CN105439829B - In the method for paraformaldehyde production polyoxymethylene dimethyl ethers - Google Patents
In the method for paraformaldehyde production polyoxymethylene dimethyl ethers Download PDFInfo
- Publication number
- CN105439829B CN105439829B CN201410429107.8A CN201410429107A CN105439829B CN 105439829 B CN105439829 B CN 105439829B CN 201410429107 A CN201410429107 A CN 201410429107A CN 105439829 B CN105439829 B CN 105439829B
- Authority
- CN
- China
- Prior art keywords
- paraformaldehyde
- polyoxymethylene dimethyl
- catalyst
- methanol
- reaction
- 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.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of method that polyoxymethylene dimethyl ethers are produced with paraformaldehyde, mainly solves the problems, such as that conventional catalyst reaction efficiency is low, metaformaldehyde is higher for cost of material.The present invention is by using methanol, dimethoxym ethane and paraformaldehyde as raw material, wherein methanol：Dimethoxym ethane：The mass ratio of paraformaldehyde is (0~10): (0~10): 1, wherein the dosage of methanol and dimethoxym ethane can not be 0 simultaneously, it it is 70~200 DEG C in reaction temperature, under the conditions of reaction pressure is 0.2~6MPa, raw material contacts with catalyst, reaction generation polyoxymethylene dimethyl ether, catalyst amount be raw material weight 0.05~10%, wherein catalyst used in terms of weight fraction including following components：A) 30~80 parts of superhigh cross-linking polymer support (HCPs)；B) technical scheme of 20~70 parts of solid super-strong acids, preferably solves the problem, available in the industrial production of polyoxymethylene dimethyl ether.
Description
Technical field
The present invention relates to a kind of method that polyoxymethylene dimethyl ethers are produced with paraformaldehyde, especially with regard to one kind with poly
Formaldehyde is the method that raw material produces polyoxymethylene dimethyl ether.
Background technology
In recent years, as the industrial revolution influences to go deep into increasingly and the resource grid of China distinctive " more coals, less oil, having gas "
Office, China's oil resource growing tension, oil supply pressure unprecedentedly increase.It is expected that following 10~20 years, China's oil supply rate
Only~50%.How the energy crisis for solving China using the coal resources of China's abundant is become as researcher urgent need solution
Certainly the problem of.Therefore the attention that new oil product substitute is increasingly subject to people is developed by coal-based methanol.
Dimethyl ether is proposed as a kind of procetane earliest, yet with its own cold starting performance is poor, normal temperature
Lower vapour pressure is high, easily produces vapour lock make it that dimethyl ether is significantly raised as the cost of vehicle alternative fuel.Polyoxymethylene dimethyl ether,
That is Polyoxymethylene dimethyl ethers (PODE), are the common names of a kind of material, and its skeleton symbol can be expressed as
CH3O(CH2O)nCH3, have higher octane number (>And oxygen content (42~51%) 30).When n value is 2~10, its thing
Rationality matter, combustibility and diesel oil are very close, preferably resolve dimethyl ether and are lacked as existing for derv fuel blend component
Fall into.Therefore polyoxymethylene dimethyl ether can be as new cleaning diesel component, and the addition in diesel oil, can up to 30% (v/v)
To improve the combustion position of diesel oil within the engine, the thermal efficiency is improved, reduces particulate matter and CO in tail gasxAnd NOxRow
Put.It is reported that the CH of addition 5~30%3OCH2OCH3NO can be reducedxDischarging 7~10%, PM reduces by 5~35%.By coal Ji Jia
Alcohol synthesis PODE can not only substitute part diesel oil, moreover it is possible to improve the efficiency of combustion of diesel oil, reduce danger of the diesel combustion to environment
Evil, has important strategic importance and good economic value.
Superhigh cross-linking microporous polymer is the pure organic poromerics of first case, and it hinders by using the mode of post-crosslinking
Caving in so as to produce substantial amounts of micropore for macromolecular chain is stopped.Just have a long time ago scientist find by Friedel-
Craflt is reacted, and two phenyl ring adjoining in linear polystyrene macromolecular chain are entered using the organic crosslinking agent of various structures
The intensive post-crosslinking of row, so as to obtain expanded polystyrene network structure.Characterize the superhigh cross-linking obtained by this method of discovery
Polystyrene material has good micro pore volume and very high specific surface area, and these characteristics make superhigh cross-linking polymer have very
More potential application field.
Polyoxymethylene dimethyl ether can be by oligomeric in 150~180 DEG C of heating in the presence of trace sulfuric acid or hydrochloric acid in laboratory
It is prepared by right paraformaldehyde or paraformaldehyde and the method for methanol reaction.In recent years, polyoxymethylene dimethyl ether synthetic technology achieves
Progress.
CN 102040491A are described using β zeolites, ZSM-5 molecular sieve, MCM-22, MCM-56 or UZM-8 molecular sieve etc.
As catalyst, pass through the method that methanol, dimethoxym ethane and paraformaldehyde are reactant synthesizing polyoxymethylene dimethyl ether.CN
102040490A is described using solid super acid catalyst, in 90~130 DEG C of reaction temperature, 0.4~4.0MPa of reaction pressure
When, conversion ratio and selectivity are all not as good as using superhigh cross-linking Polymer-supported solid super-strong acid being used as catalyst.
Although it is reported above it is middle use methanol, dimethoxym ethane and paraformaldehyde as reaction raw materials, molecular sieve and solid super-strong acid
As these synthesis techniques of catalyst, but used zeolite catalyst and solid super acid catalyst separate difficult, raw material
Conversion ratio is low, selectivity of product is poor.Particularly, superhigh cross-linking polymer support (HCPs) has high specific surface area and space
Rate, it prevents the caving in so as to produce substantial amounts of micropore of macromolecular chain, the selection to product by using the mode of post-crosslinking
Property distribution have an impact, it is considered to be unformed poromerics.Most HCPs are higher to the stability of heat, during reaction
It can be used repeatedly.
The content of the invention
The technical problems to be solved by the invention are that prior art is given birth to by reaction raw materials of methanol, dimethoxym ethane and paraformaldehyde
Have that catalyst reaction efficiency is low, metaformaldehyde is the problem of cost of material is higher in production polyoxymethylene dimethyl ether technique, there is provided one
Kind new produces the method for polyoxymethylene dimethyl ethers and the new catalyst suitable for the technique with paraformaldehyde.This method has
The advantages of catalyst low-temperature activity is high, selectivity is high, reaction condition is gentle.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：Polyformaldehyde two is produced with paraformaldehyde
The method of methyl ether, using methanol, dimethoxym ethane and paraformaldehyde as raw material, wherein methanol: dimethoxym ethane: the mass ratio of paraformaldehyde is
(0~10): (0~10): 1, the dosage of methanol and dimethoxym ethane can not be 0 simultaneously, be 70~200 DEG C in reaction temperature, reaction pressure
Under the conditions of power is 0.2~6MPa, raw material contacts with catalyst, and reaction generation polyoxymethylene dimethyl ether, catalyst amount is raw material weight
Amount 0.05~10%, wherein catalyst used in terms of parts by weight including following components：A) 30~80 parts of carrier, carrier
At least one of HCPs, SAM-HCPs, P (DVB-VBC) superhigh cross-linking polymer in HCPs；Be loaded in b thereon) 20
~70 parts are selected from SO4 2-、Cl-、S2O8 2-At least one of solid super-strong acid, preferably simultaneously include SO4 2-And S2O8 2-Two kinds of solids
Super acids.
In above-mentioned technical proposal, catalyst amount preferred scope is the 0.1~5% of raw material weight.In reactant methanol with
The dosage sum of dimethoxym ethane and the mass ratio of paraformaldehyde are preferably (0.4~5): 1；Methanol: dimethoxym ethane: the quality of paraformaldehyde
It is (0.2~10): (0.5~10): 1 than preferred scope.The preferred scope of reaction temperature is 90~130 DEG C.Reaction pressure is preferred
Scope is 0.4~4.0MPa.The degree of polymerization of the paraformaldehyde is preferably 2~8, and more preferably 4~6.Poly- first is made in catalytic reaction
Aldehyde dimethyl ether, can by way of filtering or centrifuging separating catalyst and liquid phase reactor thing.
In above-mentioned technical proposal, from invention technical problems to be solved, with prior art effect it is year-on-year for, reaction
Time is not the key point of the present invention, but considered from operational control and time efficiency other factorses, generally by the reaction time
Control as 1 to 20 hour.The reaction time used in the embodiment of the present invention is 4~12 hour.
In above-mentioned technical proposal, SO4 2-/HCPs、SO4 2-/SAM-HCPs、SO4 2-/P(DVB-VBC)、Cl-/HCPs、Cl-/
SAM-HCPs、Cl-/P(DVB-VBC)、S2O8 2-/HCPs、S2O8 2-/SAM-HCPs、S2O8 2-/ P (DVB-VBC) is known substance
Matter, it can be used for the present invention and solve present invention problem.It is wherein covalent in superhigh cross-linking polymeric material HCPs series
The mol ratio of ion and part is preferably between 1: 10 to 10: 1.
The degree of polymerization of paraformaldehyde uses Arbiso process or iodometric determination, and method comes from：Chen Yongjie, Zhao Hui, Shao Yong
Wait so long industry paraformaldehydes polymerization degree measurement and low polymerization degree paraformaldehyde preparation, Shenyang Institute of Chemical Technology journal, 15 (2)：
2001。
Due to the use of superhigh cross-linking polymeric material HCPs supported solid superacids acid being catalyst in the present invention, can realize
Methanol, dimethoxym ethane and paraformaldehyde catalytic reaction synthesizing polyoxymethylene dimethyl ether, substitute the metaformaldehyde in traditional raw material.Due to this
Method can be inexpensive to make production cost relatively low using paraformaldehyde as raw material, and distribution of reaction products is uniform.With superhigh cross-linking polymer
Material HCPs supported solid superacids acid is catalyst, and superhigh cross-linking polymer HCPs carriers can make catalyst have pole Large ratio surface
Product and while porosity with higher heat endurance and chemical stability, so as to improve the yield of polyoxymethylene dimethyl ether,
Extend the service life of catalyst.Used catalyst contains extremely strong acidity, by the method for distillation from methanol and poly first
Obtain dimethoxym ethane in the reaction product of aldehyde, make accessory substance dimethoxym ethane be recycled into acid catalytic systems again with polyformaldehyde reaction,
Therefore higher reaction conversion ratio and product yield can be kept.It is 70~200 DEG C in reaction temperature using the inventive method,
It is as follows using methanol, dimethoxym ethane and polyformaldehyde reaction, its result under the conditions of reaction pressure is 0.2~6MPa：First, production
Cost is relatively low；Second, catalyst separates simply with reaction product, makes accessory substance circular response using the method for distillation, therefore produce
The yield of thing n=2~10 is good, and selectivity of product is up to 75.0%, achieves preferable technique effect.In addition, the catalyst makes
With 10 times, its catalytic performance is not decreased obviously.
Below by embodiment, the present invention is further elaborated, the raw material paraformaldehyde used in embodiment and comparative example
The degree of polymerization be 5, selectivity of product be by 2~10 polyoxymethylene dimethyl ether of the degree of polymerization on the basis of paraformaldehyde target production
Thing calculates.
Embodiment
【Embodiment 1】
2 grams of catalyst SO are added in 300 milliliters of tank reactors4 2-(mol ratio of covalent groups and part is /HCPs
0.1), the mass fraction ratio of wherein solid super-strong acid and HCPs carriers is 20:80,100 grams of methanol and 100 grams of paraformaldehydes,
4h is reacted under 130 DEG C and 0.8MPa self-generated pressures, is extracted after sample centrifuges by gas chromatographic analysis.Poly- first is included in product
Aldehyde dimethyl ether and unreacted material benzenemethanol and paraformaldehyde, it forms distribution such as table 1.
【Embodiment 2】
2 grams of catalyst SO are added in 300 milliliters of tank reactors4 2-/ SAM-HCPs (moles of covalent groups and part
Than for 0.1), the mass fraction ratio of wherein solid super-strong acid and SAM-HCPs carriers is 20:80,100 grams of methanol and 100 grams of polies
Formaldehyde, 4h is reacted under 130 DEG C and 0.6MPa self-generated pressures, extracted after sample centrifuges by gas chromatographic analysis.In product
Comprising polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde, it forms distribution such as table 1.
【Embodiment 3】
2 grams of catalyst SO are added in 300 milliliters of tank reactors4 2-(covalent groups and part rub/P (DVB-VBC)
You are than for 0.1), the mass fraction ratio of wherein solid super-strong acid and P (DVB-VBC) carrier is 20:80,100 grams of dimethoxym ethanes and 100
Gram paraformaldehyde, 4h is reacted under 130 DEG C and 0.6MPa self-generated pressures, extracted after sample centrifuges by gas chromatographic analysis.
Polyoxymethylene dimethyl ether and unreacted raw material dimethoxym ethane and paraformaldehyde are included in product, it forms distribution such as table 1.
【Embodiment 4】
2 grams of catalyst Cl are added in 300 milliliters of tank reactors-(mol ratio of covalent groups and part is /HCPs
0.1), the mass fraction ratio of wherein solid super-strong acid and HCPs carriers is 20:80,100 grams distillation sample (87wt% dimethoxym ethane,
Remaining is methanol) and 100 grams of paraformaldehydes, 4h is reacted under 130 DEG C, 0.7MPa self-generated pressures, after extracting sample centrifugation
By through gas chromatographic analysis.Polyoxymethylene dimethyl ether and unreacted raw material dimethoxym ethane and paraformaldehyde, its group are included in product
Into distribution such as table 1.
【Embodiment 5】
2 grams of catalyst Cl are added in 300 milliliters of tank reactors-/ SAM-HCPs (the mol ratios of covalent groups and part
For 0.1), the mass fraction ratio of wherein solid super-strong acid and SAM-HCPs carriers is 20:80,100 grams of methanol and 50 grams of poly first
Aldehyde, 4h is reacted under 130 DEG C, 0.7MPa self-generated pressures, extracted after sample centrifuges by through gas chromatographic analysis.Wrapped in product
Containing polyoxymethylene dimethyl ether and unreacted raw material dimethoxym ethane and paraformaldehyde, it forms distribution such as table 1.
【Embodiment 6】
2 grams of catalyst S are added in 300 milliliters of tank reactors2O8 2-(covalent groups and part rub/P (DVB-VBC)
You are than for 0.1), the mass fraction ratio of wherein solid super-strong acid and P (DVB-VBC) carrier is 20:80,100 grams of dimethoxym ethanes and 100
Gram paraformaldehyde, 4h is reacted under 130 DEG C, 0.6MPa self-generated pressures, extracted after sample centrifuges by gas chromatographic analysis.Production
Polyoxymethylene dimethyl ether and unreacted raw material dimethoxym ethane and paraformaldehyde are included in thing, it forms distribution such as table 1.
【Embodiment 7】
2 grams of catalyst SO are added in 300 milliliters of tank reactors4 2-(mol ratio of covalent groups and part is /HCPs
10), the mass fraction ratio of wherein solid super-strong acid and HCPs carriers is 20:80,100 grams of methanol and 100 grams of paraformaldehydes,
12h is reacted under 130 DEG C and 2MPa self-generated pressures, is extracted after sample centrifuges by gas chromatographic analysis.Poly- first is included in product
Aldehyde dimethyl ether and unreacted material benzenemethanol and paraformaldehyde, it forms distribution such as table 1.
【Embodiment 8】
2 grams of catalyst SO are added in 300 milliliters of tank reactors4 2-(mol ratio of covalent groups and part is /HCPs
10), the mass fraction ratio of wherein solid super-strong acid and HCPs carriers is 70:30,100 grams of dimethoxym ethanes and 100 grams of paraformaldehydes,
4h is reacted under 120 DEG C and 4MPa nitrogen pressures, is extracted after sample centrifuges by gas chromatographic analysis.Polyformaldehyde is included in product
Dimethyl ether and unreacted raw material dimethoxym ethane and paraformaldehyde, it forms distribution such as table 1.
【Embodiment 9】
0.5 gram of catalyst SO is added in 300 milliliters of tank reactors4 2-/ HCPs (the mol ratios of covalent groups and part
For 10), the mass fraction ratio of wherein solid super-strong acid and HCPs carriers is 20:80,100 grams of dimethoxym ethanes and 100 grams of paraformaldehydes,
4h is reacted under 120 DEG C and 4MPa nitrogen pressures, is extracted after sample centrifuges by gas chromatographic analysis.Poly- first is included in product
Aldehyde dimethyl ether and unreacted raw material dimethoxym ethane and paraformaldehyde, it forms distribution such as table 1.
【Embodiment 10】
2 grams of catalyst SO are added in 300 milliliters of tank reactors4 2-(mol ratio of covalent groups and part is /HCPs
10), the mass fraction ratio of wherein solid super-strong acid and HCPs carriers is 20:80,100 grams of dimethoxym ethanes and 100 grams of paraformaldehydes,
4h is reacted under 90 DEG C and 4MPa nitrogen pressures, is extracted after sample centrifuges by gas chromatographic analysis.Polyformaldehyde is included in product
Dimethyl ether and unreacted raw material dimethoxym ethane and paraformaldehyde, it forms distribution such as table 1.
【Embodiment 11】
By the catalyst SO in embodiment 14 2-/ HCPs takes out after the completion of reaction, according to embodiment 1 after drying process
In reaction condition carry out 9 times reuse, extract sample centrifuge after by gas chromatographic analysis.Polyformaldehyde is included in product
Dimethyl ether and unreacted material benzenemethanol and paraformaldehyde, to investigate the heat endurance of the catalyst and chemical stability, its
Composition distribution such as table 2.
【Embodiment 12】
2 grams of catalyst SO are added in 300 milliliters of tank reactors4 2-(metal group and part rub/HCPs/SBA-15
You are than for 0.1), wherein the mass fraction ratio of solid super-strong acid and carrier is 20:80, HCPs and molecular sieve carrier SBA-15 weight
Amount is than being 50:50.100 grams of dimethoxym ethanes and 100 grams of paraformaldehydes, 4h is reacted under 130 DEG C and 4MPa nitrogen pressures, extract sample
By gas chromatographic analysis after centrifugation.Polyoxymethylene dimethyl ether and unreacted raw material dimethoxym ethane and poly first are included in product
Aldehyde, it forms distribution such as table 1.
【Embodiment 13】
2 grams of catalyst SO are added in 300 milliliters of tank reactors4 2-/S2O8 2-(covalent ion is with matching somebody with somebody by/P (DVB-VBC)
The mol ratio of body is 0.1；SO4 2-And S2O8 2-Mutual load is in P (DVB-VBC), SO4 2-Solid super-strong acid and S2O8 2-Solid super strong
The mass ratio of acid is 50:50), the mass fraction ratio of wherein solid super-strong acid gross mass and P (DVB-VBC) carrier is 20:80,
100 grams of dimethoxym ethanes and 100 grams of paraformaldehydes, 4h is reacted under 130 DEG C, 0.6MPa self-generated pressures, after extracting sample centrifugation
By gas chromatographic analysis.Polyoxymethylene dimethyl ether and unreacted raw material dimethoxym ethane and paraformaldehyde are included in product, it is formed
Distribution such as table 1.
【Comparative example 1】
According to patent《The synthetic method of polyoxymethylene dimethyl ether》(number of patent application：201210325102.1) methods described,
2 grams of catalyst SO are added in 300 milliliters of tank reactors4 2-/ZrO2/ SBA-15 (wherein solid super-strong acid SO4 2-With carrier
(ZrO2And molecular sieve carrier SBA-15) total mass ratio be 20:80, wherein ZrO2Mass ratio with SBA-15 is 50:50), 100
Ml methanol and 100 grams of paraformaldehydes, reacted 4 hours under 130 DEG C and 0.8MPa self-generated pressures, after extracting sample centrifugation
By gas chromatographic analysis.Polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde, its group of composition are included in product
Cloth is following (being represented with weight %)：Dimethoxym ethane is 22.2%, methanol 5.1%, paraformaldehyde 2.1%, n=2 25.1%,
N=3 is 18.4%, n=4 17.5%, n=5-10 9.6%, n>10, surplus, the selection selective to product n=2~10
Property is 70.6%.
The use of methanol, dimethoxym ethane and paraformaldehyde is raw material in comparative example, molecular sieve carried solid super-strong acid is as catalysis
Under equal conditions selectivity of product is relatively low for agent.The embodiment of the present invention 1 in contrast, the conversion ratio of reaction and product n=2~10
Selectivity is higher, is 75.0%, and paraformaldehyde content is relatively low in product.It can obtain with zeolite molecular sieve as catalyst
When more preferable reaction result.
Table 1
N is the degree of polymerization, product CH3O(CH2O)nCH3。
Table 2
N is the degree of polymerization, product CH3O(CH2O)nCH3。
Claims (9)
1. a kind of method that polyoxymethylene dimethyl ethers are produced with paraformaldehyde, using methanol, dimethoxym ethane and paraformaldehyde as raw material, its
Middle methanol: dimethoxym ethane: the mass ratio of paraformaldehyde is (0~10): (0~10): 1, the dosage of methanol and dimethoxym ethane can not be simultaneously
It it is 70~200 DEG C in reaction temperature, under the conditions of reaction pressure is 0.2~6MPa, raw material contacts with catalyst, and reaction generates for 0
Polyoxymethylene dimethyl ether, catalyst amount be raw material weight 0.05~10%, wherein catalyst used in terms of weight fraction by
Following components forms：A) 30~80 parts of carrier, carrier HCPs, SAM-HCPs, P in superhigh cross-linking polymer HCPs series
(DVB-VBC) at least one of superhigh cross-linking polymer；Be loaded in b thereon) 20~70 parts be selected from SO4 2-、Cl-、S2O8 2-In
At least one solid super-strong acid.
2. the method according to claim 1 that polyoxymethylene dimethyl ethers are produced with paraformaldehyde, it is characterised in that catalyst
Dosage is the 0.1~5% of raw material weight.
3. the method according to claim 1 that polyoxymethylene dimethyl ethers are produced with paraformaldehyde, it is characterised in that reactant
The dosage sum of middle methanol and dimethoxym ethane and the mass ratio of paraformaldehyde are (0.4~5): 1；Methanol: dimethoxym ethane: paraformaldehyde
Mass ratio is (0.2~10): (0.5~10): 1.
4. the method according to claim 1 that polyoxymethylene dimethyl ethers are produced with paraformaldehyde, it is characterised in that reaction temperature
Spend for 90~130 DEG C.
5. the method according to claim 1 that polyoxymethylene dimethyl ethers are produced with paraformaldehyde, it is characterised in that reaction pressure
Power is 0.4~4.0MPa.
6. the method according to claim 1 that polyoxymethylene dimethyl ethers are produced with paraformaldehyde, it is characterised in that described more
The degree of polymerization of polyformaldehyde is 2~8.
7. the method according to claim 6 that polyoxymethylene dimethyl ethers are produced with paraformaldehyde, it is characterised in that described more
The degree of polymerization of polyformaldehyde is 4~6.
8. the method according to claim 1 that polyoxymethylene dimethyl ethers are produced with paraformaldehyde, it is characterised in that during reaction
Between be 1 to 20 hour.
9. the method according to claim 8 that polyoxymethylene dimethyl ethers are produced with paraformaldehyde, it is characterised in that during reaction
Between be 4 to 12 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410429107.8A CN105439829B (en) | 2014-08-27 | 2014-08-27 | In the method for paraformaldehyde production polyoxymethylene dimethyl ethers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410429107.8A CN105439829B (en) | 2014-08-27 | 2014-08-27 | In the method for paraformaldehyde production polyoxymethylene dimethyl ethers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105439829A CN105439829A (en) | 2016-03-30 |
| CN105439829B true CN105439829B (en) | 2018-02-13 |
Family
ID=55550533
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410429107.8A Active CN105439829B (en) | 2014-08-27 | 2014-08-27 | In the method for paraformaldehyde production polyoxymethylene dimethyl ethers |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105439829B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103664549A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Polyformaldehyde dimethyl ether synthesis method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101869850A (en) * | 2010-05-14 | 2010-10-27 | 东北师范大学 | Crystalline catalysis material for reaction of preparing dimethyl ether from methanol by dehydration and preparation method thereof |
| CN102382132A (en) * | 2010-08-30 | 2012-03-21 | 珠海市吉林大学无机合成与制备化学重点实验室 | Porous siloxane organic skeleton material and preparation method thereof |
| CN103664547B (en) * | 2012-09-05 | 2016-01-13 | 中国石油化工股份有限公司 | The method of synthesizing polyoxymethylene dme |
| CN103664543B (en) * | 2012-09-05 | 2015-09-09 | 中国石油化工股份有限公司 | The method of polyoxymethylene dimethyl ether is prepared by paraformaldehyde |
-
2014
- 2014-08-27 CN CN201410429107.8A patent/CN105439829B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103664549A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Polyformaldehyde dimethyl ether synthesis method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105439829A (en) | 2016-03-30 |
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 | |
| CN103880612A (en) | Method for synthesizing polyoxymethylene dimethyl ether from paraformaldehyde | |
| CN103664549B (en) | The synthetic method of polyoxymethylene dimethyl ether | |
| CN102875338B (en) | Method for preparing glycerol ether by catalytic glycerol ether reaction | |
| CN103664543B (en) | The method of polyoxymethylene dimethyl ether is prepared by paraformaldehyde | |
| CN105294411B (en) | The method that polyoxymethylene dimethyl ethers are produced by paraformaldehyde | |
| CN104151147B (en) | With the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers | |
| KR20120094555A (en) | Novel metal catalyst supported on activated carbon aerogel, production method thereof and decomposition method of lignin compound using said catalyst | |
| CN105367393B (en) | By the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers | |
| CN107652169A (en) | A kind of preparation technology of polymethoxy dimethyl ether production formaldehyde alcoholic solution | |
| CN105439829B (en) | In the method for paraformaldehyde production polyoxymethylene dimethyl ethers | |
| CN105439830B (en) | In the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers | |
| CN105237368B (en) | The synthetic method of polyoxymethylene dimethyl ethers | |
| CN103772161A (en) | Method for preparing polyoxymethylene dimethyl ethers | |
| CN105585456B (en) | The 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 | |
| CN109134407B (en) | Preparation method of aviation kerosene precursor | |
| CN107626346B (en) | Immobilized ionic liquid catalyst and preparation method and application thereof | |
| CN105085196A (en) | Synthesis method of polyoxymethylene dimethyl ether from paraformaldehyde | |
| CN105585461B (en) | The synthetic method of polyoxymethylene dimethyl ethers | |
| CN105585460B (en) | The method of synthesizing polyoxymethylene dimethyl ethers | |
| CN105583008B (en) | Polyoxymethylene dimethyl ethers catalyst and preparation method thereof | |
| CN105566076B (en) | The preparation method of 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |