CN104151148A - Method for preparing polyformaldehyde dimethyl ether from paraformaldehyde - Google Patents
Method for preparing polyformaldehyde dimethyl ether from paraformaldehyde Download PDFInfo
- Publication number
- CN104151148A CN104151148A CN201310180073.9A CN201310180073A CN104151148A CN 104151148 A CN104151148 A CN 104151148A CN 201310180073 A CN201310180073 A CN 201310180073A CN 104151148 A CN104151148 A CN 104151148A
- Authority
- CN
- China
- Prior art keywords
- paraformaldehyde
- methylal
- polyoxymethylene dimethyl
- reaction
- methyl alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
Abstract
The invention relates to a method for preparing polyformaldehyde dimethyl ether from paraformaldehyde, which is used for mainly solving the problems that a conventional catalyst is low in reaction efficiency, a relatively great amount of byproducts are generated and the cost of trioxymethylene serving as a raw material is relatively high. The method solves the problems well by taking the technical scheme that methanol, methylal and paraformaldehyde are taken as raw materials, the mass ratio of methanol to methylal and paraformaldehyde is (0-10):(0-10):1, the amounts of methanol and methylal cannot be zero at the same time, the raw material is in contact with the catalyst to react to generate polyformaldehyde dimethyl under the conditions that the reaction temperature is 70-200 DEG C and the reaction pressure is 0.2-6MPa, the use amount of the catalyst accounts for 0.05-10% of that of the raw materials, and the catalyst comprises the following components in parts by weight: a) 30-80 parts of activated carbon carrier and b) 20-70 parts of at least one selected from Fe(NO3)3, Fe2(SO4)3, Cu(NO3)2 or Mn(NO3)2. The method can be used in industrial production of polyformaldehyde dimethyl ether.
Description
Technical field
The present invention relates to a kind of method of being prepared polyoxymethylene dimethyl ethers by paraformaldehyde, particularly about a kind of method taking paraformaldehyde as raw material synthesizing polyoxymethylene dme.
Background technology
In recent years, along with Industrial Revolution impact increasingly deeply and the resource general layout of China's distinctive " many coals, few oil, have gas ", China's oil resource growing tension, oil supply pressure unprecedentedly increases.Future 10～20 years, China's oil supply rate only has～and 50%.How to utilize the energy dilemma of coal resources solution China of China's abundant just to become researcher urgent problem.Therefore be day by day subject to people's attention by the oil product substitute of coal-based methanol development of new.
Dme is suggested the earliest as a kind of procetane, however because himself cold starting performance is poor, under normal temperature vapour pressure high, easily produce vapour lock dme obviously raise as the cost of vehicle alternative fuel.Polyoxymethylene dimethyl ether, i.e. Polyoxymethylene dimethyl ethers (PODE), is the common name of a class material, its skeleton symbol can be expressed as CH
3o (CH
2o)
ncH
3, there is higher octane value (> 30) and oxygen level (42～51%).In the time that the value of n is 2～10, its physical properties, combustionproperty and diesel oil are very approaching, preferably resolve the defect that dme exists as derv fuel oil blend component.Therefore polyoxymethylene dimethyl ether can be used as novel clean diesel component, and the addition in diesel oil can reach 30% (v/v), can improve the combustion position of diesel oil in engine, improves thermo-efficiency, reduces particulate matter and CO in tail gas
xand NO
xdischarge.It is reported, add 5～30% CH
3oCH
2oCH
3can reduce NO
xdischarge 7～10%, PM reduces by 5～35%.By coal-based methanol, synthetic PODE not only can replace part diesel oil, can also improve the efficiency of combustion of diesel oil, reduces the harm of diesel combustion to environment, has important strategic importance and good economic worth.
Prepared by the method that in laboratory, polyoxymethylene dimethyl ether reacts with methyl alcohol in 150～180 DEG C of heating low polymerization degree paraformaldehydes or paraformaldehyde under can existing by trace sulfuric acid or hydrochloric acid.In recent years, polyoxymethylene dimethyl ether synthetic technology has obtained progress.
CN 102040491A has introduced employing β zeolite, ZSM-5 molecular sieve, MCM-22, MCM-56 or UZM-8 molecular sieve etc. as catalyzer, is the method for reactant synthesizing polyoxymethylene dme by methyl alcohol, methylal and paraformaldehyde.CN 102040490A has introduced employing solid super acid catalyst, and 100～130 DEG C of temperature of reaction, when reaction pressure 0.4～4.0MPa, transformation efficiency and selectivity are all too late using metal-salt modified activated carbon as catalyzer.
Although it is reaction raw materials that these techniques all adopt methyl alcohol, methylal and paraformaldehyde, the zeolite catalyst adopting and solid super acid catalyst separation difficulty, feed stock conversion is low, selectivity of product is poor.
Summary of the invention
Technical problem to be solved by this invention be prior art in reaction raw materials synthesizing polyoxymethylene dme technique, have using methyl alcohol, methylal and paraformaldehyde that catalyst reaction efficiency is low, by product is more and trioxymethylene as the higher problem of raw materials cost, a kind of new method of being prepared polyoxymethylene dimethyl ethers by paraformaldehyde is provided.The method has advantages of that catalyst low-temperature activity is high, by product is less.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of being prepared polyoxymethylene dimethyl ethers by paraformaldehyde, with methyl alcohol, methylal and paraformaldehyde are raw material, wherein methyl alcohol: methylal: the mass ratio of paraformaldehyde is 0～10: 0～10: 1, the consumption of methyl alcohol and methylal can not be 0 simultaneously, it is 70～200 DEG C in temperature of reaction, reaction pressure is under 0.2～6MPa condition, raw material contacts with catalyzer, reaction generates polyoxymethylene dimethyl ether, catalyst levels is 0.05～10% of raw material weight, wherein catalyzer used comprises a) carrier of 30～80 parts of following component in parts by weight, carrier is selected from gac, with carry thereon b) 20～70 parts be selected from Fe (NO
3)
3, Fe
2(SO
4)
3, Cu (NO
3)
2or Mn (NO
3)
2in at least one.
In technique scheme, catalyst levels preferable range is raw material weight 0.1～5%.In reactant, the consumption sum of methyl alcohol and methylal and the mass ratio of paraformaldehyde are preferably 0.4～5: 1; Methyl alcohol: methylal: the mass ratio of paraformaldehyde is preferably 0.2～10: 0.5～10: 1.The preferable range of temperature of reaction is 100～130 DEG C.Reaction pressure preferable range is 0.4～4.0MPa.The polymerization degree of described paraformaldehyde is preferably 2～8, and more preferably 4～6.The preferred BET specific surface of described gac is 1000～2500m
2/ g, pore volume is 0.3～0.6ml/g; More preferably BET specific surface is 2000～2500m
2/ g, pore volume is 0.3～0.5ml/g.
In technique scheme, from the invention technical problem that will solve, with prior art effect on year-on-year basis, the reaction times is not key point of the present invention, but control and the consideration of time efficiency other factors from operation, conventionally will control in the reaction times is 1 to 20 hour.The reaction times adopting in the embodiment of the present invention is 4～12 hours.
Catalyzed reaction makes polyoxymethylene dimethyl ether, can be by filtering or centrifugal mode separating catalyst and liquid phase reaction thing.
The polymerization degree of paraformaldehyde adopts Arbiso process or iodometric determination, method comes from: Chen Yongjie, and Zhao Hui, Shao Yong waits so long. the preparation of the polymerization degree measurement of industrial paraformaldehyde and low polymerization degree paraformaldehyde, Shenyang Institute of Chemical Technology journal, 15 (2): 2001.
In the present invention, be catalyzer owing to using metal-salt modified activated carbon, can realize methyl alcohol, methylal and paraformaldehyde catalyzed reaction synthesizing polyoxymethylene dme, replace the trioxymethylene in traditional raw material.Because the method can paraformaldehyde be raw material, the inexpensive production cost that makes is lower, and products distribution is also more even.Using the inventive method, is 70～200 DEG C in temperature of reaction, and reaction pressure is under 0.2～6MPa condition, uses methyl alcohol, methylal and polyformaldehyde reaction, and its result is as follows: the first, and production cost is lower; The second, selectivity of product is nearly 76.9%, has obtained good technique effect.
Below by embodiment, the present invention is further elaborated, and the polymerization degree of the raw material paraformaldehyde adopting in embodiment and comparative example is 5, and taking paraformaldehyde as benchmark, the polyoxymethylene dimethyl ether taking the polymerization degree as 2 ~ 10 calculates as target product selectivity of product.
Embodiment
[embodiment 1]
In 300 milliliters of tank reactors, add 2 grams of catalyzer (to consist of: 80 parts of gac+20 part Cu (NO
3)
2; Gac BET2500m
2/ g, pore volume 0.3ml/g), 100 grams of methyl alcohol and 100 grams of paraformaldehydes react 4h under 130 DEG C and 0.8MPa autogenous pressure, extract after sample centrifugation by gas chromatographic analysis.In product, comprise polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde, its composition distributes as table 1.
[embodiment 2]
In 300 milliliters of tank reactors, add 2 grams of catalyzer (to consist of: 60 parts of gac+40 part Cu (NO
3)
2; Gac BET2000m
2/ g, pore volume 0.5ml/g), 100 grams of methyl alcohol and 100 grams of paraformaldehydes react 4h under 130 DEG C and 0.6 MPa autogenous pressure, extract after sample centrifugation by gas chromatographic analysis.In product, comprise polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde, its composition distributes as table 1.
[embodiment 3]
In 300 milliliters of tank reactors, add 2 grams of catalyzer (to consist of: 80 parts of gac+20 part Fe (NO
3)
3; Gac BET1100m
2/ g, pore volume 0.5ml/g), 100 grams of methylals and 100 grams of paraformaldehydes react 4h under 130 DEG C and 0.6 MPa autogenous pressure, extract after sample centrifugation by gas chromatographic analysis.In product, comprise polyoxymethylene dimethyl ether and unreacted raw material methylal and paraformaldehyde, its composition distributes as table 1.
[embodiment 4]
In 300 milliliters of tank reactors, add 2 grams of catalyzer (to consist of: 60 parts of gac+40 part Fe
2(SO
4)
3; Gac BET1100m
2/ g, pore volume 0.5ml/g), 100 grams of distillation samples (87% methylal, all the other be methyl alcohol) and 100 grams of paraformaldehydes, at 130 DEG C, react 4h under 0.7MPa autogenous pressure, after the centrifugation of extraction sample by through gas chromatographic analysis.In product, comprise polyoxymethylene dimethyl ether and unreacted raw material methylal and paraformaldehyde, its composition distributes as table 1.
[embodiment 5]
In 300 milliliters of tank reactors, add 2 grams of catalyzer (to consist of: 80 parts of gac+20 part Mn (NO
3)
2; Gac BET1100m
2/ g, pore volume 0.5ml/g), 100 grams of methyl alcohol and 50 grams of paraformaldehydes, at 130 DEG C, react 4h under 0.7MPa autogenous pressure, extracts after sample centrifugation by through gas chromatographic analysis.In product, comprise polyoxymethylene dimethyl ether and unreacted raw material methylal and paraformaldehyde, its composition distributes as table 1.
[embodiment 6]
In 300 milliliters of tank reactors, add 2 grams of catalyzer (to consist of: 60 parts of gac+40 part Mn (NO
3)
2; Gac BET1100m
2/ g, pore volume 0.5ml/g), 100 grams of methyl alcohol and 100 grams of paraformaldehydes, at 100 DEG C of reaction 4h, extract after sample centrifugation by gas chromatographic analysis.In product, comprise polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde, its composition distributes as table 1.
[embodiment 7]
In 300 milliliters of tank reactors, add 0.5 gram of catalyzer (to consist of: 80 parts of gac+20 part Fe
2(SO
4)
3; Gac BET1100m
2/ g, pore volume 0.5ml/g), 100 grams of methyl alcohol and 100 grams of paraformaldehydes react 12h under 100 DEG C and 2MPa autogenous pressure, extract after sample centrifugation by gas chromatographic analysis.In product, comprise polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde, its composition distributes as table 1.
[embodiment 8]
In 300 milliliters of tank reactors, add 1 gram of catalyzer (to consist of: 80 parts of gac+20 part Cu (NO
3)
2; Gac BET1100m
2/ g, pore volume 0.5ml/g), 100 grams of methylals and 100 grams of paraformaldehydes react 4h under 120 DEG C and 4MPa nitrogen pressure, extract after sample centrifugation by gas chromatographic analysis.In product, comprise polyoxymethylene dimethyl ether and unreacted raw material methylal and paraformaldehyde, its composition distributes as table 1.
[comparative example 1]
As described in patent CN 102040491A, in 300 milliliters of tank reactors, add 2 grams of catalyzer USM-8(Si/Al=6.6), 100 grams of distillation sample (methylals of 87wt%, all the other are methyl alcohol) and 100 grams of paraformaldehydes, at 130 DEG C, under 0.7MPa autogenous pressure, react 4h, filtering separation catalyzer and reaction product, through gas chromatographic analysis, in product, comprise methylal and polyoxymethylene dimethyl ether and unreacted raw material, its composition distributes following (representing taking % by weight): methylal is 19.7%, methyl alcohol is 0.5%, paraformaldehyde is 22.6%, n=2 is 20.3%, n=3 is 15.4%, n=4 is 10.7%, n=5-10 is 7.1%, n>10, surplus, product n=2～10 selectivity is 53.5%.
In comparative example, use methyl alcohol, methylal and paraformaldehyde and for raw material, under equal conditions product yield is lower as catalyzer for molecular sieve.In contrast, the transformation efficiency of reaction and product n=2～10 selectivity are higher for the embodiment of the present invention 1, and selectivity is 68.2%, and in product, paraformaldehyde content is lower, better reaction result can obtain with zeolite molecular sieve as catalyzer time.
1(is continued for table)
| Represent with wt% | Paraformaldehyde | Methyl alcohol | Methylal | Product n=2 | Product n=3 |
| Embodiment 1 | 1.0 | 5.3 | 22.4 | 23.4 | 22.3 |
| Embodiment 2 | 0.3 | 6.2 | 24.1 | 26.7 | 23.0 |
| Embodiment 3 | 6.1 | 0 | 27.2 | 24.4 | 21.5 |
| Embodiment 4 | 3.5 | 0.4 | 16.9 | 20.9 | 27.2 |
| Embodiment 5 | 0.2 | 30.3 | 28.0 | 23.4 | 17.0 |
| Embodiment 6 | 5.9 | 15.9 | 30.0 | 14.8 | 16.4 |
| Embodiment 7 | 12.2 | 10.2 | 23.4 | 18.1 | 12.3 |
| Embodiment 8 | 2.2 | 0 | 22.6 | 21.9 | 23.7 |
N is the polymerization degree, and product is CH
3o (CH
2o)
ncH
3
Table 1(is continuous)
| Represent with wt% | Product n=4 | Product n=5～10 | Product n > 10 | Selectivity of product, % |
| Embodiment 1 | 12.1 | 10.4 | Surplus | 68.2 |
| Embodiment 2 | 8.3 | 9.6 | Surplus | 67.6 |
| Embodiment 3 | 13.5 | 2.9 | Surplus | 62.3 |
| Embodiment 4 | 16.7 | 12.1 | Surplus | 76.9 |
| Embodiment 5 | 0.6 | 0 | Surplus | 41.0 |
| Embodiment 6 | 6.1 | 9.8 | Surplus | 47.1 |
| Embodiment 7 | 11.9 | 6.2 | Surplus | 48.5 |
| Embodiment 8 | 15.8 | 8.2 | Surplus | 69.6 |
Claims (10)
1. prepared the method for polyoxymethylene dimethyl ethers by paraformaldehyde for one kind, with methyl alcohol, methylal and paraformaldehyde are raw material, wherein methyl alcohol: methylal: the mass ratio of paraformaldehyde is 0～10: 0～10: 1, the consumption of methyl alcohol and methylal can not be 0 simultaneously, it is 70～200 DEG C in temperature of reaction, reaction pressure is under 0.2～6MPa condition, raw material contacts with catalyzer, reaction generates polyoxymethylene dimethyl ether, catalyst levels is 0.05～10% of raw material weight, wherein catalyzer used comprises following component in parts by weight: a) carrier of 30～80 parts, carrier is selected from gac, with carry thereon b) 20～70 parts be selected from Fe (NO
3)
3, Fe
2(SO
4)
3, Cu (NO
3)
2or Mn (NO
3)
2in at least one.
2. the method for being prepared polyoxymethylene dimethyl ethers by paraformaldehyde according to claim 1, is characterized in that catalyst levels is 0.1～5% of raw material weight.
3. the method for being prepared polyoxymethylene dimethyl ethers by paraformaldehyde according to claim 1, is characterized in that in reactant that methyl alcohol and the consumption sum of methylal and the mass ratio of paraformaldehyde are 0.4～5: 1; Methyl alcohol: methylal: the mass ratio of paraformaldehyde is 0.2～10: 0.5～10: 1.
4. the method for being prepared polyoxymethylene dimethyl ethers by paraformaldehyde according to claim 1, is characterized in that temperature of reaction is 100～130 DEG C.
5. the method for being prepared polyoxymethylene dimethyl ethers by paraformaldehyde according to claim 1, is characterized in that reaction pressure is 0.4～4.0 MPa.
6. the method for being prepared polyoxymethylene dimethyl ethers by paraformaldehyde according to claim 1, the polymerization degree that it is characterized in that described paraformaldehyde is 2～8.
7. the method for being prepared polyoxymethylene dimethyl ethers by paraformaldehyde according to claim 6, the polymerization degree that it is characterized in that described paraformaldehyde is 4～6.
8. the method for being prepared polyoxymethylene dimethyl ethers by paraformaldehyde according to claim 1, is characterized in that the reaction times is 1 to 20 hour.
9. the method for being prepared polyoxymethylene dimethyl ethers by paraformaldehyde according to claim 1, the BET specific surface that it is characterized in that described activated carbon is 1000 ~ 2500m
2/ g, pore volume is 0.3 ~ 0.6ml/g.
10. the method for being prepared polyoxymethylene dimethyl ethers by paraformaldehyde according to claim 9, the BET specific surface that it is characterized in that described activated carbon is 2000 ~ 2500m
2/ g, pore volume is 0.3 ~ 0.5ml/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310180073.9A CN104151148B (en) | 2013-05-16 | 2013-05-16 | Prepared the method for polyoxymethylene dimethyl ethers by paraformaldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310180073.9A CN104151148B (en) | 2013-05-16 | 2013-05-16 | Prepared the method for polyoxymethylene dimethyl ethers by paraformaldehyde |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104151148A true CN104151148A (en) | 2014-11-19 |
| CN104151148B CN104151148B (en) | 2016-05-18 |
Family
ID=51876813
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310180073.9A Active CN104151148B (en) | 2013-05-16 | 2013-05-16 | Prepared the method for polyoxymethylene dimethyl ethers by paraformaldehyde |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104151148B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237366A (en) * | 2015-09-06 | 2016-01-13 | 常州大学 | Method of preparing polyformaldehyde dimethyl ether through catalysis of sulfates supported by molecular sieve |
| CN105348053A (en) * | 2015-11-18 | 2016-02-24 | 常州大学 | Method for catalysis preparation of polyformaldehyde dimethyl ether on basis of metal salt catalyst |
| CN106278835A (en) * | 2015-06-10 | 2017-01-04 | 中国科学院兰州化学物理研究所苏州研究院 | The method of anhydrous production polymethoxy dimethyl ether |
| CN106582835A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Polyformaldehyde dimethyl ether synthesis catalyst |
| CN107915606A (en) * | 2016-10-09 | 2018-04-17 | 中国石油化工股份有限公司 | Preparation method for polyoxymethylene dimethyl ether |
| CN107915605A (en) * | 2016-10-09 | 2018-04-17 | 中国石油化工股份有限公司 | It is used to prepare the method for polyoxymethylene dimethyl ether |
| CN107915596A (en) * | 2016-10-09 | 2018-04-17 | 中国石油化工股份有限公司 | The method prepared for polyoxymethylene dimethyl ether |
| CN107915597A (en) * | 2016-10-09 | 2018-04-17 | 中国石油化工股份有限公司 | The catalyst prepared for polyoxymethylene dimethyl ether |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768058A (en) * | 2009-01-07 | 2010-07-07 | 中国石油化工股份有限公司 | Method for preparing polyoxymethylene dimethyl ether |
| CN102040490A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Synthesis method of polyformaldehyde dimethyl ether |
| CN102040488A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Method for synthesizing PODE (polyformaldehyde dimethyl ether) |
-
2013
- 2013-05-16 CN CN201310180073.9A patent/CN104151148B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768058A (en) * | 2009-01-07 | 2010-07-07 | 中国石油化工股份有限公司 | Method for preparing polyoxymethylene dimethyl ether |
| CN102040490A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Synthesis method of polyformaldehyde dimethyl ether |
| CN102040488A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Method for synthesizing PODE (polyformaldehyde dimethyl ether) |
Non-Patent Citations (1)
| Title |
|---|
| 赵光等: "MoO3/γ－Al2O3催化合成聚甲醛二甲醚", 《上海市化学化工学会2011年度学术年会论文集》, 31 October 2012 (2012-10-31), pages 101 - 103 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106278835A (en) * | 2015-06-10 | 2017-01-04 | 中国科学院兰州化学物理研究所苏州研究院 | The method of anhydrous production polymethoxy dimethyl ether |
| CN106278835B (en) * | 2015-06-10 | 2019-01-11 | 中国科学院兰州化学物理研究所苏州研究院 | The method of anhydrous production polymethoxy dimethyl ether |
| CN105237366A (en) * | 2015-09-06 | 2016-01-13 | 常州大学 | Method of preparing polyformaldehyde dimethyl ether through catalysis of sulfates supported by molecular sieve |
| CN106582835A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Polyformaldehyde dimethyl ether synthesis catalyst |
| CN105348053A (en) * | 2015-11-18 | 2016-02-24 | 常州大学 | Method for catalysis preparation of polyformaldehyde dimethyl ether on basis of metal salt catalyst |
| CN107915606A (en) * | 2016-10-09 | 2018-04-17 | 中国石油化工股份有限公司 | Preparation method for polyoxymethylene dimethyl ether |
| CN107915605A (en) * | 2016-10-09 | 2018-04-17 | 中国石油化工股份有限公司 | It is used to prepare the method for polyoxymethylene dimethyl ether |
| CN107915596A (en) * | 2016-10-09 | 2018-04-17 | 中国石油化工股份有限公司 | The method prepared for polyoxymethylene dimethyl ether |
| CN107915597A (en) * | 2016-10-09 | 2018-04-17 | 中国石油化工股份有限公司 | The catalyst prepared for polyoxymethylene dimethyl ether |
| CN107915596B (en) * | 2016-10-09 | 2020-04-17 | 中国石油化工股份有限公司 | Method for preparing polyformaldehyde dimethyl ether |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104151148B (en) | 2016-05-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102040491B (en) | Catalytic synthesis method for polyoxymethylene dimethyl ethers (PODE) by molecular sieves | |
| CN104151148B (en) | Prepared the method for polyoxymethylene dimethyl ethers by paraformaldehyde | |
| CN103880612B (en) | By the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers | |
| CN102040490A (en) | Synthesis method of polyformaldehyde dimethyl ether | |
| CN103664545B (en) | By the method for methyl alcohol, methylal and paraformaldehyde synthesizing polyoxymethylene dme | |
| CN104549443A (en) | Polyformaldehyde dimethyl ether catalyst and application thereof | |
| CN102295734B (en) | Method for synthesizing polyoxymethylene dimethyl ether | |
| CN103664549B (en) | The synthetic method of polyoxymethylene dimethyl ether | |
| CN103739458B (en) | The preparation method of polyoxymethylene dimethyl ethers | |
| CN104230684A (en) | Process for synthesis of polyoxymethylene dimethyl ether from methyl | |
| CN103664543B (en) | The method of polyoxymethylene dimethyl ether is prepared by paraformaldehyde | |
| CN102295539B (en) | Method for catalytically synthesizing polyformaldehyde dimethyl ether | |
| CN104276932A (en) | Preparation method of paraform dimethyl ether | |
| CN104151147B (en) | With the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers | |
| CN103420817A (en) | Method for synthesizing polyformaldehyde dimethyl ether from methylal and paraformaldehyde | |
| CN103772161A (en) | Method for preparing polyoxymethylene dimethyl ethers | |
| CN103880613B (en) | Prepare the method for polyoxymethylene dimethyl ethers | |
| CN103772165B (en) | By the method for paraformaldehyde polyoxymethylene dimethyl ethers processed | |
| CN105294411A (en) | Method for producing PODE (polyoxymethylene dimethyl ethers) through paraformaldehyde | |
| CN103880614B (en) | The synthetic method of polyoxymethylene dimethyl ether | |
| CN105237368B (en) | The synthetic method of polyoxymethylene dimethyl ethers | |
| CN105367393A (en) | Method for synthesizing polyoxymethylene dimethyl ether through paraformaldehyde | |
| CN102040489A (en) | Method for synthesizing polyformaldehyde dimethyl ether | |
| CN105085196A (en) | Synthesis method of polyoxymethylene dimethyl ether from paraformaldehyde | |
| CN104230683B (en) | The method of synthesizing polyoxymethylene dimethyl ethers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |