Cu (NO
3)
2Or other Cu salt, Zn (NO
3)
2Or other zinc salt, ZrOCl
2Or ZrO (NO
3)
2And one of the salt of auxiliary element is as Mg (NO
3)
2Or Sr (NO
3)
2Or the mixed solution of boric acid and Na
2CO
3Or KCO
3Or NH
4CO
3Solution or ammoniacal liquor also flow co-precipitation, stirring, filtration, washing for several times;
2) adopt commodity Na type modenite or Y or SY or ZSM-5 molecular sieve, utilize ion exchange technique to make H type zeolite, or directly adopt commodity H type modenite or Y or SY or ZSM-5 molecular sieve;
3) V
2O
5Or WO
3Or TiO
2Be supported on the above-mentioned 2 made molecular sieves;
4) with above-mentioned 2 or the fine powder of 3 described molecular sieves, add in a certain amount of distilled water and make suspension;
5) above-mentioned 1 made sediment is added in above-mentioned 4 the suspension stirring, filtration, drying, roasting, compression moulding, reduction.Sintering temperature is 300-450 ℃, and reduction temperature is 180 ℃-350 ℃.
The present invention adopts the catalyst of method for preparing, is used for the direct synthesis of dimethyl ether from synthesis gas reaction, and its reaction condition is raw material of synthetic gas H
2/ CO mol ratio (volume) is 1-5, and contains a certain amount of CO in the gaseous mixture
2, its CO/CO
2Than being 5-15, reaction pressure is 2.0-5.0MPa, and reaction temperature is at 220-400 ℃, and the forming gas air speed can be at 500-10000hr in the reaction
-1Scope, suitable air speed is 1000-3000hr
-1
The outstanding feature of catalyst of the present invention is the polymolecularity of active constituent and the cooperative effect between synthesizing methanol active component and the methanol dehydration component, make catalyst not only not only have the activity of very high synthesizing methanol but also good dewatering is arranged, and the adding of Zr has been played good effect to the stabilizing active center.
Because these characteristics of this catalyst make the present invention have following advantage,
At first, CO conversion ratio height
The second, CO
2The growing amount of accessory substance is few, and the molal quantity that generates dimethyl ether is to generate CO
2The 2.3-3.5 of molal quantity times, and according to the report that has patent, the molal quantity that generates dimethyl ether is equal to or less than and generates CO
2Molal quantity
The 3rd, the selectivity height of dimethyl ether
The 4th, to compare with industrial synthesizing methanol C301 catalyst, the stability of catalyst of the present invention improves a lot, and makes it have an application industrial.
Implementation of the present invention and most preferred embodiment
Example 1
With commodity H type ZSM-5 (Si/Al=50) molecular sieve, baking is 12 hours under 120 ℃ of temperature, then at 540 ℃ of N
2Roasting is 4 hours in the gas, after the grinding, adds a certain amount of distilled water, makes H type ZSM-5 (Si/Al=50) molecular sieve suspension.Take by weighing quantitative Cu (NO
3)
2, Zn (NO
3)
2, ZrOCl
2Be dissolved in a certain amount of distilled water, with this mixed solution and Na
2CO
3Solution also flows co-precipitation, stirs, filters, sediment washing 4-6 time.This sediment is added above-mentioned H type ZSM-5 molecular sieve suspension, stirring, filtration, 120 ℃ of oven dry, 350 ℃ of roastings behind the 16MPa lower sheeting, are broken into the particle of 20-40 mesh sieve degree again, obtain catalyst A.Its activity and selectivity are seen below table.
Example 2
Take by weighing quantitative Mg (NO
3)
2, Cu (NO
3)
2, Zn (NO
3)
2, ZrOCl
2Be dissolved in a certain amount of distilled water, with this mixed solution and Na
2CO
3Solution also flows co-precipitation, stirring, filtration, sediment washing 4-6 time.This sediment is added and example 1 H type ZSM-5 (Si/Al=50) molecular sieve suspension together, behind stirring, filtration, oven dry, roasting, the 16MPa lower sheeting, be broken into the particle of 20-40 mesh sieve degree again, obtain catalyst B.Its activity and selectivity are seen below table.
Example 3
Take by weighing quantitative Mn (NO
3)
2, Cu (NO
3)
2, Zn (NO
3)
2, ZrOCl
2Be dissolved in a certain amount of distilled water, with this mixed solution and Na
2CO
3Solution also flows co-precipitation, stirring, filtration, sediment washing 4-6 time.After this sediment added H type ZSM-5 (Si/Al=50) the molecular sieve suspension identical with example 1, stirring, filtration, oven dry, roasting, 16MPa lower sheeting, be broken into the particle of 20-40 mesh sieve degree again, obtain catalyst C.Its catalytic performance is seen below table.
Example 4
Take by weighing quantitative H
3BO
3, Cu (NO
3)
2, Zn (NO
3)
2, ZrOCl
2Be dissolved in a certain amount of distilled water, with this mixed solution and Na
2CO
3Solution also flows co-precipitation, stirring, filtration, sediment washing 4-6 time.This sediment is added and example 1 H type ZSM-5 (Si/Al=50) molecular sieve suspension together, and behind stirring, filtration, oven dry, the roasting 16MPa lower sheeting, the particle that is broken into 20-40 mesh sieve degree again obtains catalyst D.Its catalytic performance is seen below table.
Example 5
Commodity Na type ZSM-5 (Si/Al=84) molecular sieve is exchanged to HZSM-5 (Si/Al=84) for four times through 0.15N HCl solution.Roasting 4 hours (550 ℃) then gets H type ZSM-5 (Si/Al=84).This molecular sieve is added a certain amount of distilled water, make suspension.Take by weighing Cu (NO
3)
2, Zn (NO
3)
2, ZrOCl
2Be dissolved in a certain amount of distilled water, mixed solution and Na
2CO
3Solution also flows co-precipitation, and stirring, filtration, sediment wash 4-6 time.This sediment is added H type ZSM-5 (Si/Al=84) molecular sieve suspension, by example 1 described condition oven dry, roasting, compressing tablet, be broken into the particle of 20-40 mesh sieve degree, obtain catalyst E.Its activity and selectivity are seen below table.
Example 6
With commodity Na type Y molecular sieve through 1NNH
4Cl solution exchanges to NH six times
4Y.The condition roasting identical with example 5, the HY molecular sieve, grind the back and add a certain amount of distilled water, make HY molecular sieve suspension.By giving quantitatively, take by weighing Cu (NO respectively
3)
2, Zn (NO
3)
2, ZrOCl
2Be dissolved in a certain amount of distilled water, program and the condition identical with example 1 make sediment, and this sediment is added above-mentioned HY suspension, and the particle that program identical with example 1 and condition are made 20-40 mesh sieve degree obtains catalyst F.Its activity and selectivity are seen below table.
Example 7
With commodity Na type SY (super steady Y) molecular sieve through 2N NH4NO
3Solution exchanges to NH six times
4SY.With example 5 the same terms roastings, get the HSY molecular sieve, after the grinding, add a certain amount of distilled water, make HSY molecular sieve suspension.Quantitatively take by weighing Cu (NO respectively by giving
3)
2, Zn (NO
3)
2, ZrOCl
2Be dissolved in a certain amount of distilled water, program and the condition identical with example 1 make sediment, and this sediment is added above-mentioned HSY suspension, and the particle that program identical with example 1 and condition are made 20-40 mesh sieve degree obtains catalyst G.Its activity and selectivity are seen below table.
Example 8
Take by weighing the pure ammonium tungstate (NH of quantitative analysis
4)
6H
5[H
2(WO
4)
6] H
2O adds quantitative distilled water, is mixed with solution.Commodity H type ZSM-5 (Si/Al=50) molecular sieve fine powder be impregnated in the ammonium tungstate solution, stirred 24 hours, 120 ℃ of oven dry, 540 ℃ of roastings get WO
3/ HZSM-5 (Si/Al=50).Grind the back and add a certain amount of distilled water, make suspension.Quantitatively take by weighing Cu (NO respectively by giving
3)
2, Zn (NO
3)
2, ZrOCl
2Be dissolved in a certain amount of distilled water, program and the condition identical with example 1 make sediment, and this sediment is added above-mentioned WO
3/ HZSM-5 (Si/Al=50) suspension, the particle that program identical with example 1 and condition are made 20-40 mesh sieve degree obtains catalyst H.Its activity and selectivity are seen below table.
Example 9
Take by weighing the pure TiCl of quantitative analysis
4Add quantitative distilled water, add commodity H type ZSM-5 (Si/Al=50) molecular sieve fine powder again, stirred 24 hours, wash filtrate and do not have Cl
-Till the ion, identical with example 8 then program and condition are made TiO
2/ HZSM-5 (Si/Al=50) grinds the back and adds a certain amount of distilled water, makes TiO
2/ HZSM-5 (Si/Al=50) suspension.Quantitatively take by weighing Cu (NO respectively by giving
3)
2, Zn (NO
3)
2, ZrOCl
2Be dissolved in a certain amount of distilled water, program and the condition identical with example 1 make sediment, and this sediment is added the particle that said procedure and condition are made 20-40 mesh sieve degree, obtain catalyst I.Its catalytic performance is seen below table.
Example 10
Take by weighing the pure ammonium metavanadate NH of quantitative analysis
4VO
3Add quantitative distilled water, be mixed with solution.Commodity H type ZSM-5 (Si/Al=50) molecular sieve fine powder be impregnated in this solution, stirred 24 hours, program and the condition identical with example 8 make V
2O
5/ HZSM-5 (Si/al=50) grinds back a certain amount of distilled water of adding and makes V
2O
5/ HZSM-5 (Si/Al=50) suspension.Quantitatively take by weighing Cu (NO respectively by giving
3)
2, Zn (NO
3)
2, ZrOCl
2Be dissolved in a certain amount of distilled water, program and the condition identical with example 1 make sediment, and this sediment is added above-mentioned V
2O
5/ HZSM-5 (Si/Al=50) suspension, the particle that program identical with example 1 and condition are made 20-40 mesh sieve degree obtains catalyst J.Its activity and selectivity are seen below table.
Example 11
Quantitatively take by weighing Mg (NO respectively by giving
3)
2, Cu (NO
3)
2, Zn (NO
3)
2, ZrOCl
2Be dissolved in a certain amount of distilled water, prepare sediment, this sediment is added the V identical with example 10 with example 1 same program and condition
2O
5/ HZSM-5 (Si/Al=50) suspension, the particle that program identical with example 1 and condition are made 20-40 mesh sieve degree obtains catalyst K.Its catalytic performance is seen below table.
Example 12
Quantitatively take by weighing Sr (NO respectively by giving
3)
2, Cu (NO
3)
2, Zn (NO
3)
2, ZrOCl
2Be dissolved in a certain amount of distilled water, program and the condition identical with example 1 prepare sediment, and this sediment is added and example 10 V mutually
2O
5/ HZSM-5 (Si/Al=50) suspension, the particle that program identical with example 1 and condition are made 20-40 mesh sieve degree obtains catalyst L.Its catalytic performance is seen below table.
Example 13
12 controlling catalyst L1.5ml of the above-mentioned example of filling on continuous-flow fixed bed micro-reaction device at first purged 0.5 hour at 140 ℃ with Ar gas, and it is 1200hr that the flow of Ar gas approximately is controlled at GHSV
-1, then carry out the Cheng Sheng reduction with the temperature programming instrument, the air speed of hydrogen is 1500hr
-1, programming rate approximately is controlled at 1 ℃/min, and total recovery time is 6 hours, and the highest reduction temperature is no more than 250 ℃.Reduce to 200 ℃ and improve synthesis gas slowly intensification then, the reaction condition of employing is reaction pressure 4.0MPa, 285 ℃ of reaction temperatures, and reacting gases used is synthesis gas (H
2CO=2), GHSV is 1500hr
-1Reaction condition under, 100 hours life tests on catalyst L the results are shown in table 2.
Reaction result on the table 1 A-L catalyst
| Catalyst temperature ℃ | Selectivity (%) | CO conversion ratio (%) |
| CH 4?CH 3OH?C 2+C - 2?CO 2DME DME (to whole (to organic product) products) | ||
| ??A????280 ??B????280 ??C????280 ??D????290 ??E????280 ??F????280 ??G????290 ??H????280 ??I????280 ??J????280 ??K????280 ??L????285 | ?0.4??0.5????0.5???????14.8????83.8????98.8 ?0.3??0.7????0.6???????13.7????84.7????98.2 ?0.3??-??????0.6???????12.4????86.7????98.6 ?0.3??0.8????1.2???????17.5????80.2????97.8 ?0.2??0.7????0.4???????1.8?????81.9????99.0 ?0.3??3.2????0.1???????13.1????83.3????97.8 ?0.3??2.5????0.1???????11.5????85.6????98.3 ?0.5??0.6????0.9???????17.4????80.6????98.2 ?0.5??1.0????0.9???????13.7????83.9????98.1 ?0.3??0.5????0.4???????14.0????84.8????99.1 ?0.4??0.5????0.6???????13.9????84.6????97.8 ?0.4??0.4????0.7???????15.3????83.3????98.4 | ????89.9 ????90.7 ????85.6 ????86.7 ????89.3 ????87.0 ????90.6 ????87.9 ????87.8 ????90.6 ????91.4 ????92.0 |
As a result catalyst L reaction of table 2 life test cumulative time (h) is (15min) 1 17 40 65 89 100CO conversion ratios (%), 39.8 37.8 33.2 30.7 28.0 25.6 22.5CH of selective (%) 98.1 98.2 97.5 98.3 97.5 98.8 98.4 (to organic product) of 1 15 27 65 75 100CO conversion ratios (%), 88.5 88.0 88.4 86.8 81.7 79.3 74.1 dimethyl ether and the industrial catalst for synthesis of methanol C301 reactions of initial conversion 100 99.4 99.9 98.1 92.3 89.6 83.7 rate ratios (%) cumulative time (h) (15min)3OH selectivity (%) 89.7 85.5 86.4 86.9 86.5 86.6 85.4 (to organic product) is annotated with initial conversion 100 95.0 83.4 77.1 70.4 64.3 56.5 rate ratios (%): 260 ℃ of other reaction conditions of reaction temperature are identical with catalyst L
Claims (6)
1. a catalyst of producing dimethyl ether by synthesis gas one step is to form with synthesizing methanol active constituent and methanol dehydration component, it is characterized in that the synthesizing methanol active constituent is Cu, zinc oxide and zirconia, wherein the atomic ratio of copper, zinc, zirconium is: Cu: (Zn+Zr)=1: 0.5-5.0, Zn: Zr=1: 0.3-3.0, the methanol dehydration component is H type Y or SY or ZSM-5 molecular sieve or modenite, and the weight ratio of synthesizing methanol component and methanol dehydration component is 1: 0.3-3.0.
2. catalyst as claimed in claim 1, it is characterized in that the synthesizing methanol active constituent except that Cu, zinc oxide, zirconia, also can contain Sr, Mg, Mn, B one of them as auxiliary element, the atomic ratio of auxiliary element and Cu is: 1: 10-100.
3. catalyst as claimed in claim 1, it is characterized in that the methanol dehydration component is except that H type Y or SY or ZSM-5 molecular sieve or modenite, can also contain V, Ti, W one of them as auxiliary element, with the weight ratio of methanol dehydration component be: 1: 50-500, auxiliary element is oxide.
4. comprise the steps: as Preparation of catalysts method as described in claim 1 or 2 or 3
1) adopts Cu (NO
3)
2Or other Cu salt, Zn (NO
3)
2Or other zinc salt, ZrOCl
2Or ZrO (NO
3)
2And one of the salt of auxiliary element is as Mg (NO
3)
2Or Sr (NO
3)
2Or the mixed solution of boric acid and Na
2CO
3Or KCO
3Or NH
4CO
3Solution or ammoniacal liquor also flow co-precipitation, stirring, filtration, washing for several times;
2) adopt commodity Na type modenite or Y or SY or ZSM-5 molecular sieve, utilize ion exchange technique to make H type zeolite, or directly adopt commodity H type modenite or Y or SY or ZSM-5 molecular sieve;
3) V
2O
5Or WO
3Or TiO
2Be supported on the above-mentioned 2 made molecular sieves;
4) with above-mentioned 2 or the fine powder of 3 described molecular sieves, add a certain amount of distilled water and make suspension;
5) above-mentioned 1 made sediment is added in above-mentioned 4 the suspension, stirring, filtration, drying, roasting, compression moulding, reduction, sintering temperature is 300-450 ℃, reduction temperature is 180 ℃-350 ℃.
5. a utilization goes on foot the course of reaction of producing dimethyl ether according to claim 1 or 2 or 3 described catalyst by synthesis gas one, it is characterized in that reaction condition is: reaction temperature: 220-400 ℃; Reaction pressure: 2.0-5.0MPa; Reaction gas H
2/ CO mol ratio (volume): 1: 0.2-1.
6. according to the described course of reaction of claim 5, it is characterized in that containing in the reactant synthesis gas a certain amount of CO
2, CO/CO
2Than being 5-15%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95121619 CN1153080A (en) | 1995-12-29 | 1995-12-29 | Catalyst for direct preparation of dimethyl ether with synthetic gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95121619 CN1153080A (en) | 1995-12-29 | 1995-12-29 | Catalyst for direct preparation of dimethyl ether with synthetic gas |
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| Publication Number | Publication Date |
|---|---|
| CN1153080A true CN1153080A (en) | 1997-07-02 |
Family
ID=5082479
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95121619 Pending CN1153080A (en) | 1995-12-29 | 1995-12-29 | Catalyst for direct preparation of dimethyl ether with synthetic gas |
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|---|---|---|---|---|
| CN1297344C (en) * | 2004-11-30 | 2007-01-31 | 中国科学院山西煤炭化学研究所 | Cu/ZrO2 radical synthesizing methanol catalyst and its making method and application |
| CN100336589C (en) * | 2004-04-16 | 2007-09-12 | 中国石油化工股份有限公司 | Catalyst for preparing dimethyl ether from synthetic gas by one step |
| WO2009117851A1 (en) * | 2008-03-26 | 2009-10-01 | 中国石油化工股份有限公司 | A process for producing dimethyl ether from methanol |
| CN1733871B (en) * | 2004-08-10 | 2010-05-12 | 日本气体合成株式会社 | Liquefied petroleum gas production catalyst and process for producing liquefied petroleum gas using this catalyst |
| CN101104575B (en) * | 2006-07-13 | 2010-05-12 | 中国石油化工股份有限公司 | Method for producing dimethyl ether from methanol by combination hydrocarbons catalytic conversion |
| CN101722002A (en) * | 2008-10-10 | 2010-06-09 | 北京石油化工学院 | Composite catalyst used for synthesizing dimethyl ether with carbon dioxide and preparation method and application thereof |
| CN101172936B (en) * | 2006-10-31 | 2010-10-20 | 中国石油化工股份有限公司 | Liquefaction catalytic conversion method for producing dimethyl ether with methanol having flue gas heat exchange |
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| RU2466980C2 (en) * | 2008-03-26 | 2012-11-20 | Чайна Петролеум & Кемикал Корпорейшн | Method of producing dimethyl ether from methanol |
| CN103170360A (en) * | 2011-12-23 | 2013-06-26 | 中国科学院大连化学物理研究所 | Dimethyl ether carbonylation catalyst, and preparation method and application thereof |
| CN105289709A (en) * | 2015-11-09 | 2016-02-03 | 沧州临港华茂化工科技有限公司 | Metal catalyst and method thereof for catalytic synthesis of 2,2-dimorpholinodiethylether |
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1995
- 1995-12-29 CN CN 95121619 patent/CN1153080A/en active Pending
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| CN1733871B (en) * | 2004-08-10 | 2010-05-12 | 日本气体合成株式会社 | Liquefied petroleum gas production catalyst and process for producing liquefied petroleum gas using this catalyst |
| CN1297344C (en) * | 2004-11-30 | 2007-01-31 | 中国科学院山西煤炭化学研究所 | Cu/ZrO2 radical synthesizing methanol catalyst and its making method and application |
| CN101104575B (en) * | 2006-07-13 | 2010-05-12 | 中国石油化工股份有限公司 | Method for producing dimethyl ether from methanol by combination hydrocarbons catalytic conversion |
| CN101172936B (en) * | 2006-10-31 | 2010-10-20 | 中国石油化工股份有限公司 | Liquefaction catalytic conversion method for producing dimethyl ether with methanol having flue gas heat exchange |
| WO2009117851A1 (en) * | 2008-03-26 | 2009-10-01 | 中国石油化工股份有限公司 | A process for producing dimethyl ether from methanol |
| RU2466980C2 (en) * | 2008-03-26 | 2012-11-20 | Чайна Петролеум & Кемикал Корпорейшн | Method of producing dimethyl ether from methanol |
| US8541630B2 (en) | 2008-03-26 | 2013-09-24 | China Petroleum & Chemical Corporation | Process for producing dimethyl ether from methanol |
| CN101722002A (en) * | 2008-10-10 | 2010-06-09 | 北京石油化工学院 | Composite catalyst used for synthesizing dimethyl ether with carbon dioxide and preparation method and application thereof |
| CN102372582A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Fluidized catalytic method for toluene methylation |
| CN103170360A (en) * | 2011-12-23 | 2013-06-26 | 中国科学院大连化学物理研究所 | Dimethyl ether carbonylation catalyst, and preparation method and application thereof |
| CN103170360B (en) * | 2011-12-23 | 2015-03-25 | 中国科学院大连化学物理研究所 | Dimethyl ether carbonylation catalyst, and preparation method and application thereof |
| CN105289709A (en) * | 2015-11-09 | 2016-02-03 | 沧州临港华茂化工科技有限公司 | Metal catalyst and method thereof for catalytic synthesis of 2,2-dimorpholinodiethylether |
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