CN103420814A - Polymethoxy dimethyl ether preparation method - Google Patents
Polymethoxy dimethyl ether preparation method Download PDFInfo
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- CN103420814A CN103420814A CN2012101503386A CN201210150338A CN103420814A CN 103420814 A CN103420814 A CN 103420814A CN 2012101503386 A CN2012101503386 A CN 2012101503386A CN 201210150338 A CN201210150338 A CN 201210150338A CN 103420814 A CN103420814 A CN 103420814A
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- dimethyl ether
- polymethoxy dimethyl
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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 reaction pressure of 0.1-10 MPa to produce polymethoxy dimethyl ether, wherein the catalyst is a ZSM-11 molecular sieve with a grain diameter of less than or equal to 5 mum. 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 the polymethoxy dimethyl ether, polyoxymethylene dimethyl ethers, polymethoxy methylal, polyoxymethylene dimethyl ethers, polymethoxy dimethyl ether, polyoxymethylene dimethyl ether 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.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.
The 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 the 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 the polymethoxy dimethyl ether, has equally the problem that catalytic erosion is serious.
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.
In order to solve 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 the polymethoxy dimethyl ether; Catalyst levels is 0.01～15% of reaction raw materials weight; The ZSM-11 molecular sieve that wherein catalyzer used is crystal grain diameter≤5 micron.
In technique scheme, the crystal grain diameter preferable range of described ZSM-11 molecular sieve is 0.1～5 micron, and more preferably scope is 0.1～2 micron.The silica alumina ratio preferable range of described ZSM-11 molecular sieve is 10～500, and more preferably scope is 40～150.Described ZSM-11 molecular sieve preferred version is processed 0.1～10 hour for the alkali lye that is 0.01～2 mol/L by concentration under 30～100 ℃, the concentration preferable range of alkali lye is 0.1～1 mol/L, the treatment temp preferable range of alkali lye is 50～80 ℃, and the treatment time preferable range is 0.5～4 hour.Wherein, alkali lye is 1～20 with the ratio of the weight of molecular sieve, and preferable range is 2～10.Described alkali lye preferred version is at least one being selected from aqueous sodium hydroxide solution or potassium hydroxide aqueous solution.
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 inventive method, the molecular sieve after alkali lye is processed, before for the preparation of the reaction of polymethoxy dimethyl ether, adopt known ammonium exchange, drying and roasting technology, obtains catalyzer.
The ZSM-11 molecular sieve is a member in high-silicon ZSM-5 series, 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.The present invention is catalyzer by the ZSM-11 molecular sieve that adopts crystal grain diameter to be less than 5 microns, because fine grain ZSM-5-11 molecular sieve is compared conventional ZSM-11 molecular sieve and is had larger external surface area and higher intracrystalline rate of diffusion, in the utilization ratio that improves catalyzer, strengthen the macromole conversion capability, reduce deep reaction, improve selectivity and reduce the aspects such as coking and deactivation and all show superior performance.In addition, preferably this fine grain ZSM-5-11 molecular sieve is processed through alkali lye, the molten silicon character due to alkali lye has produced again a certain amount of hole in the ZSM-11 molecular sieve, these newly-increased holes have increased catalyzer and have held burnt ability, have improved the stability of catalyzer; Alkali lye can be removed in molecular sieve pore passage the amorphous silicon oxide material or remove the material such as non-skeleton silicon oxide from framework of molecular sieve on the other hand, make originally by amorphous active centre of waiting material to cover, fully to be exposed in molecular sieve pore passage, play the modification to molecular sieve pore passage, activity of molecular sieve catalysts is increased to some extent, the burnt ability of the appearance of catalyzer improves greatly, and activity stability has had very large improvement.Adopt the inventive method, under 110 ℃ of temperature, pressure 3MPa, reaction is 3 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.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
40% silicon sol, sodium metaaluminate, Tetrabutyl amonium bromide, sodium-chlor, 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 crystal grain diameter is 0.5 micron.In reaction mixture, the mol ratio of each raw material is: SiO
2/ Al
2O
3=145, H
2O/SiO
2=32.8, NaCl/SiO
2=0.6, NaOH/SiO
2=0.08, TBABr/SiO
2=0.12.
Get the ZSM-11 molecular sieve (SiO that 50 gram crystal grain diameters are 0.5 micron
2/ Al
2O
3=145), put into the aqueous sodium hydroxide solution that 250 gram concentration are 0.5 mol/L, under refluxing, in 80 ℃ of constant temperature, stir 0.5 hour, filter, use distilled water wash, then exchange three times under 80 ℃ with the aqueous ammonium nitrate solution of 10% mass concentration, aqueous ammonium nitrate solution is 10 with the ratio of the weight of molecular sieve, 120 ℃ of dryings 12 hours, 550 ℃ of roastings 5 hours, the gained identified as samples is designated as A.
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]
Get the ZSM-11 molecular sieve (SiO that 50 gram crystal grain diameters are 1 micron
2/ Al
2O
3=40), put into the aqueous sodium hydroxide solution that 100 gram concentration are 1 mol/L, stir 3 hours in 60 ℃ of constant temperature under refluxing, filter, use distilled water wash, with the exchange of [embodiment 1] ammonium, drying, roasting, moulding, the gained identified as samples is designated as B.
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.Add 1.5 gram catalyzer in autoclave, 80 gram dme, 100 gram trioxymethylenes, 110 ℃ and by inflated with nitrogen, make pressure be under 4MPa the reaction 4 hours, filtering separation catalyzer and reaction product, through gas chromatographic analysis, the compositions of mixtures of acquisition is as table 1.
[embodiment 3]
Get the ZSM-11 molecular sieve (SiO that 50 gram crystal grain diameters are 0.8 micron
2/ Al
2O
3=100), put into the potassium hydroxide aqueous solution that 500 gram concentration are 0.2 mol/L, stir 3.5 hours in 50 ℃ of constant temperature under refluxing, filter, use distilled water wash, with the exchange of [embodiment 1] ammonium, drying, roasting, moulding, the gained identified as samples is designated as C.
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.Add 1.2 gram catalyzer in autoclave, 50 gram methyl alcohol, 50 gram dme, 100 gram trioxymethylenes, 100 ℃ and by inflated with nitrogen, make pressure be under 1MPa 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 4]
Get the ZSM-11 molecular sieve (SiO that 50 gram crystal grain diameters are 1.8 microns
2/ Al
2O
3=120), put into the potassium hydroxide aqueous solution that 400 gram concentration are 0.3 mol/L, stir 2 hours in 70 ℃ of constant temperature under refluxing, filter, use distilled water wash, with the exchange of [embodiment 1] ammonium, drying, roasting, moulding, the gained identified as samples is designated as D.
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.Add 1 gram catalyzer in autoclave, 100 gram dme, 90 gram formaldehyde, 80 ℃ and by inflated with nitrogen, make pressure be under 2MPa 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]
Get the ZSM-11 molecular sieve (SiO that 50 gram crystal grain diameters are 1.2 microns
2/ Al
2O
3=80), put into the aqueous sodium hydroxide solution that 200 gram concentration are 0.6 mol/L, stir 1.5 hours in 65 ℃ of constant temperature under refluxing, filter, use distilled water wash, with the exchange of [embodiment 1] ammonium, drying, roasting, moulding, the gained identified as samples is designated as E.
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.Add 1 gram catalyzer in autoclave, 100 gram dme, 90 gram trioxymethylenes, 90 ℃ and by inflated with nitrogen, make pressure be under 2MPa 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 6]
Get the ZSM-11 molecular sieve (SiO that 50 gram crystal grain diameters are 0.2 micron
2/ Al
2O
3=70), put into the aqueous sodium hydroxide solution that 300 gram concentration are 0.3 mol/L, stir 1.5 hours in 55 ℃ of constant temperature under refluxing, filter, use distilled water wash, with the exchange of [embodiment 1] ammonium, drying, roasting, moulding, the gained identified as samples is designated as F.
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.Add 1 gram catalyzer in autoclave, 80 gram dme, 10 gram methyl alcohol, 90 gram formaldehyde, 110 ℃ and by inflated with nitrogen, make pressure be under 3MPa the reaction 3 hours, filtering separation catalyzer and reaction product, through gas chromatographic analysis, the compositions of mixtures of acquisition is as table 1.
[embodiment 7]
[embodiment 1] catalyzer, just do not process through alkali lye, and the gained identified as samples is designated as G.
Press the performance of each Step By Condition evaluate catalysts of [embodiment 1], reaction result is in Table 1.
[embodiment 8]
[embodiment 6] catalyzer, just do not process through alkali lye, and the gained identified as samples is designated as H.
Press the performance of each Step By Condition evaluate catalysts of [embodiment 1], reaction result is in Table 1.
[Comparative Examples 1]
Get the ZSM-11 molecular sieve (SiO that 50 gram crystal grain diameters are 11 microns
2/ Al
2O
3=100),, with the exchange of [embodiment 1] ammonium, dry, roasting, the gained identified as samples is designated as I.
Press the performance of each Step By Condition evaluate catalysts of [embodiment 1], reaction result is in Table 1.
[Comparative Examples 2]
[Comparative Examples 1] catalyzer, the alkali lye treatment condition are with [embodiment 1], and the gained identified as samples is designated as J.
Press the performance of each Step By Condition evaluate catalysts of [embodiment 1], reaction result is in Table 1.
Table 1
Claims (10)
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 the polymethoxy dimethyl ether; Catalyst levels is 0.01～15% of reaction raw materials weight; The ZSM-11 molecular sieve that wherein catalyzer used is crystal grain diameter≤5 micron.
2. the preparation method of polymethoxy dimethyl ether according to claim 1, the crystal grain diameter that it is characterized in that described ZSM-11 molecular sieve is 0.1～5 micron.
3. the preparation method of polymethoxy dimethyl ether according to claim 2, the crystal grain diameter that it is characterized in that the ZSM-11 molecular sieve is 0.1～2 micron.
4. the preparation method of polymethoxy dimethyl ether according to claim 1, the silica alumina ratio that it is characterized in that described ZSM-11 molecular sieve is 10～500.
5. the preparation method of polymethoxy dimethyl ether according to claim 1, is characterized in that the alkali lye that described ZSM-11 molecular sieve is 0.01～2 mol/L by concentration processes 0.1～10 hour under 30～100 ℃; Wherein alkali lye is 1～20 with the ratio of the weight of molecular sieve, and described alkali lye is selected from least one in aqueous sodium hydroxide solution or potassium hydroxide aqueous solution.
6. the preparation method of polymethoxy dimethyl ether according to claim 1, the concentration that it is characterized in that alkali lye is 0.1～1 mol/L, and the treatment temp of alkali lye is 50～80 ℃, and the treatment time is 0.5～4 hour, and alkali lye is 2～10 with the ratio of the weight of molecular sieve.
7. 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.
8. 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.
9. 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.
10. 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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112898102A (en) * | 2021-01-21 | 2021-06-04 | 军事科学院系统工程研究院军事新能源技术研究所 | Oxygen-containing nontoxic high-energy cloud blasting agent |
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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2012
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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) |
Non-Patent Citations (1)
| Title |
|---|
| 赵亮等: "ZSM-5分子筛碱处理的研究进展", 《化学工程与装备》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112898102A (en) * | 2021-01-21 | 2021-06-04 | 军事科学院系统工程研究院军事新能源技术研究所 | Oxygen-containing nontoxic high-energy cloud blasting agent |
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