CN103772165A - Method for preparing polyoxymethylene dimethyl ether from paraformaldehyde - Google Patents

Method for preparing polyoxymethylene dimethyl ether from paraformaldehyde Download PDF

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Publication number
CN103772165A
CN103772165A CN201210412560.9A CN201210412560A CN103772165A CN 103772165 A CN103772165 A CN 103772165A CN 201210412560 A CN201210412560 A CN 201210412560A CN 103772165 A CN103772165 A CN 103772165A
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paraformaldehyde
polyoxymethylene dimethyl
dimethyl ether
raw material
reaction
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CN103772165B (en
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高晓晨
杨为民
刘志成
高焕新
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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

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Abstract

The invention relates to a method for preparing polyoxymethylene dimethyl ether from paraformaldehyde, and mainly solves the problem in the prior art that the cost is relative high when triformol is adopted as a raw material to synthesize polyoxymethylene dimethyl ether. According to the invention, methanol, dimethoxymethane, and paraformaldehyde are adopted as raw materials, wherein the mass ratio of methanol : dimethoxymethane : paraformaldehyde is (0-10) : (0-10) : 1, wherein the quantities of methanol and dimethoxymethane cannot both be 0; the catalyst is chosen from at least one component of the following tombarthite modified solid superacid: SO4<2->/ZrO2-La2O3, SO4<2->/ZrO2-Ce2O3, Cl<->/TiO2-La2O3, Cl<->/TiO2-Ce2O3, Cl<->/Fe2O3-Ce2O3, SO4<2->/Al2O3-La2O3 or S2O8<2->/ZrO2-La2O3. The technical scheme excellently solves the problem, and can be applied to the industrial production of polyoxymethylene dimethyl ether.

Description

By the method for paraformaldehyde polyoxymethylene dimethyl ethers processed
Technical field
The present invention relates to a kind of method by paraformaldehyde polyoxymethylene dimethyl ethers processed, particularly about a kind of method take paraformaldehyde as raw material synthesizing polyoxymethylene dme.
Background technology
In recent years, along with Industrial Revolution impact increasingly deeply and the resource general layout of China's distinctive " many coals, few oil, have gas ", China's oil resource growing tension, oil supply pressure unprecedentedly increases.Future 10～20 years, China's oil supply rate only has～and 50%.How to utilize the energy dilemma of coal resources solution China of China's abundant just to become researcher urgent problem.Therefore be day by day subject to people's attention by the oil product substitute of coal-based methanol development of new.
Dme is suggested the earliest as a kind of procetane, however because himself cold starting performance is poor, under normal temperature vapour pressure high, easily produce vapour lock dme obviously raise as the cost of vehicle alternative fuel.Polyoxymethylene dimethyl ether, i.e. Polyoxymethylene dimethyl ethers (PODE), is the common name of a class material, its skeleton symbol can be expressed as CH 3o (CH 2o) ncH 3, there is higher octane value (> 30) and oxygen level (42～51%).In the time that the value of n is 2～10, its physical properties, combustionproperty and diesel oil are very approaching, preferably resolve the defect that dme exists as derv fuel oil blend component.Therefore polyoxymethylene dimethyl ether can be used as novel clean diesel component, and the addition in diesel oil can reach 30% (v/v), can improve the combustion position of diesel oil in engine, improves thermo-efficiency, reduces particulate matter and CO in tail gas xand NO xdischarge.It is reported, add 5～30% CH 3oCH 2oCH 3can reduce NO xdischarge 7～10%, PM reduces by 5～35%.By coal-based methanol, synthetic PODE not only can replace part diesel oil, can also improve the efficiency of combustion of diesel oil, reduces the harm of diesel combustion to environment, has important strategic importance and good economic worth.
Prepared by the method that in laboratory, polyoxymethylene dimethyl ether reacts with methyl alcohol in 150～180 ℃ of heating low polymerization degree paraformaldehydes or paraformaldehyde under can existing by trace sulfuric acid or hydrochloric acid.In recent years, polyoxymethylene dimethyl ether synthetic technology has obtained progress.
CN 101182367A has introduced employing acidic ionic liquid as catalyzer, is the method for reactant synthesizing polyoxymethylene dme by methyl alcohol and trioxymethylene.US5,746,785 have described take protonic acid (as formic acid, sulfuric acid and trifluoromethanesulfonic acid) as catalyzer with WO2006/045506A1, synthesis technique take methylal and trioxymethylene as the polyoxymethylene dimethyl ether of raw material, although this bronsted acid catalyst is cheap and easy to get, corrodibility is strong, is difficult to separate, environmental pollution is large, to equipment require high.We have also developed employing solid acid catalyst (molecular sieve CN 200910056820.1, solid super-strong acid CN 200910056819.9) ourselves and have prepared polyoxymethylene dimethyl ether take methyl alcohol and trioxymethylene as raw material.
But these techniques all adopt trioxymethylene to be reaction raw materials, known according to market study, the price of trioxymethylene is 14000 yuan/ton; The price of contrast paraformaldehyde, only has 5000 yuan/ton.We are not difficult to find, can greatly reduce production cost take paraformaldehyde as raw material production polyoxymethylene dimethyl ether.
Summary of the invention
That prior art exists because raw material trioxymethylene price is high take methyl alcohol and trioxymethylene in raw material synthesizing polyoxymethylene dme technique in technical problem to be solved by this invention, can cause the problem that production cost is higher, a kind of new method by paraformaldehyde polyoxymethylene dimethyl ethers processed is provided.It is cheap that the method has raw material paraformaldehyde, the advantage that production cost is low.
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 method by paraformaldehyde polyoxymethylene dimethyl ethers processed, with methyl alcohol, methylal and paraformaldehyde are raw material, wherein methyl alcohol: methylal: the mass ratio of paraformaldehyde is 0～10: 0～10: 1, the consumption of methyl alcohol and methylal can not be 0 simultaneously, it is 70～200 ℃ in temperature of reaction, reaction pressure is under 0.2～6MPa condition, raw material contacts with catalyzer, reaction generates polyoxymethylene dimethyl ether, wherein catalyzer used is selected from following: at least one in rare earth modified solid super-strong acid: SO 4 2-/ ZrO 2-La 2o 3, SO 4 2-/ ZrO 2-Ce 2o 3, Cl -/ TiO 2-La 2o 3, Cl -/ TiO 2-Ce 2o 3, Cl -/ Fe 2o 3-Ce 2o 3, SO 4 2-/ Al 2o 3-La 2o 3or S 2o 8 2-/ ZrO 2-La 2o 3, 0.05～10 % that catalyst levels is raw material weight.
In technique scheme, catalyst levels preferable range is raw material weight 0.1～5%.Methyl alcohol: methylal: the quality of paraformaldehyde is 0.2～10: 0.5～10 than preferable range: 1.The preferable range of temperature of reaction is 100～150 ℃.Reaction pressure preferable range is 0.4～4.0MPa.The polymerization degree of described paraformaldehyde is preferably 2～8, and more preferably 4～6.Catalyzed reaction makes polyoxymethylene dimethyl ether, can be by filtering or centrifugal mode separating catalyst and liquid phase reaction thing.
In technique scheme, from the invention technical problem that will solve, with prior art effect on year-on-year basis, the reaction times is not key point of the present invention, but control and the consideration of time efficiency other factors from operation, conventionally will control in the reaction times is 1 to 20 hour.The reaction times adopting in the embodiment of the present invention is 4～12 hours.
In technique scheme, described rare earth modified solid super-strong acid SO 4 2-/ ZrO 2-La 2o 3, SO 4 2-/ ZrO 2-Ce 2o 3, Cl -/ TiO 2-La 2o 3, Cl -/ TiO 2-Ce 2o 3, Cl -/ Fe 2o 3-Ce 2o 3, SO 4 2-/ Al 2o 3-La 2o 3and S 2o 8 2-/ ZrO 2-La 2o 3be known substance, can be used for the present invention and solve the technology of the present invention problem; Wherein solid super strong acid content is preferably 0.05～20% of rare earth weight, and the metal oxide in rare earth and the mol ratio of nonmetal oxide are preferably 0.1 ~ 500.
The polymerization degree of paraformaldehyde adopts Arbiso process or iodometric determination, method comes from: Chen Yongjie, and Zhao Hui, Shao Yong waits so long. the preparation of the polymerization degree measurement of industrial paraformaldehyde and low polymerization degree paraformaldehyde, Shenyang Institute of Chemical Technology journal, 15 (2): 2001.
In the present invention, be catalyzer owing to using rare earth modified solid super-strong acid, can realize methyl alcohol, methylal and paraformaldehyde catalyzed reaction synthesizing polyoxymethylene dme, replace the trioxymethylene in traditional raw material.Because the method can paraformaldehyde be raw material, the inexpensive production cost that makes is lower.And products distribution is even.Take rare earth modified solid super-strong acid as catalyzer, in solid super-strong acid, introducing rare earth element can make catalyst surface in keeping B acid site, produce new L acid site, improve thermostability, adjusting surface acid center intensity and density, the antitoxin thing ability of increase, the improved mechanical strength of B acid in catalyzer, thereby improve the productive rate of polyoxymethylene dimethyl ether, extended the work-ing life of catalyzer.Used catalyst contains extremely strong acidity, method by distillation obtains methylal from the reaction product of methyl alcohol and paraformaldehyde, make by product methylal circulation enter acid catalysis system again with polyformaldehyde reaction, therefore can keep higher reaction conversion ratio and product yield.Using the inventive method, is 70～200 ℃ in temperature of reaction, and reaction pressure is under 0.2～6MPa condition, uses methyl alcohol, methylal and polyformaldehyde reaction, and its result is as follows: the first, and production cost is lower; The second, catalyzer separates simple with reaction product, adopts the way of distillation to make by product circulating reaction, and therefore the yield of product n=2～10 is good, and selectivity is up to 81.5%.Obtain good technique effect.
Below by embodiment, the present invention is further elaborated, the polymerization degree of the raw material paraformaldehyde adopting in embodiment is 5, take paraformaldehyde as benchmark, the polyoxymethylene dimethyl ether take the polymerization degree as 2 ~ 10 calculates as target product selectivity of product, and in comparative example, the selectivity of product is take trioxymethylene as benchmark.
Embodiment
[embodiment 1]
In 300 milliliters of tank reactors, add 2 grams of catalyst S O 4 2-/ ZrO 2-La 2o 3, wherein SO 4 2-content is ZrO 2-La 2o 35% of weight, ZrO 2with La 2o 3mol ratio be 1,100 gram of methyl alcohol and 100 grams of paraformaldehydes, under 130 ℃ and 0.8MPa autogenous pressure, react 4h, extract after sample centrifugation by gas chromatographic analysis.In product, comprise polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde, its composition distributes as table 1.
[embodiment 2]
In 300 milliliters of tank reactors, add 2 grams of catalyst S O 4 2-/ ZrO 2-Ce 2o 3, wherein SO 4 2-content is ZrO 2-La 2o 310% of weight, ZrO 2with La 2o 3mol ratio be 10,100 grams of methyl alcohol and 100 grams of paraformaldehydes, under 130 ℃ and 0.6 MPa autogenous pressure, react 4h, extract after sample centrifugation by gas chromatographic analysis.In product, comprise polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde, its composition distributes as table 1.
[embodiment 3]
In 300 milliliters of tank reactors, add 2 grams of catalyzer Cl -/ TiO 2-La 2o 3, wherein Cl -content is TiO 2-La 2o 35% of weight, TiO 2with La 2o 3mol ratio be 20,100 grams of methylals and 100 grams of paraformaldehydes, under 130 ℃ and 0.6 MPa autogenous pressure, react 4h, extract after sample centrifugation by gas chromatographic analysis.In product, comprise polyoxymethylene dimethyl ether and unreacted raw material methylal and paraformaldehyde, its composition distributes as table 1.
[embodiment 4]
In 300 milliliters of tank reactors, add 2 grams of catalyzer Cl -/ TiO 2-Ce 2o 3, wherein Cl -content is TiO 2-Ce 2o 310% of weight, TiO 2with Ce 2o 3mol ratio be 200,100 grams of distillation sample (methylal of 87wt%, all the other be methyl alcohol) and 100 grams of paraformaldehydes, at 130 ℃, under 0.7MPa autogenous pressure, react 4h, after the centrifugation of extraction sample by through gas chromatographic analysis.In product, comprise polyoxymethylene dimethyl ether and unreacted raw material methylal and paraformaldehyde, its composition distributes as table 1.
[embodiment 5]
In 300 milliliters of tank reactors, add 2 grams of catalyst S 2o 8 2-/ ZrO 2-La 2o 3, wherein S 2o 8 2-content is ZrO 2-La 2o 35% of weight, ZrO 2with La 2o 3mol ratio be 5,100 grams of methyl alcohol and 50 grams of paraformaldehydes, at 130 ℃, under 0.7MPa autogenous pressure, react 4h, extract after sample centrifugation by through gas chromatographic analysis.In product, comprise polyoxymethylene dimethyl ether and unreacted raw material methylal and paraformaldehyde, its composition distributes as table 1.
[embodiment 6]
In 300 milliliters of tank reactors, add 2 grams of catalyst S O 4 2-/ ZrO 2-La 2o 3, wherein SO 4 2-content is ZrO 2-La 2o 320% of weight, ZrO 2with La 2o 3mol ratio be 100,100 grams of methyl alcohol and 100 grams of paraformaldehydes, at 80 ℃ of reaction 4h, extract after sample centrifugation by gas chromatographic analysis.In product, comprise polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde, its composition distributes as table 1.
[embodiment 7]
In 300 milliliters of tank reactors, add 0.5 gram of catalyst S O 4 2-/ Al 2o 3-La 2o 3, wherein SO 4 2-content is Al 2o 3-La 2o 31% of weight, Al 2o 3with La 2o 3mol ratio be 300,100 grams of methyl alcohol and 100 grams of paraformaldehydes, under 80 ℃ and 2MPa autogenous pressure, react 12h, extract after sample centrifugation by gas chromatographic analysis.In product, comprise polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde, its composition distributes as table 1.
[embodiment 8]
In 300 milliliters of tank reactors, add 1 gram of catalyzer Cl -/ Fe 2o 3-Ce 2o 3, wherein Cl -content is Fe 2o 3-Ce 2o 35% of weight, Fe 2o 3with Ce 2o 3mol ratio be 50,100 grams of methylals and 100 grams of paraformaldehydes, under 130 ℃ and 4MPa nitrogen pressure, react 4h, extract after sample centrifugation by gas chromatographic analysis.In product, comprise polyoxymethylene dimethyl ether and unreacted raw material methylal and paraformaldehyde, its composition distributes as table 1.
[comparative example 1]
As described in patent CN200910056819.9, in 300 milliliters of tank reactors, add 2 grams of catalyzer Cl -/ TiO 2, 100 grams of methyl alcohol and 100 grams of trioxymethylenes react 4h under 130 ℃ and 0.7 MPa autogenous pressure, extract after sample centrifugation by gas chromatographic analysis.Its composition distributes following (representing with % by weight): methyl alcohol, 7.0%; Trioxymethylene, 2.5%; Methylal, 19.4%; N=2,21.9%; N=3,26.2%; N=4,13.0%; N=5～10,10.0%; N>11, surplus.
  
In comparative example, use trioxymethylene and methyl alcohol for raw material, trioxymethylene price is higher, has caused production cost high.In contrast, the price of raw material paraformaldehyde will be far below trioxymethylene for the embodiment of the present invention 1, and production cost significantly reduces.
  
Table 1
Represent with wt% Paraformaldehyde Methyl alcohol Methylal Product n=2 Product n=3 Product n=4 Product n=5～10 Product n > 10 Selectivity of product, %
Embodiment 1 1.5 6.7 20.3 23.3 23.0 14.9 10.1 Surplus 71.3
Embodiment 2 0.8 7.4 21.9 22.8 18.5 7.7 14.6 Surplus 63.6
Embodiment 3 9.2 0 3.5 17.5 22.4 8.4 7.8 Surplus 56.1
Embodiment 4 4.1 0.3 14.1 10.7 33.4 23.5 13.9 Surplus 81.5
Embodiment 5 0 40.2 31.8 16.7 8.3 0 0 Surplus 25.0
Embodiment 6 6.2 16.3 41.2 6.1 5.0 2.3 18.4 Surplus 31.8
Embodiment 7 13.3 21.8 26.5 11.6 8.8 7.6 3.9 Surplus 31.9
Embodiment 8 5.2 0 21.5 19.8 26.3 10.4 8.2 Surplus 64.7
N is the polymerization degree, and product is CH 3o (CH 2o) ncH 3.

Claims (9)

1. the method by paraformaldehyde polyoxymethylene dimethyl ethers processed, take methyl alcohol, methylal and paraformaldehyde as raw material, wherein methyl alcohol: methylal: the mass ratio of paraformaldehyde is 0～10: 0～10: 1, the consumption of methyl alcohol and methylal can not be 0 simultaneously, be 70～200 ℃ in temperature of reaction, reaction pressure is under 0.2～6MPa condition, and raw material contacts with catalyzer, reaction generates polyoxymethylene dimethyl ether, and wherein catalyzer used is selected from least one in following rare earth modified solid super-strong acid: SO 4 2-/ ZrO 2-La 2o 3, SO 4 2-/ ZrO 2-Ce 2o 3, Cl -/ TiO 2-La 2o 3, Cl -/ TiO 2-Ce 2o 3, Cl -/ Fe 2o 3-Ce 2o 3, SO 4 2-/ Al 2o 3-La 2o 3or S 2o 8 2-/ ZrO 2-La 2o 3, 0.05～10 % that catalyst levels is raw material weight.
2. the method by paraformaldehyde polyoxymethylene dimethyl ethers processed according to claim 1, is characterized in that described catalyst levels is 0.1～5 % of raw material weight.
3. the method by paraformaldehyde polyoxymethylene dimethyl ethers processed according to claim 1, is characterized in that methyl alcohol: methylal: the mass ratio of paraformaldehyde is 0.2～10: 0.5～10: 1.
4. the method by paraformaldehyde polyoxymethylene dimethyl ethers processed according to claim 1, is characterized in that temperature of reaction is 100～150 ℃.
5. the method by paraformaldehyde polyoxymethylene dimethyl ethers processed according to claim 1, is characterized in that reaction pressure is 0.4～4.0 MPa.
6. the method by paraformaldehyde polyoxymethylene dimethyl ethers processed according to claim 1, the polymerization degree that it is characterized in that described paraformaldehyde is 2～8.
7. the method by paraformaldehyde polyoxymethylene dimethyl ethers processed according to claim 6, the polymerization degree that it is characterized in that described paraformaldehyde is 4～6.
8. the method by paraformaldehyde polyoxymethylene dimethyl ethers processed according to claim 1, is characterized in that the reaction times is 1 to 20 hour.
9. the method by paraformaldehyde polyoxymethylene dimethyl ethers processed according to claim 8, is characterized in that the reaction times is 4 to 12 hours.
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CN105294411A (en) * 2014-07-24 2016-02-03 中国石油化工股份有限公司 Method for producing PODE (polyoxymethylene dimethyl ethers) through paraformaldehyde
CN105367393A (en) * 2014-08-27 2016-03-02 中国石油化工股份有限公司 Method for synthesizing polyoxymethylene dimethyl ether through paraformaldehyde

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Publication number Priority date Publication date Assignee Title
CN105294411A (en) * 2014-07-24 2016-02-03 中国石油化工股份有限公司 Method for producing PODE (polyoxymethylene dimethyl ethers) through paraformaldehyde
CN105294411B (en) * 2014-07-24 2017-06-20 中国石油化工股份有限公司 The method that polyoxymethylene dimethyl ethers are produced by paraformaldehyde
CN105367393A (en) * 2014-08-27 2016-03-02 中国石油化工股份有限公司 Method for synthesizing polyoxymethylene dimethyl ether through paraformaldehyde

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