CN103420814B - Polymethoxy dimethyl ether preparation method - Google Patents
Polymethoxy dimethyl ether preparation method Download PDFInfo
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- CN103420814B CN103420814B CN201210150338.6A CN201210150338A CN103420814B CN 103420814 B CN103420814 B CN 103420814B CN 201210150338 A CN201210150338 A CN 201210150338A CN 103420814 B CN103420814 B CN 103420814B
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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 also can be polyoxymethylene dimethyl ether to polymethoxy dimethyl ether, polyoxymethylene dimethyl ethers, polymethoxy methylal, polyoxymethylene dimethyl ethers, polymethoxy dimethyl ether, polyoxy methylene 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.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, using sulfuric acid as the method for 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.
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.
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, 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 ZSM-11 molecular sieve of 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 at 30 ~ 100 DEG C, process 0.1 ~ 10 hour with the alkali lye that concentration is 0.01 ~ 2 mol/L, the concentration preferences of alkali lye is 0.1 ~ 1 mol/L, the treatment temp preferable range of alkali lye is 50 ~ 80 DEG C, and 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 be selected from least one in 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.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 inventive method, the molecular sieve after base extraction, before for the preparation of the reaction of polymethoxy dimethyl ether, adopts the exchange of known ammonium, dry and roasting technology, obtains catalyzer.
ZSM-11 molecular sieve is a member in high-silicon ZSM-5 series, 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 have fabulous thermostability, acid resistance, shape selectivity, water vapor stability and hydrophobicity.The ZSM-11 molecular sieve that the present invention is less than 5 microns by employing crystal grain diameter is catalyzer, compare conventional ZSM-11 molecular sieve due to fine grain ZSM-5-11 molecular sieve and there is the higher micropore diffusion speed of larger Extra specific surface area sum, improve catalyzer utilization ratio, strengthen macromole conversion capability, reduce deep reaction, improve selectivity and reduce in coking and deactivation etc. and all show superior performance.In addition, preferably to this fine grain ZSM-5-11 molecular sieve through base extraction, due to the molten silicon character of alkali lye, in ZSM-11 molecular sieve, produced again a certain amount of hole, these newly-increased holes add catalyzer and hold burnt ability, improve the stability of catalyzer; On the other hand alkali lye can be removed in molecular sieve pore passage amorphous silicon matter or remove the materials such as non-framework silica from framework of molecular sieve, make originally fully to be exposed by amorphous active centre of waiting material to cover 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 appearance of catalyzer improves greatly, and activity stability has had very large improvement.Adopt the inventive method, under temperature 110 DEG C, pressure 3MPa react 3 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.
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, 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, 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 grams of crystal grain diameters are 0.5 micron
2/ Al
2o
3=145), put into the aqueous sodium hydroxide solution that 250 grams of concentration are 0.5 mol/L, 0.5 hour is stirred under reflux in 80 DEG C of constant temperature, filter, with distilled water wash, then exchange three times at 80 DEG C 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 DEG C of dryings 12 hours, 550 DEG C of roastings 5 hours, gained identified as samples is designated as A.
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]
Get the ZSM-11 molecular sieve (SiO that 50 grams of crystal grain diameters are 1 micron
2/ Al
2o
3=40), put into the aqueous sodium hydroxide solution that 100 grams of concentration are 1 mol/L, stir 3 hours under reflux in 60 DEG C of constant temperature, filter, with distilled water wash, with [embodiment 1] ammonium exchange, drying, roasting, shaping, gained identified as samples is designated as B.
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.In autoclave, add 1.5 grams of catalyzer, 80 grams of dme, 100 grams of trioxymethylenes, at 110 DEG C with react 4 hours made pressure be 4MPa 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 3]
Get the ZSM-11 molecular sieve (SiO that 50 grams of crystal grain diameters are 0.8 micron
2/ Al
2o
3=100), put into the potassium hydroxide aqueous solution that 500 grams of concentration are 0.2 mol/L, stir 3.5 hours under reflux in 50 DEG C of constant temperature, filter, with distilled water wash, with [embodiment 1] ammonium exchange, drying, roasting, shaping, gained identified as samples is designated as C.
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.1.2 grams of catalyzer are added, 50 grams of methyl alcohol, 50 grams of dme in autoclave, 100 grams of trioxymethylenes, 100 DEG C and made pressure be 1MPa 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 4]
Get the ZSM-11 molecular sieve (SiO that 50 grams of crystal grain diameters are 1.8 microns
2/ Al
2o
3=120), put into the potassium hydroxide aqueous solution that 400 grams of concentration are 0.3 mol/L, stir 2 hours under reflux in 70 DEG C of constant temperature, filter, with distilled water wash, with [embodiment 1] ammonium exchange, drying, roasting, shaping, gained identified as samples is designated as D.
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.In autoclave, add 1 gram of catalyzer, 100 grams of dme, 90 grams of formaldehyde, at 80 DEG C with react 5 hours made pressure be 2MPa 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 5]
Get the ZSM-11 molecular sieve (SiO that 50 grams of crystal grain diameters are 1.2 microns
2/ Al
2o
3=80), put into the aqueous sodium hydroxide solution that 200 grams of concentration are 0.6 mol/L, stir 1.5 hours under reflux in 65 DEG C of constant temperature, filter, with distilled water wash, with [embodiment 1] ammonium exchange, drying, roasting, shaping, gained identified as samples is designated as E.
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.In autoclave, add 1 gram of catalyzer, 100 grams of dme, 90 grams of trioxymethylenes, at 90 DEG C with react 5 hours made pressure be 2MPa 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 6]
Get the ZSM-11 molecular sieve (SiO that 50 grams of crystal grain diameters are 0.2 micron
2/ Al
2o
3=70), put into the aqueous sodium hydroxide solution that 300 grams of concentration are 0.3 mol/L, stir 1.5 hours under reflux in 55 DEG C of constant temperature, filter, with distilled water wash, with [embodiment 1] ammonium exchange, drying, roasting, shaping, gained identified as samples is designated as F.
The performance evaluation of catalyzer is carried out on 300ml autoclave reaction unit.In autoclave, add 1 gram of catalyzer, 80 grams of dme, 10 grams of methyl alcohol, 90 grams of formaldehyde, at 110 DEG C with react 3 hours made pressure be 3MPa 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 7]
[embodiment 1] catalyzer, just not through base extraction, gained identified as samples is designated as G.
By the performance of each Step By Condition evaluate catalysts of [embodiment 1], reaction result is in table 1.
[embodiment 8]
[embodiment 6] catalyzer, just not through base extraction, gained identified as samples is designated as H.
By the performance of each Step By Condition evaluate catalysts of [embodiment 1], reaction result is in table 1.
[comparative example 1]
Get the ZSM-11 molecular sieve (SiO that 50 grams of crystal grain diameters are 11 microns
2/ Al
2o
3=100), with the exchange of [embodiment 1] ammonium, dry, roasting, gained identified as samples is designated as I.
By the performance of each Step By Condition evaluate catalysts of [embodiment 1], reaction result is in table 1.
[comparative example 2]
[comparative example 1] catalyzer, base extraction condition is with [embodiment 1], and gained identified as samples is designated as J.
By the performance of each Step By Condition evaluate catalysts of [embodiment 1], reaction result is in table 1.
Table 1
Claims (8)
1. the preparation method of a 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 to be crystal grain diameter the be ZSM-11 molecular sieve of 0.1 ~ 5 micron; The silica alumina ratio of described ZSM-11 molecular sieve is 10 ~ 500.
2. the preparation method of polymethoxy dimethyl ether according to claim 1, is characterized in that the crystal grain diameter of ZSM-11 molecular sieve is 0.1 ~ 2 micron.
3. the preparation method of polymethoxy dimethyl ether according to claim 1, is characterized in that described ZSM-11 molecular sieve concentration is that the alkali lye of 0.01 ~ 2 mol/L processes 0.1 ~ 10 hour at 30 ~ 100 DEG C; 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.
4. the preparation method of polymethoxy dimethyl ether according to claim 1, it is characterized in that the concentration of alkali lye is 0.1 ~ 1 mol/L, the treatment temp of alkali lye is 50 ~ 80 DEG C, and the treatment time is 0.5 ~ 4 hour, and alkali lye is 2 ~ 10 with the ratio of the weight of molecular sieve.
5. 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.
6. 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.
7. 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.
8. the preparation method of polymethoxy dimethyl ether according to claim 1, it is characterized in that temperature of reaction is 70 ~ 150 DEG C, reaction pressure is 0.5 ~ 6MPa.
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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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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 |
|---|
| ZSM-5分子筛碱处理的研究进展;赵亮等;《化学工程与装备》;20100430(第4期);103-105 * |
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