CN101602646B - Method for producing arene from methanol/dimethyl ether and special reaction device therefor - Google Patents
Method for producing arene from methanol/dimethyl ether and special reaction device therefor Download PDFInfo
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- CN101602646B CN101602646B CN200910089699A CN200910089699A CN101602646B CN 101602646 B CN101602646 B CN 101602646B CN 200910089699 A CN200910089699 A CN 200910089699A CN 200910089699 A CN200910089699 A CN 200910089699A CN 101602646 B CN101602646 B CN 101602646B
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- revivifier
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a method for producing arene from methanol/dimethyl ether and a special reaction device therefor. The method comprises the following step: 1) performing contact reaction on a raw material and a catalyst to obtain the arene. In the method, the raw material is a mixture of water and at least one of the methanol and the dimethyl; the catalyst to oil ratio of the catalyst to the raw material is 1-20, and preferably 3-10; the temperature of the contact reaction is between 400 and 650DEG C, and preferably between 450 and 550DEG C; the pressure of the contact reaction is between 0.01 and 2.0MPa, and preferably between 0.01 and 1.0MPa; and the reaction time is between 0.1 and 15 seconds, and preferably between 1 and 10 seconds. The reaction device of the contact reaction is a continuous reaction regenerative fluidized bed. In the method for producing the arene, the conversion rate of the methanol or the dimethyl is more than 80 percent, and the content of the arene in products is between 50 and 60 weight percent.
Description
Technical field
The present invention relates to a kind of methyl alcohol/dme and produce the method and the special reaction device thereof of aromatic hydrocarbons.
Background technology
It is the technological line that methyl alcohol direct aromizing on metal and molecular sieve compound catalyzer is transformed into aromatic hydrocarbons that methyl alcohol directly prepares aromatic hydrocarbons (MTA) technology, has opened up and has utilized coal or natural gas source to prepare the new way of petroleum chemicals.
The aromatization of methanol temperature of reaction is 400-600 ℃, has temperature similarity and real operability with the catalytic process of existing refining of petroleum.
Aromatization of methanol comprises the process of methanol dehydration, dehydrocyclization; The dehydrogenation metal catalyzer generally can cause the decomposition of methyl alcohol, thus select suitable methanol dehydrogenation component and with the research and development of acidic molecular sieve compound catalyzer will be the key that realizes that this process technology is broken through.
Aromatization of methanol is a strong exothermal reaction, and under the temperature of reaction of aromizing, catalyzer meeting coking deactivation is so exploitation aromizing and continuous catalyst regenerating technology also are to realize the key of this process industrialization.Fluidized-bed process has the unrivaled meliority of fixed-bed process aspect the heat exchange of reactor drum and the solid conveying, thereby is particularly suitable for the reaction process that catalyzer needs cyclic regeneration.In the existing apparatus, all be difficult to control to deciding parameters such as carbon on temperature of reaction, regeneration temperature, the regeneration rear catalyst.
Summary of the invention
The objective of the invention is a kind of methyl alcohol/dme and produce the method and the special reaction device thereof of aromatic hydrocarbons.
Methyl alcohol provided by the invention/dme is produced the isolated plant of aromatic hydrocarbons, comprises settling vessel, reactor drum and revivifier;
Be provided with gas-solid separator in the said settling vessel, said gas-solid separator links to each other with said reactor head through pipeline, and said settling vessel bottom is provided with stripping stage;
Said sidewall of reactor is provided with reaction heat collector nozzle, feed nozzle from top to bottom successively and promotes vapor-nozzle in advance, bottom degassing vessel, communicates through regenerator sloped tube at said feed nozzle and the sidewall that promotes in advance between the vapor-nozzle;
Said degassing vessel communicates with said revivifier through two tilted tubes, and coke-burning riser extends to said revivifier outside and the mouth of pipe links to each other with the main air nozzle; At the revivifier sidewall relative with said degassing vessel, the port that port that the outlet, storage tank that is provided with the inlet of gas-solid separator, said gas-solid separator from top to bottom successively and said revivifier communicate through pipeline and heat collector and said revivifier communicate through pipeline;
The other end of said storage tank and heat collector communicates with said coke-burning riser through pipeline respectively; The port that said heat collector is connected with coke-burning riser is positioned on said storage tank and the port that coke-burning riser is connected; On the pipeline that pipeline reaches with coke-burning riser communicates that said heat collector communicates with said revivifier, communicate through return tube; Said stripping stage bottom communicates with said coke-burning riser through pipeline.
In the above-mentioned isolated plant, various gas-solid separators commonly used all are suitable for, and preferred, the gas-solid separator that is arranged in settling vessel is the cyclone gas-solid separator, and the gas-solid separator that links to each other with revivifier is the two-stage gas-solid separator.Equipment therefor is the conventional fast device that divides step by step soon.
Methyl alcohol provided by the invention/dme is produced the method for aromatic hydrocarbons, is in above-mentioned isolated plant, produces aromatic hydrocarbons according to the method that comprises the steps:
1) with raw material from feed nozzle or promote vapor-nozzle in advance and get into reactor drum, with the catalyzer contact reacts that gets into from regenerator sloped tube; The reaction heat that produces in the reaction process is taken out by the reaction heat collector;
Said raw material is the mixture of at least a and water in methyl alcohol and the dme;
Said catalyst system is made up of metal and combined modified sieve catalyst, sticker and the matrix of silylanization;
2) the mixture oil gas of said reactor drum internal reaction generation passes through the gas-solid separator sharp separation: said catalyzer gets into the settling vessel bottom, and oil gas gets into the water cooler refrigerated separation from settling vessel top;
3) said catalyzer gets into stripping stage in the settling vessel bottom, and the oil gas in the said catalyzer is by stripping, and said catalyzer gets into coke-burning riser;
4) in coke-burning riser, said catalyzer contacts with the main air that gets into from the main air nozzle, mixes, burns, divides the back to get into revivifier soon; Said main air is an air;
5) in revivifier, burn the catalyzer that finishes and flow into regenerator sloped tube, the flue gas that regenerated catalyst is taken away returns revivifier after in degassing vessel, deviating from;
Wherein, said method of burning the bed temperature of the catalyzer that finishes is in the control revivifier: the said catalyzer that finishes that burns is used the heat collector heat-obtaining, and cooled catalyzer returns in the coke-burning riser;
Said method of burning the carbon content of the catalyzer that finishes is in the control revivifier: the said catalyzer that finishes that burns is returned in the coke-burning riser through return tube;
6) flue gas that produces in the revivifier is told catalyzer through gas-solid separator, and said flue gas produces steam in waste heat boiler, and said catalyzer is turned back in the revivifier by gas-solid separator.
In this method, the agent-oil ratio of catalyst quality and raw material is 1-20, preferred 3-10; In the said catalyst system, matrix all is selected from least a in kaolin, the aluminum oxide, and sticker all is selected from least a in aluminum oxide, aluminium colloidal sol and the pseudo-boehmite; The ratio of quality and the number of copies of sieve catalyst, sticker and matrix that metal and silylanization are combined modified is 30-70: 30-10: 40-20, preferred 40-60: 10-20: 30-40.Catalytic temperature is 400-650 ℃, preferred 450-550 ℃; Catalytic pressure is 0.01-2.0MPa, preferred 0.01-1.0MPa; The catalytic time is 0.1-15 second, preferred 1-10 second.
This catalytic reaction unit is a successive reaction regenerated fluidized-bed.Valve is set on said heat collector, storage tank, regenerator sloped tube and the return tube controls out the catalyst recirculation amount.Stop work or when drawing off said catalyzer, said catalyzer is discharged in the storage tank; During make-up catalyst, in storage tank, put in the catalyzer entering coke-burning riser.
The Si-Al molecular sieve catalyzer of metal and silylanization modification is to prepare according to the method that comprises the steps:
1) is that properties-correcting agent carries out modification to molecular sieve with soluble metallic salt or MOX, obtains metal modified molecular screen; Said properties-correcting agent is selected from the soluble salt or the oxide compound of following any one metallic element: Mn, Co, Ni, Cu, Zn, Mo and Ga; The structure type of said molecular sieve is MFI type or MEL type;
2) with the siloxanes compound metal modified molecular screen that step 1) obtains is carried out modification, obtain the combined modified sieve catalyst of said metal and silylanization;
Said siloxanes structural general formula is suc as formula shown in the I:
(formula I)
Wherein, R
1, R
2, R
3And R
4All be selected from C
1-C
10Alkyl.
In the Si-Al molecular sieve catalyzer of metal and silylanization modification, the quality percentage composition of said metallic element is 0.1-8%.
In the step 1), said MFI type molecular sieve is a type ZSM 5 molecular sieve, and said MEL type molecular sieve is a ZSM-11 type molecular sieve; Preferred type ZSM 5 molecular sieve; Said properties-correcting agent is selected from the soluble salt or the oxide compound of following any one metallic element: Mn, Zn and Mo; Step 2) in, said siloxanes compound is a tetraethyl silicate.
In the method for production aromatic hydrocarbons provided by the invention,, heat of reaction in the reactor drum is taken out through heat collector or taken out of through aqueous vaporization, accurately the carbon content of control reaction temperature and revivifier inner catalyst through special reaction device.Utilize in the aromatic hydrocarbons of this method production, the transformation efficiency of methyl alcohol or dme is greater than 80%, and the content of aromatic hydrocarbons in the product (benzene, toluene and YLENE) is at 50-60wt%.
Description of drawings
Fig. 1 is the fluidized bed reaction synoptic diagram.
Embodiment
The reaction unit of production aromatic hydrocarbons provided by the invention is a fluidized-bed, and its structural representation is as shown in Figure 1, and 1 is revivifier, and 2 is coke-burning riser, and 3 is heat collector; 4 is storage tank, and 5 is the two-stage gas-solid separator, and 6 is degassing vessel, and 7 is regenerator sloped tube, and 8 is reactor drum; 9 are the reaction heat collector, and 10 is feed nozzle, and 11 is settling vessel, and 12 is stripping stage, and 13 is to promote vapor-nozzle in advance; 14 is the cyclone gas-solid separator, and 15 is return tube, and 16 is the main air nozzle, and 17 is the fast device that divides.
Below in conjunction with specific embodiment the present invention is described further, but the present invention is not limited to following examples.
With the former powder of ZSM-5 zeolite molecular sieve (Catalyst Factory, Nankai Univ) (SiO
2/ Al
2O
3=50) remove template 550 ℃ of following roastings, in 80 ℃ of water-baths, exchange 4 times with ammonium nitrate solution, dry in 120 ℃ of air the exchange back, and 550 ℃ of following roastings 3 hours obtain the HZSM-5 zeolite molecular sieve.
Get the HZSM-5 zeolite molecular sieve 50Kg of above-mentioned preparation, the use mass percent concentration is 9% zinc nitrate [Zn (NO
3)
26H
2O] aqueous solution normal temperature dipping 4 hours; Roasting is 6 hours in 120 ℃ of back 550 ℃ of air of oven dry; Zn content is 5wt% in the catalyzer; Adopt the HZSM-5 zeolite molecular sieve 24 hours behind tetraethoxy (TEOS) the normal temperature dipping zinc modification, inclining behind the supernatant liquid in 120 ℃ of oven dry, the 550 ℃ of air roasting 6 hours, obtained the molecular sieve of metal and silylanization modification.After adding 20Kg kaolin matrix and 10Kg alumina binder, spray drying forming obtains catalyzer, called after MTA-026 catalyst system.
In successive reaction regenerated fluidised bed system, charging is a methyl alcohol, liquid phase feeding; Adopt method for preparing gained MTA-026 catalyst system, temperature of reaction is 480 ℃, and regenerator temperature is 650 ℃; The residence time is 5 seconds, catalyst/feed mass ratio 10, reaction pressure 125KPa; Conversion of methanol 81.89%, the mass content of benzene, toluene and YLENE (BTX) is greater than 50wt% in the product.
Prepare in reaction unit shown in Figure 1 according to following flow process:
Methyl alcohol from feed nozzle 10 or promote vapor-nozzle 13 in advance and get into reactor drums 8, is contacted with the catalyzer of putting into from regenerator sloped tube 7, react.
Methyl alcohol is emitted big calorimetric and is taken out through reaction heat collector 9 at reactor drum 8 internal reaction.
The aromatic hydrocarbons that reactor drum 8 internal reactions generate and hydrocarbon and water vapour and unreacted methanol oil gas separate through 14 speed of cyclone gas-solid quick disconnector, catalyzer entering settling vessel 11 bottoms, oil gas aerator refrigerated separation after the entering of settling vessel 11 tops.
Catalyzer gets into stripping stage 12 after getting into settling vessel 11 bottoms, and oil gas is by steam stripped on stripping stage 12 inner catalysts, and the catalyzer that stripping is clean gets in the coke-burning riser 2.
In coke-burning riser 2, catalyzer with contact wind with main air and mix from main air nozzle 16, burn, wind and catalyzer reach in the revivifier 1 through too fast assigning to together.
Burn good catalyzer in the revivifier 1 and flow into regenerator sloped tube 7, the flue gas that regenerated catalyst is taken away is deviate to return in the revivifier 1 in degassing vessel 6.
In order to control revivifier inner catalyst bed temperature, the part catalyzer is through heat collector 3 heat-obtainings, and the refrigerative catalyzer returns in the coke-burning riser 2, and in order to control revivifier inner catalyst carbon content, the part catalyzer returns in the coke-burning riser 2 through return tube 15.
During shut-down or system when drawing off catalyzer, be discharged to catalyzer in the storage tank 4, put catalyzer in the storage tank 4 when system needs fresh makeup catalyst and get in the coke-burning riser 2.
Flue gas is told catalyzer through two-stage gas-solid separator 5 in the revivifier 1, and flue gas goes the back waste heat boiler to produce steam.Heat collector, storage tank, regenerator sloped tube, return tube etc. go out the catalyst recirculation amount through valve control.
After reaction finishes, be utilized in linear flow rate meter record mensuration and can know that conversion of methanol is greater than 80%, the quality percentage composition of benzene, toluene and YLENE (BTX) is greater than 50wt% in the product.
With embodiment 1 identical device be in the successive reaction regenerated fluidised bed system, charging is a first alcohol and water liquid phase feeding, adopts embodiment 1 preparation gained MTA-026 catalyst system; Temperature of reaction is 500 ℃, and regenerator temperature is 650 ℃, and the residence time is 10 seconds; Catalyst/feed mass ratio 5; Reaction pressure 125KPa, conversion of methanol is 83.56%, the content of benzene, toluene and YLENE (BTX) is greater than 50wt% in the product.
With embodiment 1 identical device be in the successive reaction regenerated fluidised bed system, charging be the dme gas-phase feed from preparatory lifting vapor-nozzle 13 chargings, adopt embodiment 1 preparation gained MTA-026 catalyst system; Temperature of reaction is 450 ℃, and regenerator temperature is 580 ℃, and the residence time is 5 seconds; The catalyst/feed mass ratio; Reaction pressure 125KPa, the transformation efficiency of dme is 86.17%, the content of benzene, toluene and YLENE (BTX) is greater than 50wt% in the product.
With embodiment 1 identical device be in the successive reaction regenerated fluidised bed system, charging is the dme liquid phase feeding, adopts embodiment 1 preparation gained MTA-026 catalyst system; Temperature of reaction is 400 ℃, and regenerator temperature is 620 ℃, and the residence time is 10 seconds; Catalyst/feed mass ratio 8; Reaction pressure 1.0MPa, the dimethyl ether conversion rate is 86.33%, the content of benzene, toluene and YLENE (BTX) is greater than 50wt% in the product.
With embodiment 1 identical device be in the successive reaction regenerated fluidised bed system, charging is the methyl alcohol liquid phase feeding that contains the 10wt% dme, adopts embodiment 1 preparation gained MTA-026 catalyst system; Temperature of reaction is 450 ℃, and regenerator temperature is 620 ℃, and the residence time is 5 seconds; Catalyst/feed mass ratio 6; Reaction pressure 0.5MPa, conversion of raw material is 87.94%, the content of benzene, toluene and YLENE (BTX) is greater than 50wt% in the product.
Claims (10)
1. an isolated plant of producing aromatic hydrocarbons comprises settling vessel, reactor drum and revivifier;
Be provided with gas-solid separator in the said settling vessel, said gas-solid separator links to each other with said reactor head through pipeline, and said settling vessel bottom is provided with stripping stage;
Said sidewall of reactor is provided with reaction heat collector nozzle, feed nozzle from top to bottom successively and promotes vapor-nozzle in advance, bottom degassing vessel, communicates through regenerator sloped tube at said feed nozzle and the sidewall that promotes in advance between the vapor-nozzle;
Said degassing vessel communicates with said revivifier through two tilted tubes, and coke-burning riser extends to said revivifier outside and the mouth of pipe links to each other with the main air nozzle; At the revivifier sidewall relative with said degassing vessel, the port that port that the outlet, storage tank that is provided with the inlet of gas-solid separator, said gas-solid separator from top to bottom successively and said revivifier communicate through pipeline and heat collector and said revivifier communicate through pipeline;
The other end of said storage tank and heat collector communicates with said coke-burning riser through pipeline respectively; The port that said heat collector is connected with coke-burning riser is positioned on said storage tank and the port that coke-burning riser is connected; On the pipeline that pipeline reaches with coke-burning riser communicates that said heat collector communicates with said revivifier, communicate through return tube; Said stripping stage bottom communicates with said coke-burning riser through pipeline.
2. device according to claim 1 is characterized in that: the gas-solid separator that is arranged in settling vessel is the cyclone gas-solid separator, and the gas-solid separator that links to each other with revivifier is the two-stage gas-solid separator.
3. the method that methyl alcohol/dme is produced aromatic hydrocarbons is in the said isolated plant of claim 1, produces aromatic hydrocarbons according to the method that comprises the steps:
1) with raw material from feed nozzle or promote vapor-nozzle in advance and get into reactor drum, with the catalyzer contact reacts that gets into from regenerator sloped tube; The reaction heat that produces in the reaction process is taken out by the reaction heat collector;
Said raw material is the mixture of at least a and water in methyl alcohol and the dme;
Said catalyst system is made up of metal and combined modified sieve catalyst, sticker and the matrix of silylanization;
2) the mixture oil gas of said reactor drum internal reaction generation passes through the gas-solid separator sharp separation: said catalyzer gets into the settling vessel bottom, and oil gas gets into the water cooler refrigerated separation from settling vessel top;
3) said catalyzer gets into stripping stage in the settling vessel bottom, and the oil gas in the said catalyzer is by stripping, and said catalyzer gets into coke-burning riser;
4) in coke-burning riser, said catalyzer contacts, mixes with the main air that gets into from the main air nozzle, burns, divides the back to get into revivifier soon;
5) in revivifier, burn the catalyzer that finishes and flow into regenerator sloped tube through degassing vessel by revivifier, the said flue gas that burns the catalyst entrainment that finishes returns revivifier after degassing vessel is deviate from;
Wherein, said method of burning the bed temperature of the catalyzer that finishes is in the control revivifier: the said catalyzer that finishes that burns is used the heat collector heat-obtaining, and cooled catalyzer returns in the coke-burning riser;
Said method of burning the carbon content of the catalyzer that finishes is in the control revivifier: the said catalyzer that finishes that burns is returned in the coke-burning riser through return tube;
6) flue gas that produces in the revivifier is told the wherein said catalyzer that finishes that burns through gas-solid separator, and said flue gas produces steam in waste heat boiler, and the said catalyzer that finishes that burns is turned back in the revivifier by gas-solid separator.
4. method according to claim 3 is characterized in that: the agent-oil ratio of said catalyst quality and raw material is 1-20; In the said catalyst system, the ratio of quality and the number of copies of sieve catalyst, sticker and matrix that metal and silylanization are combined modified is 30-70: 30-10: 40-20.
5. according to claim 3 or 4 described methods, it is characterized in that: in the said catalyst system, matrix is selected from least a in kaolin, the aluminum oxide, and sticker is selected from least a in aluminum oxide, aluminium colloidal sol and the pseudo-boehmite.
6. method according to claim 5 is characterized in that: catalytic temperature is 400-650 ℃; Catalytic pressure is 0.01-2.0MPa; The catalytic time is 0.1-15 second.
7. method according to claim 6 is characterized in that: said main air is an air;
The gas-solid separator that is arranged in settling vessel is the cyclone gas-solid separator, and the gas-solid separator that links to each other with revivifier is the two-stage gas-solid separator.
8. method according to claim 7 is characterized in that: valve is set on said heat collector, storage tank, regenerator sloped tube and the return tube controls out the catalyst recirculation amount.
9. method according to claim 8 is characterized in that: stop work or when drawing off said catalyzer, said catalyzer is discharged in the storage tank; During make-up catalyst, in storage tank, put in the catalyzer entering coke-burning riser.
10. method according to claim 9 is characterized in that: said catalytic reaction unit is a successive reaction regenerated fluidized-bed; Said aromatic hydrocarbons is benzene, toluene and YLENE.
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| CN101792362A (en) * | 2010-02-11 | 2010-08-04 | 清华大学 | Method and device for continuously aromatizing dimethyl ether and regenerating catalyst |
| CN103121901B (en) * | 2011-11-18 | 2015-09-09 | 中国石油化工股份有限公司 | The method of converting oxygen-containing compound to low-carbon olefins |
| CN103007985B (en) * | 2012-12-20 | 2014-09-24 | 清华大学 | Catalyst for converting alcohols and ethers into aromatic hydrocarbons as well as preparation method and use method thereof |
| WO2014154509A1 (en) * | 2013-03-27 | 2014-10-02 | Basf Se | Passivation of a zeolite catalyst for dehydroaromatization |
| JP2016520415A (en) * | 2013-03-27 | 2016-07-14 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Passivation of zeolite catalyst in fluidized bed. |
| CN104250183B (en) * | 2013-06-26 | 2016-06-08 | 中石化洛阳工程有限公司 | A kind of Methanol aromatic hydrocarbons the method for by-product low-carbon alkene and device |
| CN103664482B (en) * | 2013-12-03 | 2015-09-30 | 浙江大学 | A kind of reaction process using moving bed technique oxygenatedchemicals to be converted into aromatic hydrocarbons |
| CN108017484B (en) * | 2016-11-04 | 2020-09-04 | 中国石油化工股份有限公司 | Method for maintaining high aromatic selectivity in process of preparing aromatic hydrocarbon from methanol |
| CN106622344A (en) * | 2016-12-06 | 2017-05-10 | 中国科学院山西煤炭化学研究所 | Metal-nonmetal modified catalyst and preparation method thereof |
| CN108212029B (en) * | 2017-02-03 | 2020-09-11 | 青岛京润石化设计研究院有限公司 | Catalytic conversion reaction method and reactor |
| CN107522618A (en) * | 2017-10-12 | 2017-12-29 | 中石化炼化工程（集团）股份有限公司 | Method of Dimethyl ether carbonylation and application thereof and consersion unit |
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| CN101274879A (en) * | 2007-03-30 | 2008-10-01 | 中国石油化工股份有限公司 | Fluidizer for producing dimethyl ether by methanol dehydration |
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| CN101274879A (en) * | 2007-03-30 | 2008-10-01 | 中国石油化工股份有限公司 | Fluidizer for producing dimethyl ether by methanol dehydration |
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