CN103420818A - Polyformaldehyde dimethyl ether preparation method - Google Patents
Polyformaldehyde dimethyl ether preparation method Download PDFInfo
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- CN103420818A CN103420818A CN2012101503988A CN201210150398A CN103420818A CN 103420818 A CN103420818 A CN 103420818A CN 2012101503988 A CN2012101503988 A CN 2012101503988A CN 201210150398 A CN201210150398 A CN 201210150398A CN 103420818 A CN103420818 A CN 103420818A
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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 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 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 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〔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 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〔Su〕 and trioxymethylene, is the method that raw material prepares polyoxymethylene dimethyl ethers, has equally the problem that catalytic erosion is serious.
The MEL molecular sieve is a member in high-silicon ZSM-5 series, at first phase early 1970s synthesizes [US 3709979] by U.S. Mobil company, 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 fabulous thermostability, acid resistance, shape selectivity, water vapor stability and hydrophobicity arranged, 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 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 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 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.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 MEL structure molecular screen, it is characterized in that 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 the silicon source, the 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 the MEL 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 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 its Raw 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 known ammonium exchange, drying and roasting technology, obtain catalyzer.
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, and under 100 ℃ of temperature, pressure 3MPa, reaction is 5 hours, and the product that n is 3～8 can reach 32.4% 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 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 the MEL topological framework, is the 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, in the reactor of packing into, 170 ℃ of crystallization 1 day.The crystallization product chilling, to filter, be washed to the pH value be 8, dries 12 hours in 120 ℃, makes the 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, 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 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.Exchange 10 hours with 1.0 mol/L citric acids at 80 ℃.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 each Step By Condition of [embodiment 2], be synthesizing formula Raw, batching proportioning difference.The aluminium source is Tai-Ace S 150, and the 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, 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, 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, product after filtration, is washed, and drying, obtain the MEL 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 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 1:0.5～6.
3. the preparation method of polyoxymethylene dimethyl ethers 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 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 ℃, and reaction pressure is 0.5～6MPa.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| EP2905293A1 (en) * | 2013-12-09 | 2015-08-12 | Lanzhou Institute Of Chemical Physics Chinese Academy of Sciences | Process for catalytic synthesis of low-carbon polyether-based compound by using acidic ionic liquid |
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) |
-
2012
- 2012-05-16 CN CN201210150398.8A patent/CN103420818B/en active Active
Patent 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) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| EP2905293A1 (en) * | 2013-12-09 | 2015-08-12 | Lanzhou Institute Of Chemical Physics Chinese Academy of Sciences | Process for catalytic synthesis of low-carbon polyether-based compound by using acidic ionic liquid |
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