CN104549443B - polyformaldehyde dimethyl ether catalyst and application thereof - Google Patents
polyformaldehyde dimethyl ether catalyst and application thereof Download PDFInfo
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- CN104549443B CN104549443B CN201310512505.1A CN201310512505A CN104549443B CN 104549443 B CN104549443 B CN 104549443B CN 201310512505 A CN201310512505 A CN 201310512505A CN 104549443 B CN104549443 B CN 104549443B
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Abstract
The invention relates to a catalyst for synthesizing polyformaldehyde dimethyl ether, application of the catalyst in synthesis of polyformaldehyde dimethyl and a synthetic method of polyformaldehyde dimethyl ether. According to the catalyst, the application and the synthetic method, the problems that a catalyst has low selectivity to the polyformaldehyde dimethyl ether with a polymerization degree that n is equal to 2-10 and is low in yield in the prior art are mainly solved. The catalyst is a metal-ion-modified hydrogen type strong acid molecular sieve, wherein modifying metal is selected from at least one of Sn, Mn, Cu and Ti, and the exchange degree of the modifying metal in the catalyst is more than 0 and less than or equal to 50%. According to the technical scheme, the technical problems are well solved. The catalyst can be applied to the industrial production of the polyformaldehyde dimethyl ether.
Description
Technical field
The present invention relates to be used for polyoxymethylene dimethyl ether synthesis catalyst, the catalyst polyoxymethylene dimethyl ether synthesis in
Application and polyoxymethylene dimethyl ether synthetic method.
Background technology
In recent years, China's oil price is constantly high, and the petrol and diesel oil famine that takes place frequently；Petroleum resources growing tension, oil supply
Pressure unprecedentedly increases.Estimated following 10～20 years, China's oil supply rate only has 50% or so.Therefore Novel oil product succedaneum
Exploitation is increasingly subject to the attention of people.
Dimethyl ether is proposed as a kind of procetane earliest, yet with its own cold starting performance is poor, room temperature
Lower vapour pressure is high, easily produce vapour lock causes dimethyl ether significantly raised as the cost of vehicle alternative fuel.Polyoxymethylene dimethyl ether,
That is Polyoxymethylene dimethyl ethers (PODE), are the common names of a class material, and its skeleton symbol can be expressed as
CH3O(CH2O)nCH3, with higher octane number (>30) with oxygen content (42～51 %).When the value of n is 2～10, its
Physical property, combustibility and diesel oil closely, preferably resolve what dimethyl ether was present as derv fuel blend component
Defect.Polyoxymethylene dimethyl ether can improve diesel oil combustion position within the engine as new cleaning diesel component, improve
The thermal efficiency, reduces the particulate matter and CO in tail gasxAnd NOxDischarge.It is reported that, add 5～30% CH3OCH2OCH3Can drop
Low NOx7～10%, PM of discharge reduces by 5～35%.It is expected that China's diesel oil consumption figure in 2013 will be up to 1.64 hundred million tons, if there is 10% bavin
Oil is replaced by PODE, and China will reduce 16,000,000 tons to the importation dependence of diesel oil, and this is by with important energy resource safety strategy
Meaning.
PODE is usually to be increased with chain is provided by compound such as methanol, dimethoxym ethane, dimethyl ether etc. for providing end-blocking methyl
Section-（CH2O）- compound such as formaldehyde, metaformaldehyde, paraformaldehyde etc. react under acid catalysis be obtained.
In laboratory, polyoxymethylene dimethyl ether can be by oligomeric in 150～180 DEG C of heating in the presence of trace sulfuric acid or hydrochloric acid
Right paraformaldehyde or paraformaldehyde are prepared with the method for methanol reaction.In recent years, polyoxymethylene dimethyl ether synthetic technology is achieved
Progress.
US2,449,469 describes a kind of with dimethoxym ethane and paraformaldehyde as raw material, using sulphuric acid as catalyst high temperature system
The method of the polyoxymethylene dimethyl ether of standby n=2～4.
CN 101182367A are described using acidic ionic liquid as catalyst, are reaction by methanol and metaformaldehyde
The method of thing synthesizing polyoxymethylene dimethyl ether.CN 200910056820.1 and CN 200910056819.9 are described with methanol and three
Polyformaldehyde is that raw material prepares polyoxymethylene dimethyl ether under solid acid catalysis effect.But these techniques all have a general character, produce
In thing, 20～50%, dimethoxym ethane can reduce the flash-point of diesel fuel mixtures and therefore compromise which selectivity of by-product dimethoxym ethane
Quality so that product is unsuitable for as diesel fuel additives.Using methanol as raw material, water in reaction system, is unavoidably had
Generate；The presence of water can cause PODE yields to reduce, and be unfavorable for that product rectification is separated.
US5,746,785 and WO2006/045506A1 is described
Catalyst, the synthesis technique of the polyoxymethylene dimethyl ether with dimethoxym ethane and paraformaldehyde as raw material, although this bronsted acid catalyst
It is cheap and easy to get, but corrosivity are strong, it is difficult to separate, environmental pollution is big, and equipment is had high demands.CN101898943 and
Polyoxymethylene dimethyl ether is obtained using metal oxide supporting catalyst described in CN101972644.Although effectively avoiding this
Defect, but reaction conversion ratio is low, and yield is not high.
The content of the invention
One of the technical problem to be solved is prior art with dimethoxym ethane and polyformaldehyde as the poly- first of Material synthesis
A kind of low problem of poor selectivity, yield during aldehyde dimethyl ether, there is provided new catalysis for polyoxymethylene dimethyl ether synthesis
Agent.The catalyst is with the good product selectivity to polymerization degree n=2～10, the advantage of high income.
The two of the technical problem to be solved are the applications of catalyst corresponding with one of the problems referred to above.
The three of the technical problem to be solved are polyoxymethylene dimethyl ethers corresponding with one of above-mentioned technical problem
Synthetic method.
In order to solve one of above-mentioned technical problem, technical scheme is as follows：Polyoxymethylene dimethyl ether catalyst, it is described
Catalyst is metal ion-modified hydrogen type strong acid molecular sieve；The modified metal in Sn, Mn, Cu, Ti at least one
Kind, in the catalyst, the exchange degree of modified metal is ＞ 0 and≤50%.Particularly preferably the modified metal include Sn and Mn,
At least one in Cu, Ti；More preferably described modified metal includes Sn and Ti.When the modified metal includes Sn and Ti, most
The ratio for having the Sn exchange degrees and the exchange degree of Ti selected in the metal-modified acidic molecular sieve is 1:13~6:1.
In above-mentioned technical proposal, the purpose of the present invention can reach using any hydrogen type strong acid molecular sieve, but it is described
Highly acid molecular sieve is preferably the one kind in HZSM-5, HMCM-22, HUZM-5.
In order to solve the two of above-mentioned technical problem, technical scheme is as follows：The technology of one of above-mentioned technical problem
Application of the catalyst any one of scheme in polyoxymethylene dimethyl ether synthesis.
In order to solve the three of above-mentioned technical problem, technical scheme is as follows：The synthetic method of polyoxymethylene dimethyl ether,
In the presence of catalyst any one of technical scheme in one of above-mentioned technical problem, with dimethoxym ethane and polyformaldehyde as raw material,
Reaction generates polyoxymethylene dimethyl ether.
In above-mentioned technical proposal, dimethoxym ethane is preferably (0.5～10) with the mass ratio of polyformaldehyde: 1, more preferably（0.5～
3.0）∶1.
The temperature reacted in above-mentioned technical proposal is preferably 50～200 DEG C, more preferably 70～130 DEG C.
The pressure reacted in above-mentioned technical proposal is preferably 0～10MPa, more preferably 0.2～5.0 MPa.
In above-mentioned technical proposal, those skilled in the art can rationally determine the consumption of catalyst, but preferably raw material weight
0.1～10.0%, more preferably the 1.0～5.0% of amount.Response time is preferably 1-10h, more preferably 3～7h.
In the present invention, the exchange degree of metal-modified degree metal represents which has connotation generally in the art, is hydrogen
H in type molecular sieve+Ion is by the molal quantity percentage ratio of the metal exchange.
In the present invention, catalyst is metal-modified highly acid molecular sieve, and which not only maintains highly acid（Bronsted acid
Or B-acid）, and by proton exchange, a part of proton acid site is by lewis acid（L acid）Center replaces, so that catalysis is lived
Property center species have change, synergism can be produced between B-acid L acid, particularly when i.e. two kinds between modified different metal
Above L acid can produce higher synergism when compounding, and make catalysis activity higher.In addition, the inventive method is used, due to catalysis
Agent is metal-modified solid acid catalyst, therefore will not produce acid waste liquid, and catalyst is separated with product simply, and can be adopted
Recycle by-product with the method for distillation, thus the product yield high of polymerization degree n=2～10.Under the conditions of on year-on-year basis, without gold
The modified molecular sieve of category is only 41% for the product yield of catalyst n=2～10, and the product of catalyst n=2～10 of the present invention is received
Rate achieves preferable technique effect up to more than 60%.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
【Embodiment 1】
1st, prepare metal-modified acidic molecular sieve：By SiO2/Al2O3Mol ratio is that 100 Hydrogen ZSM-5 molecular sieve is placed in
16h is dried in 95 DEG C of baking ovens, the SnCl of dried hydrogen type molecular sieve 48g and 200 ml concentration for 0.02M is taken4Ethanol solution
Stirring reaction 15h together, with absolute ethanol washing 6 times, each 15min is dried 24h in transferring vacuum drying oven at 90 DEG C and obtains final product
To metal-modified acidic molecular sieve.
2nd, this molecular sieve catalyst of addition 2.44g, 60g dimethoxym ethanes and 60g trimerization first in 300 milliliters of tank reactors
Aldehyde, reacts 4h, under 90 DEG C and 0.4MPa self-generated pressures by gas chromatographic analysiss after extraction sample centrifugation.Wrap in product
Containing polyoxymethylene dimethyl ether and unreacted raw material, its composition distribution is shown in Table 1.
【Embodiment 2】
1st, prepare metal-modified acidic molecular sieve：By SiO2/Al2O3Mol ratio is that 100 Hydrogen ZSM-5 molecular sieve is placed in
16h is dried in 95 DEG C of baking ovens, the MnCl of dried hydrogen type molecular sieve 48g and 200 ml concentration for 0.02M is taken3Ethanol solution
Stirring reaction 15h together, with absolute ethanol washing 6 times, each 15min is dried 24h in transferring vacuum drying oven at 90 DEG C and obtains final product
To metal-modified acidic molecular sieve.
2nd, this molecular sieve catalyst of addition 2.43g, 60g dimethoxym ethanes and 60g trimerization first in 300 milliliters of tank reactors
Aldehyde, reacts 4h, under 90 DEG C and 0.4MPa self-generated pressures by gas chromatographic analysiss after extraction sample centrifugation.Include in product
Polyoxymethylene dimethyl ether and unreacted raw material, its composition distribution are shown in Table 1.
【Embodiment 3】
1st, prepare metal-modified acidic molecular sieve：By SiO2/Al2O3Mol ratio is that 100 Hydrogen ZSM-5 molecular sieve is placed in
16h is dried in 95 DEG C of baking ovens, the CuCl of dried hydrogen type molecular sieve 48g and 200 ml concentration for 0.02M is taken2Ethanol solution
Stirring reaction 15h together, with absolute ethanol washing 6 times, each 15min is dried 24h in transferring vacuum drying oven at 90 DEG C and obtains final product
To metal-modified acidic molecular sieve.
2nd, this molecular sieve catalyst of addition 2.45g, 60g dimethoxym ethanes and 60g trimerization first in 300 milliliters of tank reactors
Aldehyde, reacts 4h, under 90 DEG C and 0.4MPa self-generated pressures by gas chromatographic analysiss after extraction sample centrifugation.Include in product
Polyoxymethylene dimethyl ether and unreacted raw material, its composition distribution are shown in Table 1.
【Embodiment 4】
1st, prepare metal-modified acidic molecular sieve：By SiO2/Al2O3Mol ratio is that 100 Hydrogen ZSM-5 molecular sieve is placed in
16h is dried in 95 DEG C of baking ovens, the TiCl of dried hydrogen type molecular sieve 48g and 200 ml concentration for 0.02M is taken4Ethanol solution
Stirring reaction 15h together, with absolute ethanol washing 6 times, each 15min is dried 24h in transferring vacuum drying oven at 90 DEG C and obtains final product
To metal-modified acidic molecular sieve.
2nd, this molecular sieve catalyst of addition 2.42g, 60g dimethoxym ethanes and 60g trimerization first in 300 milliliters of tank reactors
Aldehyde, reacts 4h, under 90 DEG C and 0.4MPa self-generated pressures by gas chromatographic analysiss after extraction sample centrifugation.Wrap in product
Containing polyoxymethylene dimethyl ether and unreacted raw material, its composition distribution is shown in Table 1.
【Embodiment 5】
1st, prepare metal-modified acidic molecular sieve：By SiO2/Al2O3Mol ratio is that 100 Hydrogen ZSM-5 molecular sieve is placed in
16h is dried in 95 DEG C of baking ovens, the SnCl of dried hydrogen type molecular sieve 48g and 200 ml concentration for 0.01M is taken4Ethanol solution
15h is stirred together, with absolute ethanol washing 6 times, each 5min, is dried 24h in transferring vacuum drying oven at 90 DEG C；It is dried
Molecular sieve again with 200 ml concentration for 0.01M MnCl3Ethanol solution stirring reaction 15h together, with absolute ethanol washing 6 times,
15min, is dried 24h in transferring vacuum drying oven at 90 DEG C and obtains metal-modified acidic molecular sieve every time.
2nd, this molecular sieve catalyst of addition 2.44g, 60g dimethoxym ethanes and 60g trimerization first in 300 milliliters of tank reactors
Aldehyde, reacts 4h, under 90 DEG C and 0.4MPa self-generated pressures by gas chromatographic analysiss after extraction sample centrifugation.Include in product
Polyoxymethylene dimethyl ether and unreacted raw material, its composition distribution are shown in Table 1.
【Embodiment 6】
1st, prepare metal-modified acidic molecular sieve：By SiO2/Al2O3Mol ratio is that 100 Hydrogen ZSM-5 molecular sieve is placed in
16h is dried in 95 DEG C of baking ovens, the SnCl of dried hydrogen type molecular sieve 48g and 200 ml concentration for 0.01M is taken4Ethanol solution
15h is stirred together, with absolute ethanol washing 6 times, each 5min, is dried 24h in transferring vacuum drying oven at 90 DEG C；It is dried
Molecular sieve again with 200 ml concentration for 0.01M CuCl2Ethanol solution stirring reaction 15h together, with absolute ethanol washing 6 times,
15min, is dried 24h in transferring vacuum drying oven at 90 DEG C and obtains metal-modified acidic molecular sieve every time.
2nd, this molecular sieve catalyst of addition 2.45g, 60g dimethoxym ethanes and 60g trimerization first in 300 milliliters of tank reactors
Aldehyde, reacts 4h, under 90 DEG C and 0.4MPa self-generated pressures by gas chromatographic analysiss after extraction sample centrifugation.Include in product
Polyoxymethylene dimethyl ether and unreacted raw material, its composition distribution are shown in Table 1.
【Embodiment 7】
1st, prepare metal-modified acidic molecular sieve：By SiO2/Al2O3Mol ratio is that 100 Hydrogen ZSM-5 molecular sieve is placed in
16h is dried in 95 DEG C of baking ovens, the SnCl of dried hydrogen type molecular sieve 48g and 200 ml concentration for 0.01M is taken4Ethanol solution
15h is stirred together, with absolute ethanol washing 6 times, each 5min, is dried 24h in transferring vacuum drying oven at 90 DEG C；It is dried
Molecular sieve again with 200 ml concentration for 0.01M TiCl4Ethanol solution stirring reaction 15h together, with absolute ethanol washing 6 times,
15min, is dried 24h in transferring vacuum drying oven at 90 DEG C and obtains metal-modified acidic molecular sieve every time.
2nd, this molecular sieve catalyst of addition 2.43g, 60g dimethoxym ethanes and 60g trimerization first in 300 milliliters of tank reactors
Aldehyde, reacts 4h, under 90 DEG C and 0.4MPa self-generated pressures by gas chromatographic analysiss after extraction sample centrifugation.Include in product
Polyoxymethylene dimethyl ether and unreacted raw material, its composition distribution are shown in Table 1.
【Embodiment 8】
1st, prepare metal-modified acidic molecular sieve：By SiO2/Al2O3Mol ratio is that 100 Hydrogen ZSM-5 molecular sieve is placed in
16h is dried in 95 DEG C of baking ovens, the MnCl of dried hydrogen type molecular sieve 48g and 200 ml concentration for 0.01M is taken3Ethanol solution
15h is stirred together, with absolute ethanol washing 6 times, each 5min, is dried 24h in transferring vacuum drying oven at 90 DEG C；It is dried
Molecular sieve again with 200 ml concentration for 0.01M CuCl2Ethanol solution stirring reaction 15h together, with absolute ethanol washing 6 times,
15min, is dried 24h in transferring vacuum drying oven at 90 DEG C and obtains metal-modified acidic molecular sieve every time.
2nd, this molecular sieve catalyst of addition 2.44g, 60g dimethoxym ethanes and 60g trimerization first in 300 milliliters of tank reactors
Aldehyde, reacts 4h, under 90 DEG C and 0.4MPa self-generated pressures by gas chromatographic analysiss after extraction sample centrifugation.Include in product
Polyoxymethylene dimethyl ether and unreacted raw material, its composition distribution are shown in Table 1.
【Embodiment 9】
1st, prepare metal-modified acidic molecular sieve：By SiO2/Al2O3Mol ratio is that 100 Hydrogen ZSM-5 molecular sieve is placed in
16h is dried in 95 DEG C of baking ovens, the MnCl of dried hydrogen type molecular sieve 48g and 200 ml concentration for 0.01M is taken3Ethanol solution
15h is stirred together, with absolute ethanol washing 6 times, each 5min, is dried 24h in transferring vacuum drying oven at 90 DEG C；It is dried
Molecular sieve again with 200 ml concentration for 0.01M TiCl4Ethanol solution stirring reaction 15h together, with absolute ethanol washing 6 times,
15min, is dried 24h in transferring vacuum drying oven at 90 DEG C and obtains metal-modified acidic molecular sieve every time.
2nd, this molecular sieve catalyst of addition 2.42g, 60g dimethoxym ethanes and 60g trimerization first in 300 milliliters of tank reactors
Aldehyde, reacts 4h, under 90 DEG C and 0.4MPa self-generated pressures by gas chromatographic analysiss after extraction sample centrifugation.Include in product
Polyoxymethylene dimethyl ether and unreacted raw material, its composition distribution are shown in Table 1.
【Embodiment 10】
1st, prepare metal-modified acidic molecular sieve：By SiO2/Al2O3Mol ratio is that 100 Hydrogen ZSM-5 molecular sieve is placed in
16h is dried in 95 DEG C of baking ovens, the CuCl of dried hydrogen type molecular sieve 48g and 200 ml concentration for 0.01M is taken2Ethanol solution
15h is stirred together, with absolute ethanol washing 6 times, each 5min, is dried 24h in transferring vacuum drying oven at 90 DEG C；It is dried
Molecular sieve again with 200 ml concentration for 0.01M TiCl4Ethanol solution stirring reaction 15h together, with absolute ethanol washing 6 times,
15min, is dried 24h in transferring vacuum drying oven at 90 DEG C and obtains metal-modified acidic molecular sieve every time.
2nd, this molecular sieve catalyst of addition 2.43g, 60g dimethoxym ethanes and 60g trimerization first in 300 milliliters of tank reactors
Aldehyde, reacts 4h, under 90 DEG C and 0.4MPa self-generated pressures by gas chromatographic analysiss after extraction sample centrifugation.Include in product
Polyoxymethylene dimethyl ether and unreacted raw material, its composition distribution are shown in Table 1.
【Embodiment 11】
1st, prepare metal-modified acidic molecular sieve：By SiO2/Al2O3Mol ratio is that 100 Hydrogen ZSM-5 molecular sieve is placed in
16h is dried in 95 DEG C of baking ovens, the SnCl of dried hydrogen type molecular sieve 48g and 240 ml concentration for 0.01M is taken4Ethanol solution
15h is stirred together, with absolute ethanol washing 6 times, each 5min, is dried 24h in transferring vacuum drying oven at 90 DEG C；It is dried
Molecular sieve again with 160 ml concentration for 0.01M TiCl4Ethanol solution stirring reaction 15h together, with absolute ethanol washing 6 times,
15min, is dried 24h in transferring vacuum drying oven at 90 DEG C and obtains metal-modified acidic molecular sieve every time.
2nd, this molecular sieve catalyst of addition 2.43g, 60g dimethoxym ethanes and 60g trimerization first in 300 milliliters of tank reactors
Aldehyde, reacts 4h, under 90 DEG C and 0.4MPa self-generated pressures by gas chromatographic analysiss after extraction sample centrifugation.Include in product
Polyoxymethylene dimethyl ether and unreacted raw material, its composition distribution are shown in Table 1.
【Embodiment 12】
1st, prepare metal-modified acidic molecular sieve：By SiO2/Al2O3Mol ratio is that 100 Hydrogen ZSM-5 molecular sieve is placed in
16h is dried in 95 DEG C of baking ovens, the SnCl of dried hydrogen type molecular sieve 48g and 320 ml concentration for 0.01M is taken4Ethanol solution
15h is stirred together, with absolute ethanol washing 6 times, each 5min, is dried 24h in transferring vacuum drying oven at 90 DEG C；It is dried
Molecular sieve again with 80 ml concentration for 0.01M TiCl4Ethanol solution stirring reaction 15h together, with absolute ethanol washing 6 times,
15min, is dried 24h in transferring vacuum drying oven at 90 DEG C and obtains metal-modified acidic molecular sieve every time.
2nd, this molecular sieve catalyst of addition 2.44g, 60g dimethoxym ethanes and 60g trimerization first in 300 milliliters of tank reactors
Aldehyde, reacts 4h, under 90 DEG C and 0.4MPa self-generated pressures by gas chromatographic analysiss after extraction sample centrifugation.Include in product
Polyoxymethylene dimethyl ether and unreacted raw material, its composition distribution are shown in Table 1.
【Embodiment 13】
1st, prepare metal-modified acidic molecular sieve：By SiO2/Al2O3Mol ratio is that 100 Hydrogen ZSM-5 molecular sieve is placed in
16h is dried in 95 DEG C of baking ovens, the SnCl of dried hydrogen type molecular sieve 48g and 224 ml concentration for 0.01M is taken4Ethanol solution
15h is stirred together, with absolute ethanol washing 6 times, each 5min, is dried 24h in transferring vacuum drying oven at 90 DEG C；It is dried
Molecular sieve again with 176 ml concentration for 0.01M TiCl4Ethanol solution stirring reaction 15h together, with absolute ethanol washing 6 times,
15min, is dried 24h in transferring vacuum drying oven at 90 DEG C and obtains metal-modified acidic molecular sieve every time.
2nd, this molecular sieve catalyst of addition 2.43g, 60g dimethoxym ethanes and 60g trimerization first in 300 milliliters of tank reactors
Aldehyde, reacts 4h, under 90 DEG C and 0.4MPa self-generated pressures by gas chromatographic analysiss after extraction sample centrifugation.Include in product
Polyoxymethylene dimethyl ether and unreacted raw material, its composition distribution are shown in Table 1.
【Embodiment 14】
1st, prepare metal-modified acidic molecular sieve：By SiO2/Al2O3Mol ratio is that 100 Hydrogen ZSM-5 molecular sieve is placed in
16h is dried in 95 DEG C of baking ovens, the SnCl of dried hydrogen type molecular sieve 48g and 336 ml concentration for 0.01M is taken4Ethanol solution
15h is stirred together, with absolute ethanol washing 6 times, each 5min, is dried 24h in transferring vacuum drying oven at 90 DEG C；It is dried
Molecular sieve again with 64 ml concentration for 0.01M TiCl4Ethanol solution stirring reaction 15h together, with absolute ethanol washing 6 times,
15min, is dried 24h in transferring vacuum drying oven at 90 DEG C and obtains metal-modified acidic molecular sieve every time.
2nd, this molecular sieve catalyst of addition 2.44g, 60g dimethoxym ethanes and 60g trimerization first in 300 milliliters of tank reactors
Aldehyde, reacts 4h, under 90 DEG C and 0.4MPa self-generated pressures by gas chromatographic analysiss after extraction sample centrifugation.Include in product
Polyoxymethylene dimethyl ether and unreacted raw material, its composition distribution are shown in Table 1.
【Comparative example 1】
1st, molecular sieve pre-treatment：Hydrogen type molecular sieve is placed in 95 DEG C of baking ovens and is dried 16h, be placed in drying basin after cooling
It is standby.
2nd, this molecular sieve catalyst of addition 2.4g, 60g dimethoxym ethanes and 60g metaformaldehydes in 300 milliliters of tank reactors,
4h is reacted under 90 DEG C and 0.4MPa self-generated pressures, by gas chromatographic analysiss after extraction sample centrifugation.Comprising poly- in product
Formaldehyde dimethyl ether and unreacted raw material, its composition distribution are shown in Table 1.
It was found by the inventors of the present invention that the modified metal include Sn and at least one in Mn, Cu or Ti other
During metal, stronger interaction between Sn and other metals, is there occurs.And the interaction of Sn and Ti is most strong.This is from table 1
Intuitively can find out in the data on year-on-year basis of 1～embodiment of embodiment 14 and comparative example 1.Can also be from embodiment 15 in table 2 to reality
Intuitively find out in the data on year-on-year basis for applying example 28 and comparative example 2.
It was found by the inventors of the present invention that the modified metal include Sn and at least one in Mn, Cu or Ti other
During metal, stronger interaction between Sn and other metals, is there occurs.And the interaction of Sn and Ti is most strong.This is from table 1
Intuitively can find out in the data on year-on-year basis of 1～embodiment of embodiment 14 and comparative example 1.
【Embodiment 15】
1st, prepare metal-modified acidic molecular sieve：By SiO2/Al2O3Mol ratio is that 50 Hydrogen MCM-22 molecular sieves are placed in
16h is dried in 95 DEG C of baking ovens, the SnCl of dried hydrogen type molecular sieve 24g and 160 ml concentration for 0.02M is taken4Ethanol solution
Stirring reaction 15h together, with absolute ethanol washing 6 times, each 15min is dried 24h in transferring vacuum drying oven at 90 DEG C and obtains final product
To metal-modified acidic molecular sieve.
2nd, this molecular sieve catalyst of addition 4.87g, 80g dimethoxym ethanes and 40g poly first in 300 milliliters of tank reactors
Aldehyde, reacts 6h, under 115 DEG C and 0.6Pa self-generated pressures by gas chromatographic analysiss after extraction sample centrifugation.Include in product
Polyoxymethylene dimethyl ether and unreacted raw material, its composition distribution are shown in Table 2.
【Embodiment 16】
1st, prepare metal-modified acidic molecular sieve：By SiO2/Al2O3Mol ratio is that 50 Hydrogen MCM-22 molecular sieves are placed in
16h is dried in 95 DEG C of baking ovens, the MnCl of dried hydrogen type molecular sieve 24g and 160 ml concentration for 0.02M is taken3Ethanol solution
Stirring reaction 15h together, with absolute ethanol washing 6 times, each 15min is dried 24h in transferring vacuum drying oven at 90 DEG C and obtains final product
To metal-modified acidic molecular sieve.
2nd, this molecular sieve catalyst of addition 4.84g, 80g dimethoxym ethanes and 40g poly first in 300 milliliters of tank reactors
Aldehyde, reacts 6h, under 115 DEG C and 0.6MPa self-generated pressures by gas chromatographic analysiss after extraction sample centrifugation.Wrap in product
Containing polyoxymethylene dimethyl ether and unreacted raw material, its composition distribution is shown in Table 2.
【Embodiment 17】
1st, prepare metal-modified acidic molecular sieve：By SiO2/Al2O3Mol ratio is that 50 Hydrogen MCM-22 molecular sieves are placed in
16h is dried in 95 DEG C of baking ovens, the CuCl of dried hydrogen type molecular sieve 24g and 160 ml concentration for 0.02M is taken2Ethanol solution
Stirring reaction 15h together, with absolute ethanol washing 6 times, each 15min is dried 24h in transferring vacuum drying oven at 90 DEG C and obtains final product
To metal-modified acidic molecular sieve.
2nd, this molecular sieve catalyst of addition 4.87g, 80g dimethoxym ethanes and 40g poly first in 300 milliliters of tank reactors
Aldehyde, reacts 6h, under 115 DEG C and 0.6MPa self-generated pressures by gas chromatographic analysiss after extraction sample centrifugation.Wrap in product
Containing polyoxymethylene dimethyl ether and unreacted raw material, its composition distribution is shown in Table 2.
【Embodiment 18】
1st, prepare metal-modified acidic molecular sieve：By SiO2/Al2O3Mol ratio is that 100 Hydrogen ZSM-5 molecular sieve is placed in
16h is dried in 95 DEG C of baking ovens, the TiCl of dried hydrogen type molecular sieve 24g and 160 ml concentration for 0.02M is taken4Ethanol solution
Stirring reaction 15h together, with absolute ethanol washing 6 times, each 15min is dried 24h in transferring vacuum drying oven at 90 DEG C and obtains final product
To metal-modified acidic molecular sieve.
2nd, this molecular sieve catalyst of addition 4.83g, 80g dimethoxym ethanes and 40g poly first in 300 milliliters of tank reactors
Aldehyde, reacts 6h, under 115 DEG C and 0.6MPa self-generated pressures by gas chromatographic analysiss after extraction sample centrifugation.Wrap in product
Containing polyoxymethylene dimethyl ether and unreacted raw material, its composition distribution is shown in Table 2.
【Embodiment 19】
1st, prepare metal-modified acidic molecular sieve：By SiO2/Al2O3Mol ratio is that 50 Hydrogen MCM-22 molecular sieves are placed in
16h is dried in 95 DEG C of baking ovens, the SnCl of dried hydrogen type molecular sieve 24g and 80 ml concentration for 0.02M is taken4Ethanol solution one
Stirring 15h is played, and with absolute ethanol washing 6 times, each 5min, is dried 24h in vacuum drying oven being transferred at 90 DEG C；Dried point
Son sieve again with 80 ml concentration for 0.02M MnCl3Ethanol solution stirring reaction 15h together, with absolute ethanol washing 6 times, often
Secondary 15min, is dried 24h in transferring vacuum drying oven at 90 DEG C and obtains metal-modified acidic molecular sieve.
2nd, this molecular sieve catalyst of addition 4.86g, 80g dimethoxym ethanes and 40g poly first in 300 milliliters of tank reactors
Aldehyde, reacts 6h, under 115 DEG C and 0.6MPa self-generated pressures by gas chromatographic analysiss after extraction sample centrifugation.Wrap in product
Containing polyoxymethylene dimethyl ether and unreacted raw material, its composition distribution is shown in Table 2.
【Embodiment 20】
1st, prepare metal-modified acidic molecular sieve：By SiO2/Al2O3Mol ratio is that 50 Hydrogen MCM-22 molecular sieves are placed in
16h is dried in 95 DEG C of baking ovens, the SnCl of dried hydrogen type molecular sieve 24g and 80 ml concentration for 0.02M is taken4Ethanol solution one
Stirring 15h is played, and with absolute ethanol washing 6 times, each 5min, is dried 24h in vacuum drying oven being transferred at 90 DEG C；Dried point
Son sieve again with 80 ml concentration for 0.02M CuCl2Ethanol solution stirring reaction 15h together, with absolute ethanol washing 6 times, often
Secondary 15min, is dried 24h in transferring vacuum drying oven at 90 DEG C and obtains metal-modified acidic molecular sieve.
2nd, this molecular sieve catalyst of addition 4.87g, 80g dimethoxym ethanes and 40g poly first in 300 milliliters of tank reactors
Aldehyde, reacts 6h, under 115 DEG C and 0.6MPa self-generated pressures by gas chromatographic analysiss after extraction sample centrifugation.Wrap in product
Containing polyoxymethylene dimethyl ether and unreacted raw material, its composition distribution is shown in Table 2.
【Embodiment 21】
1st, prepare metal-modified acidic molecular sieve：By SiO2/Al2O3Mol ratio is that 50 Hydrogen MCM-22 molecular sieves are placed in
16h is dried in 95 DEG C of baking ovens, the SnCl of dried hydrogen type molecular sieve 24g and 80 ml concentration for 0.02M is taken4Ethanol solution one
Stirring 15h is played, and with absolute ethanol washing 6 times, each 5min, is dried 24h in vacuum drying oven being transferred at 90 DEG C；Dried point
Son sieve again with 80 ml concentration for 0.02M TiCl4Ethanol solution stirring reaction 15h together, with absolute ethanol washing 6 times, often
Secondary 15min, is dried 24h in transferring vacuum drying oven at 90 DEG C and obtains metal-modified acidic molecular sieve.
2nd, this molecular sieve catalyst of addition 4.85g, 80g dimethoxym ethanes and 40g poly first in 300 milliliters of tank reactors
Aldehyde, reacts 6h, under 115 DEG C and 0.6MPa self-generated pressures by gas chromatographic analysiss after extraction sample centrifugation.Wrap in product
Containing polyoxymethylene dimethyl ether and unreacted raw material, its composition distribution is shown in Table 2.
【Embodiment 22】
1st, prepare metal-modified acidic molecular sieve：By SiO2/Al2O3Mol ratio is that 50 Hydrogen MCM-22 molecular sieves are placed in
16h is dried in 95 DEG C of baking ovens, the MnCl of dried hydrogen type molecular sieve 24g and 80 ml concentration for 0.02M is taken3Ethanol solution one
Stirring 15h is played, and with absolute ethanol washing 6 times, each 5min, is dried 24h in vacuum drying oven being transferred at 90 DEG C；Dried point
Son sieve again with 80 ml concentration for 0.02M CuCl2Ethanol solution stirring reaction 15h together, with absolute ethanol washing 6 times, often
Secondary 15min, is dried 24h in transferring vacuum drying oven at 90 DEG C and obtains metal-modified acidic molecular sieve.
2nd, this molecular sieve catalyst of addition 4.86g, 80g dimethoxym ethanes and 40g poly first in 300 milliliters of tank reactors
Aldehyde, reacts 6h, under 115 DEG C and 0.6MPa self-generated pressures by gas chromatographic analysiss after extraction sample centrifugation.Wrap in product
Containing polyoxymethylene dimethyl ether and unreacted raw material, its composition distribution is shown in Table 2.
【Embodiment 23】
1st, prepare metal-modified acidic molecular sieve：By SiO2/Al2O3Mol ratio is that 50 Hydrogen MCM-22 molecular sieves are placed in
16h is dried in 95 DEG C of baking ovens, the MnCl of dried hydrogen type molecular sieve 24g and 80 ml concentration for 0.02M is taken3Ethanol solution one
Stirring 15h is played, and with absolute ethanol washing 6 times, each 5min, is dried 24h in vacuum drying oven being transferred at 90 DEG C；Dried point
Son sieve again with 80 ml concentration for 0.02M TiCl4Ethanol solution stirring reaction 15h together, with absolute ethanol washing 6 times, often
Secondary 15min, is dried 24h in transferring vacuum drying oven at 90 DEG C and obtains metal-modified acidic molecular sieve.
2nd, this molecular sieve catalyst of addition 4.84g, 80g dimethoxym ethanes and 40g poly first in 300 milliliters of tank reactors
Aldehyde, reacts 6h, under 115 DEG C and 0.6MPa self-generated pressures by gas chromatographic analysiss after extraction sample centrifugation.Wrap in product
Containing polyoxymethylene dimethyl ether and unreacted raw material, its composition distribution is shown in Table 2.
【Embodiment 24】
1st, prepare metal-modified acidic molecular sieve：By SiO2/Al2O3Mol ratio is that 50 Hydrogen MCM-22 molecular sieves are placed in
16h is dried in 95 DEG C of baking ovens, the CuCl of dried hydrogen type molecular sieve 24g and 80 ml concentration for 0.02M is taken2Ethanol solution one
Stirring 15h is played, and with absolute ethanol washing 6 times, each 5min, is dried 24h in vacuum drying oven being transferred at 90 DEG C；Dried point
Son sieve again with 80 ml concentration for 0.02M TiCl4Ethanol solution stirring reaction 15h together, with absolute ethanol washing 6 times, often
Secondary 15min, is dried 24h in transferring vacuum drying oven at 90 DEG C and obtains metal-modified acidic molecular sieve.
2nd, this molecular sieve catalyst of addition 4.85g, 80g dimethoxym ethanes and 40g poly first in 300 milliliters of tank reactors
Aldehyde, reacts 6h, under 115 DEG C and 0.6MPa self-generated pressures by gas chromatographic analysiss after extraction sample centrifugation.Wrap in product
Containing polyoxymethylene dimethyl ether and unreacted raw material, its composition distribution is shown in Table 2.
【Embodiment 25】
1st, prepare metal-modified acidic molecular sieve：By SiO2/Al2O3Mol ratio is that 50 Hydrogen MCM-22 molecular sieves are placed in
16h is dried in 95 DEG C of baking ovens, dried hydrogen type molecular sieve 24g is taken and the SnCl that 20ml concentration is 0.02M4Ethanol solution one
Stirring 15h is played, and with absolute ethanol washing 6 times, each 5min, is dried 24h in vacuum drying oven being transferred at 90 DEG C；Dried point
Son sieve again with 140ml concentration for 0.02M TiCl4Ethanol solution stirring reaction 15h together, with absolute ethanol washing 6 times, often
Secondary 15min, is dried 24h in transferring vacuum drying oven at 90 DEG C and obtains metal-modified acidic molecular sieve.
2nd, this molecular sieve catalyst of addition 4.83g, 80g dimethoxym ethanes and 40g poly first in 300 milliliters of tank reactors
Aldehyde, reacts 6h, under 115 DEG C and 0.6MPa self-generated pressures by gas chromatographic analysiss after extraction sample centrifugation.Wrap in product
Containing polyoxymethylene dimethyl ether and unreacted raw material, its composition distribution is shown in Table 2.
【Embodiment 26】
1st, prepare metal-modified acidic molecular sieve：By SiO2/Al2O3Mol ratio is that 50 Hydrogen MCM-22 molecular sieves are placed in
16h is dried in 95 DEG C of baking ovens, dried hydrogen type molecular sieve 24g is taken and the SnCl that 60ml concentration is 0.02M4Ethanol solution one
Stirring 15h is played, and with absolute ethanol washing 6 times, each 5min, is dried 24h in vacuum drying oven being transferred at 90 DEG C；Dried point
Son sieve again with 100 ml concentration for 0.02M TiCl4Ethanol solution stirring reaction 15h together, with absolute ethanol washing 6 times, often
Secondary 15min, is dried 24h in transferring vacuum drying oven at 90 DEG C and obtains metal-modified acidic molecular sieve.
2nd, this molecular sieve catalyst of addition 4.84g, 80g dimethoxym ethanes and 40g poly first in 300 milliliters of tank reactors
Aldehyde, reacts 6h, under 115 DEG C and 0.6MPa self-generated pressures by gas chromatographic analysiss after extraction sample centrifugation.Wrap in product
Containing polyoxymethylene dimethyl ether and unreacted raw material, its composition distribution is shown in Table 2.
【Embodiment 27】
1st, prepare metal-modified acidic molecular sieve：By SiO2/Al2O3Mol ratio is that 50 Hydrogen MCM-22 molecular sieves are placed in
16h is dried in 95 DEG C of baking ovens, the SnCl of dried hydrogen type molecular sieve 24g and 12 ml concentration for 0.02M is taken4Ethanol solution one
Stirring 15h is played, and with absolute ethanol washing 6 times, each 5min, is dried 24h in vacuum drying oven being transferred at 90 DEG C；Dried point
Son sieve again with 148ml concentration for 0.02M TiCl4Ethanol solution stirring reaction 15h together, with absolute ethanol washing 6 times, often
Secondary 15min, is dried 24h in transferring vacuum drying oven at 90 DEG C and obtains metal-modified acidic molecular sieve.
2nd, this molecular sieve catalyst of addition 4.83g, 80g dimethoxym ethanes and 40g poly first in 300 milliliters of tank reactors
Aldehyde, reacts 6h, under 115 DEG C and 0.6MPa self-generated pressures by gas chromatographic analysiss after extraction sample centrifugation.Wrap in product
Containing polyoxymethylene dimethyl ether and unreacted raw material, its composition distribution is shown in Table 2.
【Embodiment 28】
1st, prepare metal-modified acidic molecular sieve：By SiO2/Al2O3Mol ratio is that 50 Hydrogen MCM-22 molecular sieves are placed in
16h is dried in 95 DEG C of baking ovens, the SnCl of dried hydrogen type molecular sieve 24g and 68 ml concentration for 0.02M is taken4Ethanol solution one
Stirring 15h is played, and with absolute ethanol washing 6 times, each 5min, is dried 24h in vacuum drying oven being transferred at 90 DEG C；Dried point
Son sieve again with 92 ml concentration for 0.02M TiCl4Ethanol solution stirring reaction 15h together, with absolute ethanol washing 6 times, often
Secondary 15min, is dried 24h in transferring vacuum drying oven at 90 DEG C and obtains metal-modified acidic molecular sieve.
2nd, this molecular sieve catalyst of addition 4.85g, 80g dimethoxym ethanes and 40g poly first in 300 milliliters of tank reactors
Aldehyde, reacts 6h, under 115 DEG C and 0.6MPa self-generated pressures by gas chromatographic analysiss after extraction sample centrifugation.Wrap in product
Containing polyoxymethylene dimethyl ether and unreacted raw material, its composition distribution is shown in Table 2.
【Comparative example 2】
1st, molecular sieve pre-treatment：By SiO2/Al2O3Mol ratio is that 50 Hydrogen MCM-22 molecular sieves are placed in 95 DEG C of baking ovens
16h is dried, is placed in after cooling standby in drying basin.
2nd, this molecular sieve catalyst of addition 4.8g, 80g dimethoxym ethanes and 40g paraformaldehydes in 300 milliliters of tank reactors,
6h is reacted under 115 DEG C and 0.6MPa self-generated pressures, by gas chromatographic analysiss after extraction sample centrifugation.Comprising poly- in product
Formaldehyde dimethyl ether and unreacted raw material, its composition distribution are shown in Table 2.
It was found by the inventors of the present invention that the modified metal include Sn and at least one in Mn, Cu or Ti other
During metal, stronger interaction between Sn and other metals, is there occurs.And the interaction of Sn and Ti is most strong.This is from table 2
Intuitively can find out in the data on year-on-year basis of embodiment 15 to embodiment 28 and comparative example 2.
Table 1（It is continued）
N is the degree of polymerization, and constituent content is represented with wt%
Table 1（It is continuous）
Table 2（It is continued）
N is the degree of polymerization, and constituent content is represented with wt%
Table 2（It is continuous）
| The product of n=4 | The product of n=5～10 | Other | N=2～10 product is amounted to | |
| Embodiment 15 | 9.9 | 7.0 | Surplus | 56.3 |
| Embodiment 16 | 7.9 | 6.1 | Surplus | 47 |
| Embodiment 17 | 8.1 | 6.6 | Surplus | 48.7 |
| Embodiment 18 | 9.2 | 6.7 | Surplus | 52.6 |
| Embodiment 19 | 10.9 | 7.3 | Surplus | 61.2 |
| Embodiment 20 | 11.7 | 7.7 | Surplus | 62.5 |
| Embodiment 21 | 12.6 | 8.2 | Surplus | 63.6 |
| Embodiment 22 | 6.8 | 5.9 | Surplus | 48.3 |
| Embodiment 23 | 9.5 | 6.9 | Surplus | 52.5 |
| Embodiment 24 | 9.8 | 7.6 | Surplus | 54.3 |
| Embodiment 25 | 14.8 | 8.0 | Surplus | 67.1 |
| Embodiment 26 | 14.5 | 7.9 | Surplus | 67.7 |
| Embodiment 27 | 12.5 | 8.4 | Surplus | 65.5 |
| Embodiment 28 | 12.9 | 8.5 | Surplus | 65.2 |
| Comparative example 2 | 7.6 | 6.2 | Surplus | 45.9 |
Claims (8)
1. polyoxymethylene dimethyl ether catalyst, the catalyst is metal ion-modified hydrogen type strong acid molecular sieve；It is described modified
Metal includes Sn and at least one in Mn, Cu, Ti, in the catalyst exchange degree of modified metal be ＞ 0 and≤
50%.
2. catalyst according to claim 1, it is characterised in that the hydrogen type strong acid molecular sieve is HZSM-5, HMCM-
22nd, one kind in HUZM-5.
3. application of the catalyst any one of claim 1 to 2 in polyoxymethylene dimethyl ether synthesis.
4. the synthetic method of polyoxymethylene dimethyl ether, in the presence of catalyst any one of claim 1 to 2, with dimethoxym ethane
It is raw material with polyformaldehyde, reacts and generate polyoxymethylene dimethyl ether.
5. synthetic method according to claim 4, it is characterised in that dimethoxym ethane is (0.5～10) with the mass ratio of polyformaldehyde
∶1。
6. synthetic method according to claim 4, it is characterised in that the temperature of reaction is 50～200 DEG C.
7. synthetic method according to claim 4, it is characterised in that the pressure of reaction is 0～10MPa.
8. synthetic method according to claim 4, it is characterised in that catalyst amount for raw material weight 0.1～
10.0%.
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