CN102786397A - Method for continuous production of polyformaldehyde dimethyl ether - Google Patents
Method for continuous production of polyformaldehyde dimethyl ether Download PDFInfo
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- CN102786397A CN102786397A CN2012102659936A CN201210265993A CN102786397A CN 102786397 A CN102786397 A CN 102786397A CN 2012102659936 A CN2012102659936 A CN 2012102659936A CN 201210265993 A CN201210265993 A CN 201210265993A CN 102786397 A CN102786397 A CN 102786397A
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Abstract
The invention provides a method for continuous production of polyformaldehyde dimethyl ether. The method is characterized by comprising the following steps: a) feeding dimethoxymethane and hot-melted paraformaldehyde into a fixed bed reactor and adopting an acidic resin catalyst, so as to prepare polyformaldehyde dimethyl ether (DMM3-8), wherein the reaction temperature is 120-180 DEG C and the pressure is 0.1-10 MPa; b) cooling the reaction product, and then performing adsorptive separation through a dehydrating tower, so as to obtain polyformaldehyde dimethyl ether of which most water, cytidine glycol and hemiacetal are desorbed; c) feeding the polyformaldehyde dimethyl ether subjected to desorption into a distillation tower for separation, wherein most of a low-boiling component (dimethoxymethane (DMM)), poly-di-formaldehyde dimethyl ether (DMM2), a by-product (methanol) and triformol are extracted first, and then the materials in a tower kettle are fed into a rectifying tower in the next step, so as to extract the rest of the DMM2 and the triformol; and d) returning the low-boiling component (dimethoxymethane (DMM)), the methanol, the DMM2 and the triformol, which are evaporated out by the distillation tower and the rectifying tower in the last step, into the fixed bed reactor to continue to react to prepare polyformaldehyde dimethyl ether.
Description
Technical field
The present invention relates to oil refinery oil dope technical field; Be specially a kind of method of continuous production polyoxymethylene dimethyl ether; Being to utilize Paraformaldehyde 96 and methylal to be raw material, is catalyzer with acidic resins, through fixed bed continuous production polyoxymethylene dimethyl ether and separate and obtain DMM
3-8Method.
Background technology
Polyoxymethylene dimethyl ether (DMM
3-8) be the homologue that constitutes following general formula:
CH
3O(CH
2O)
nCH
3
Wherein n is a positive integer.Say that from chemical terms they are and methylal (CH
3OCH
2OCH
3) similar acetal, the i.e. parent of n in the molecular formula=1.Polyoxymethylene dimethyl ether has high oxygen level (42 % ~ 49 %) and high cetane value (DMM
3-8Cetane value all more than 78), and good with the mutual solubility of diesel oil, be considered to a kind of good diesel oil and mix the burning component.In the recent period; Along with the energy dilemma continuous increase with the consumption of petroleum amount that is on the rise, because ultra clean diesel is used in environmental requirement, can reduce the exploitation of many emerging substitute diesels of pollutant emission and just arise at the historic moment simultaneously; This wherein; Use diesel oil to mix the burning component, need not to increase in addition device or change engine structure, be considered to a kind of convenient, effective measures.In order in the conventional diesel engine process combustion, to reduce the formation of flue dust and cigarette ash; Add the oxygenatedchemicals that only comprises seldom (if any) C-C; Methyl alcohol for example, but such compound usually is insoluble to diesel oil and reduces the flash-point of cetane value and/or diesel fuel mixtures.And polyoxymethylene dimethyl ether exactly can overcome above shortcoming, so polyoxymethylene dimethyl ether is just obvious day by day as the importance of diesel-dope.
Polyoxymethylene dimethyl ether can be converted into methyl alcohol and formaldehyde through hydrolysis.With other acetalses seemingly, they have the height chemicalstability.Under neutral and alkaline condition, can not be hydrolyzed, but be prone to hydrolysis under the diluted acid situation.The part boiling point of n in the molecular formula=2 is 91 ~ 93
oC.Calculating from pressure equation, under the 760 mmHg pressure, is 105.0 from n=2 boiling points
oC is 242.3 to n=5 boiling points
oC (Walker; Joseph Frederic, " Formaldehyde ", Robert E Krieger Publishing Co.; Issued as No. 159 of American Chemical Society Monograph series (1975), page 167-169).Receive the influence of solubleness in vp, boiling point and the diesel oil, the suitable polyoxymethylene dimethyl ether (DMM that is generally 3≤n≤8 that makes diesel-dope
3-8).
In early days, polyoxymethylene dimethyl ether is by polymethoxy glycol or polyoxymethylene and methyl alcohol tube sealing 150 in the presence of trace sulfuric acid or hydrochloric acid in the laboratory
oC reacts that 15 h obtain, or the short period of time (12 h) is 165 ~ 180
oThe C prepared in reaction.Its system pressure is because reaction decomposes produces oxycarbide, forms due to some dme.The molecular-weight average of ether products increases with polyoxymethylene or the polymethoxy glycol ratio with quantity of methyl alcohol.Superpolymer is made by formaldehyde, the methyl alcohol ratio of 6:1.In these polymkeric substance, the n value surpasses 100, usually between 300 to 500.Product washs purifying through sulfite solution, and this solution can't lysate, with after all kinds of SOLVENTS substep recrystallization separate.
In recent years, with BASF be the synthetic DMM of liquid acid catalysis of representative
3-8Research certain progress has been arranged.Use sulfuric acid, trifluoromethanesulfonic acid to be catalyzer; Methyl alcohol, methylal, trioxymethylene, Paraformaldehyde 96 etc. are raw material; Obtained the series product of n=1 ~ 10, but this system exists that catalytic erosion, products distribution are unreasonable, transformation efficiency and can be used for the not high shortcoming of component of oil dope.
BP company is at patent US 5959156, and US 6160174, and US 6160186; US 6265538; US 6350915, described among the US 6392102 a series ofly to prepare the method for polyoxymethylene dimethyl ether for raw material through catalytic distillation by formaldehyde, methyl alcohol, dme etc., but these methods all exist device complicated; And products distribution is unreasonable, the lower (DMM of productive rate
3-8Be lower than 30 %) shortcoming.
BASF AG has described in patent US 2007/0260094 and has a kind ofly prepared the method for polyoxymethylene dimethyl ether by trioxymethylene and methylal, mixes the still lower (DMM of polyoxymethylene dimethyl ether content that burns component but can be used for diesel oil in this method products therefrom
3-8Be lower than 30 %).Although this method is mentioned with strongly acidic cationic exchange resin and is replaced the strong liquid acid of corrodibility in addition; Like sulfuric acid, trifluoromethanesulfonic acid; But the strongly acidic cationic exchange resin use temperature is limited; This reaction needs is carried out at a lower temperature, influenced reaction efficiency, need (the catalyst quality mark is greater than 10%) long-time reaction (reaction times was greater than 12 hours) in the presence of a large amount of catalyzer.Simultaneously, this method adopts tank reactor, can not continuous production, be not easy to realize suitability for industrialized production.
The domestic research that also has part unit trust to carry out polyoxymethylene dimethyl ether of China.The Lanzhou Chemistry and Physics Institute of the Chinese Academy of Sciences has carried out big quantity research with the ionic liquid for the Preparation of Catalyst polyoxymethylene dimethyl ether.Reported that at patent CN 101182367 and CN 101665414 with methyl alcohol, trioxymethylene be raw material and Yi Jia contracts, trioxymethylene is the research of feedstock production polyoxymethylene dimethyl ether respectively, also be in tank reactor, to carry out.
In addition, all there are the bibliographical information of preparation polyoxymethylene dimethyl ether in other companies such as E.I.Du Pont Company, Italian Snamprogetti S.P.A., U.S. Southwest Research Inst. etc.
Up to now, because there are various shortcomings in catalyst system therefor, there are etching apparatus, contaminate environment like mineral acid; The low reaction efficiency that influences of routine resin catalyst use temperature, high, the easy inactivation of ionic-liquid catalyst cost, separation relative complex, more crucial is conventional tank reactor operation inconvenience; Can not continuous production; In the selection of raw material, trioxymethylene expensive cost is more high, makes this product slowly fail to realize suitability for industrialized production.
Summary of the invention
The technical problem that the present invention will solve is to overcome in the past in the report, and preparation polyoxymethylene dimethyl ether process is complicated, the liquid acid catalyst etching apparatus of use, contaminate environment; Separate complex; High or the stable and active problem that can not take into account of production cost is considered from economy, uses the trioxymethylene of the costliness of comparatively cheap Paraformaldehyde 96 instead of part patent employing; Replace conventional tank reactor with fixed-bed reactor; Meanwhile, replace methyl alcohol etc. that the methoxyl group part is provided, reduce the ratio of water in products with methylal; Subsequent separation process is simplified, provided a kind of by acidic resins catalysis methylal and Paraformaldehyde 96 method through fixed-bed reactor continuous production polyoxymethylene dimethyl ether.The method outstanding behaviours that this patent provides replaces the conventional at present trioxymethylene that uses at the Paraformaldehyde 96 by relative low price, adopts fixed bed quantity-produced mode to replace the mode of production of intermittent formula reaction, has improved production efficiency.This catalystsystem has good activity and selectivity, high stability, the characteristics of etching apparatus, simple to operate, convenient separation not, is very beneficial for realizing the suitability for industrialized production of polyoxymethylene dimethyl ether.
The present invention is a kind of method of continuous production polyoxymethylene dimethyl ether, it is characterized in that:
Comprise the steps:
A) Paraformaldehyde 96 with methylal and hot melt feeds in the fixed-bed reactor, and used methylal and Paraformaldehyde 96 mass ratio are 0.1 ~ 10:1; Adopt acid resin catalyst, control reaction temperature is 120 ~ 180 ℃, and reaction pressure is 0.1 ~ 10 MPa, and air speed is 0.1 ~ 5 hr
-1, catalyzed reaction prepares polyoxymethylene dimethyl ether DMM
3-8Wherein used acid resin catalyst is selected from vinylbenzene-divinyl benzene series resin, the vinylformic acid-divinyl benzene series resin of modification, the methylacrylic acid-divinyl benzene series resin of modification, the sulfonation tetrafluoroethylene resin of modification;
B) after the reaction product cooling; Carry out fractionation by adsorption through dehydration tower; Obtain removing the polyoxymethylene dimethyl ether of most of water, born of the same parents' glycol, semi-acetal, wherein used dewatering agent is selected from 3A molecular sieve, 4A molecular sieve, 5A molecular sieve, 13X molecular sieve, calcium chloride, silica gel;
The polyoxymethylene dimethyl ether feeding distillation tower that c) will remove water, born of the same parents' glycol, semi-acetal separates, and at first in distillation tower, isolates most low boiling component methylal DMM, gathers dicarbaldehyde dme DMM
2And by-product carbinol, trioxymethylene feeds the DMM that isolates residual content in next step the rectifying tower with tower still thing then
2And trioxymethylene, the tower still is product polyoxymethylene dimethyl ether DMM
3-8The distillation of two steps is that 0.001 ~ 0.1 MPa is to separate in 20 ~ 200 ℃ of following minute two steps with temperature at pressure, at first in normal pressure and 20 ~ 150 ℃ of operations down, isolates most DMM, methyl alcohol, DMM
2And trioxymethylene, secondly in pressure and 40 ~ 200 ℃ of operations down of 0.001 ~ 0.1 MPa, isolate the DMM of residual content
2And trioxymethylene, the tower still is DMM
3-8
D) low boiling component methylal DMM, the methyl alcohol that back distillation tower and rectifying tower is steamed, gather dicarbaldehyde dme DMM
2And trioxymethylene returns the polyoxymethylene dimethyl ether DMM that fixed-bed reactor continuation prepared in reaction is fit to mix as diesel oil the burning component
3-8Thereby, improve utilization ratio of raw materials.
According to this clearly demarcated described method, it is characterized in that:
Comprise the steps:
A) Paraformaldehyde 96 with methylal and hot melt feeds in the fixed-bed reactor, and used methylal and Paraformaldehyde 96 mass ratio are 0.5 ~ 5:1; Adopt an acidic catalyst, control reaction temperature is 140 ~ 160 ℃, and reaction pressure is 1 ~ 4 MPa, and air speed is 0.5 ~ 2 hr
-1, catalyzed reaction prepares polyoxymethylene dimethyl ether; Wherein used acid resin catalyst is selected from vinylbenzene-divinyl benzene series resin, the sulfonation tetrafluoroethylene resin of modification;
B) after the reaction product cooling, carry out fractionation by adsorption through dehydration column, obtain removing the polyoxymethylene dimethyl ether of most of water, born of the same parents' glycol, semi-acetal, wherein used dewatering agent is selected from 4A molecular sieve, 5A molecular sieve, 13X;
The polyoxymethylene dimethyl ether feeding distillation tower that c) will remove water, born of the same parents' glycol, semi-acetal separates, and at first in distillation tower, isolates most low boiling component methylal DMM, gathers dicarbaldehyde dme DMM
2And by-product carbinol, trioxymethylene feeds the DMM that isolates residual content in next step the rectifying tower with tower still thing then
2And trioxymethylene, the tower still is product polyoxymethylene dimethyl ether DMM
3-8;The distillation of two steps is that 0.001 ~ 0.1 MPa is to separate in 20 ~ 200 ℃ of following minute two steps with temperature at pressure, at first in normal pressure and 40 ~ 140 ℃ of operations down, isolates most DMM, methyl alcohol, DMM
2And trioxymethylene, secondly in pressure and 80 ~ 180 ℃ of operations down of 0.005 ~ 0.1 MPa, isolate the DMM of residual content
2And trioxymethylene, the tower still is polyoxymethylene dimethyl ether DMM
3-8
The preparation of polyoxymethylene dimethyl ether is to carry out being enough to make under the temperature of methylal and Paraformaldehyde 96 polycondensation among the present invention, preferably under 120 ~ 180 ℃, carries out, and more preferably under 140 ~ 160 ℃, carries out.The residence time is 0.1 ~ 5 hr, more preferably carries out under 0.5 ~ 2 hr.Under 0.1 ~ 10 MPa pressure, carry out preferably reaction under 1 ~ 4 MPa pressure.
According to the present invention, the separation of polyoxymethylene dimethyl ether is purified and is made up of three steps.At first reaction product is passed through most water, born of the same parents' two pure and mild semi-acetals in the dehydration tower removal system; Wherein used dewatering agent is selected from one or more in 3A molecular sieve, 4A molecular sieve, 5A molecular sieve, 13X molecular sieve, calcium chloride, the silica gel etc., preferred 3A molecular sieve, 4A molecular sieve or 13X molecular sieve.Second step was that the polyoxymethylene dimethyl ether that removes water, born of the same parents' glycol, semi-acetal is separated in atmospheric distillation tower, and tower still temperature is 20 ~ 150 ℃ of substep separation down, preferred 40 ~ 140 ℃.The 3rd step was in rectifying tower, and pressure is 0.001 ~ 0.1MPa, preferred 0.005 ~ 0. 1MPa, and tower still temperature is 40 ~ 200 ℃, preferred 80 ~ 180 ℃, isolate low boiling component by cat head, the tower still is DMM
3-8With minute quantity high-polymerization degree polyoxymethylene dimethyl ether (content is lower than 1%).
Description of drawings
Fig. 1 is the synoptic diagram of fixed-bed reactor of the present invention.
Below in conjunction with Fig. 1 the fixed bed synthesizing polyoxymethylene dme operational path that adopts of the present invention is specified.Methylal and Paraformaldehyde 96 are from getting into fixed-bed reactor from raw material pipeline 1 and 2 respectively; Reaction product gets into dehydration tower by pipeline 3, and wherein dehydration tower parallel connection configuration is 2 ~ 3, after one of them dehydration tower absorption is saturated, pipeline 3 is switched to another dehydration tower, adsorbs saturated dehydration tower and behind thermal regeneration, can continue to use; The polyoxymethylene dimethyl ether that removes most of water, born of the same parents' glycol, semi-acetal gets into atmospheric distillation tower by pipeline 4, contains DMM and DMM
2Low boiling component return fixed-bed reactor and fresh methylal, Paraformaldehyde 96 continue reaction by pipeline 5 through relay tank; Tower still material gets into rectifying tower by pipeline 6 and carries out rectifying separation, and wherein low boiling component is the DMM of residual content
2With minute quantity DMM
3, returning fixed-bed reactor and fresh methylal, Paraformaldehyde 96 continuation reaction by pipeline 7 through relay tank, the tower still is highly purified DMM
3-8, get into the product jar by pipeline 8.
Embodiment
Embodiment 1
At internal diameter is that to add 30 ml particle diameters in the reaction tubes of 2.5 mm be the Nafion resin of 0.5 ~ 1.0 mm, and temperature of reaction is controlled at 140 ℃, and reaction pressure is 3 MPa, liquid volume space-time speed (LHSV) 1 hr
-1, methylal, Paraformaldehyde 96 mass ratio are 2.0, reaction product cooling back sampling is analyzed with gc, DMM 32.2 % wherein, MeOH 4.0 %, DMM
220.6 %, DMM
3-827.0 %, DMM
n(n>8) do not detect.
At internal diameter is that to add 30 ml particle diameters in the reaction tubes of 2.5 mm be the Nafion resin of 0.5 ~ 1.0 mm, and temperature of reaction is controlled at 160 ℃, and reaction pressure is 3 MPa, liquid volume space-time speed (LHSV) 1 hr
-1, methylal, Paraformaldehyde 96 mass ratio are 2.0, reaction product cooling back sampling is analyzed with gc, DMM 30.6 % wherein, MeOH 3.9 %, DMM
220.2 %, DMM
3-826.7 %, DMM
n(n>8) do not detect.
Embodiment 3
At internal diameter is that to add 30 ml particle diameters in the reaction tubes of 2.5 mm be the Nafion resin of 0.5 ~ 1.0 mm, and temperature of reaction is controlled at 140 ℃, and reaction pressure is 3 MPa, liquid volume space-time speed (LHSV) 0.5 hr
-1, methylal, Paraformaldehyde 96 mass ratio are 2.0, reaction product cooling back sampling is analyzed with gc, DMM 26.2 % wherein, MeOH 4.0 %, DMM
218.4 %, DMM
3-830.0 %, DMM
n(n>8) do not detect.
Embodiment 4
At internal diameter is that to add 30 ml particle diameters in the reaction tubes of 2.5 mm be the modification acidic resins (TC106 of 0.5 ~ 1.0 mm; CNOOC's Tianjin Chemical Research & Desing Inst); Temperature of reaction is controlled at 140 ℃, and reaction pressure is 3 MPa, liquid volume space-time speed (LHSV) 1 hr
-1, methylal, Paraformaldehyde 96 mass ratio are 2.0, reaction product cooling back sampling is analyzed with gc, DMM 39.2 % wherein, MeOH 6.6 %, DMM
220.4 %, DMM
3-616.6 %, DMM
n(n>6) do not detect.
At internal diameter is that to add 30 ml particle diameters in the reaction tubes of 2.5 mm be the modification acidic resins (TC106 of 0.5 ~ 1.0 mm; CNOOC's Tianjin Chemical Research & Desing Inst); Temperature of reaction is controlled at 140 ℃, and reaction pressure is 3 MPa, liquid volume space-time speed (LHSV) 1 hr
-1, methylal, Paraformaldehyde 96 mass ratio are 1.8, reaction product cooling back sampling is analyzed with gc, DMM 33.2 % wherein, MeOH 8.9 %, DMM
219.4 %, DMM
3-720.8 %, DMM
n(n>7) do not detect.
At internal diameter is that to add 30 ml particle diameters in the reaction tubes of 2.5 mm be the Nafion resin of 0.5 ~ 1.0 mm, and temperature of reaction is controlled at 140 ℃, and reaction pressure is 3 MPa, liquid volume space-time speed (LHSV) 1 hr
-1, methylal, Paraformaldehyde 96 mass ratio are 2.2, reaction product cooling back sampling is analyzed with gc, DMM 38.8 % wherein, MeOH 4.3 %, DMM
225.4 %, DMM
3-724.8 %, DMM
n(n>7) do not detect.
Claims (2)
1. the method for a continuous production polyoxymethylene dimethyl ether is characterized in that:
Comprise the steps:
A) Paraformaldehyde 96 with methylal and hot melt feeds in the fixed-bed reactor, and used methylal and Paraformaldehyde 96 mass ratio are 0.1 ~ 10:1; Adopt acid resin catalyst, control reaction temperature is 120 ~ 180 ℃, and reaction pressure is 0.1 ~ 10 MPa, and air speed is 0.1 ~ 5 hr
-1, catalyzed reaction prepares polyoxymethylene dimethyl ether DMM
3-8Wherein used acid resin catalyst is selected from vinylbenzene-divinyl benzene series resin, the vinylformic acid-divinyl benzene series resin of modification, the methylacrylic acid-divinyl benzene series resin of modification, the sulfonation tetrafluoroethylene resin of modification;
B) after the reaction product cooling; Carry out fractionation by adsorption through dehydration tower; Obtain removing the polyoxymethylene dimethyl ether of most of water, born of the same parents' glycol, semi-acetal, wherein used dewatering agent is selected from 3A molecular sieve, 4A molecular sieve, 5A molecular sieve, 13X molecular sieve, calcium chloride, silica gel;
The polyoxymethylene dimethyl ether feeding distillation tower that c) will remove water, born of the same parents' glycol, semi-acetal separates, and at first in distillation tower, isolates most low boiling component methylal DMM, gathers dicarbaldehyde dme DMM
2And by-product carbinol, trioxymethylene feeds the DMM that isolates residual content in next step the rectifying tower with tower still thing then
2And trioxymethylene, the tower still is product polyoxymethylene dimethyl ether DMM
3-8The distillation of two steps is that 0.001 ~ 0.1 MPa is to separate in 20 ~ 200 ℃ of following minute two steps with temperature at pressure, at first in normal pressure and 20 ~ 150 ℃ of operations down, isolates most DMM, methyl alcohol, DMM
2And trioxymethylene, secondly in pressure and 40 ~ 200 ℃ of operations down of 0.001 ~ 0.1 MPa, isolate the DMM of residual content
2And trioxymethylene, the tower still is DMM
3-8
D) low boiling component methylal DMM, the methyl alcohol that back distillation tower and rectifying tower is steamed, gather dicarbaldehyde dme DMM
2And trioxymethylene returns the polyoxymethylene dimethyl ether DMM that fixed-bed reactor continuation prepared in reaction is fit to mix as diesel oil the burning component
3-8Thereby, improve utilization ratio of raw materials.
2. according to the described method of claim 1, it is characterized in that:
Comprise the steps:
A) Paraformaldehyde 96 with methylal and hot melt feeds in the fixed-bed reactor, and used methylal and Paraformaldehyde 96 mass ratio are 0.5 ~ 5:1; Adopt an acidic catalyst, control reaction temperature is 140 ~ 160 ℃, and reaction pressure is 1 ~ 4 MPa, and air speed is 0.5 ~ 2 hr
-1, catalyzed reaction prepares polyoxymethylene dimethyl ether; Wherein used acid resin catalyst is selected from vinylbenzene-divinyl benzene series resin, the sulfonation tetrafluoroethylene resin of modification;
B) after the reaction product cooling, carry out fractionation by adsorption through dehydration column, obtain removing the polyoxymethylene dimethyl ether of most of water, born of the same parents' glycol, semi-acetal, wherein used dewatering agent is selected from 4A molecular sieve, 5A molecular sieve, 13X;
The polyoxymethylene dimethyl ether feeding distillation tower that c) will remove water, born of the same parents' glycol, semi-acetal separates, and at first in distillation tower, isolates most low boiling component methylal DMM, gathers dicarbaldehyde dme DMM
2And by-product carbinol, trioxymethylene feeds the DMM that isolates residual content in next step the rectifying tower with tower still thing then
2And trioxymethylene, the tower still is product polyoxymethylene dimethyl ether DMM
3-8;The distillation of two steps is that 0.001 ~ 0.1 MPa is to separate in 20 ~ 200 ℃ of following minute two steps with temperature at pressure, at first in normal pressure and 40 ~ 140 ℃ of operations down, isolates most DMM, methyl alcohol, DMM
2And trioxymethylene, secondly in pressure and 80 ~ 180 ℃ of operations down of 0.005 ~ 0.1 MPa, isolate the DMM of residual content
2And trioxymethylene, the tower still is polyoxymethylene dimethyl ether DMM
3-8
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| CN104230685A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Process for producing polyoxymethylene dimethyl ether from methanol and paraformaldehyde |
| CN104276931A (en) * | 2013-07-09 | 2015-01-14 | 中国石油化工股份有限公司 | Technological process for synthesizing polyoxymethylene dimethyl ethers from methanol and paraformaldehyde |
| CN104355976A (en) * | 2014-11-07 | 2015-02-18 | 中国海洋石油总公司 | Method for synthesizing mesityl oxide from acetone by one-step process |
| CN104449897A (en) * | 2014-11-25 | 2015-03-25 | 四川省大气投资有限公司 | Ether-mixed burning fuel for vehicle and preparation method thereof |
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| CN103848730B (en) * | 2014-01-09 | 2015-06-17 | 东营市润成碳材料科技有限公司 | Production device system and production process for polymethoxy dimethyl ether (PODE) |
| CN104860801A (en) * | 2015-06-10 | 2015-08-26 | 李敬珍 | Method and device for continuously producing polyoxy dimethyl ether |
| CN106220481A (en) * | 2016-07-27 | 2016-12-14 | 中国科学院山西煤炭化学研究所 | A kind of technique of continuous production polyoxymethylene dimethyl ether |
| CN106957221A (en) * | 2017-05-05 | 2017-07-18 | 凯瑞环保科技股份有限公司 | The device and method of polymethoxy dimethyl ether is produced in a kind of methanol oxidation |
| CN108191615A (en) * | 2017-12-29 | 2018-06-22 | 中国人民解放军62025部队 | A kind of method with circulating fixed bed reactor synthesis polymethoxy dialkyl ether |
| CN110156576A (en) * | 2019-04-29 | 2019-08-23 | 中国科学院山西煤炭化学研究所 | A kind of technique of low temperature continuous production polyoxymethylene dimethyl ether |
| CN111153776A (en) * | 2020-02-14 | 2020-05-15 | 四川纬邦亿科技有限公司 | DMMn production process and device |
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