CN103420818B - Polyformaldehyde dimethyl ether preparation method - Google Patents
Polyformaldehyde dimethyl ether preparation method Download PDFInfo
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- CN103420818B CN103420818B CN201210150398.8A CN201210150398A CN103420818B CN 103420818 B CN103420818 B CN 103420818B CN 201210150398 A CN201210150398 A CN 201210150398A CN 103420818 B CN103420818 B CN 103420818B
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Abstract
The present invention relates to a polyformaldehyde 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 polyformaldehyde dimethyl ether, wherein the catalyst is a molecular sieve with a MEL 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 polyformaldehyde dimethyl ether.
Description
Technical field
The present invention relates to a kind of preparation method of polyoxymethylene dimethyl ethers.
Background technology
(Chinese also can be polyoxymethylene dimethyl ether to polyoxymethylene dimethyl ethers, polymethoxy methylal, polymethoxy dimethyl ether, 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.
Polyoxymethylene dimethyl ethers 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 polyoxymethylene dimethyl ethers 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 polyoxymethylene dimethyl ethers 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 polyoxymethylene dimethyl ethers prepared by raw material, there is the problem that catalytic erosion is serious equally by methylal and trioxymethylene.
MEL molecular sieve is a member in high-silicon ZSM-5 series, first phase early 1970s is synthesized [US 3709979] by Mobil company of the U.S., form oval ten-ring two-dimensional direct duct (0.51 × 0.55nm) intersecting, belong to micro-pore zeolite, because it does not have cage, so in catalytic process not easily carbon distribution, and there are fabulous thermostability, acid resistance, shape selectivity, water vapor stability and hydrophobicity, have great application prospect in multiple field such as acid catalysis, shape selective catalysis.Therefore, polyoxymethylene dimethyl ethers can be produced by MEL 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 polyoxymethylene dimethyl ethers.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, 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 polyoxymethylene dimethyl ethers; Catalyst levels is 0.01 ~ 15% of reaction raw materials weight; Catalyzer wherein used is the molecular sieve with MTW 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 MEL structure molecular screen, and it is characterized in that its X-ray diffracting spectrum is 11.1 ± 0.1,10.0 ± 0.1,6.7 ± 0.1,6.0 ± 0.1,3.8 ± 0.1, there is d-spacing maximum 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 DEG C ~ 180 DEG C 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, wherein feed components mol ratio 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.Then adopt the exchange of known ammonium, dry and roasting technology, obtain catalyzer.
In technique scheme, because synthesis MEL 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 32.4% 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 ZSM-11 zeolite that the present invention's [embodiment 1] synthesizes.
In Fig. 1, X-ray diffracting spectrum has strong diffraction peak at 23.0,23.9,7.9,8.8 and 45.1 degree of 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, stirs 20 minutes, in loading reactor, 170 DEG C of crystallization 1 day.Crystallization product chilling, to filter, be washed to pH value be 8, dries 12 hours in 120 DEG C, and obtained ZSM-11 molecular screen primary powder, 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.
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 each Step By Condition of [embodiment 1], just SiO in synthesizing formula
2/ Al
2o
3=52, template adopts TBAH, crystallization temperature 120 DEG C of crystallization 8 days.10 hours are exchanged at 80 DEG C with 1.0 mol/L citric acids.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 each Step By Condition of [embodiment 2], just synthesizing formula Raw, batching proportioning difference.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.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, tetrabutylammonium chloride, potassium hydroxide and water stoichiometrically mix, and wherein feed components mol ratio 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 DEG C of crystallization, after filtration, washing, drying, obtains MEL 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 polyoxymethylene dimethyl ethers, step is as follows:
The silicon sol of 40%, sodium metaaluminate, Tetrabutyl amonium bromide, sodium hydroxide and water are mixed, stirs 20 minutes, in loading reactor, 170 DEG C of crystallization 1 day; Crystallization product chilling, to filter, be washed to pH value be 8, dries 12 hours in 120 DEG C, obtained ZSM-11 molecular screen primary powder, and XRD spectra is shown in Figure of description 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;
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 75.1%, as follows with the distribution of weight PODE product: n=1 ~ 2 are 60.1%, n=3 ~ 8 is that 32.1%, n>8 is for 7.8%.
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| CN103739459A (en) * | 2012-10-17 | 2014-04-23 | 中国石油化工股份有限公司 | Preparation method of polyoxymethylene dimethyl ethers |
| CN103709019A (en) * | 2013-12-09 | 2014-04-09 | 中国科学院兰州化学物理研究所 | Acidic ionic liquid catalyzed synthesis method of low carbon polyether compound |
Citations (2)
| 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) |
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| 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) |
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