CN104045530A - System using supported ionic liquid catalyst for continuous preparation of polyoxymethylene dimethyl ether - Google Patents
System using supported ionic liquid catalyst for continuous preparation of polyoxymethylene dimethyl ether Download PDFInfo
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- CN104045530A CN104045530A CN201410205012.8A CN201410205012A CN104045530A CN 104045530 A CN104045530 A CN 104045530A CN 201410205012 A CN201410205012 A CN 201410205012A CN 104045530 A CN104045530 A CN 104045530A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
- C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/58—Separation; Purification; Stabilisation; Use of additives
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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
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- 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
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Abstract
The invention discloses a reaction system and process using methanol and concentrated formaldehyde as initial reaction raw materials and a supported ionic liquid for catalyzed acetalation for preparation of polyoxymethylene dimethyl ether. The reaction system mainly comprises a reaction zone and a refining zone, the reaction zone includes a raw material pre mixing tank, a tank reactor, a reactor circulating pump, a circulating heat exchanger and the like, and the refining zone includes a reaction liquid distillation system, an extraction system, a catalyst concentration circulation system, an alkali washing system, a rectification separation system and the like. The reaction system uses the methanol and concentrated formaldehyde as the initial reaction raw materials for continuous acetalation for preparation of the polyoxymethylene dimethyl ether. The process is simple, the energy consumption is low, an extractive distillation separation mode is used, the ionic liquid catalyst is in no need of separation, and is supported on a carrier, the catalyst loss is reduced, the energy consumption is reduced, the product purity is high, the new tank reactor is used, and the reaction system and the process are suitable for large-scale industrialized production.
Description
Technical field
The present invention relates to a kind of reactive system and technique of reacting synthetic polymethoxy dimethyl ether with load-type ion liquid catalysis methanol with concentrated formaldehyde or paraformaldehyde.
Background technology
In recent decades, along with the continuous increase of being on the rise of energy dilemma, consumption of petroleum amount, meanwhile, environmental regulation is more and more stricter.Require to use super clean diesel, can reduce the exploitation of many emerging substitute diesels of pollutant emission and just arise at the historic moment, wherein, use diesel oil blending component, without increasing in addition device or changing engine structure, be considered to a kind of convenient, effective measures.
In recent years, investigator has added oxygenated fuel as methyl alcohol, methylal etc. in diesel oil, effectively reduces the discharge of soot and waste gas, but these compound steams are pressed and cetane value is low, poor with diesel oil solubility property.
Polymethoxy dimethyl ether is to take the low-molecular weight polymer that methoxyl group is main chain, and general formula is CH
3(OCH
2)
noCH
3, be high boiling point colourless liquid, can be used as properties-correcting agent, solvent, softening agent and the releasing agent etc. of resol.The compound of n=3～6 is diesel oil oxygenation agents of a kind of excellent property, its physical property and diesel oil are close, there is very high cetane value and oxygen level, the in the situation that of adding 15% in diesel oil, do not need vehicle motor oil supply system to transform, can obviously improve the combustioncharacteristics of diesel oil, improve diesel quality, oxygen level is increased to more than 7%, and comprehensive exhaust emissions can reduce more than 50%, significantly reduces the discharge of oxynitrides and carbon monoxide.
In early days, polymethoxy dimethyl ether is by polymethoxy dialkyl ether or polyoxymethylene and methyl alcohol reaction preparation under sulfuric acid or hydrochloric acid existence, temperature of reaction is 150 ℃, and the reaction times is 15 hours, and reaction system pressure is due to due to the oxycarbide of reaction decomposes and dme vapour pressure.The molecular-weight average of reaction product is along with the proportion of raw material increases and increases.Product washs passivation through sulfite solution, through all kinds of SOLVENTS distribution recrystallization and separation obtains.
In recent years, take the liquid acid that BASF is representative catalyzes and synthesizes DMM
3-6research had certain progress.Using sulfuric acid, trifluoromethanesulfonic acid is catalyzer, methyl alcohol, methylal, trioxymethylene, paraformaldehyde etc. are raw material, obtain the series product of n=1 ~ 10, but catalytic erosion is serious, products distribution is unreasonable, transformation efficiency and to can be used for the component of oil dope not high.
BP company is at patent US 5959156, US 6160174, US 61600186, US 6265538, and US 6350915, and in US 63392102, having described series, to take formaldehyde, methyl alcohol, dme etc. be raw material, the method of preparing polymethoxy dimethyl ether through catalytic distillation, these methods exist device complicated, and products distribution is unreasonable, the lower (DMM of productive rate
3-6lower than 30%) shortcoming.
A kind of method of being prepared polymethoxy dimethyl ether by trioxymethylene and methylal has been described in patent US 2007/0260094 by BASF AG, can be used for still lower (DMM of polymethoxy dimethyl ether content that diesel oil burns component disastrously in the resulting product of the method
3-6lower than 30%).In addition, although mentioning with storng-acid cation exchange resin, the method replaces the strong liquid acid of corrodibility, but storng-acid cation exchange resin use temperature is limited, this reaction making need be carried out at lower temperature, affected reaction efficiency, need to (catalyst quality mark is greater than 10%) long-time reaction (reaction times is greater than 12 hours) under a large amount of catalyzer exist.
In addition, all there is the bibliographical information of preparing polymethoxy dimethyl ether in other companies as E.I.Du Pont Company, Italian Snamprogetti S.P.A., U.S. Southwest Research Inst. etc.But up to now, because used catalyst exists various shortcomings, as mineral acid exists etching apparatus, contaminate environment, conventional resin catalyst use temperature is compared with low and affect reaction efficiency, and the mature industry gasifying device of product fails to realize always.
Summary of the invention
Main purpose of the present invention is to provide a kind of method and system that adopts load-type ion liquid catalyst continuous production polymethoxy dimethyl ether.
A method that adopts load-type ion liquid catalyst continuous production polymethoxy dimethyl ether, step is as follows:
A, acetalation
Take load-type ion liquid as catalyzer, using methyl alcohol and concentrated formaldehyde or paraformaldehyde as reactant, at reactor, carry out continuous acetalation, temperature of reaction is 110 ℃ ~ 130 ℃, reaction pressure is 1.0MPaG ~ 3.0 MPaG, reaction time is 40 ~ 120min, and load-type ion liquid catalyst accounts for 5 ~ 20wt% of reaction raw materials, and the mol ratio of methyl alcohol and concentrated formaldehyde or paraformaldehyde is 1.0 ~ 3.0; Reaction product is mainly DMM1-6, the water that reaction generates;
B, refining
The reactant that reaction product and unreacted are complete, is separated into the first light constituent and product mixture through anti-the first light constituent recovery tower C1, and the first light constituent condensing reflux continues reaction to reactor, and product mixture enters extraction tower C2 and carries out separation and recovery of catalyst; Waste water goes out to enter the second light constituent recovery tower C3 from extraction tower C2 underflow, top output the second light constituent of the second light constituent recovery tower C3 is back to reactor and continues reaction, waste water is discharged in the bottom of the second light constituent recovery tower C3, the extraction phase of extraction tower C2 tower top is through soda-wash tower C4 alkali cleaning, after Multistage rectifying tower rectifying, obtain in order respectively the 3rd light constituent, extraction agent, the 4th light constituent, DMM3-6, the 3rd light constituent, the 4th light constituent Returning reactor R1 continue reaction, and extraction agent returns to extraction tower C2 and continues extraction.
Described acetalation is carried out under the state of continuous feeding and discharging, and the mean residence time of reactant is controlled by reactant liquid level.
Described ionic liquid is acidic ionic liquid catalysts, cationic moiety is selected from one or more in quaternary ammonium cation, season phosphine positively charged ion, glyoxaline cation, pyridylium and heterocycle positively charged ion, and anionicsite is selected from p-methyl benzenesulfonic acid root, trifluoromethane sulfonic acid root, methylsulphonic acid with one or more in, bisulfate ion and trifluoroacetic acid root; Described load carriers is selected from polystyrene resin, silica gel, mesopore molecular sieve (MCM-41, SBA-15 etc.), organic polymer (chitosan etc.), metal oxide (aluminum oxide, silicon monoxide, magnesium oxide, titanium oxide, zirconium white), spinel, mullite or wherein one or more of trichroite.
Described cationic moiety is selected from glyoxaline cation, and anionicsite is selected from methylsulphonic acid root or bisulfate ion.
The material of described reactor is 316L stainless steel.
A kind of system that adopts load-type ion liquid catalyst continuous production polymethoxy dimethyl ether, it comprises raw material premixing tank V1, reactor R1, anti-the first light constituent recovery tower C1, extraction tower C2, the second light constituent recovery tower C3, soda-wash tower C4, the 3rd light constituent recovery tower C5, extraction agent recovery tower C6, the 4th light constituent recovery tower C7, raw material premixing tank V1 is connected with the opening for feed of reactor R1, the discharge port of reactor R1 is connected with the opening for feed of anti-the first light constituent recovery tower C1, anti-the first light constituent recovery tower C1 tower reactor is connected with the opening for feed of extraction tower C2, the tower top of extraction tower C2 is connected with the opening for feed of soda-wash tower C4, the tower top of soda-wash tower C4 is connected with the opening for feed of the 3rd light constituent recovery tower C5, the 3rd light constituent recovery tower C5 tower reactor is connected with the opening for feed of extraction agent recovery tower C6, the tower reactor of extraction agent recovery tower C6 is connected with the opening for feed of the 4th light constituent recovery tower C7, the tower top of the 4th light constituent recovery tower C7 is connected with the feed-pipe of raw material premixing tank V1, the tower top of extraction agent recovery tower C6 is connected with the feed-pipe of extraction tower C2, the tower top of the 3rd light constituent recovery tower C5 is connected with the feed-pipe of raw material premixing tank V1, the tower reactor of extraction tower C2 is connected with the opening for feed of the second light constituent recovery tower C3, the tower top of the second light constituent recovery tower C3 is connected with the feed-pipe of raw material premixing tank V1,
Described reactor R1 is stirred autoclave, is further provided with reaction temperature control unit E1.
The material of described reactor is 316L stainless steel.
Described extraction tower C2 adopts structured packing, packed height is 10 ~ 40 meters, inner-tower filling material or the column plate of the 3rd light constituent recovery tower C5, extraction agent recovery tower C6, the 4th light constituent recovery tower C7 all adopt stainless steel, and packed height is 10 ~ 40 meters, and theoretical plate number is 10 ~ 50.
Beneficial effect of the present invention:
1) to adopt methyl alcohol and concentrated formaldehyde or paraformaldehyde be initial reaction raw material in the present invention, adopt continuous acetalation to prepare polymethoxy dimethyl ether, wherein, the preparation technology of methyl alcohol, concentrated formaldehyde, paraformaldehyde belongs to maturation process, industrial through the synthetic polymethoxy dimethyl ether of trioxymethylene with respect to methyl alcohol, the method technical process is simple, and energy consumption significantly reduces.
2) load-type ion liquid catalyst system of the present invention, has improved transformation efficiency and the yield of reaction greatly; Solved ionic-liquid catalyst recycle problem, avoided the loss of catalyzer, improved the activity of catalyzer, simplified technical process, reduced energy consumption;
3) this process using tank reactor, has improved the deficiency that unit scale is little, floor space is large of annular reactor existence used in the past, not limited by industrial scale, is conducive to the large-scale promotion of this technology.
Accompanying drawing explanation
Fig. 1 is structural representation of the present invention, only draws main equipment, and the equipment such as other instrument, pump, valve, tundish omit.
Embodiment
As shown in Figure 1,1) methyl alcohol, concentrated formaldehyde, recovery light constituent, circulation ionic-liquid catalyst and reclaim heavy constituent as reactant, enter into raw material premixing tank V1 and carry out proportioning mixing, sends into tank reactor R1 and carry out continuous acetalation; Under the state of reactor continuous feeding and discharging, reactor provides strong turbulence by agitator and the recycle system, reactant is fully mixed with catalyzer, the mean residence time of reactant is controlled by input speed and reactor liquid level, temperature of reaction is controlled by external heat exchanger E1, the seperating range control valve regulation nitrogen pressure of reactor head provides reaction required pressure, and the reaction product that reactor flows out continuously mainly contains the DMM that reaction generates
1-6, water, catalyzer and unreacted formaldehyde, methyl alcohol.
The mol ratio of concentrated formaldehyde or paraformaldehyde and methyl alcohol is 1.0 ~ 3.0, the consumption of load-type ion liquid catalyst is 5 ~ 20wt% of total reactant, temperature of reaction is 110 ℃ ~ 130 ℃, and reaction pressure is 1.0MPaG ~ 3.0 MPaG, and reaction time is 40 ~ 120min.
2) reaction solution flows out from reactor R1, enters into anti-the first light constituent recovery tower C1; Wherein, the part light constituent in reaction solution, is mainly formaldehyde, methyl alcohol, water and DMM
1deng, after overhead condensation is cooling, extraction is back to raw material and premixed device V1; At the bottom of tower, component is sent to extraction tower C2 and extracts;
The service temperature of anti-the first light constituent recovery tower tower is 40 ~ 60 ℃, and working pressure is-0.01 ~ 0.1MPaG, adopts packing tower, and packed height is 10 ~ 20 meters.
3), from the reaction mixture of coming at the bottom of C1 tower and the extraction agent of coming from extraction agent storage tank, respectively from extraction tower C2 two endfeeds, after extraction tower extraction, the water in reaction solution, goes out to the second light constituent recovery tower C3 from tower bottom flow; Product component in reaction solution, along with extraction agent flows out from tower top, enters into soda-wash tower C4;
The service temperature of extraction tower C2 is 30 ~ 60 ℃, and working pressure is 0 ~ 0.1MPaG, adopts packing tower, and packed height is 20 ~ 35 meters.
4) the second light constituent recovery tower is mainly by component recovery tower C3, the useful component in water to be steamed from water, is back to raw material premixing tank V1, and the moisture in water is sent to sewage work and processes;
5) extraction tower tower top out extraction phase enter into the soda-wash tower C4 corrosivess such as alkali cleaning, the formic acid in neutralized product that circulate, prevent the corrosion of equipment and the decomposition of product;
The service temperature of soda-wash tower is 50 ~ 100 ℃, and working pressure is 0 ~ 0.1MPaG, adopts packing tower, and packed height is 10 ~ 20 meters.
6) reaction solution after soda-wash tower alkali cleaning, enters into the 3rd light constituent recovery tower C5; Light constituent in reaction solution is as DMM
1from overhead extraction, be back to raw material premixing tank V1; At the bottom of tower, component enters into extraction agent recovery tower C6 and carries out the recovery of extraction agent;
The service temperature of the 3rd light constituent recovery tower is 40 ~ 60 ℃, and working pressure is 0 ~ 0.3MPaG, adopts tray column, and number of theoretical plate is 10 ~ 20.
7) Main Function of extraction agent recovery tower C6 is that extraction agent is separated with reaction solution, and extraction agent, from overhead extraction, is back to extraction tower C2 and reuses, and at the bottom of tower, component enters into the 4th light constituent recovery tower C7 and carries out component recovery;
The service temperature of extraction agent recovery tower is 60 ~ 100 ℃, and working pressure is 0 ~ 0.1MPaG, adopts tray column, and number of theoretical plate is 10 ~ 30.
8) effect of the 4th light constituent recovery tower C7 is mainly by the DMM in reaction solution
2deng material and product separation, DMM
2from overhead extraction, be back to raw material premixing tank V1; Product, from extraction at the bottom of tower, after overcooling, is sent to products pot and stores;
The service temperature of the 4th light constituent recovery tower is 80 ~ 150 ℃, and working pressure is-0.01 ~ 0.1MPaG, adopts tray column, and number of theoretical plate is 10 ~ 40.
embodiment mono-
Temperature of reaction: 120 ℃;
Reaction pressure: 2.0 MPaG;
Concentrated formaldehyde and methanol feeding ratio: 2.5:1;
Catalyst levels: 10%;
After product and each component reaction reach balance, sample, by gas chromatograph quantitative analysis, its result is as shown in table 1 below:
embodiment bis-
Temperature of reaction: 130 ℃;
Reaction pressure: 3.0 MPaG;
Concentrated formaldehyde and methanol feeding mol ratio: 3:1;
Catalyst levels: 20%;
After product and each component reaction reach balance, sample, by gas chromatograph quantitative analysis, its result is as shown in table 2 below:
embodiment tri-
Temperature of reaction: 110 ℃;
Reaction pressure: 1.0 MPaG;
Concentrated formaldehyde and methanol feeding mol ratio: 1:1;
Catalyst levels: 5%;
After product and each component reaction reach balance, sample, by gas chromatograph quantitative analysis, its result is as shown in table 3 below:
Claims (9)
1. a method that adopts load-type ion liquid catalyst continuous production polymethoxy dimethyl ether, is characterized in that, step is as follows:
A, acetalation
Take load-type ion liquid as catalyzer, with methyl alcohol, concentrated formaldehyde or paraformaldehyde are as reactant, at reactor, carry out continuous acetalation, temperature of reaction is 110 ℃ ~ 130 ℃, and reaction pressure is 1.0MPaG ~ 3.0 MPaG, and reaction time is 40 ~ 120min, load-type ion liquid catalyst accounts for 5 ~ 20wt% of reaction raw materials, and the mol ratio of concentrated formaldehyde or paraformaldehyde and methyl alcohol is 1.0 ~ 3.0; Reaction product is mainly DMM1-6, the water that reaction generates;
B, refining
The reactant that reaction product and unreacted are complete, is separated into the first light constituent and product mixture through anti-the first light constituent recovery tower C1, and the first light constituent condensing reflux to reactor continues reaction, and product mixture enters extraction tower C2 to carry out profit and be separated; Water goes out to enter the second light constituent recovery tower C3 from extraction tower C2 underflow, top output the second light constituent of the second light constituent recovery tower C3 is back to reactor and continues reaction, waste water is discharged in the bottom of the second light constituent recovery tower C3, the extraction phase of extraction tower C2 tower top is through soda-wash tower C4 alkali cleaning, after Multistage rectifying tower rectifying, obtain in order respectively the 3rd light constituent, extraction agent, the 4th light constituent, DMM3-6, the 3rd light constituent, the 4th light constituent Returning reactor R1 continue reaction, and extraction agent returns to extraction tower C2 and continues extraction.
2. method according to claim 1, is characterized in that, described acetalation is carried out under the state of continuous feeding and discharging, and the mean residence time of reactant is controlled by reactant liquid level.
3. method according to claim 1, it is characterized in that, described ionic liquid is acidic ionic liquid catalysts, cationic moiety is selected from one or more in quaternary ammonium cation, season phosphine positively charged ion, glyoxaline cation, pyridylium and heterocycle positively charged ion, and anionicsite is selected from p-methyl benzenesulfonic acid root, trifluoromethane sulfonic acid root, methylsulphonic acid with one or more in, bisulfate ion and trifluoroacetic acid root; Described load carriers is selected from polystyrene resin, silica gel, mesopore molecular sieve, organic polymer, metal oxide, spinel, mullite or wherein one or more of trichroite.
4. method according to claim 3, is characterized in that, described cationic moiety is selected from glyoxaline cation, and anionicsite is selected from methylsulphonic acid root or bisulfate ion.
5. method according to claim 1, is characterized in that, the material of described reactor is 316L stainless steel.
6. a system that adopts load-type ion liquid catalyst continuous production polymethoxy dimethyl ether, it is characterized in that, it comprises raw material premixing tank V1, reactor R1, anti-the first light constituent recovery tower C1, extraction tower C2, the second light constituent recovery tower C3, soda-wash tower C4, the 3rd light constituent recovery tower C5, extraction agent recovery tower C6, the 4th light constituent recovery tower C7, raw material premixing tank V1 is connected with the opening for feed of reactor R1, the discharge port of reactor R1 is connected with the opening for feed of anti-the first light constituent recovery tower C1, anti-the first light constituent recovery tower C1 tower reactor is connected with the opening for feed of extraction tower C2, the tower top of extraction tower C2 is connected with the opening for feed of soda-wash tower C4, the tower top of soda-wash tower C4 is connected with the opening for feed of the 3rd light constituent recovery tower C5, the 3rd light constituent recovery tower C5 tower reactor is connected with the opening for feed of extraction agent recovery tower C6, the tower reactor of extraction agent recovery tower C6 is connected with the opening for feed of the 4th light constituent recovery tower C7, the tower top of the 4th light constituent recovery tower C7 is connected with the feed-pipe of raw material premixing tank V1, the tower top of extraction agent recovery tower C6 is connected with the feed-pipe of extraction tower C2, the tower top of the 3rd light constituent recovery tower C5 is connected with the feed-pipe of raw material premixing tank V1, the tower reactor of extraction tower C2 is connected with the opening for feed of the second light constituent recovery tower C3, the tower top of the second light constituent recovery tower C3 is connected with the feed-pipe of raw material premixing tank V1.
7. system according to claim 6, is characterized in that, described reactor R1 is stirred autoclave, is further provided with reaction temperature control unit E1.
8. system according to claim 6, is characterized in that, the material of described reactor is 316L stainless steel.
9. system according to claim 6, it is characterized in that, described extraction tower C2 adopts structured packing, packed height is 10 ~ 40 meters, inner-tower filling material or the column plate of the 3rd light constituent recovery tower C5, extraction agent recovery tower C6, the 4th light constituent recovery tower C7 all adopt stainless steel, packed height is 10 ~ 40 meters, and theoretical plate number is 10 ~ 50.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160168307A1 (en) * | 2014-12-12 | 2016-06-16 | Dongfang Hongsheng New Energy Application Technology Research Institute Co., Ltd | Method for producing polyoxymethylene dimethyl ethers from feedstock of concentrated formaldehyde |
| CN106748677A (en) * | 2016-12-09 | 2017-05-31 | 苏州双湖化工技术有限公司 | Take support type acidic ion liquid as the method for catalyst preparation diethoxymethane |
| CN107188789A (en) * | 2017-07-17 | 2017-09-22 | 中央军委后勤保障部油料研究所 | A kind of method that catalytic reaction rectification produces polymethoxy dialkyl ether |
| CN108299166A (en) * | 2018-02-07 | 2018-07-20 | 中国科学院兰州化学物理研究所 | A kind of method that load-type ion liquid catalyzes and synthesizes polymethoxy dimethyl ether |
| CN108623441A (en) * | 2018-06-04 | 2018-10-09 | 山东辰信新能源有限公司 | A kind of preparation method and device of polymethoxy dimethyl ether |
| CN109503336A (en) * | 2019-01-21 | 2019-03-22 | 中信国安化工有限公司 | A kind of device and method handling unqualified material DMMn material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160168307A1 (en) * | 2014-12-12 | 2016-06-16 | Dongfang Hongsheng New Energy Application Technology Research Institute Co., Ltd | Method for producing polyoxymethylene dimethyl ethers from feedstock of concentrated formaldehyde |
| CN106748677A (en) * | 2016-12-09 | 2017-05-31 | 苏州双湖化工技术有限公司 | Take support type acidic ion liquid as the method for catalyst preparation diethoxymethane |
| CN107188789A (en) * | 2017-07-17 | 2017-09-22 | 中央军委后勤保障部油料研究所 | A kind of method that catalytic reaction rectification produces polymethoxy dialkyl ether |
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| CN108299166A (en) * | 2018-02-07 | 2018-07-20 | 中国科学院兰州化学物理研究所 | A kind of method that load-type ion liquid catalyzes and synthesizes polymethoxy dimethyl ether |
| CN108623441A (en) * | 2018-06-04 | 2018-10-09 | 山东辰信新能源有限公司 | A kind of preparation method and device of polymethoxy dimethyl ether |
| CN108623441B (en) * | 2018-06-04 | 2021-09-28 | 山东辰信新能源有限公司 | Preparation method and device of polymethoxy dimethyl ether |
| CN109503336A (en) * | 2019-01-21 | 2019-03-22 | 中信国安化工有限公司 | A kind of device and method handling unqualified material DMMn material |
| CN109503336B (en) * | 2019-01-21 | 2023-10-20 | 中信国安化工有限公司 | Equipment and method for treating unqualified DMMn material |
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Application publication date: 20140917 |