CN103739459A - Preparation method of polyoxymethylene dimethyl ethers - Google Patents
Preparation method of polyoxymethylene dimethyl ethers Download PDFInfo
- Publication number
- CN103739459A CN103739459A CN201210393007.5A CN201210393007A CN103739459A CN 103739459 A CN103739459 A CN 103739459A CN 201210393007 A CN201210393007 A CN 201210393007A CN 103739459 A CN103739459 A CN 103739459A
- Authority
- CN
- China
- Prior art keywords
- preparation
- dimethyl ethers
- polyoxymethylene dimethyl
- sio
- formaldehyde
- 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.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/30—Compounds having groups
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a preparation method of polyoxymethylene dimethyl ethers, mainly solving a problem that catalysts are corrosive in the prior art. According to the technical scheme adopted by the preparation method, methanol or dimethyl ether, and formaldehyde or trioxymethylene are adopted as raw materials, the molar ratio of the methanol or the dimethyl ether to the formaldehyde or the trioxymethylene is 1:(0.1-10), the raw materials are contacted with a catalyst and reacted at 50-200 DEG C under 0.1-10 MPa to produce the polyoxymethylene dimethyl ethers, and the catalyst is a molecular sieve with an MEL topological structure. By the scheme, the problem is solved well and the preparation method can be used in industrial production of the polyoxymethylene dimethyl ethers.
Description
Technical field
The present invention relates to a kind of preparation method of polyoxymethylene dimethyl ethers.
Background technology
(Chinese can be also polyoxymethylene dimethyl ether to polyoxymethylene dimethyl ethers, polymethoxy methylal, polymethoxy dimethyl ether, polyoxymethylene dimethyl ethers etc.), be polyoxymethylene dimethyl ethers (PODE), it is the common name of a class material, and its molecular structural formula is CH
3o (CH
2o)
ncH
3, there is higher cetane value (cetane number, CN.N=3～8 o'clock, CN>76) and oxygen level (42～49%).When the value of n is 3～8, its physical and chemical performance, combustionproperty and diesel oil are very approaching, can be used as diesel-dope, and the addition in diesel oil can reach 30% (v/v), keep higher cetane value and combustionproperty simultaneously.Can improve the oilness of diesel oil, reduce combustion fumes and generate, can improve the combustion position of diesel oil in engine, improve thermo-efficiency, reduce particulate matter and NO in combustion tail gas
xdischarge.Also may diesel oil substitute, directly as diesel-fuel.
Polyoxymethylene dimethyl ethers is to solve dme to make the defect that derv fuel oil blend component exists as the main purpose of Novel clean oil dope research and development.Rich coal resources in China, has strategic importance and good economic worth by coal-based methanol combined diesel oil blend component, is day by day subject to people's attention.
US2449469 discloses that a kind of to take methylal and paraformaldehyde be raw material, and the sulfuric acid of usining is prepared the method for the polyoxymethylene dimethyl ethers of n=2～4 as catalyzer, but has the problem that catalytic erosion is serious.
WO2006/045506A1 discloses BASF AG and has used sulfuric acid or trifluoromethanesulfonic acid as catalyzer, and take methyl alcohol, methylal, trioxymethylene, paraformaldehyde etc. is raw material, has obtained the series product of n=1～10, has equally the problem that catalytic erosion is serious.
It is catalyzer that US5746785 discloses a kind of 0.1wt% of take formic acid, take methylal and paraformaldehyde or methyl alcohol and paraformaldehyde as raw material, and the series product of preparation n=1～10, exist the problem that catalytic erosion is serious equally.
CN101182367A and CN101962318A disclose employing acidic ion liquid as catalyzer, by methyl alcohol and trioxymethylene, are the method that raw material is prepared polyoxymethylene dimethyl ethers, have equally the problem that catalytic erosion is serious.
CN101665414A discloses a kind of employing acidic ion liquid as catalyzer, by methylal and trioxymethylene, is the method that raw material is prepared polyoxymethylene dimethyl ethers, has equally the problem that catalytic erosion is serious.
MEL molecular sieve is a member in high-silicon ZSM-5 series, early 1970s Qi You U.S. Mobil company is synthetic [US 3709979] first, being that oval ten-ring two-dimensional direct duct (0.51 * 0.55nm) is crossing forms, belong to micro-pore zeolite, because it does not have cage, so be difficult for carbon distribution in catalytic process, and have fabulous thermostability, acid resistance, shape selectivity, water vapor stability and hydrophobicity, have great application prospect in a plurality of fields such as acid catalysis, shape selective catalysiss.Therefore, can produce polyoxymethylene dimethyl ethers by MEL structure catalyst catalyzed reaction.
In sum, the catalyzer adopting in conventional art has corrosive shortcoming.
Summary of the invention
Technical problem to be solved by this invention is in conventional art, to exist catalyzer to have corrosive problem, and a kind of preparation method of new polyoxymethylene dimethyl ethers is provided.The method has the free from corrosion advantage of catalyzer.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of polyoxymethylene dimethyl ethers, take methyl alcohol or dme and formaldehyde or trioxymethylene as raw material, methyl alcohol or dme: formaldehyde or trioxymethylene mol ratio 1:(0.1～10), in temperature of reaction, it is 50～200 ℃, reaction pressure is under 0.1～10MPa condition, and reaction raw materials contacts with catalyzer and generates polyoxymethylene dimethyl ethers; Catalyst levels is 0.01～15% of reaction raw materials weight; Wherein catalyzer used is the molecular sieve with MEL topological framework.
In technique scheme, methyl alcohol or dme: formaldehyde or trioxymethylene mol ratio preferable range are 1:(0.5～6).Formaldehyde can be the formaldehyde solution of 10～80 % by weight, or paraformaldehyde, or trioxymethylene.Catalyst levels preferable range is that the preferable range of reaction raw materials weight is 0.1～10%.Temperature of reaction preferable range is 70～150 ℃, and reaction pressure preferable range is 0.5～6MPa.Described MEL structure molecular screen, its X-ray diffracting spectrum is 11.1 ± 0.1, and 10.0 ± 0.1,6.7 ± 0.1,6.0 ± 0.1,3.8 ± 0.1, there is d-spacing maximum value at 3.7 ± 0.1 and 3.0 ± 0.1 dust places.The preparation method of MEL structure molecular screen, comprise the following steps: by silicon source, aluminium source, organic formwork agent, mineral alkali and water mix by required stoichiometric ratio, 100 ℃～180 ℃ crystallization 1～20 day, product after filtration, washing, dry, obtain MEL structure, wherein silicon source is selected from silicon sol, silicon ester, diatomite, at least one in water glass or solid oxidation silicon, aluminium source is selected from sodium aluminate, pseudo-boehmite, Tai-Ace S 150, aluminum nitrate, aluminum chloride, aluminium hydroxide, at least one in kaolin or polynite, organic formwork agent is selected from TBAH, at least one in Tetrabutyl amonium bromide or tetrabutylammonium chloride, mineral alkali is selected from least one in sodium hydroxide or potassium hydroxide, each component mol ratio of raw material is: SiO
2/ Al
2o
3=20～300, H
2o/SiO
2=10～150, OH
-/ SiO
2=0.001～1, organic formwork agent/SiO
2=0.01～1.Wherein, crystallization temperature preferable range is 110～170 ℃, and crystallization time preferable range is 2～15 days.Each component mol ratio preferable range of raw material is: SiO
2/ Al
2o
3=50～250, H
2o/SiO
2=30～120, OH
-/ SiO
2=0.005～0.8, organic formwork agent/SiO
2=0.03～0.08.
Catalyzer described in the present invention uses the known ammonium of front employing to exchange, be dried and roasting technology is processed.
In technique scheme, because synthetic MEL structure molecular screen has acid and continuous duct, be conducive to the diffusion of reaction raw materials, so catalyst catalytic performance is good.The inventor finds uncannily, adopts this catalyzer, under 100 ℃ of temperature, pressure 3MPa, reacts 5 hours, and the product that n is 3～8 can reach 32.4% in products distribution; The most important thing is that catalyzer non-corrosiveness has been obtained good technique effect.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the synthetic ZSM-11 zeolite of the present invention [embodiment 1].
In Fig. 1, X-ray diffracting spectrum is 23.0,23.9, and there is strong diffraction peak at 7.9,8.8 and 45.1 degree places, illustrates that this zeolite has MEL topological framework, is ZSM-11 zeolite.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
40% silicon sol, sodium metaaluminate, Tetrabutyl amonium bromide, sodium hydroxide and water are mixed, stir 20 minutes, pack in reactor, 170 ℃ of crystallization 1 day.Crystallization product chilling, to filter, be washed to pH value be 8, dries 12 hours in 120 ℃, makes ZSM-11 molecular screen primary powder, and XRD spectra is shown in Fig. 1.In reaction mixture, the mol ratio of each raw material is: SiO
2/ Al
2o
3=149.3, H
2o/SiO
2=32.8, NaOH/SiO
2=0.08, TBABr/SiO
2=0.12.
With the aqueous ammonium nitrate solution of 10% mass concentration, at 80 ℃, exchange three times again, the ratio of aqueous ammonium nitrate solution and the weight of molecular sieve be 10,120 ℃ dry 12 hours, 550 ℃ of roastings 5 hours, obtain catalyzer.
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.In autoclave, add 2 grams of catalyzer, 100 grams of methyl alcohol, 100 grams of trioxymethylenes, at 130 ℃ with make pressure by inflated with nitrogen be to react under 6MPa 2 hours, filtering separation catalyzer and reaction product, through gas chromatographic analysis, the compositions of mixtures of acquisition is as table 1.
[embodiment 2]
By each Step By Condition of [embodiment 1], be SiO in synthesizing formula
2/ Al
2o
3=52, template adopts TBAH, 120 ℃ of crystallization of crystallization temperature 8 days.With 1.0 mol/L citric acids, at 80 ℃, exchange 10 hours.Obtain catalyzer.
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.In autoclave, add 1.5 grams of catalyzer, 50 grams of methyl alcohol, 30 grams of dme, 100 grams of formaldehyde, at 100 ℃ with make pressure by inflated with nitrogen be to react under 3MPa 5 hours, filtering separation catalyzer and reaction product, through gas chromatographic analysis, the compositions of mixtures of acquisition is as table 1.
[embodiment 3]
By each Step By Condition of [embodiment 2], be that synthesizing formula Raw, batching proportioning are different.Aluminium source is Tai-Ace S 150, and silicon source is water glass, and template is TBAH.In reaction mixture, the mol ratio of each raw material is: SiO
2/ Al
2o
3=80.9, H
2o/SiO
2=58.5, NaOH/SiO
2=0.30, TBAOH/SiO
2=0.19.With the aqueous ammonium nitrate solution of 10% mass concentration, at 80 ℃, exchange three times again, the ratio of aqueous ammonium nitrate solution and the weight of molecular sieve be 10,120 ℃ dry 12 hours, 550 ℃ of roastings 5 hours, obtain catalyzer.
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.In autoclave, add 1 gram of catalyzer, 80 grams of methyl alcohol, 100 grams of formaldehyde, at 80 ℃ with make pressure by inflated with nitrogen be to react under 1MPa 10 hours, filtering separation catalyzer and reaction product, through gas chromatographic analysis, the compositions of mixtures of acquisition is as table 1.
[embodiment 4]
By solid oxidation silicon, aluminum nitrate, tetrabutylammonium chloride, potassium hydroxide and water mix by stoichiometric ratio, and each component mol ratio of its Raw is: SiO
2/ Al
2o
3=100.0, H
2o/SiO
2=30.5, KOH/SiO
2=0.20, TBACl/SiO
2=0.21.In the 5 day time of 150 ℃ of crystallization, after filtration, washing, is dried product, obtains MEL structure molecular screen.With the aqueous ammonium nitrate solution of 10% mass concentration, at 80 ℃, exchange three times again, the ratio of aqueous ammonium nitrate solution and the weight of molecular sieve be 10,120 ℃ dry 12 hours, 550 ℃ of roastings 5 hours, obtain catalyzer.
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.In autoclave, add 0.9 gram of catalyzer, 50 grams of methyl alcohol, 30 grams of dme, 100 grams of formaldehyde, at 120 ℃ with make pressure by inflated with nitrogen be to react under 4MPa 5 hours, filtering separation catalyzer and reaction product, through gas chromatographic analysis, the compositions of mixtures of acquisition is as table 1.
[comparative example 1]
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.In autoclave, add 4g acid ion resin catalyst, 80 grams of methyl alcohol, 90 grams of trioxymethylenes, at 150 ℃ with make pressure by inflated with nitrogen be to react under 4MPa 2 hours, filtering separation catalyzer and reaction product, through gas chromatographic analysis, the compositions of mixtures of acquisition is as table 1.
Table 1
Claims (10)
1. the preparation method of a polyoxymethylene dimethyl ethers, take methyl alcohol or dme and formaldehyde or trioxymethylene as raw material, methyl alcohol or dme: formaldehyde or trioxymethylene mol ratio 1:(0.1～10), in temperature of reaction, it is 50～200 ℃, reaction pressure is under 0.1～10MPa condition, and reaction raw materials contacts with catalyzer and generates polyoxymethylene dimethyl ethers; Catalyst levels is 0.01～15% of reaction raw materials weight; Wherein catalyzer used is the molecular sieve with MEL topological framework.
2. the preparation method of polyoxymethylene dimethyl ethers according to claim 1, is characterized in that methyl alcohol or dme: formaldehyde or trioxymethylene mol ratio are 1:(0.5～6).
3. the preparation method of polyoxymethylene dimethyl ethers according to claim 1, is characterized in that formaldehyde is the formaldehyde solution of 10～80 weight t%, or paraformaldehyde or trioxymethylene.
4. the preparation method of polyoxymethylene dimethyl ethers according to claim 1, is characterized in that catalyst levels is 0.1～10% of reaction raw materials weight.
5. the preparation method of polyoxymethylene dimethyl ethers according to claim 1, is characterized in that temperature of reaction is 70～150 ℃.
6. the preparation method of polyoxymethylene dimethyl ethers according to claim 1, is characterized in that reaction pressure is 0.5～6MPa.
7. the preparation method of polyoxymethylene dimethyl ethers according to claim 1, is characterized in that the X-ray diffracting spectrum of described MEL structure molecular screen is 11.1 ± 0.1,10.0 ± 0.1,6.7 ± 0.1, there is d-spacing maximum value at 6.0 ± 0.1,3.8 ± 0.1,3.7 ± 0.1 and 3.0 ± 0.1 dust places.
8. the preparation method of polyoxymethylene dimethyl ethers according to claim 1, the preparation method who it is characterized in that described MEL structure molecular screen, comprise the following steps: silicon source, aluminium source, organic formwork agent, mineral alkali and water are mixed by required stoichiometric ratio, 100～180 ℃ of crystallization 1～20 day, product after filtration, washing, dry, obtain MEL structure molecular screen; Wherein silicon source is selected from least one in silicon sol, silicon ester, diatomite, water glass or solid oxidation silicon, aluminium source is selected from least one in sodium aluminate, pseudo-boehmite, Tai-Ace S 150, aluminum nitrate, aluminum chloride, aluminium hydroxide, kaolin or polynite, organic formwork agent is selected from TBAH, at least one in Tetrabutyl amonium bromide or tetrabutylammonium chloride, mineral alkali is selected from least one in sodium hydroxide or potassium hydroxide; Each component mol ratio of raw material is: SiO
2/ Al
2o
3=20～300, H
2o/SiO
2=10～150, OH
-/ SiO
2=0.001～1, organic formwork agent/SiO
2=0.01～1.
9. the preparation method of polyoxymethylene dimethyl ethers according to claim 8, is characterized in that crystallization temperature is 110～170 ℃, and crystallization time is 2～15 days.
10. the preparation method of polyoxymethylene dimethyl ethers according to claim 8, is characterized in that each component mol ratio of raw material is: SiO
2/ Al
2o
3=50～250, H
2o/SiO
2=30～120, OH
-/ SiO
2=0.005～0.8, organic formwork agent/SiO
2=0.03～0.08.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210393007.5A CN103739459A (en) | 2012-10-17 | 2012-10-17 | Preparation method of polyoxymethylene dimethyl ethers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210393007.5A CN103739459A (en) | 2012-10-17 | 2012-10-17 | Preparation method of polyoxymethylene dimethyl ethers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103739459A true CN103739459A (en) | 2014-04-23 |
Family
ID=50496552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210393007.5A Pending CN103739459A (en) | 2012-10-17 | 2012-10-17 | Preparation method of polyoxymethylene dimethyl ethers |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103739459A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109134210A (en) * | 2017-06-19 | 2019-01-04 | 镇江瑞德新材料科技研发有限公司 | A method of polyoxymethylene dimethyl ether is produced using molecular catalyst |
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 |
| 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) |
| CN103420818A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Polyformaldehyde dimethyl ether preparation method |
-
2012
- 2012-10-17 CN CN201210393007.5A patent/CN103739459A/en active Pending
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 |
| 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) |
| CN103420818A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Polyformaldehyde dimethyl ether preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 刘师前等: "ZSM-11的合成及表征", 《精细石油化工进展》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109134210A (en) * | 2017-06-19 | 2019-01-04 | 镇江瑞德新材料科技研发有限公司 | A method of polyoxymethylene dimethyl ether is produced using molecular catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101768057B (en) | Method for synthesizing polyoxymethylene dimethyl ether | |
| CN103739458B (en) | The preparation method of polyoxymethylene dimethyl ethers | |
| CN102295734A (en) | Method for synthesizing polyoxymethylene dimethyl ether | |
| CN106588595A (en) | Synthetic method of polyoxymethylene dimethyl ethers | |
| CN103420816B (en) | Polyformaldehyde dimethyl ether preparation method | |
| CN103420812B (en) | Polymethoxy dimethyl ether preparation method | |
| CN103121927B (en) | Preparation method of polymethoxymethylal | |
| CN103420818B (en) | Polyformaldehyde dimethyl ether preparation method | |
| CN101722001A (en) | Composite catalyst for dimethyl ether synthesis and preparation method and application thereof | |
| CN102295539A (en) | Method for catalytically synthesizing polyformaldehyde dimethyl ether | |
| CN103739459A (en) | Preparation method of polyoxymethylene dimethyl ethers | |
| CN103664546B (en) | Prepare the method for polymethoxy dimethyl ether | |
| CN101993356B (en) | Method for preparing daicel dimethyl ether | |
| CN103539644B (en) | The preparation method of polyoxy methylene dimethyl ether | |
| CN103121924B (en) | Preparation method of polyformaldehyde dimethyl ether | |
| EP2810928B1 (en) | A method for synthesizing polyoxymethylene dimethyl ethers | |
| CN107915589B (en) | Method for generating polyoxymethylene dimethyl ether | |
| CN103420814B (en) | Polymethoxy dimethyl ether preparation method | |
| CN107915593B (en) | Method for synthesizing polyoxymethylene dimethyl ether | |
| CN107915597B (en) | Catalyst for preparing polyformaldehyde dimethyl ether | |
| CN107915594B (en) | Synthetic method for polyformaldehyde dimethyl ether | |
| CN107915602B (en) | Polyoxymethylene dimethyl ether catalyst | |
| CN107915595B (en) | Method for producing polyoxymethylene dimethyl ethers | |
| CN103420813B (en) | Polyformaldehyde dimethyl ether preparation method | |
| CN107915603B (en) | Method for synthesizing polyformaldehyde dimethyl ether |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140423 |
|
| RJ01 | Rejection of invention patent application after publication |