CN1043739C - Catalyst and process for prodn. of dimethyl ether by using synthetic gas as raw material - Google Patents
Catalyst and process for prodn. of dimethyl ether by using synthetic gas as raw material Download PDFInfo
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- CN1043739C CN1043739C CN93115774A CN93115774A CN1043739C CN 1043739 C CN1043739 C CN 1043739C CN 93115774 A CN93115774 A CN 93115774A CN 93115774 A CN93115774 A CN 93115774A CN 1043739 C CN1043739 C CN 1043739C
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Abstract
The present invention relates to a catalyst for directly converting into dimethyl ether by using synthetic gas, which is used in reaction. The catalyst is prepared from an industrial synthetic methanol catalyst and gamma-Al2O3 treated with modification by using boron, titanium or phosphorous oxide in a compound mode. The process for preparing the catalyst with high catalytic activity is simple, the selectivity of the dimethyl ether is high, and the reaction performance is stable. The technology for directly preparing dimethyl ether by using synthetic gas, which is provided by the present invention, comprises three main working procedures of synthesis reaction, extractive separation and desorption fractionation. In the method, ethanol or water are used as extraction solvent, and a dimethyl ether product with 99% of purity can be directly prepared at a normal temperature and low pressure.
Description
The invention provides and a kind ofly directly produce dimethyl ether and catalyst for application and utilize this catalyst to set up a kind of new process that can directly obtain carrying dense dimethyl ether by synthesis gas.
Dimethyl ether has purposes widely in industrial aspect such as pharmacy, dyestuff, agricultural chemicals, coating and daily use chemicals.It and oleum or sulfur trioxide reaction can generate dimethyl suflfate, can get N with aniline reaction, accelerine, and in depress and can make acetic anhydride etc. from dimethyl ether.In addition, it also can be used as refrigerant and replaces freon (especially fluorine Lyons 12,2 chlorine 2 fluoromethane), aerosol type propellant and the substitute that also can be used as town gas or liquefied gas as fuel, thereby be subjected to extensive attention.Traditional commercial run of producing dimethyl ether is the Dehydration of methanol of being carried out on solid acid (comprising all kinds of zeolites) catalyst.As U.S. Pat 707606, US4560807, Japan Patent JP123672, JP124172 and European patent EP 305256, EP107317 etc. made report to the progress of preparing dimethyl ether by dewatering methanol.In recent years, developed that with the synthesis gas be the new process that raw material is directly produced dimethyl ether, also more and more came into one's own.As U.S. Pat 405112, US592324, and Japan Patent JP155496 etc. all synthesis gas to be converted into dimethyl ether on metal composite catalyst be that report was carried out in the main dimethyl ether and the work of carbinol mixture.These patents mostly adopt industrial methanol synthetic with metal oxide component and methanol dehydration with the acidic components multifunction catalyst that is composited.Used metal component all concentrates on the oxide of Cu, Zn and Cr.The acidic dehydration component then concentrates on the γ-Al without upgrading
2O
3Or on the Hydrogen y zeolite molecular sieve.The operating pressure that they adopt is higher, and all more than 5.0MPa, and the selectivity of dimethyl ether is lower in the product.
The purpose of this invention is to provide a kind of Catalysts and its preparation method that is used for directly transforming dimethyl ether synthesizing reaction by synthesis gas.Simultaneously, utilize this catalyst to set up a kind of process by direct synthesis of dimethyl ether from synthesis gas.This process can directly obtain purity up to 99% product dimethyl ether.
Of the present invention being used for by synthesis gas (H
2+ CO＞96%, surplus is CO
2) directly the catalyst of dimethyl ether synthesis be to adopt industrial synthesizing methanol to be composited with metal oxide and acidic components, it is characterized in that the aluminium oxide of used acidic components for handling through chemical modification, promptly the oxide that adds elements such as boracic, titanium or phosphorus in the aluminium oxide carries out upgrading, and the weight of being added accounts for 0.5～20% of acidic components.The weight percent content of acidic components in catalyst is 30～50%; Contain its active constituent that is of metal oxides such as Cu, Zn and Cr, the weight percent content of metal active component is 70～50%.
Preparation of catalysts method of the present invention is to use following step:
1. synthetic voluntarily or employing commodity three water (a perhaps water) pseudobochmite roasting under 550～600 ℃ of conditions is no less than 4 hours, transforms into γ-Al
2O
3
2. by dipping or the past gained γ-Al of mechanical impurity method
2O
3The middle compound that adds a certain amount of boracic, titanium or P elements, roasting is no less than 2 hours under 500～550 ℃ of conditions again, makes acidic components;
3. utilize above-mentioned 2 made acidic components and a certain amount of industrial catalst for synthesis of methanol powder, mechanical agitation mixes, and compression molding can obtain catalyst of the present invention.The weight content of acidic components is 30～50% in this catalyst, and the weight of boracic, titanium or phosphorous oxides is 0.5～20% of acidic components, and preferable content is 5～15%.
The process of directly producing dimethyl ether by synthesis gas of the present invention comprises following three main processes: 1. synthetic reaction; 2. extract and separate; 3. desorb and fractionation.In process 1, utilize catalyst provided by the present invention to use synthesis gas (H
2+ CO＞96%, surplus is CO
2) be the direct dimethyl ether synthesis of raw material, product tail gas goes out purpose product dimethyl ether through extract and separate, adopts desorb and fractional method to obtain purity again from extract and is higher than 99% dimethyl ether product.Accompanying drawing 1 is process flow diagram of the present invention.
At directly producing in the dimethyl ether technological process shown in the accompanying drawing 1,1. reactor by synthesis gas; 2. absorption tower; 3. extraction tower; 4. desorb-fractionating column; 5. vapour liquid separator; 6. heat exchanger; 7. gas compressor; 8. condensate cooler; 9. water pump.Above-mentioned synthetic reaction 1 is carried out in reactor 1, and reaction end gas is finished extract and separate operation 2 in extraction tower, and extract enters desorb-fractionating column 4 and carries out the desorb fractionation, finishes the extraction to the product dimethyl ether.Specifically, synthesis gas is after reactor 1 reacts, reaction end gas (product) is through heat exchanger 6 and material synthesis gas heat exchange, tell liquid (be mainly and generate water) at vapour liquid separator 5,2 remove methyl alcohol on the absorption tower, product dimethyl ether in the reaction end gas in extraction tower 3 by under the solution extraction, compressed machine 7 superchargings of unreacted material synthesis gas mix with fresh synthesis gas and enter reactor 1 again, the dimethyl ether that is extracted enters desorb-fractionating column 4 with solvent, carry out desorb and carry dense, remove dimethyl ether solvent cooling after pump 9 to return extraction tower 3 recycling.Carry the dense product dimethyl ether steel cylinder of after 7 compressions of condensate cooler 8 condensations and compressor, packing into.
Be used for synthesis gas and directly change into the dimethyl ether reaction in above-mentioned reactor, its reaction condition is: raw material of synthetic gas H
2/ CO volume (molecule) is than being 1～4, and optimum ratio is 1～2, and preferably contains a certain amount of CO in the unstripped gas
2, its CO/CO
2Volume ratio is 15～25.Operating pressure 2.0～5.0MPa, its comparatively suitable operating pressure is 2.5～4.0MPa, and reaction temperature is at 200～400 ℃, and it is than 230～300 ℃ of suitable reaction temperatures.Raw material of synthetic gas air inlet air speed is at 500～5000h
-1, comparatively Shi Yi air speed is 700～1500h
-1
In addition, adopt solvent extraction method from product tail gas, to reclaim purpose product dimethyl ether, adopt desorb and fractional method from extract, to obtain purity again and be higher than 99% purpose product dimethyl ether.Its extractant can be ethanol or water, and extraction conditions is that room temperature and pressure are not less than 1.0MPa, the volume ratio of extractant/reacting gas 〉=0.03 (when being extractant) with water and 〉=0.01 (when being extractant) with ethanol.Separation employing theoretical cam curve is about 10 common fractionation apparatus.Operating pressure is 0.3～0.8MPa, is preferably 0.5～0.6MPa, and temperature (desorber bottom temp) is 100～160 ℃, is preferably 120～140 ℃.The compressed cooling of isolated dimethyl ether product can obtain liquid dimethyl ether for the dress steel cylinder.Below by example content of the present invention is given to illustrate in further detail.
The preparation of embodiment 1 acidic dehydration component
With homemade or commodity three water pseudobochmites (is Al (OH)
3) roasting constant temperature 5 hours under 550 ℃ of conditions of temperature, make γ-Al
2O
3, take by weighing the prepared γ-Al of 20 grams
2O
3Toward wherein adding boric acid 4 grams, ground and mixed evenly after again 550 ℃ of roasting constant temperature of temperature 3 hours, can obtain the acidic dehydration component of required boracic.
The preparation of embodiment 2 catalyst A
With industrial methanol synthetic be broken into copper-based catalysts 20 grams Powdered, and with example 1 in gained boracic acidic dehydration component 10 to restrain ground and mixed even, and compression molding is Φ 3～5 * 8～10m/m garden column, promptly obtains catalyst A.The weight composition of used methanol synthesis catalyst is roughly CuO 40～55%, and ZnO 30～15%, Al
2O
320～15% and B
2O 10～15%.
The preparation of comparative example 1 catalyst B
To make by oneself or commodity three water pseudobochmites roasting constant temperature 5 hours under 550 ℃ of conditions of temperature, obtain γ-Al
2O
310 grams and industrial methanol are synthetic to mix both pulverizing and machinery with copper-based catalysts 20 grams, is pressed into Φ 3～5 * 8～10m/m garden column type, is catalyst B.
Embodiment 3
The broken also sieve of above-mentioned catalyst A is got 10～40 order particle 2ml, be seated on the miniature continuous flow fixed bed reactor, at first use pure N
2The H of dilution
2(H in the gaseous mixture
2Content is about 10%) catalyst A is reduced, the reducing condition that is adopted is: reducing gases space velocity 10,000h
-1About, pressure 0.2MPa, the programming rate of us1 ℃/min rises to 280 ℃ with beds, and at 280 ℃ of constant temperature 4hr.Continuing reaction bed temperature to be dropped to about 200 ℃ swap-in synthesis gas (H under the condition of reducing gases into
2About/CO=2) raw material.Catalyst A is at reaction pressure 3.5MPa, 260 ℃ of temperature and GHSV 1,000 hr
-1Condition under reaction result be mainly: CO conversion ratio 85%, dimethyl ether selectivity 90～94% and methyl alcohol selectivity 6～10%.
Comparative example 2
Loading catalyst B2ml on the reaction unit of above-mentioned example 3 (particle is 10～40 orders), adopt and above-mentioned example 3 identical reducing condition and reaction conditions, the key reaction result of catalyst B is: CO conversion ratio 83%, dimethyl ether selectivity 77～84% and methyl alcohol selectivity 23～16%.
Embodiment 4
Catalyst A adopts and example 3 identical reaction unit and reducing conditions, changes reaction temperature, reaction pressure and material synthesis gas charging space velocity, has investigated reaction process condition to the catalyst reaction Effect on Performance, reaction result such as following table 1:
The reaction process condition result of the test of table 1 catalyst A
| Temperature ℃ | Pressure MPa | GHSV hr -1 | CO conversion ratio %mol | Dimethyl ether selectivity %mol | Dimethyl ether content %mol in the product |
| 255 | 3.0 | 1000 | 70.59 | 89.31 | 14.02 |
| 260 | 3.0 | 1000 | 84.39 | 92.09 | 16.58 |
| 265 | 3.0 | 1000 | 86.20 | 92.19 | 17.10 |
| 270 | 3.0 | 1000 | 88.09 | 92.15 | 19.51 |
| 265 | 3.5 | 880 | 88.99 | 91.86 | 19.57 |
| 265 | 3.5 | 1570 | 87.10 | 92.66 | 17.50 |
| 265 | 3.5 | 2400 | 77.09 | 92.31 | 15.86 |
| 265 | 3.5 | 3000 | 64.80 | 90.09 | 12.67 |
| 260 | 3.5 | 3700 | 49.62 | 88.10 | 9.10 |
| 260 | 2.5 | 1000 | 68.06 | 90.73 | 13.47 |
| 260 | 3.0 | 1000 | 84.39 | 91.09 | 16.58 |
| 260 | 3.5 | 1000 | 85.19 | 91.76 | 17.93 |
| 260 | 4.0 | 1000 | 87.11 | 91.19 | 19.50 |
By the foregoing description, the preparation process of catalyst provided by the present invention (A) is simple, and the selectivity that is used for being converted into by synthesis gas dimethyl ether is good.And this catalyst also experiences hundreds of hours life tests to be investigated, and performance is not seen significant change, shows this catalyst performance stabilised.
The extraction 1 of embodiment 5 dimethyl ether
The catalyst A that adopts example 2 to be provided, and adopt example 3 used reaction unit and reaction condition, and according to technological process shown in Figure 1, by the solvent extraction absorption process, purpose product dimethyl ether in reaction (product) tail gas is separated recovery, when being extractant with water, volume that temperature about 30 ℃ (room temperature), pressure of 3 extraction towers are higher than 1.0MPa and solvent and reaction end gas greater than 0.03 condition under, the recovery of extraction of the dimethyl ether in the reaction end gas＞94% (CO in this moment reaction end gas
2Also there is 5% left and right sides soluble in water).Send in 4 desorbs-fractionating column with the aqueous solution that is about to contain dimethyl ether.When about 140 ℃ of the tower still temperature and the pressure 0.5MPa left and right sides, can obtain purity near 99% purpose product dimethyl ether from cat head.
The extraction 2 of embodiment 6 dimethyl ether
With ethanol is extractant, other condition such as catalyst and reaction process condition are same as example 5 fully, volume ratio that temperature about 30 ℃ (room temperature), pressure of 3 extraction towers are higher than 1.0MPa and alcohol solvent and reaction end gas greater than 0.01 condition under, (the CO in this moment reaction end gas of dimethyl ether recovery of extraction＞96% in the reaction end gas
2Uptake in alcohol solvent reaches 40%), the CO that adopts suitable way in advance alcohol solvent to be carried secretly
2Remove, send in 4 desorbs-fractionating column with the ethanolic solution that is about to contain dimethyl ether.During when about 120 ℃ of tower still temperature and in the pressure 0.5MPa left and right sides, can cat head obtain purity near 99% purpose product dimethyl ether.
Claims (2)
1. one kind is used for synthesis gas and is converted into dimethyl ether reaction catalyst, it is to adopt the synthetic composite catalyst made from copper-based catalysts and acidic components catalyst mix of industrial methanol, it is characterized in that described acidic components catalyst adopts the γ-Al through chemical modification
2O
3, the oxide that promptly adds boracic, titanium or P elements in aluminium oxide carries out upgrading, and the weight of being added accounts for 0.5～20% of acidic components, and the weight percent content that acidic components account for catalyst is 30～50%.
2. according to the described catalyst of claim 1, it is 5～15% that the oxide of boracic, titanium or the P elements that it is characterized in that in the acidic components being added accounts for its percentage by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93115774A CN1043739C (en) | 1993-08-31 | 1993-08-31 | Catalyst and process for prodn. of dimethyl ether by using synthetic gas as raw material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93115774A CN1043739C (en) | 1993-08-31 | 1993-08-31 | Catalyst and process for prodn. of dimethyl ether by using synthetic gas as raw material |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98114227A Division CN1095457C (en) | 1998-08-12 | 1998-08-12 | Process for preparing dimethyl ether from synthetic gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1085824A CN1085824A (en) | 1994-04-27 |
| CN1043739C true CN1043739C (en) | 1999-06-23 |
Family
ID=4991311
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93115774A Expired - Lifetime CN1043739C (en) | 1993-08-31 | 1993-08-31 | Catalyst and process for prodn. of dimethyl ether by using synthetic gas as raw material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8779014B2 (en) | 2006-12-14 | 2014-07-15 | Taiyuan University Of Technology | Slurry catalyst and the preparation thereof |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1077809C (en) * | 1996-08-02 | 2002-01-16 | 中国科学院大连化学物理研究所 | Catalyst for preparing dimethyl ether from gas containing carbon monoxide and hydrogen |
| US5753716A (en) * | 1997-02-21 | 1998-05-19 | Air Products And Chemicals, Inc. | Use of aluminum phosphate as the dehydration catalyst in single step dimethyl ether process |
| US6458856B1 (en) | 2001-11-07 | 2002-10-01 | Air Products And Chemicals, Inc. | Separation process for one-step production of dimethyl ether from synthesis gas |
| CN101380585B (en) * | 2007-09-07 | 2011-07-27 | 新奥科技发展有限公司 | Wide temperature type methanol dehydration catalyst for producing dimethyl ether and preparation method thereof |
| US9610568B2 (en) * | 2012-02-15 | 2017-04-04 | Basf Se | Catalytically active body for the synthesis of dimethyl ether from synthesis gas |
| US8835517B2 (en) | 2012-05-30 | 2014-09-16 | Cool Planet Energy Systems, Inc. | Method for producing dimethyl ether using a separator |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4776945A (en) * | 1984-11-30 | 1988-10-11 | Shell Oil Company | Single-stage hydrotreating process |
| CN1070418A (en) * | 1991-09-11 | 1993-03-31 | 中国石油化工总公司抚顺石油化工研究院 | A kind of Hydrobon catalyst and method for making thereof |
-
1993
- 1993-08-31 CN CN93115774A patent/CN1043739C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4776945A (en) * | 1984-11-30 | 1988-10-11 | Shell Oil Company | Single-stage hydrotreating process |
| CN1070418A (en) * | 1991-09-11 | 1993-03-31 | 中国石油化工总公司抚顺石油化工研究院 | A kind of Hydrobon catalyst and method for making thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8779014B2 (en) | 2006-12-14 | 2014-07-15 | Taiyuan University Of Technology | Slurry catalyst and the preparation thereof |
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| Publication number | Publication date |
|---|---|
| CN1085824A (en) | 1994-04-27 |
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