CN1132664A - Composite catalyst for one-step process preparing dimethyl ether from synthetic gas and its prepn - Google Patents
Composite catalyst for one-step process preparing dimethyl ether from synthetic gas and its prepn Download PDFInfo
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- CN1132664A CN1132664A CN 95103655 CN95103655A CN1132664A CN 1132664 A CN1132664 A CN 1132664A CN 95103655 CN95103655 CN 95103655 CN 95103655 A CN95103655 A CN 95103655A CN 1132664 A CN1132664 A CN 1132664A
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- catalyst
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- composite catalyst
- dimethyl ether
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- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 title claims description 21
- 238000000034 method Methods 0.000 title claims description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims description 30
- 239000011701 zinc Substances 0.000 claims description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 26
- 229910052802 copper Inorganic materials 0.000 claims description 26
- 229910052725 zinc Inorganic materials 0.000 claims description 23
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 22
- 238000003786 synthesis reaction Methods 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 15
- 238000000975 co-precipitation Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 9
- 229910002651 NO3 Inorganic materials 0.000 claims description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 9
- 229910052796 boron Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims 1
- 239000003426 co-catalyst Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000002955 isolation Methods 0.000 abstract description 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract 1
- 150000004706 metal oxides Chemical class 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 45
- 239000000243 solution Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 3
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- -1 zinc basic salt Chemical class 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A one-step coprecipitation-impregnating process for preparing metal oxide mixture catalyst used to prepare dimethyl ether features no need of a part of alumina only playing isolation role and use of B as catalyst promoter. The mole contents of metals are Cu (20-40%), Zn (10-30%), Al (40-60%) and B (0.5-2%). Said catalyst has the advantages of mild reaction condition and high yield of dimethyl ether.
Description
The invention relates to a composite catalyst for preparing dimethyl ether by a one-step method of synthesis gas and a preparation method thereof, belonging to the technical field of chemical catalyst preparation.
A one-step process for the production of dimethyl ether from synthesis gas (a mixture of carbon monoxide and hydrogen) was developed as part of the process for the production of gasoline from synthesis gas. The process for the preparation of gasoline from synthesis gas (MTG), originally developed by Mobil corporation, comprises three steps, respectively carrying out the following three chemical reactions:
wherein, the reaction (1) uses traditional methanol synthesis catalyst, such as copper/zinc/aluminum, copper/zinc/chromium, etc.; reaction (2) uses a solid acid catalyst such as gamma-alumina, aluminum silicate, molecular sieves, and the like.
Subsequently, the TIGAS process developed by Topsoe corporation completed reaction (1) and reaction (2) in one step in one reactor using a catalyst which was a composite catalyst consisting of a methanol synthesis catalyst and a methanol dehydration catalyst (U.S. patent 4520216). The main advantage of this is that the methanol produced in reaction (1) is continuously converted to dimethyl ether by reaction (2), overcoming the thermodynamic equilibrium limitation of reaction (1), and the per pass conversion of carbon monoxide and hydrogen can be greatly increased.
Numerous patents disclose hybrid catalysts for the one-step preparation of dimethyl ether from syngas, such as U.S. patents 3894102, 4417000, 4520216; japanese patents 60-179494, 63-254188; european patents 0148126a2, 0164156a 1; british patent 2093365a, et al. The composite catalysts used in these patents are all mechanical mixtures of methanol synthesis catalysts and methanol dehydration catalysts. This composite catalyst has two disadvantages: firstly, the two catalyst particles cannot be in close contact with each other, and secondly, the carrier (alumina and chromium oxide) which plays a role in isolation in the methanol catalyst loses the function in the composite catalyst, and the existence of the carrier increases the volume of the catalyst unnecessarily. Both of the above disadvantages result in a decrease in catalyst activity. For example: the composite catalyst disclosed in us patent 4520216 is a mixture of particles of a methanol synthesis catalyst (a mixed oxide catalyst prepared by a general coprecipitation method and having a copper/zinc/chromium molar ratio of 30-40/10-60/50-18) and particles of a methanol dehydration catalyst (γ -alumina) or a mixture of two catalysts mechanically mixed and molded. The preparation method of the composite catalyst disclosed in European patent 164156 comprises the following steps: a) preparing a mixed solution of copper, zinc, aluminum and/or chromium, wherein the molar ratio of each metal is as follows: copper/zinc<10, (chromium + aluminum)/(copper + zinc)<2, copper/(copper + zinc + chromium + aluminum)>0.1; b) adding alkali at the temperature lower than 70 ℃ to perform coprecipitation; c) drying and calcining the obtained precipitate; d) the resulting product is mixed with a dehydration catalyst (gamma-alumina, etc.).
The object of the present invention is to overcome the above two disadvantages and to improve the activity of the composite catalyst.
The invention will now be summarized.
The invention relates to a composite catalyst for preparing dimethyl ether by a one-step method of synthesis gas, which is a mixed metal oxide, wherein the mole percentage of each metal is as follows:
20-40% of copper
10-30% of zinc
40-60 aluminum is characterized in that the aluminum is prepared by a coprecipitation dipping method. A small amount of boron can be added into the composite catalyst to serve as a cocatalyst, and the molar content of the boron is 0.5-2%.
The invention also relates to a preparation method of the composite catalyst, which is characterized in that nitrate of copper and zinc is prepared into mixed nitrate solution with the concentration of about 1 mol per liter by deionized water according to the proportion of the copper and the zinc in the catalyst; dripping the solution and 1 mol/L sodium carbonate solution into a beaker filled with gamma-alumina for coprecipitation impregnation, wherein the dosage of the gamma-alumina is in accordance with the content of aluminum in the catalyst, the gamma-alumina is soaked by a small amount of deionized water before impregnation, the coprecipitation impregnation is carried out under continuous stirring, the temperature is 50-90 ℃, the pH value is 6-8, and the relative flow rate of the two solutions is controlled; continuing to stir the obtained precipitate after stopping feeding, and aging for 15-60 minutes by keeping constant temperature; filtering the aged precipitate and washing with deionized water; drying the washed precipitate in a drying oven at 80-120 ℃ for 8-16 hours; then placing the mixture into a muffle furnace to be calcined for 8 to 16 hours at the temperature of 350 to 450 ℃; the obtained solid was molded by a tablet press.
In the preparation method, boric acid with the boron molar content of 0.5-2% in the catalyst can be added into the mixed nitrate solution of copper and zinc.
Example (b):
comparative example 1: firstly, preparing a methanol synthesis catalyst by using a traditional coprecipitation method, wherein the method comprises the following steps: 14.5 g of Cu (NO)3)2·3H2O (copper nitrate trihydrate), 8.9 g Zn (NO)3)2·6H2O (Zinc nitrate hexahydrate) and 3.8 g Al (NO)3)3·9H2O (aluminum nitrate nonahydrate) is dissolved in 100 ml of deionized water. The mixed nitrate solution was coprecipitated by dropping 1 mol per liter of an aqueous sodium carbonate solution (prepared by dissolving 10.6 g of anhydrous sodium carbonate in 100 ml of deionized water) simultaneously into a beaker containing a small amount of deionized water. Stirring continuously during the coprecipitation process, keeping the temperature at 70 ℃ and keeping the pH value at about 7. And aging for 30 minutes after the coprecipitation is finished. The precipitate was filtered and then washed with deionized water. And drying the cleaned precipitate in an oven at 100 ℃ for 12 hours, and calcining the precipitate in a muffle furnace at 400 ℃ for 12 hours to obtain the unformed methanol synthesis catalyst. Wherein the molar ratio of copper/zinc/aluminum is 6: 3: 1. Mixing the obtained unformed methanol synthesis catalyst with 5.1 g of gamma-alumina powder, grinding to 200 meshes, and then tabletting and forming to obtain the composite catalyst prepared by a mechanical mixing method, wherein the molar ratio of copper/zinc/aluminum is 6: 3: 11.
Example 1: 14.5 g of Cu (NO)3)2·3H2O (copper nitrate trihydrate) and 8.9 g Zn (NO)3)2·6H2O (zinc nitrate hexahydrate) was dissolved in 100 ml of deionized water to prepare a mixed nitrate solution. This solution was simultaneously added dropwise to a beaker containing 5.1 g of gamma-alumina together with 1 mol/l of sodium carbonate solution for coprecipitation impregnation. Before impregnation, a small amount of deionized water is used for soaking the gamma-alumina. The coprecipitation dipping is carried out under the condition of continuous stirring, the temperature is 70 ℃, the pH value is kept at about 7, the obtained precipitate is continuously stirred after the feeding is stopped, and the constant temperature is kept for aging for 30 minutes; filtering the aged precipitate and washing with deionized water; and (3) drying the washed precipitate in an oven at 100 ℃ for 12 hours, then calcining thedried precipitate in a muffle furnace at 350 ℃ for 6 hours, and forming the obtained solid by a tablet press to obtain the boron-free composite catalyst, wherein the molar ratio of copper to zinc to aluminum is 6: 3: 10.
Example 2: the procedure, procedure and conditions were as in example 1 except that 2.1 g of boric acid was added to the mixed nitrate solution of copper and zinc. The molar ratio of copper/zinc/aluminum/boron in the obtained catalyst is 6: 3: 10: 0.2. The catalyst is the composite catalyst containing boron.
Comparative example 2: as comparative example 1, except that the molar ratio of Cu/Zn/Al in the methanol synthesis catalyst was 5: 7: 2, the molar ratio of Cu/Zn/Al in the composite catalyst prepared by mechanical mixing was 5: 7: 14.
Example 3: the same as example 1, except that the copper/zinc/aluminum molar ratio in the composite catalyst was 5: 7: 12.
Example 4: the same as example 2 except that the molar ratio of copper/zinc/aluminum/boron was 5: 7: 12: 0.3.
Catalyst activity evaluation method:
and crushing and screening the prepared catalyst, and filling 20-40-mesh particles into a tubular reactor with the inner diameter of 6 mm. Reducing by 1-10% hydrogen (the balance being nitrogen) at normal pressure according to a certain temperature rise program (raising the temperature from room temperature to 250 ℃ at the speed of 0.5 ℃ per minute, keeping the temperature constant at 250 ℃ for 4 hours), and then reacting. The raw material gas composition is that hydrogen/carbon monoxide is 2: 1 (mol ratio), reaction pressure is 3 MPa, space velocity is 1000 per hour, catalyst activity is measured at three temperatures of 230, 250 and 270 ℃, and product gas is analyzed by gas chromatography. The results of the measurements in terms of yield of dimethyl ether are shown in Table 1.
TABLE 1 evaluation results of catalyst Activity
| Examples of the invention | Yield of dimethyl ether (mol per liter per hour) | ||
| 230℃ | 250℃ | 270℃ | |
| Comparative example 1 Example 1 Example 2 Comparative example 2 Example 3 Example 4 | 0.87 1.84 3.72 0.82 1.71 3.45 | 1.97 4.25 5.92 1.79 4.01 5.70 | 3.72 5.72 6.14 3.54 5.40 6.03 |
As can be seen from the table, the catalyst prepared by the method has greatly improved catalytic activity for preparing dimethyl ether by one step from synthesis gas. The reason is that: 1. during coprecipitation impregnation, gamma-Al2O3The copper and zinc basic salt precipitate formed in the pore canal is limited by the pores, the particles are fine, and after calcination and decomposition, highly dispersed and mutually closely contacted mixed metal oxides can be formed, so that the synergistic effect among the components is enhanced, and methanol generated on the copper and zinc oxides can be timely converted into dimethyl ether on gamma-alumina. 2. Infrared spectroscopy experiments show that the adsorption of carbon monoxide on copper is enhanced by the presence of boron, thereby promoting the methanol synthesis reaction.
Claims (4)
1. A composite catalyst for preparing dimethyl ether by a one-step method of synthesis gas is a mixed metal oxide, wherein the mole percentage of each metal is as follows:
20-40% of copper
10-30% of zinc
40-60 aluminum is characterized in that the aluminum is prepared by a coprecipitation impregnation method.
2. The composite catalyst of claim 1, wherein a small amount of boron is added as a co-catalyst in a molar amount of 0.5 to 2%.
3. A method for preparing the composite catalyst of claim 1, characterized by that make the nitrate of copper, zinc into the mixed nitrate solution with the concentration of about 1 mol per liter with deionized water according to the proportion of copper, zinc in the above-mentioned catalyst, drip this solution and 1 mol per liter of sodium carbonate solution into the beaker containing gamma-alumina at the same time and carry on the coprecipitation and impregnate, the consumption of gamma-alumina accords with the content of aluminium in the catalyst, soak by a small amount of deionized water before impregnating, the coprecipitation is impregnated under constantly stirring, the temperature is 50-90 degrees C, pH value is between 6-8, is controlled by the relative flow rate of two kinds of solutions; after the feeding is stopped, continuously stirring the obtained precipitate, keeping the constant temperature and aging for 15-60 minutes; filtering the aged precipitate and washing with deionized water; drying the washed precipitate in a drying oven at 80-120 ℃ for 8-16 hours; then placing the mixture into a muffle furnace to be calcined for 8 to 16 hours at the temperature of 350 to 450 ℃; the obtained solid was molded by a tablet press.
4. A process according to claim 3, wherein boric acid is added to the mixed nitrate solution of copper and zinc so that the molar content of boron in the catalyst is 0.5 to 2%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95103655 CN1132664A (en) | 1995-04-07 | 1995-04-07 | Composite catalyst for one-step process preparing dimethyl ether from synthetic gas and its prepn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95103655 CN1132664A (en) | 1995-04-07 | 1995-04-07 | Composite catalyst for one-step process preparing dimethyl ether from synthetic gas and its prepn |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1132664A true CN1132664A (en) | 1996-10-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95103655 Pending CN1132664A (en) | 1995-04-07 | 1995-04-07 | Composite catalyst for one-step process preparing dimethyl ether from synthetic gas and its prepn |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318138C (en) * | 2004-02-18 | 2007-05-30 | 中国石油化工股份有限公司 | Catalyst used for preparing dimethyl ether directly from synthetic gas |
| CN101850254A (en) * | 2010-06-08 | 2010-10-06 | 浙江大学 | Preparation method of catalyst used for synthesizing methanol and dimethyl ether from synthesis gas |
| CN101190415B (en) * | 2006-11-28 | 2011-05-11 | 韩国燃气公社 | Method of producing a catalyst used for synthesizing dimethylether from a synthesis gas containing carbon dioxide |
| CN101745403B (en) * | 2008-12-18 | 2012-09-12 | 中国石油化工股份有限公司 | Method for preparation of methanol, dimethyl ether and low-carbon olefin with synthetic gas |
| CN103084203A (en) * | 2011-10-31 | 2013-05-08 | 东北大学 | Method for preparing CuZnAlFe system catalyst for catalyzing preparation of dimethyl ether through reacting CO2 with H2 |
| CN103949258A (en) * | 2014-04-08 | 2014-07-30 | 太原理工大学 | Method and application of catalyst for slurry-state bed synthesis gas preparation of dimethyl ether |
| CN114920627A (en) * | 2022-04-11 | 2022-08-19 | 南方海洋科学与工程广东省实验室(广州) | Method for preparing dimethyl ether by one-step catalytic method of natural gas hydrate |
-
1995
- 1995-04-07 CN CN 95103655 patent/CN1132664A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318138C (en) * | 2004-02-18 | 2007-05-30 | 中国石油化工股份有限公司 | Catalyst used for preparing dimethyl ether directly from synthetic gas |
| CN101190415B (en) * | 2006-11-28 | 2011-05-11 | 韩国燃气公社 | Method of producing a catalyst used for synthesizing dimethylether from a synthesis gas containing carbon dioxide |
| CN101745403B (en) * | 2008-12-18 | 2012-09-12 | 中国石油化工股份有限公司 | Method for preparation of methanol, dimethyl ether and low-carbon olefin with synthetic gas |
| CN101850254A (en) * | 2010-06-08 | 2010-10-06 | 浙江大学 | Preparation method of catalyst used for synthesizing methanol and dimethyl ether from synthesis gas |
| CN103084203A (en) * | 2011-10-31 | 2013-05-08 | 东北大学 | Method for preparing CuZnAlFe system catalyst for catalyzing preparation of dimethyl ether through reacting CO2 with H2 |
| CN103949258A (en) * | 2014-04-08 | 2014-07-30 | 太原理工大学 | Method and application of catalyst for slurry-state bed synthesis gas preparation of dimethyl ether |
| CN114920627A (en) * | 2022-04-11 | 2022-08-19 | 南方海洋科学与工程广东省实验室(广州) | Method for preparing dimethyl ether by one-step catalytic method of natural gas hydrate |
| CN114920627B (en) * | 2022-04-11 | 2024-02-20 | 南方海洋科学与工程广东省实验室(广州) | Method for preparing dimethyl ether by catalyzing natural gas hydrate through one-step method |
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