CN103420812B - Polymethoxy dimethyl ether preparation method - Google Patents
Polymethoxy dimethyl ether preparation method Download PDFInfo
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- CN103420812B CN103420812B CN201210150287.7A CN201210150287A CN103420812B CN 103420812 B CN103420812 B CN 103420812B CN 201210150287 A CN201210150287 A CN 201210150287A CN 103420812 B CN103420812 B CN 103420812B
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- dimethyl ether
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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 also can be polyoxymethylene dimethyl ether to polymethoxy dimethyl ether, polyoxymethylene dimethyl ethers, polymethoxy methylal, polyoxymethylene dimethyl ethers etc.), i.e. 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.During n=3 ~ 8, CN>76) and oxygen level (42 ~ 49%).When the value of n is 3 ~ 8, its physical and chemical performance, combustionproperty and diesel oil closely, can be used as diesel-dope, and the addition in diesel oil can reach 30% (v/v), keeps higher cetane value and combustionproperty simultaneously.The oilness of diesel oil can be improved, reduce combustion fumes and generate, diesel oil combustion position within the engine can be improved, improve thermo-efficiency, reduce the particulate matter in combustion tail gas and NO
xdischarge.Also possibility diesel oil substitute, directly as diesel-fuel.
Polymethoxy dimethyl ether is solve the defect that dme does the existence of derv fuel oil blend component as the main purpose that Novel clean oil dope is researched and developed.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 disclose a kind of with methylal and paraformaldehyde for raw material, the method using sulfuric acid as the polymethoxy dimethyl ether of catalyst preparing n=2 ~ 4, but there is the serious problem of catalytic erosion.
WO2006/045506A1 discloses BASF AG and uses sulfuric acid or trifluoromethanesulfonic acid as catalyzer, with methyl alcohol, methylal, trioxymethylene, paraformaldehyde etc. for raw material, obtains the series product of n=1 ~ 10, there is the problem that catalytic erosion is serious equally.
US5746785 disclose a kind of with 0.1wt% formic acid for catalyzer, with methylal and paraformaldehyde or methyl alcohol and paraformaldehyde for raw material, there is the problem that catalytic erosion is serious in the series product of preparation n=1 ~ 10 equally.
CN101182367A and CN101962318A discloses and adopts acidic ion liquid as catalyzer, is the method that polymethoxy dimethyl ether prepared by raw material, there is the problem that catalytic erosion is serious equally by methyl alcohol and trioxymethylene.
CN101665414A discloses a kind of acidic ion liquid that adopts as catalyzer, is the method that polymethoxy dimethyl ether prepared by raw material, there is the problem that catalytic erosion is serious equally by methylal and trioxymethylene.
RUT structure molecular screen has great application prospect in multiple field such as acid catalysis, shape selective catalysis.Therefore, polymethoxy dimethyl ether can be produced 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 there is catalyzer in conventional art to have corrosive problem, provides a kind of preparation method of new polymethoxy dimethyl ether.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, with methyl alcohol or dme and formaldehyde or trioxymethylene for raw material, methyl alcohol or dme: formaldehyde or trioxymethylene mol ratio 1:0.1 ~ 10, it is 50 ~ 200 DEG C in temperature of reaction, reaction pressure is under 0.1 ~ 10MPa condition, and reaction raw materials and catalyst exposure generate polymethoxy dimethyl ether; Catalyst levels is 0.01 ~ 15% of reaction raw materials weight; Catalyzer wherein 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.Catalyst levels is the preferable range of reaction raw materials weight is 0.1 ~ 10%.Temperature of reaction preferable range is 70 ~ 150 DEG C, and 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, there is d-spacing maximum at 3.8 ± 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 silicon source, aluminium source, organic formwork agent, mineral alkali and water mix by required stoichiometric ratio, 120 DEG C ~ 200 DEG C crystallization 1 ~ 20 day, product after filtration, washing, dry, obtain RUT 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 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, wherein feed components mol ratio 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, and M represents Na or K.Then adopt the exchange of known ammonium, dry and roasting technology, obtain catalyzer.
In technique scheme, because synthesis RUT structure molecular screen has acid and continuous duct, be conducive to the diffusion of reaction raw materials, therefore catalyst catalytic performance is good.The present inventor finds uncannily, adopts this catalyzer, under temperature 100 DEG C, pressure 3MPa react 5 hours, n be 3 ~ 8 product can reach 32.2% in products distribution; The most important thing is that catalyzer non-corrosiveness achieves good technique effect.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the RUT zeolite that the present invention's [embodiment 1] synthesizes.
In Fig. 1, X-ray diffracting spectrum has strong diffraction peak at 22.0,20.6,14.0,22.7,10.6,13.4 and 19.8 degree of places, illustrates that this zeolite has RUT topological framework, is RUB-10 zeolite.
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 stoichiometrically mix, and wherein feed components mol ratio 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 DEG C of crystallization, after filtration, washing, dry, obtain RUT structure molecular screen, XRD spectra is shown in Fig. 1 to product.X-ray diffracting spectrum has strong diffraction peak at 22.0,20.6,14.0,22.7,10.6,13.4 and 19.8 degree of places, illustrates that this zeolite has RUT topological framework, is RUB-10 zeolite.Exchange three times at 80 DEG C with the aqueous ammonium nitrate solution of 10% mass concentration, aqueous ammonium nitrate solution and the ratio of the weight of molecular sieve are 10,120 DEG C of dryings 12 hours again, and 550 DEG C 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 DEG C with react 2 hours made pressure be 6MPa by inflated with nitrogen under, filtering separation catalyzer and reaction product, through gas chromatographic analysis, the mixture of acquisition composition is as table 1.
[embodiment 2]
By tetraethyl silicate, Tai-Ace S 150,4 bromide, sodium hydroxide and water stoichiometrically mix, and wherein feed components mol ratio 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 DEG C of crystallization, after filtration, washing, drying, obtains RUT structure molecular screen to product.Exchange three times at 80 DEG C with the aqueous ammonium nitrate solution of 10% mass concentration, aqueous ammonium nitrate solution and the ratio of the weight of molecular sieve are 10,120 DEG C of dryings 12 hours again, and 550 DEG C of roastings 5 hours, obtain catalyzer.
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.1.5 grams of catalyzer are added, 50 grams of methyl alcohol, 30 grams of dme in autoclave, 100 grams of formaldehyde, 100 DEG C and made pressure be 3MPa by inflated with nitrogen under react 5 hours, filtering separation catalyzer and reaction product, through gas chromatographic analysis, the mixture composition of acquisition is as table 1.
[embodiment 3]
By water glass, Tai-Ace S 150, tetramethyl ammonium chloride, potassium hydroxide and water stoichiometrically mix, and wherein feed components mol ratio 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 DEG C of crystallization, after filtration, washing, drying, obtains RUT structure molecular screen to product.Exchange three times at 80 DEG C with the aqueous ammonium nitrate solution of 10% mass concentration, aqueous ammonium nitrate solution and the ratio of the weight of molecular sieve are 10,120 DEG C of dryings 12 hours again, and 550 DEG C 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 DEG C with react 10 hours made pressure be 1MPa by inflated with nitrogen under, filtering separation catalyzer and reaction product, through gas chromatographic analysis, the mixture of acquisition composition is as table 1.
[embodiment 4]
By solid oxidation silicon, aluminum nitrate, 4 bromide, potassium hydroxide and water stoichiometrically mix, and wherein feed components mol ratio 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 DEG C of crystallization, after filtration, washing, drying, obtains RUT structure molecular screen to product.Exchange three times at 80 DEG C with the aqueous ammonium nitrate solution of 10% mass concentration, aqueous ammonium nitrate solution and the ratio of the weight of molecular sieve are 10,120 DEG C of dryings 12 hours again, and 550 DEG C of roastings 5 hours, obtain catalyzer.
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.0.9 gram of catalyzer is added, 50 grams of methyl alcohol, 30 grams of dme in autoclave, 100 grams of formaldehyde, 120 DEG C and made pressure be 4MPa by inflated with nitrogen under react 5 hours, filtering separation catalyzer and reaction product, through gas chromatographic analysis, the mixture composition of acquisition is as table 1.
[comparative example 1]
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.4g acid ion resin catalyst is added in autoclave, 80 grams of methyl alcohol, 90 grams of trioxymethylenes, 150 DEG C and made pressure be 4MPa by inflated with nitrogen under react 2 hours, filtering separation catalyzer and reaction product, through gas chromatographic analysis, the mixture composition of acquisition is as table 1.
Table 1
Claims (1)
1. a preparation method for polymethoxy dimethyl ether, step is as follows:
Be the silicon sol of 40% by weight concentration, sodium aluminate, Tetramethylammonium hydroxide, sodium hydroxide and water stoichiometrically mix, and wherein feed components mol ratio is, SiO
2: Al
2o
3: R:Na
2o:H
2o=1:0.01:0.4:0.01:40, wherein R represents Tetramethylammonium hydroxide; In the 7 day time of 160 DEG C of crystallization, product after filtration, is washed, and dry, obtain RUT structure molecular screen, XRD spectra is shown in Figure of description 1; X-ray diffracting spectrum has strong diffraction peak at 22.0,20.6,14.0,22.7,10.6,13.4 and 19.8 degree of places, illustrates that this zeolite has RUT topological framework, is RUB-10 zeolite; Exchange three times at 80 DEG C with the aqueous ammonium nitrate solution of 10% mass concentration, aqueous ammonium nitrate solution and the ratio of the weight of molecular sieve are 10,120 DEG C of dryings 12 hours again, and 550 DEG C of roastings 5 hours, obtain catalyzer;
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit; 2 grams of catalyzer are added in autoclave, 100 grams of methyl alcohol, 100 grams of trioxymethylenes, 130 DEG C and made pressure be 6MPa by inflated with nitrogen under react 2 hours, filtering separation catalyzer and reaction product, through gas chromatographic analysis, the transformation efficiency of trioxymethylene is 78.2%, and by weight percentage, the products distribution of PODE is n=1 ~ 2 is 60.0%, n=3 ~ 8 are 32.1%, n>8 is 7.9%.
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| 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 |
| 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 |
Citations (4)
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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 |
|---|---|---|---|---|
| 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 |
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