CN103420812A - Polymethoxy dimethyl ether preparation method - Google Patents
Polymethoxy dimethyl ether preparation method Download PDFInfo
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- CN103420812A CN103420812A CN2012101502877A CN201210150287A CN103420812A CN 103420812 A CN103420812 A CN 103420812A CN 2012101502877 A CN2012101502877 A CN 2012101502877A CN 201210150287 A CN201210150287 A CN 201210150287A CN 103420812 A CN103420812 A CN 103420812A
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- dimethyl ether
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- polymethoxy dimethyl
- catalyzer
- formaldehyde
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Abstract
The present invention relates to a polymethoxy dimethyl ether preparation method, wherein the problem that the catalyst has corrosion in the prior art is mainly solved with the present invention. The technical scheme comprises that: methanol or dimethyl ether and formaldehyde or trioxymethylene are adopted as raw materials, a molar ratio of the methanol or the dimethyl ether to the formaldehyde or the trioxymethylene is 1:0.1-10, and the reaction raw materials contact a catalyst at a reaction temperature of 50-200 DEG C under a reaction pressure of 0.1-10 MPa to produce polymethoxy dimethyl ether, wherein the catalyst is a molecular sieve with a RUT topological structure. With the technical scheme, the problem in the prior art is well solved, and the preparation method can be used for industrial production of the polymethoxy dimethyl ether.
Description
Technical field
The present invention relates to a kind of preparation method of polymethoxy dimethyl ether.
Background technology
(Chinese can be also polyoxymethylene dimethyl ether to polymethoxy dimethyl ether, polyoxymethylene dimethyl ethers, polymethoxy methylal, 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.
Polymethoxy dimethyl ether is to solve dme to make the defect that the derv fuel oil blend component exists as the main purpose of Novel clean oil dope research and development.Rich coal resources in China, have strategic importance and good economic worth by coal-based methanol combined diesel oil blend component, day by day is subject to people's attention.
US2449469 discloses that a kind of to take methylal〔Su〕 and paraformaldehyde be raw material, and the sulfuric acid of usining prepares the method for the polymethoxy dimethyl ether 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〔Su〕, 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〔Su〕 and paraformaldehyde or methyl alcohol and paraformaldehyde as raw material, and, there is the problem that catalytic erosion is serious equally in the series product of preparation n=1～10.
CN101182367A and CN101962318A disclose the employing acidic ion liquid as catalyzer, by methyl alcohol and trioxymethylene, are the method that raw material prepares polymethoxy dimethyl ether, have equally the problem that catalytic erosion is serious.
CN101665414A discloses a kind of employing acidic ion liquid as catalyzer, by methylal〔Su〕 and trioxymethylene, is the method that raw material prepares polymethoxy dimethyl ether, has equally the problem that catalytic erosion is serious.
The RUT structure molecular screen has great application prospect in a plurality of fields such as acid catalysis, shape selective catalysiss.Therefore, can produce polymethoxy dimethyl ether by RUT structure catalyst catalyzed reaction.
In sum, the catalyzer adopted 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 polymethoxy dimethyl ether 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 polymethoxy dimethyl ether, 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 polymethoxy dimethyl ether; Catalyst levels is 0.01～15% of reaction raw materials weight; Wherein catalyzer used is the molecular sieve with RUT topological framework.
Methyl alcohol or dme: formaldehyde or trioxymethylene mol ratio preferable range are 1:0.5～6.Formaldehyde can be the formaldehyde solution of 10～80wt%, or paraformaldehyde or trioxymethylene.The preferable range that catalyst levels is reaction raw materials weight is 0.1～10%.The temperature of reaction preferable range is 70～150 ℃, and the reaction pressure preferable range is 0.5～6MPa.
In the present invention, the preparation method of catalyzer is: a kind of RUT structure molecular screen, it is characterized in that its X-ray diffracting spectrum is 8.7 ± 0.1,8.2 ± 0.1,6.5 ± 0.1,6.1 ± 0.1,4.3 ± 0.1,4.2 ± 0.1,4.0 ± 0.1,3.9 ± 0.1,3.8 there is d-spacing maximum value at ± 0.1,3.4 ± 0.1 and 3.2 ± 0.1 dust places.The preparation method of RUT structure molecular screen, comprise the following steps: by the silicon source, the aluminium source, organic formwork agent, mineral alkali and water mix by required stoichiometric ratio, 120 ℃～200 ℃ crystallization 1～20 day, product after filtration, washing, dry, obtain the RUT structure, wherein the silicon source is selected from silicon sol, silicon ester, diatomite, at least one in water glass or solid oxidation silicon, the 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 tetramethyleneimine, Tetramethylammonium hydroxide, at least one in 4 bromide or tetramethyl ammonium chloride, mineral alkali is selected from least one in sodium hydroxide or potassium hydroxide, each component mol ratio of its Raw is, SiO
2: Al
2O
3: R:M
2O:H
2O=1:0.004～0.1:0.05～1:0.01～0.2:10～200, R represents organic formwork agent, M represents Na or K.Then adopt known ammonium exchange, drying and roasting technology, obtain catalyzer.
In technique scheme, because synthetic RUT 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, and under 100 ℃ of temperature, pressure 3MPa, reaction is 5 hours, and the product that n is 3～8 can reach 32.2% in products distribution; The most important thing is that the catalyzer non-corrosiveness has been obtained technique effect preferably.
The accompanying drawing explanation
The XRD spectra that Fig. 1 is the synthetic RUT zeolite of the present invention [embodiment 1].
In Fig. 1, X-ray diffracting spectrum is 22.0,20.6, and there is strong diffraction peak at 14.0,22.7,10.6,13.4 and 19.8 degree places, illustrate that this zeolite has the RUT topological framework, are the RUB-10 zeolites.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
By silicon sol (40%, weight), sodium aluminate, Tetramethylammonium hydroxide, sodium hydroxide and water mix by stoichiometric ratio, and each component mol ratio of its Raw is, SiO
2: Al
2O
3: R:Na
2O:H
2O=1:0.01:0.4:0.01:40.In the 7 day time of 160 ℃ of crystallization, product after filtration, is washed, and drying, obtain the RUT structure molecular screen, and XRD spectra is shown in Fig. 1.X-ray diffracting spectrum is 22.0,20.6, and there is strong diffraction peak at 14.0,22.7,10.6,13.4 and 19.8 degree places, illustrates that this zeolite has the RUT topological framework, is the RUB-10 zeolite.With the aqueous ammonium nitrate solution of 10% mass concentration, under 80 ℃, exchange three times, aqueous ammonium nitrate solution is 10,120 ℃ of dryings 12 hours with the ratio of the weight of molecular sieve again, and 550 ℃ of roastings 5 hours, obtain catalyzer.
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.Add 2 gram catalyzer in autoclave, 100 gram methyl alcohol, 100 gram trioxymethylenes, 130 ℃ and by inflated with nitrogen, make pressure be under 6MPa the reaction 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 tetraethyl silicate, Tai-Ace S 150,4 bromide, sodium hydroxide and water mix by stoichiometric ratio, and each component mol ratio of its Raw is, SiO
2: Al
2O
3: R:Na
2O:H
2O=1:0.0125:0.31:0.035:30.In the 8 day time of 150 ℃ of crystallization, product after filtration, is washed, and drying, obtain the RUT structure molecular screen.With the aqueous ammonium nitrate solution of 10% mass concentration, under 80 ℃, exchange three times, aqueous ammonium nitrate solution is 10,120 ℃ of dryings 12 hours with the ratio of the weight of molecular sieve again, and 550 ℃ of roastings 5 hours, obtain catalyzer.
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.Add 1.5 gram catalyzer in autoclave, 50 gram methyl alcohol, 30 gram dme, 100 gram formaldehyde, 100 ℃ and by inflated with nitrogen, make pressure be under 3MPa the reaction 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 water glass, Tai-Ace S 150, tetramethyl ammonium chloride, potassium hydroxide and water mix by stoichiometric ratio, and each component mol ratio of its Raw is, SiO
2: Al
2O
3: R:K
2O:H
2O=1:0.02:0.2:0.08:60.In the 10 day time of 140 ℃ of crystallization, product after filtration, is washed, and drying, obtain the RUT structure molecular screen.With the aqueous ammonium nitrate solution of 10% mass concentration, under 80 ℃, exchange three times, aqueous ammonium nitrate solution is 10,120 ℃ of dryings 12 hours with the ratio of the weight of molecular sieve again, and 550 ℃ of roastings 5 hours, obtain catalyzer.
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.Add 1 gram catalyzer in autoclave, 80 gram methyl alcohol, 100 gram formaldehyde, 80 ℃ and by inflated with nitrogen, make pressure be under 1MPa the reaction 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, 4 bromide, potassium hydroxide and water mix by stoichiometric ratio, and each component mol ratio of its Raw is, SiO
2: Al
2O
3: R:K
2O:H
2O=1:0.008:0.55:0.03:50.In the 20 day time of 130 ℃ of crystallization, product after filtration, is washed, and drying, obtain the RUT structure molecular screen.With the aqueous ammonium nitrate solution of 10% mass concentration, under 80 ℃, exchange three times, aqueous ammonium nitrate solution is 10,120 ℃ of dryings 12 hours with the ratio of the weight of molecular sieve again, and 550 ℃ of roastings 5 hours, obtain catalyzer.
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.Add 0.9 gram catalyzer in autoclave, 50 gram methyl alcohol, 30 gram dme, 100 gram formaldehyde, 120 ℃ and by inflated with nitrogen, make pressure be under 4MPa the reaction 5 hours, filtering separation catalyzer and reaction product, through gas chromatographic analysis, the compositions of mixtures of acquisition is as table 1.
[Comparative Examples 1]
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.Add 4g acid ion resin catalyst in autoclave, 80 gram methyl alcohol, 90 gram trioxymethylenes, 150 ℃ and by inflated with nitrogen, make pressure be under 4MPa the reaction 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 (5)
1. the preparation method of a polymethoxy dimethyl ether, 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 polymethoxy dimethyl ether; Catalyst levels is 0.01～15% of reaction raw materials weight; Wherein catalyzer used is the molecular sieve with RUT topological framework.
2. the preparation method of polymethoxy dimethyl ether according to claim 1, is characterized in that methyl alcohol or dme: formaldehyde or trioxymethylene mol ratio 1:0.5～6.
3. the preparation method of polymethoxy dimethyl ether according to claim 1, is characterized in that formaldehyde can be the formaldehyde solution of 10～80wt%, or paraformaldehyde or trioxymethylene.
4. the preparation method of polymethoxy dimethyl ether according to claim 1, is characterized in that catalyst levels is 0.1～10% of reaction raw materials weight.
5. the preparation method of polymethoxy dimethyl ether according to claim 1, is characterized in that temperature of reaction is 70～150 ℃, and reaction pressure is 0.5～6MPa.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104086380A (en) * | 2014-07-07 | 2014-10-08 | 中国科学院山西煤炭化学研究所 | Preparation method of polyoxymethylene dimethyl ethers |
| CN106378162A (en) * | 2016-08-30 | 2017-02-08 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesis of polyoxymethylene dimethyl ethers by direct oxidation of dimethyl ether and preparation method and application thereof |
| CN107064331A (en) * | 2017-01-13 | 2017-08-18 | 上海化工研究院有限公司 | A kind of standardlcss analysis detection method of polymethoxy dimethyl ether product system |
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| 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 |
| CN102040491A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Catalytic synthesis method for polyoxymethylene dimethyl ethers (PODE) by molecular sieves |
| CN102249870A (en) * | 2011-07-14 | 2011-11-23 | 河南煤业化工集团研究院有限责任公司 | Method for preparing polyoxyether |
| CN102372613A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for producing polyformaldehyde dimethyl ether |
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2012
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN102040491A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Catalytic synthesis method for polyoxymethylene dimethyl ethers (PODE) by molecular sieves |
| CN102372613A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for producing polyformaldehyde dimethyl ether |
| CN102249870A (en) * | 2011-07-14 | 2011-11-23 | 河南煤业化工集团研究院有限责任公司 | Method for preparing polyoxyether |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104086380A (en) * | 2014-07-07 | 2014-10-08 | 中国科学院山西煤炭化学研究所 | Preparation method of polyoxymethylene dimethyl ethers |
| CN104086380B (en) * | 2014-07-07 | 2016-04-20 | 中国科学院山西煤炭化学研究所 | The preparation method of polymethoxy dimethyl ether |
| CN106378162A (en) * | 2016-08-30 | 2017-02-08 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesis of polyoxymethylene dimethyl ethers by direct oxidation of dimethyl ether and preparation method and application thereof |
| CN107064331A (en) * | 2017-01-13 | 2017-08-18 | 上海化工研究院有限公司 | A kind of standardlcss analysis detection method of polymethoxy dimethyl ether product system |
| CN107064331B (en) * | 2017-01-13 | 2020-01-31 | 上海化工研究院有限公司 | Analysis and detection method of polymethoxy dimethyl ether product systems |
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