CN104003855A - System for continuously preparing polymethoxy dimethyl ether by using methanol as initial reaction raw material - Google Patents
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Abstract
The invention discloses a system for continuously preparing polymethoxy dimethyl ether by using methanol as an initial reaction raw material, which mainly comprises a formaldehyde preparation unit, a methylal preparation unit and a polymethoxy dimethyl ether preparation unit, wherein the formaldehyde preparation unit is mainly used for oxidizing the raw material methanol into a formaldehyde solution under the action of a catalyst; the methylal preparation unit is used for reacting part of the formaldehyde solution with methanol under the action of a solid acidic resin catalyst to prepare methylal; and the polymethoxy dimethyl ether preparation unit is used for respectively carrying out condensation reaction on the methanol and methylal with the formaldehyde solution under the action of an ionic liquid catalyst to prepare the polymethoxy dimethyl ether, and separating and purifying the reaction product to obtain the polymethoxy dimethyl ether product. Compared with the trioxymethylene or oligomer formaldehyde route, the system has the advantages of simple process and low energy consumption, is simple to operate, implements recovery treatment of sewage on the premise of cyclic recovering the intermediate product, and thus, is very suitable for large-scale industrial production.
Description
Technical field
The invention discloses one using methyl alcohol as initial reaction raw material, the process unit system of continuous production polymethoxy dimethyl ether.
Background technology
Along with the minimizing day by day of petroleum resources, and countries in the world are growing to the demand of fuel oil, and various countries have all strengthened dynamics to the research and development of novel energy.
Along with the continuous lifting of rapid development of economy and living standards of the people, China constantly increases petroleum demand, and due to scarcity of resources, China became net importer from 1993 from net exporter, and externally interdependency improves year by year, within 2012 years, has exceeded 55%.Petroleum resources have become affects one of the most responsive, weakest link of economical operation.Along with the rapid growth of vehicle guaranteeding organic quantity, the consumption of oil product sharply increases in recent years, and the pollution that fuel oil causes is also day by day serious.More than 80% carbon monoxide in big city, more than 40% oxynitride at present, from automotive emission.
In the face of the contradiction of resource, environment and economic development, in conjunction with the national conditions of China relatively abundant coal-based chemical industry product innovation of exploiting natural resources, efficiently utilizing under the prerequisite of methyl alcohol, produce the blend component of clean diesel with Non oil-based route technological development, the deficiency of supplementing China's clean diesel, is very important.
China is maximum in the world coal production state, 75% of China's coal mining amount uses as fuel poor benefit at present, and synthetic gas and methyl alcohol become the main outlet of Coal Chemical Industry.The nineties in last century, due to oil crisis, coal liquefaction and methanol-to-olefins technology have obtained exploitation, but due to raw material availability less than 45%, energy expenditure is high, and expend great lot of water resources, and its technical development and industrial application are very limited.
Coal-based methanol is China's development Chemical Industry the most rapidly, is the product of the first link in Chemical Industry chain, and its downstream may extend to multiple other Chemicals.The latest data of issuing according to Chinese nitrogen fertilizer industry association shows, by the end of the year 2012, China's methyl alcohol aggregated capacity reaches 5149.1 ten thousand tons, accounts for 50% of global aggregated capacity.The whole industry methanol device duty ratio that goes into operation has improved 4.3 percentage points last year, but still only has 60.8%, and output is 3,129 ten thousand tons, 3,622 ten thousand tons of apparent consumption amounts, and production capacity surplus situation is serious, and existing consumer field cannot digest the production capacity of rapid growth.
The production of the output of methyl alcohol and consumption and derived product and utilisation technology exploitation are closely related, have technology barrier at present in the exploitation of this type of products production technology.Develop these domestic markets in short supply, Downstream Products of Methanol production technology that particularly can petroleum replacing Chemicals, not only for methyl alcohol problem of excess production capacity finds a way out, and be the important technology route of producing clean fuel oil from coal, be conducive to make up China's oil problem in short supply, promote China's methanol industry to develop well.
Polymethoxy dimethyl ether is the lower molecular weight acetal polymer taking methoxyl group as 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, not only have very high cetane value, its oxygen level is also very high, 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, increase oxygen level more than 7%, reduce discharging more than 50% tail gas pollution, significantly reduce the discharge of oxynitrides and carbon monoxide.
It is raw material that polymethoxy dimethyl ether (DMMn) getting up early adopts methyl alcohol, formaldehyde, concentrated formaldehyde, paraformaldehyde or ethylene glycol acetal, synthetic with sulfuric acid or hydrochloric acid catalysis.In recent years, it is catalyzer that BASF AG (WO 2006/045506 A1, CA 2581502) is used the protonic acids such as sulfuric acid, trifluoromethanesulfonic acid, methyl alcohol and trioxymethylene (or paraformaldehyde) are raw material, react 8 ~ 12h at 100 DEG C, obtain the content of DMM3-8 lower than 26%.The method severe reaction conditions, transformation efficiency is low with the component concentration that can be used as oil dope.2005, the people (EP 1505049 AI) such as De Gregori adopted bronsted acid catalyst, and reaction is carried out under the N2 of 1.0MPa, has shortened widely the reaction times, and DMM3-8 productive rate can reach 51.2%.There is seriously corroded, separation difficulty in above-mentioned catalyzer, can not recycle, to process energy consumption large, and products distribution is unreasonable, trioxymethylene transformation efficiency and can be used for the not high defect of component DMM3-8 selectivity of oil dope.BP company (US 6160174, US 62655284) is studied heterogeneous catalyst, and taking methyl alcohol, formaldehyde, dme and methyl alcohol as raw material, wherein the content of DMM3-8 only has 11.6%.The method catalyst activity is low, and complex process is difficult to realize industrialization.
Summary of the invention
In order to overcome the deficiencies in the prior art, main purpose of the present invention is to provide the system that methyl alcohol is initial reaction raw material continuous production polymethoxy dimethyl ether.
Methyl alcohol is a system for initial reaction raw material continuous production polymethoxy dimethyl ether, and it comprises that formaldehyde is prepared unit, methylal prepares unit and polymethoxy dimethyl ether is prepared unit,
A, formaldehyde are prepared unit
Using methyl alcohol, air and water vapour as reactant, after evaporation gasification, enter the reaction of carrying out continuous producing formaldehyde by methanol oxidation in reactor, reaction product is after absorption tower absorbs, obtain two bursts of formaldehyde solutions as intermediate product, wherein one offers polymethoxy dimethyl ether as raw material and prepares unit, and one formaldehyde solution offers methylal as raw material and prepares unit in addition;
B, methylal are prepared unit
Prepare unit and polymethoxy dimethyl ether from formaldehyde respectively and prepare the unit solution of two strands of by-products containing formaldehyde of coming, with methanol solution after proportioning, enter reactive distillation column reaction and prepare methylal solution, reaction product, after rectification and purification, obtains highly purified methylal solution; Water reactive distillation in formaldehyde solution reaches effluent-disposal standard and is directly sent to sewage treatment unit after processing;
C, polymethoxy dimethyl ether are prepared unit
Prepare from formaldehyde the formaldehyde solution of coming in unit, prepare the methylal solution of coming unit with methyl alcohol and from methylal, under the effect of ionic-liquid catalyst, generate polymethoxy dimethyl ether through acetalation, reaction product is after rectification process, obtain polymethoxy dimethyl ether product and one solution that contains formaldehyde, this solution that contains formaldehyde returns to methylal to be prepared unit and carries out formaldehyde and recycle and process.
Described formaldehyde is prepared unit, and it comprises methanol evaporator E101, formaldehyde reaction device R101, the first absorption tower C110, second absorption tower C120; Methanol evaporator E101 is connected with the opening for feed of formaldehyde reaction device R101, the discharge port of formaldehyde reaction device R101 is connected with the opening for feed of the first absorption tower C110, the first absorption tower C110 tower top is connected with the opening for feed of second absorption tower C120, the tower top of second absorption tower C120 is connected with the opening for feed of methanol evaporator E101, and the tower reactor of second absorption tower C120 is connected with the tower top feeding line of the first absorption tower C110.
Described methylal is prepared unit, and it comprises methylal pre-reactor R201, reactive distillation column C210, methylal rectifying tower C220, component recovery tower C230; Methylal pre-reactor R201 is connected with the opening for feed of reactive distillation column C210, the tower top of reactive distillation column C210 is connected with the opening for feed of methylal rectifying tower C220, methylal rectifying tower C220 tower top is connected with the opening for feed of component recovery tower C230, the tower top of component recovery tower C230 is connected with the refluxing opening of reactive distillation column C210, and the tower reactor of component recovery tower C230 is connected with methylal pre-reactor R201 feeding line.
Described polymethoxy dimethyl ether is prepared unit, and it comprises reactor R301, the first light constituent recovery tower C310, extraction tower C320, soda-wash tower C330, the second light constituent recovery tower C340, extraction agent recovery tower C350, the 3rd light constituent recovery tower C360, vaporizer E301, the discharge port of reactor R301 is connected with the opening for feed of the first light constituent recovery tower C310, the first light constituent recovery tower C310 tower reactor is connected with the opening for feed of extraction tower C320, the tower top of extraction tower C320 is connected with the opening for feed of soda-wash tower C330, the tower top of soda-wash tower C330 is connected with the opening for feed of the second light constituent recovery tower C340, the second light constituent recovery tower C340 tower reactor is connected with the opening for feed of extraction agent recovery tower C350, the tower reactor of extraction agent recovery tower C350 is connected with the opening for feed of the 3rd light constituent recovery tower C360, the tower top of the 3rd light constituent recovery tower C360 is connected with the feed-pipe of reactor R301, the tower top of extraction agent recovery tower C350 is connected with the feed-pipe of extraction tower C320, the tower top of the second light constituent recovery tower C340 is connected with the feed-pipe of reactor R301, the tower reactor of extraction tower C320 is connected with the feed-pipe of reactor R301 by vaporizer E301.
Described formaldehyde is prepared the second absorption tower C120 tower reactor of unit, is that the opening for feed of preparing the methylal pre-reactor R201 of unit with methylal is connected.
Described formaldehyde is prepared the first absorption tower C110 tower reactor of unit, is that the opening for feed of preparing the reactor R301 of unit with polymethoxy dimethyl ether is connected.
Described methylal is prepared the methylal rectifying tower C220 tower reactor of unit, is that the opening for feed of preparing the reactor R301 of unit with polymethoxy dimethyl ether is connected.
Described polymethoxy dimethyl ether is prepared the another one outlet of the vaporizer E301 of unit, is that the opening for feed of preparing the reactor R201 of unit with methylal is connected.
The ionic-liquid catalyst that polymethoxy dimethyl ether is prepared described in unit 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.
Beneficial effect of the present invention: prepare polymethoxy dimethyl ether for the route of formaldehyde and methylal intermediates by Methanol, it is a brand-new preparation system, compared with preparing polymethoxy dimethyl ether with trioxymethylene, paraformaldehyde, paraformaldehyde route, its flow process is simplified greatly, facility investment, simple to operate, all large reductions of energy consumption are applicable to large-scale industrial production very much.
Linking between unit is very smooth, compared with the formaldehyde solution that reclaims by-product with the high-pressure rectification of other devices, this device can well be recycled formaldehyde and prepare the formaldehyde solution that unit and polymethoxy dimethyl ether are prepared unit by-product, it is turned waste into wealth, making it become polymethoxy dimethyl ether prepares the reaction raw materials of unit and reuses, high-pressure rectification reclaims formaldehyde, can not energy consumption large, in High Temperature High Pressure situation, formaldehyde is strong to equipment corrosion, equipment material requires high, by route of the present invention, greatly reduces investment and the energy consumption of equipment.
The formaldehyde-containing wastewater producing in native system, unified recovery enters methylal and prepares unit and recycle, its treating processes is simple, energy consumption is low, processes the emission standard that can reach sewage work later, efficient recovery the useful component in formaldehyde waste water.
Brief description of the drawings
Fig. 1 is the structural representation of system of the present invention, only draws main equipment, and the equipment such as other instrument, pump, valve, tundish omits.
Embodiment
As shown in Figure 1,
A, formaldehyde are prepared unit
Formaldehyde is prepared unit, and it comprises methanol evaporator E101, formaldehyde reaction device R101, the first absorption tower C110, second absorption tower C120.Methyl alcohol, air and water vapour, in certain proportion, enter into vaporizer E101, after vaporizer E101 evaporation gasification, enter in formaldehyde reaction device R101, under the effect of silver catalyst, carry out the reaction that continuous methanol oxidation generates formaldehyde, reaction product is after the first absorption tower C110 and second absorption tower C120 absorption, obtain two bursts of formaldehyde solutions as intermediate product, wherein, the formaldehyde solution that the first absorption tower C110 tower reactor is produced, offer as raw material the reactor R301 that polymethoxy dme is prepared unit, the formaldehyde solution of second absorption tower C120 tower reactor institute by-product, offer as raw material the methylal pre-reactor R201 that methylal is prepared unit.
Wherein, the mol ratio of air and methyl alcohol is 1.5 ~ 1.7, and the mol ratio of water vapour and methyl alcohol is that the concentration of formaldehyde that the 0.1 ~ 0.5, first absorption tower C110 tower reactor is produced is 60% ~ 80%, and the formaldehyde solution concentration of second absorption tower C120 tower reactor institute by-product is 15% ~ 25%.
B, methylal are prepared unit
Methylal is prepared unit, and it comprises methylal pre-reactor R201, reactive distillation column C210, methylal rectifying tower C220, component recovery tower C230;
Prepare the second absorption tower C120 tower reactor of unit and polymethoxy dimethyl ether from formaldehyde respectively and prepare the unit vaporizer E301 two bursts of formaldehyde solutions of coming, with methanol solution after proportioning, enter methylal pre-reactor R201 and carry out pre-reaction, reaction product enters reactive distillation column C210 continuation reaction again and prepares methylal, reaction product is after methylal rectifying tower C220 rectification and purification, obtain highly purified methylal solution, be sent to as raw material the reactor R301 that polymethoxy dimethyl ether is prepared unit; The water of reactive distillation column C210 tower reactor, can reach effluent-disposal standard and directly be sent to sewage treatment unit.
Wherein, it is 15% ~ 25% that formaldehyde is prepared the formaldehyde solution concentration of coming unit, it is 13% ~ 23% that polymethoxy dimethyl ether is prepared the formaldehyde solution concentration of coming unit, and the mass ratio of methyl alcohol and formaldehyde solution is 0.3 ~ 0.5, and the concentration of the methylal solution obtaining is 90% ~ 99%.
C, polymethoxy dimethyl ether are prepared unit
Polymethoxy dimethyl ether is prepared unit, and it comprises reactor R301, the first light constituent recovery tower C310, extraction tower C320, soda-wash tower C330, the second light constituent recovery tower C340, extraction agent recovery tower C350, the 3rd light constituent recovery tower C360, vaporizer E301.Prepare from formaldehyde the formaldehyde solution of coming in unit, and prepare the methylal solution of coming unit from methylal, also has methanol solution, send into together reactor R301, under the effect of ionic-liquid catalyst, generate polymethoxy dimethyl ether through acetalation, reaction product enters into the first light constituent recovery tower C310, the first light constituent of the first light constituent recovery tower C310 recovered overhead Returning reactor R301 continues to participate in reaction, and the product mixture at the bottom of tower is sent into extraction tower C320; Product mixture is after extraction tower C320 extraction, tower top extraction phase enters into soda-wash tower C330 and carries out alkali cleaning neutralizing treatment, the catalyzer of tower reactor is sent into vaporizer E301 mutually and is evaporated, one after evaporator evaporation is containing formaldehyde solution, as raw material be sent to methylal prepare the methylal pre-reactor R201 of unit repeat recycle, remaining catalyzer phase in vaporizer, Returning reactor R301 continues to participate in reaction; Through in soda-wash tower C330 alkali cleaning and after extraction phase, enter into the second light constituent recovery tower C340 and carry out the second light constituent recovery, the second light constituent of recovered overhead Returning reactor continues to participate in reaction, the extraction phase of tower reactor, send into extraction agent recovery tower C350 and carry out the recovery of extraction agent, after extraction agent recovery tower C350 tower top steams, be back to extraction tower C320 and continue to participate in extraction; Tower reactor component continues to be fed into the 3rd light constituent recovery tower C360 and carries out the recovery of the 3rd light constituent, and the 3rd light constituent, from overhead extraction, is back to reactor R301 and continues to participate in reaction, the tower reactor polymethoxy dimethyl ether product that output purity is very high.
Wherein, preparing the formaldehyde solution concentration of coming unit from formaldehyde is 60% ~ 80%, the concentration of preparing the methylal solution of coming unit from methylal is 90% ~ 99%, going to methylal from vaporizer E301, to prepare the concentration of the formaldehyde solution of unit methylal pre-reactor R201 be 13% ~ 23%, and the mol ratio of methyl alcohol, methylal and formaldehyde solution is 2:1:1 ~ 5.
Claims (9)
1. methyl alcohol is a system for initial reaction raw material continuous production polymethoxy dimethyl ether, it is characterized in that, it comprises that formaldehyde is prepared unit, methylal prepares unit and polymethoxy dimethyl ether is prepared unit,
A, formaldehyde are prepared unit
Using methyl alcohol, air and water vapour as reactant, after evaporation gasification, enter the reaction of carrying out continuous producing formaldehyde by methanol oxidation in reactor, reaction product is after absorption tower absorbs, obtain two bursts of formaldehyde solutions as intermediate product, wherein one offers polymethoxy dimethyl ether as raw material and prepares unit, and one formaldehyde solution offers methylal as raw material and prepares unit in addition;
B, methylal are prepared unit
Prepare unit and polymethoxy dimethyl ether from formaldehyde respectively and prepare the unit solution of two strands of by-products containing formaldehyde of coming, with methanol solution after proportioning, enter reactive distillation column reaction and prepare methylal solution, reaction product, after rectification and purification, obtains highly purified methylal solution; Water reactive distillation in formaldehyde solution reaches effluent-disposal standard and is directly sent to sewage treatment unit after processing;
C, polymethoxy dimethyl ether are prepared unit
Prepare from formaldehyde the formaldehyde solution of coming in unit, prepare the methylal solution of coming unit with methyl alcohol and from methylal, under the effect of ionic-liquid catalyst, generate polymethoxy dimethyl ether through acetalation, reaction product is after rectification process, obtain polymethoxy dimethyl ether product and one solution that contains formaldehyde, this solution that contains formaldehyde returns to methylal to be prepared unit and carries out formaldehyde and recycle and process.
2. system according to claim 1, is characterized in that, described formaldehyde is prepared unit, and it comprises methanol evaporator E101, formaldehyde reaction device R101, the first absorption tower C110, second absorption tower C120; Methanol evaporator E101 is connected with the opening for feed of formaldehyde reaction device R101, the discharge port of formaldehyde reaction device R101 is connected with the opening for feed of the first absorption tower C110, the first absorption tower C110 tower top is connected with the opening for feed of second absorption tower C120, the tower top of second absorption tower C120 is connected with the opening for feed of methanol evaporator E101, and the tower reactor of second absorption tower C120 is connected with the tower top feeding line of the first absorption tower C110.
3. system according to claim 1, is characterized in that, described methylal is prepared unit, and it comprises methylal pre-reactor R201, reactive distillation column C210, methylal rectifying tower C220, component recovery tower C230; Methylal pre-reactor R201 is connected with the opening for feed of reactive distillation column C210, the tower top of reactive distillation column C210 is connected with the opening for feed of methylal rectifying tower C220, methylal rectifying tower C220 tower top is connected with the opening for feed of component recovery tower C230, the tower top of component recovery tower C230 is connected with the refluxing opening of reactive distillation column C210, and the tower reactor of component recovery tower C230 is connected with methylal pre-reactor R201 feeding line.
4. system according to claim 1, it is characterized in that, described polymethoxy dimethyl ether is prepared unit, and it comprises reactor R301, the first light constituent recovery tower C310, extraction tower C320, soda-wash tower C330, the second light constituent recovery tower C340, extraction agent recovery tower C350, the 3rd light constituent recovery tower C360, vaporizer E301, the discharge port of reactor R301 is connected with the opening for feed of the first light constituent recovery tower C310, the first light constituent recovery tower C310 tower reactor is connected with the opening for feed of extraction tower C320, the tower top of extraction tower C320 is connected with the opening for feed of soda-wash tower C330, the tower top of soda-wash tower C330 is connected with the opening for feed of the second light constituent recovery tower C340, the second light constituent recovery tower C340 tower reactor is connected with the opening for feed of extraction agent recovery tower C350, the tower reactor of extraction agent recovery tower C350 is connected with the opening for feed of the 3rd light constituent recovery tower C360, the tower top of the 3rd light constituent recovery tower C360 is connected with the feed-pipe of reactor R301, the tower top of extraction agent recovery tower C350 is connected with the feed-pipe of extraction tower C320, the tower top of the second light constituent recovery tower C340 is connected with the feed-pipe of reactor R301, the tower reactor of extraction tower C320 is connected with the feed-pipe of reactor R301 by vaporizer E301.
5. system according to claim 1, is characterized in that, described formaldehyde is prepared the second absorption tower C120 tower reactor of unit, is that the opening for feed of preparing the methylal pre-reactor R201 of unit with methylal is connected.
6. system according to claim 1, is characterized in that, described formaldehyde is prepared the first absorption tower C110 tower reactor of unit, is that the opening for feed of preparing the reactor R301 of unit with polymethoxy dimethyl ether is connected.
7. system according to claim 1, is characterized in that, described methylal is prepared the methylal rectifying tower C220 tower reactor of unit, is that the opening for feed of preparing the reactor R301 of unit with polymethoxy dimethyl ether is connected.
8. system according to claim 1, is characterized in that, described polymethoxy dimethyl ether is prepared the another one outlet of the vaporizer E301 of unit, is that the opening for feed of preparing the reactor R201 of unit with methylal is connected.
9. system according to claim 1, it is characterized in that, the ionic-liquid catalyst that polymethoxy dimethyl ether is prepared described in unit 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.
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| CN104628539A (en) * | 2015-02-04 | 2015-05-20 | 中国科学院兰州化学物理研究所苏州研究院 | Method and system for separating polyoxymethylene dimethyl ether |
| WO2016180085A1 (en) * | 2015-05-14 | 2016-11-17 | 江苏凯茂石化科技有限公司 | Formaldehyde absorption process device and method in polyoxymethylene dimethyl ether synthesis |
| CN106278836A (en) * | 2016-08-16 | 2017-01-04 | 鄂尔多斯市易臻石化科技有限公司 | Intermediate concentration formaldehyde and the apparatus and method of methylal synthesis polymethoxy dimethyl ether |
| CN106800500A (en) * | 2017-01-17 | 2017-06-06 | 凯瑞环保科技股份有限公司 | A kind of process for preparing polymethoxy dimethyl ether |
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| CN109384652A (en) * | 2017-08-07 | 2019-02-26 | 中国石化扬子石油化工有限公司 | The synthetic method and application of polyethoxy dimethyl ether |
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| CN110156575A (en) * | 2019-04-17 | 2019-08-23 | 天津大学 | Reactive distillation-Steam soak coupling technique for polymethoxy dimethyl ether synthesis |
| CN111517926A (en) * | 2020-04-27 | 2020-08-11 | 陈华 | System and method for synthesizing polymethoxy dimethyl ether from methylal |
| CN111574340A (en) * | 2020-04-27 | 2020-08-25 | 陈华 | System and method for synthesizing polymethoxy dimethyl ether from methanol |
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| CN104591984A (en) * | 2014-12-12 | 2015-05-06 | 北京东方红升新能源应用技术研究院有限公司 | Method for preparing polymethoxy dimethyl ether from concentrated formaldehyde serving as raw material |
| CN104628539A (en) * | 2015-02-04 | 2015-05-20 | 中国科学院兰州化学物理研究所苏州研究院 | Method and system for separating polyoxymethylene dimethyl ether |
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| CN111574340A (en) * | 2020-04-27 | 2020-08-25 | 陈华 | System and method for synthesizing polymethoxy dimethyl ether from methanol |
| CN111517926B (en) * | 2020-04-27 | 2023-05-02 | 陈华 | System and method for synthesizing polymethoxy dimethyl ether by methylal |
| CN111574340B (en) * | 2020-04-27 | 2023-05-02 | 陈华 | System and method for synthesizing polymethoxy dimethyl ether from methanol |
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