CN103739458B - The preparation method of polyoxymethylene dimethyl ethers - Google Patents

The preparation method of polyoxymethylene dimethyl ethers Download PDF

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Publication number
CN103739458B
CN103739458B CN201210392998.5A CN201210392998A CN103739458B CN 103739458 B CN103739458 B CN 103739458B CN 201210392998 A CN201210392998 A CN 201210392998A CN 103739458 B CN103739458 B CN 103739458B
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polyoxymethylene dimethyl
dimethyl ethers
catalyzer
preparation
reaction
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CN103739458A (en
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何欣
袁志庆
滕加伟
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • C07C41/50—Preparation of compounds having groups by reactions producing groups
    • C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones

Abstract

The present invention relates to a kind of preparation method of polyoxymethylene dimethyl ethers, mainly there is catalyzer in solution prior art and there is corrosive problem.The present invention is by adopting with methyl alcohol or dme and formaldehyde or trioxymethylene as 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 polyoxymethylene dimethyl ethers; The technical scheme that catalyzer wherein used is selected from least one in Al-MCM-41, Al-MCM-48, Al-SBA-15, Al-HMS, Al-MSU-1 or Al-MSU-2 solves this problem preferably, can be used in the industrial production of polyoxymethylene dimethyl ethers.

Description

The preparation method of polyoxymethylene dimethyl ethers
Technical field
The present invention relates to a kind of preparation method of polyoxymethylene dimethyl ethers.
Background technology
(Chinese also can be polyoxymethylene dimethyl ether to polyoxymethylene dimethyl ethers, polymethoxy methylal, polymethoxy dimethyl ether, polyoxymethylene dimethyl ethers, polymethoxy dimethyl ether, polyoxy methylene dimethyl ether etc.), i.e. polyoxymethylenedimethylethers (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 (cetanenumber, 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.
Polyoxymethylene dimethyl ethers 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, the method using sulfuric acid as the polyoxymethylene dimethyl ethers 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 polyoxymethylene dimethyl ethers 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 polyoxymethylene dimethyl ethers 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 polyoxymethylene dimethyl ethers.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, 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 polyoxymethylene dimethyl ethers; Catalyst levels is 0.01 ~ 15% of reaction raw materials weight; Catalyzer wherein used is selected from least one in Al-MCM-41, Al-MCM-48, Al-SBA-15, Al-HMS, Al-MSU-1 or Al-MSU-2.
In technique scheme, described catalyzer preferred version is at least one be selected from Al-MCM-41, Al-MCM-48, Al-SBA-15 or Al-HMS.The SiO of described catalyzer 2/ Al 2o 3mol ratio preferable range is 10 ~ 300, and more preferably scope is 20 ~ 200, and most preferred range is 40 ~ 150.Methyl alcohol or dme: formaldehyde or trioxymethylene mol ratio preferable range are 1:(0.5 ~ 5), more preferably scope is 1:(1 ~ 3.5).Formaldehyde can be the formaldehyde solution of 10 ~ 80 % by weight, 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.
The mesopore molecular sieve containing aluminium used in the present invention; commercially available product can be used; also can according to document CatalysisLetters; 1997; 44:123 ~ 128 (Al-MCM-41), SCI; 1999; 20 (3): 344 ~ 349 (Al-MCM-48); the heteroatoms nitrate just used is aluminum nitrate, catalysis journal; 2006; 27 (1): 9-~ 4 (Al-SBA-15), ChemistryofMaterials, 1996,8 (1): 114 ~ 122 (Al-HMS) disclosed method preparation.
The present inventor finds uncannily, adopts the mesoporous molecular sieve catalyst containing aluminium, because specific surface area of catalyst is comparatively large, surface hydroxyl is more, makes catalyst activity and target product selectivity significantly improve.Adopt the inventive method, under temperature 120 DEG C, pressure 6MPa react 2 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.
Further instruction is given to the present invention below by embodiment.
Embodiment
[embodiment 1]
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.Catalyzer is Al-MCM-41, its SiO 2/ Al 2o 3mol ratio is 50.
[embodiment 2]
By each step of [embodiment 1], just catalyzer adopts different catalyzer, adds 1.5 grams of catalyzer, 100 grams of methyl alcohol, 150 grams of trioxymethylenes, and at 120 DEG C with react 2 hours made pressure be 6MPa by inflated with nitrogen under, concrete test conditions and reaction result are in table 1.
[embodiment 3]
By each step of [embodiment 1], just catalyzer adopts different catalyzer, adds 2 grams of catalyzer, 80 grams of methyl alcohol, 200 grams of trioxymethylenes, and at 130 DEG C with react 5 hours made pressure be 4MPa by inflated with nitrogen under, concrete test conditions and reaction result are in table 1.
[embodiment 4]
By each step of [embodiment 1], just catalyzer adopts different catalyzer, adds 1.5 grams of catalyzer in autoclave, 50 grams of methyl alcohol, 30 grams of dme, 100 grams of formaldehyde, 100 DEG C and made pressure be 3MPa by inflated with nitrogen under react 5 hours, concrete test conditions and reaction result are in table 1.
[embodiment 5]
By each step of [embodiment 1], just catalyzer adopts different catalyzer, adds 1 gram of catalyzer, 80 grams of methyl alcohol, 100 grams of formaldehyde, and at 80 DEG C with react 10 hours made pressure be 1MPa by inflated with nitrogen under, concrete test conditions and reaction result are in table 1.
[embodiment 6]
By each step of [embodiment 1], just catalyzer adopts different catalyzer, adds 0.9 gram of catalyzer, 50 grams of methyl alcohol, 30 grams of dme, 100 grams of formaldehyde, 120 DEG C and made pressure be 4MPa by inflated with nitrogen under react 5 hours, concrete test conditions and reaction result are in table 1.
[comparative example 1]
Silica MCM-41 is catalyzer.By the condition evaluating catalyst performance of [embodiment 1], reaction result is in table 1.
Table 1

Claims (8)

1. the preparation method of a polyoxymethylene dimethyl ethers, 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 polyoxymethylene dimethyl ethers; Catalyst levels is 0.01 ~ 15% of reaction raw materials weight; Catalyzer wherein used is selected from least one in Al-MCM-41, Al-MCM-48, Al-SBA-15, Al-HMS, Al-MSU-1 or Al-MSU-2; The SiO of described catalyzer 2/ Al 2o 3mol ratio is 10 ~ 300; Methyl alcohol or dme: formaldehyde or trioxymethylene mol ratio are 1:(0.5 ~ 5).
2. the preparation method of polyoxymethylene dimethyl ethers according to claim 1, is characterized in that described catalyzer is selected from least one in Al-MCM-41, Al-MCM-48, Al-SBA-15 or Al-HMS.
3. the preparation method of polyoxymethylene dimethyl ethers according to claim 1, is characterized in that the SiO of described catalyzer 2/ Al 2o 3mol ratio is 20 ~ 200.
4. the preparation method of polyoxymethylene dimethyl ethers according to claim 3, is characterized in that the SiO of described catalyzer 2/ Al 2o 3mol ratio is 40 ~ 150.
5. the preparation method of polyoxymethylene dimethyl ethers according to claim 1, is characterized in that methyl alcohol or dme: formaldehyde or trioxymethylene mol ratio are 1:(1 ~ 3.5).
6. 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.
7. the preparation method of polyoxymethylene dimethyl ethers according to claim 1, is characterized in that temperature of reaction is 70 ~ 150 DEG C.
8. the preparation method of polyoxymethylene dimethyl ethers according to claim 1, is characterized in that reaction pressure is 0.5 ~ 6MPa.
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CN104058940B (en) * 2014-06-30 2015-10-14 西安市尚华科技开发有限责任公司 Methyl alcohol synthesizes the method for polymethoxy dimethyl ether through condensation, oxidation, polycondensation and etherificate
CN104086380B (en) * 2014-07-07 2016-04-20 中国科学院山西煤炭化学研究所 The preparation method of polymethoxy 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)
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
CN105601479B (en) * 2016-02-03 2017-12-08 陕西恒华能源科技有限公司 A kind of preparation method of polymethoxy dimethyl ether
CN105753666A (en) * 2016-05-10 2016-07-13 中国人民解放军总后勤部油料研究所 Method for preparing polyoxymethylene dimethyl ether
CN106957402B (en) * 2017-03-31 2019-05-07 四川达兴能源股份有限公司 A kind of preparation method of low cost polymethoxy dibutyl ethers

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CN101993356A (en) * 2009-08-31 2011-03-30 中国石油化工股份有限公司上海石油化工研究院 Method for preparing daicel dimethyl ether
CN102040489A (en) * 2009-10-13 2011-05-04 中国石油化工股份有限公司 Method for synthesizing polyformaldehyde dimethyl ether
CN102249870A (en) * 2011-07-14 2011-11-23 河南煤业化工集团研究院有限责任公司 Method for preparing polyoxyether

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WO2006045506A1 (en) * 2004-10-25 2006-05-04 Basf Aktiengesellschaft Method for producing polyoxymethylene dimethyl ethers

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CN101993356A (en) * 2009-08-31 2011-03-30 中国石油化工股份有限公司上海石油化工研究院 Method for preparing daicel dimethyl ether
CN102040489A (en) * 2009-10-13 2011-05-04 中国石油化工股份有限公司 Method for synthesizing polyformaldehyde dimethyl ether
CN102249870A (en) * 2011-07-14 2011-11-23 河南煤业化工集团研究院有限责任公司 Method for preparing polyoxyether

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