CN103420816A - Polyformaldehyde dimethyl ether preparation method - Google Patents
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- CN103420816A CN103420816A CN2012101503850A CN201210150385A CN103420816A CN 103420816 A CN103420816 A CN 103420816A CN 2012101503850 A CN2012101503850 A CN 2012101503850A CN 201210150385 A CN201210150385 A CN 201210150385A CN 103420816 A CN103420816 A CN 103420816A
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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 MTW topological structure or an organosilicon-containing SAPO-5 molecular sieve. With the technical scheme, the problem in the prior art is well solved, and the preparation method can be used for industrial production of 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 MTW molecular sieve is a member in high-silicon ZSM-5 series, within 1974, by U.S. Mobil company, at first synthesize [US 3832449], it is the non-intersection of the one-dimensional linear duct that twelve-ring forms, aperture is 0.57 * 0.61 nanometer, 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 are arranged, have great application prospect in a plurality of fields such as acid catalysis, shape selective catalysiss.Therefore, can produce polyoxymethylene dimethyl ethers by MTW structure catalyst catalyzed reaction.
In addition, SAPO-5, due to the special construction with AFI, has great application prospect in a plurality of fields such as acid catalysis, shape selective catalysis, support of the catalyst.Patent CN101302015A has reported that diethylamine is the synthetic SAPO-5 of template and template recovery method.But, owing to not containing organic group in its framework of molecular sieve, the molecular sieve hydrophobicity is poor.And introduce organic group in the process of synthesis of molecular sieve, be conducive to improve the hydrophobicity of molecular sieve, many catalyzed reactions require catalyzer that hydrophobic lipophilic performance is preferably arranged, therefore, structurally-modified to meet the requirement of this respect by microporous catalyst is carried out, more and more cause the concern of chemist.Therefore, can be by containing organosilicon SAPO-5 molecular sieve catalyst catalyzed reaction, producing polymethoxy dimethyl ether.
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 have the molecular sieve of MTW topological framework or contain organosilicon SAPO-5 molecular sieve.
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 one embodiment of the invention, the preparation method of catalyzer is: a kind of MTW structure molecular screen is characterized in that its X-ray diffracting spectrum is 11.8 ± 0.2,11.6 ± 0.3,9.9 ± 0.3,4.2 ± 0.2,3.9 there is d-spacing maximum value at ± 0.2,3.8 ± 0.1 and 3.4 ± 0.1 dust places.The preparation method of MTW 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 MTW 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 tetraethyl ammonium hydroxide, methyl triethyl ammonium hydroxide, at least one in methyl triethyl brometo de amonio or tetraethylammonium bromide, 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=1:0.004～0.1:0.05～0.5:0.01～0.1:10～100, 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 MTW 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 120 ℃ of temperature, pressure 4MPa, reaction is 5 hours, and the product that n is 3～8 can reach 31.2% in products distribution; The most important thing is that the catalyzer non-corrosiveness has been obtained technique effect preferably.
In another embodiment of the invention, the preparation method of catalyzer is: a kind of SAPO-5 molecular sieve is characterized in that in the ir data of molecular sieve at 1213～1278cm
-1Corresponding organosilyl infrared absorption peak is arranged.The preparation method of SAPO-5 molecular sieve, comprise the following steps: by the inorganic silicon source, the organosilicon source, the aluminium source, organic formwork agent, phosphorus source and water mix by required stoichiometric ratio, in 1～20 day time of 120 ℃～220 ℃ crystallization, product after filtration, washing, dry, obtain the SAPO-5 molecular sieve, wherein the inorganic silicon source is selected from silicon sol, silicon ester, diatomite, at least one in water glass or solid oxidation silicon, the organosilicon source is two (triethoxy is silica-based) methane, 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, the phosphorus source is phosphoric acid.Organic formwork agent is selected from least one in triethylamine, diethylamine, dipropyl amine or tetraethyl ammonium hydroxide, and each component mol ratio of its Raw is: inorganic silicon source: organosilicon source: aluminium source: phosphorus source: organic formwork agent: water=0.1～0.3:0.1～0.3:0.8～1.2:0.8～1.2:0.4～1.5:25～100.Then adopt known drying and roasting technology, obtain catalyzer.
In technique scheme, organosilicon source and inorganic silicon source have been applied in synthetic simultaneously, therefore synthetic skeletal structure of compound part have a Si-CH-Si structure, replaced the Si-O-Si structure in conventional microvoid structure, therefore this material has good hydrophobicity.SAPO-5 molecular sieve of the present invention, its normal hexane is 32mg/g the adsorptive capacity of 50 ℃, and containing organosilyl SAPO-5 molecular sieve, is not only 7.8mg/g, visible SAPO-5 molecular sieve hydrophobicity of the present invention is apparently higher than not containing organosilyl SAPO-5 molecular sieve.The inventor finds uncannily, adopts this catalyzer, and under 140 ℃ of temperature, pressure 2MPa, reaction is 8 hours, and the product that n is 3～8 can reach 32.5% 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-12 zeolite of the present invention [embodiment 1].
The IR spectrogram that Fig. 2 is the synthetic SAPO-5 zeolite of the present invention [embodiment 5].
In Fig. 1, X-ray diffracting spectrum is 20.8,23.1, and there is strong diffraction peak at 7.4,7.6 and 8.8 degree places, illustrates that this zeolite has the MTW topological framework, is the ZSM-12 zeolite.
1275cm in Fig. 2
-1The absorption peak at wave number place is corresponding to organosilyl infrared absorption peak.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
By silicon sol (40%, weight), sodium aluminate, tetraethyl ammonium 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=1:0.01:0.1:0.03:20.In the 3 day time of 160 ℃ of crystallization, product after filtration, is washed, and drying, obtain the MTW structure molecular screen, and XRD spectra is shown in Fig. 1.It is characterized in that its X-ray diffracting spectrum is 11.8 ± 0.2,11.6 ± 0.3,9.9 ± 0.3,4.2 ± 0.2,3.9 ± 0.2, there is d-spacing maximum value at 3.8 ± 0.1 and 3.4 ± 0.1 dust places.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, tetraethylammonium 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=1:0.0125:0.12:0.035:40.In the 5 day time of 150 ℃ of crystallization, product after filtration, is washed, and drying, obtain the MTW 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 silicon sol (40%, weight), Tai-Ace S 150, methyl triethyl ammonium hydroxide, 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=1:0.02:0.2:0.04:40.In the 10 day time of 140 ℃ of crystallization, product after filtration, is washed, and drying, obtain the MTW 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, methyl triethyl brometo de amonio, 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=1:0.025:0.25:0.035:60.In the 20 day time of 130 ℃ of crystallization, product after filtration, is washed, and drying, obtain the MTW 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.
[embodiment 5]
Weighing 4.15 gram phosphoric acid and 26 gram water mix, and then in the situation that stirring adds 2.63 gram pseudo-boehmites, after stirring, are adding 0.8 silicon sol (containing 40 % by weight SiO
2), then add 3 gram triethylamine (Et
3N), finally add two (triethoxy the is silica-based) methane (BTESM) of 1.23 grams.The material proportion of reactant is: SiO
2: BTESM:Al
2O
3: H
3PO
4: Et
3N:H
2O=0.15:0.2:1:1:1.2:90, after the question response mixture stirs, in the Stainless Steel reactor of packing into, in 210 ℃ of crystallization 54 hours.Taking-up is by filtration, washing, drying.Dried sample after measured, in its ir data at 1275cm
-1Corresponding organosilyl infrared absorption peak is arranged.Dried sample is 30mg/g in the adsorptive capacity of 50 ℃ of normal hexanes.Then 550 ℃ of roastings are 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 6]
Weighing 4.98 gram phosphoric acid and 14 gram water mix, then in the situation that stirring adds 2.9 gram Aluminium chloride hexahydrates, adding 1.05 gram tetraethoxys after stirring, add again 13.4 gram tetraethyl ammonium hydroxides (containing 25 % by weight), finally add two (triethoxy the is silica-based) methane (BTESM) of 1.84 grams.The material proportion of reactant is: SiO
2: BTESM:Al
2O
3: H
3PO
4: tetraethyl ammonium hydroxide: H
2O=0.15:0.3:1:1.2:1.5:50, after the question response mixture stirs, in the Stainless Steel reactor of packing into, in 160 ℃ of crystallization 24 hours.Taking-up is by filtration, washing, drying.Dried sample after measured, in its ir data at 1275cm
-1Corresponding organosilyl infrared absorption peak is arranged.Dried sample is 31mg/g in the adsorptive capacity of 50 ℃ of normal hexanes.Then 550 ℃ of roastings are 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 7]
Weighing 4.57 gram phosphoric acid and 28 gram water mix, then in the situation that stirring adds 3.3 gram sodium aluminates, add 0.4 gram water glass after stirring, then adding 0.48 gram diethylamine, finally adding two (triethoxy the is silica-based) methane (BTESM) of 0.92 gram.The material proportion of reactant is: SiO
2: BTESM:Al
2O
3: H
3PO
4: diethylamine: H
2O=0.1:0.15:1.1:1.1:0.6:100, after the question response mixture stirs, in the Stainless Steel reactor of packing into, in 220 ℃ of crystallization 48 hours.Taking-up is by filtration, washing, drying.Dried sample after measured, in its ir data at 1275cm
-1Corresponding organosilyl infrared absorption peak is arranged.Dried sample is 29mg/g in the adsorptive capacity of 50 ℃ of normal hexanes.Then 550 ℃ of roastings are 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 8]
Weighing 3.74 gram phosphoric acid and 20 gram water mix, then in the situation that stirring adds 3.4 gram aluminium hydroxides, add 0.6 diatomite after stirring, then adding 0.4 gram dipropyl amine, finally adding two (triethoxy the is silica-based) methane (BTESM) of 0.92 gram.The material proportion of reactant is: SiO
2: BTESM:Al
2O
3: H
3PO
4: dipropyl amine: H
2O=0.3:0.15:1.2:0.9:0.4:70, after the question response mixture stirs, in the Stainless Steel reactor of packing into, in 170 ℃ of crystallization 480 hours.Taking-up is by filtration, washing, drying.Dried sample after measured, in its ir data at 1275cm
-1Corresponding organosilyl infrared absorption peak is arranged.Dried sample is 30mg/g in the adsorptive capacity of 50 ℃ of normal hexanes.Then 550 ℃ of roastings are 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.
[embodiment 9]
Weighing 4.15 gram phosphoric acid and 23 gram water mix, and then in the situation that stirring adds 12.2 gram ANN aluminium nitrate nonahydrate, after stirring, are adding 0.8 silicon sol (containing 40 % by weight SiO
2), then add 2 gram triethylamine (Et
3N), finally add two (triethoxy the is silica-based) methane (BTESM) of 0.92 gram.The material proportion of reactant is: SiO
2: BTESM:Al
2O
3: H
3PO
4: Et
3N:H
2O=0.15:0.15:0.9:1:0.8:80, after the question response mixture stirs, in the Stainless Steel reactor of packing into, in 180 ℃ of crystallization 200 hours.Taking-up is by filtration, washing, drying.Dried sample after measured, in its ir data at 1275cm
-1Corresponding organosilyl infrared absorption peak is arranged.Dried sample is 32mg/g in the adsorptive capacity of 50 ℃ of normal hexanes.Then 550 ℃ of roastings are 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, 140 ℃ and by inflated with nitrogen, make pressure be under 2MPa the reaction 8 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.
[Comparative Examples 2]
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.In autoclave, add 4 grams not containing organosilicon SAPO-5 molecular sieve catalyst (dried sample is 7.8mg/g in the adsorptive capacity of 50 ℃ of normal hexanes), 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 have the molecular sieve of MTW topological framework or contain organosilicon SAPO-5 molecular sieve.
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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| CN103922362A (en) * | 2014-04-19 | 2014-07-16 | 复旦大学 | MTW zeolite and preparation method thereof |
| CN106582837A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst for producing polyoxymethylene dimethyl ether |
| CN106582836A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst for PODE (polyoxymethylene dimethyl ether) |
| CN113426480A (en) * | 2021-05-25 | 2021-09-24 | 武汉理工大学 | Preparation method and catalytic application of organic-inorganic hybrid ZOF-TS-1 molecular sieve |
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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 |
| 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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| CN1631778A (en) * | 2004-11-12 | 2005-06-29 | 南开大学 | Fractional crystallization method for preparing organic functionalized micellization molecular sieve |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103922362A (en) * | 2014-04-19 | 2014-07-16 | 复旦大学 | MTW zeolite and preparation method thereof |
| CN106582837A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst for producing polyoxymethylene dimethyl ether |
| CN106582836A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst for PODE (polyoxymethylene dimethyl ether) |
| CN113426480A (en) * | 2021-05-25 | 2021-09-24 | 武汉理工大学 | Preparation method and catalytic application of organic-inorganic hybrid ZOF-TS-1 molecular sieve |
| CN113426480B (en) * | 2021-05-25 | 2023-06-27 | 武汉理工大学 | Preparation method and catalytic application of organic-inorganic hybrid ZOF-TS-1 molecular sieve |
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