CN103880614A - Synthetic method for polyoxymethylene dimethyl ether - Google Patents
Synthetic method for polyoxymethylene dimethyl ether Download PDFInfo
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- CN103880614A CN103880614A CN201210553952.7A CN201210553952A CN103880614A CN 103880614 A CN103880614 A CN 103880614A CN 201210553952 A CN201210553952 A CN 201210553952A CN 103880614 A CN103880614 A CN 103880614A
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- dimethyl ether
- polyoxymethylene dimethyl
- synthetic method
- paraformaldehyde
- methylal
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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 synthetic method for polyoxymethylene dimethyl ether, and mainly overcomes the problem of relatively high cost in a conventional method for synthesizing polyoxymethylene dimethyl ether by using trioxymethylene as a raw material. The synthetic method takes use of methanol, methylal and paraformaldehyde as raw materials, wherein a mass ratio of methanol to methylal to paraformaldehyde is 0-10 : 0-10 : 1; and the usage amount of methanol and methylal is not zero at the same time; and the raw materials are contacted with a catalyst under a reaction pressure of 0.2-6 MPa to produce polyoxymethylene dimethyl ether (CH3O(CH2O)nCH3), wherein the used catalyst is selected from activated carbon. By adopting the above technical solution, the problem is overcome relatively well; and the synthetic method can be used for industrial production of polyoxymethylene dimethyl ether.
Description
Technical field
The present invention relates to a kind of synthetic method of polyoxymethylene dimethyl ether.
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 DEG C 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 taking protonic acid (as formic acid, sulfuric acid and trifluoromethanesulfonic acid) as catalyzer with WO2006/045506A1, synthesis technique taking 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 taking 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 taking paraformaldehyde as raw material production polyoxymethylene dimethyl ether.
Summary of the invention
Technical problem to be solved by this invention is that prior art exists because raw material trioxymethylene price is high taking methyl alcohol and trioxymethylene in raw material synthesizing polyoxymethylene dme technique, can cause the problem that production cost is higher, a kind of synthetic method of new polyoxymethylene dimethyl ether 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 synthetic method of polyoxymethylene dimethyl ether, 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 DEG C 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 the technical scheme of gac, catalyst levels is 0.05～10 % of raw material weight.
In technique scheme, methyl alcohol: methylal: the quality of paraformaldehyde is 0.2～10: 0.5～10 than preferable range: 1, the consumption preferable range of catalyst activity charcoal is raw material weight 0.1～5%.The preferable range of temperature of reaction is 100～150 DEG C, and reaction pressure preferable range is 0.4～4.0MPa.The polymerization degree of described paraformaldehyde is preferably 2～8, and more preferably 4～6.In technique scheme, gac of the prior art all can be used for the present invention and solves the technology of the present invention problem; The BET specific surface area of described activated carbon is preferably 1000 ~ 2500m
2/ g, pore volume is preferably 0.3 ~ 0.6ml/g; More preferably 2000 ~ the 2500m of BET specific surface area of described activated carbon
2/ g, pore volume is 0.3 ~ 0.5ml/g more preferably.
Catalyzed reaction makes polyoxymethylene dimethyl ether, can be by filtering or centrifugal mode separating catalyst and liquid phase reaction thing.
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 gac, 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 therefrom distributes more even.Gac has fabulous genetic prerequisite, abundant surface micropore makes its adsorption potential high, Surface chemical functional group of wood makes it the in the situation that of loaded metal cation activity center not, still have good catalytic performance, and physical strength is high, and cost is lower than metal oxide catalyst.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 DEG C 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 77.0%, has obtained 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, taking paraformaldehyde as benchmark, the polyoxymethylene dimethyl ether taking the polymerization degree as 2 ~ 10 calculates as target product selectivity of product, and in comparative example, the selectivity of product is taking trioxymethylene as benchmark.
Embodiment
[embodiment 1]
In 300 milliliters of tank reactors, add 2 grams of catalyst activity C(gac BET specific surface area 2000m
2/ g, pore volume 0.3ml/g), 100 grams of methyl alcohol and 100 grams of paraformaldehydes react 4h under 130 DEG C and 0.8MPa autogenous pressure, 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 activity C(gac BET specific surface area 2000m
2/ g, pore volume 0.3ml/g), 100 grams of methyl alcohol and 100 grams of paraformaldehydes react 4h under 130 DEG C and 0.6 MPa autogenous pressure, 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 catalyst activity C(gac BET specific surface area 2500m
2/ g, pore volume 0.3ml/g), 100 grams of methylals and 100 grams of paraformaldehydes react 4h under 130 DEG C and 0.6 MPa autogenous pressure, 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 catalyst activity C(gac BET specific surface area 2500m
2/ g, pore volume 0.3ml/g), 100 grams of distillation samples (methylal of 87wt%, all the other be methyl alcohol and 100 grams of paraformaldehydes, at 130 DEG C, 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 activity C(gac BET specific surface area 1000m
2/ g, pore volume 0.3ml/g), 100 grams of methyl alcohol and 50 grams of paraformaldehydes, at 130 DEG C, react 4h under 0.7MPa autogenous pressure, extracts 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 activity C(gac BET specific surface area 1000m
2/ g, pore volume 0.3ml/g), 100 grams of methyl alcohol and 100 grams of paraformaldehydes, at 80 DEG C 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 activity C(gac BET specific surface area 1000m
2/ g, pore volume 0.3ml/g), 100 grams of methyl alcohol and 100 grams of paraformaldehydes react 12h under 80 DEG C and 2MPa autogenous pressure, 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 catalyst activity C(gac BET specific surface area 800m
2/ g, pore volume 0.3ml/g), 100 grams of methylals and 100 grams of paraformaldehydes react 4h under 130 DEG C and 4MPa nitrogen pressure, 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 DEG C 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 the high and solid super strong acid production process more complicated of production cost.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
N is the polymerization degree, and product is CH
3o (CH
2o)
ncH
3.
Claims (10)
1. the synthetic method of a polyoxymethylene dimethyl ether, taking 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, is 70～200 DEG C in temperature of reaction, and reaction pressure is under 0.2～6MPa condition, raw material contacts with catalyzer, reaction generates polyoxymethylene dimethyl ether, and wherein catalyzer used is selected from the technical scheme of gac, 0.05～10 % that catalyst levels is raw material weight.
2. the synthetic method of polyoxymethylene dimethyl ether according to claim 1, is characterized in that the technical scheme of gac, 0.1～5 % that catalyst levels is raw material weight.
3. the synthetic method of polyoxymethylene dimethyl ether 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 synthetic method of polyoxymethylene dimethyl ether according to claim 1, is characterized in that temperature of reaction is 100～150 DEG C.
5. the synthetic method of polyoxymethylene dimethyl ether according to claim 1, is characterized in that reaction pressure is 0.4～4.0 MPa.
6. the synthetic method of polyoxymethylene dimethyl ether according to claim 1, the polymerization degree that it is characterized in that described paraformaldehyde is 2～8.
7. the synthetic method of polyoxymethylene dimethyl ether according to claim 6, the polymerization degree that it is characterized in that described paraformaldehyde is 4～6.
8. the synthetic method of polyoxymethylene dimethyl ether according to claim 1, is characterized in that the reaction times is 1 to 20 hour.
9. the synthetic method of polyoxymethylene dimethyl ether according to claim 1, the BET specific surface area that it is characterized in that described activated carbon is 1000 ~ 2500m
2/ g, pore volume is 0.3 ~ 0.6ml/g.
10. the synthetic method of polyoxymethylene dimethyl ether according to claim 9, the BET specific surface area that it is characterized in that described activated carbon is 2000 ~ 2500m
2/ g, pore volume is 0.3 ~ 0.5ml/g.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104086380A (en) * | 2014-07-07 | 2014-10-08 | 中国科学院山西煤炭化学研究所 | Preparation method of polyoxymethylene dimethyl ethers |
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| WO1999002626A1 (en) * | 1997-07-07 | 1999-01-21 | Southwest Research Institute | Diesel fuel having improved qualities and method of forming |
| US6160174A (en) * | 1998-11-12 | 2000-12-12 | Bp Amoco Corporation | Preparation of polyoxymethylene dimethyl ethers by catalytic conversion of dimethyl ether with formaldehyde formed by oxy-dehydrogenation of methanol |
| CN101116810A (en) * | 2007-07-24 | 2008-02-06 | 宁夏大学 | Modified coal-radicle activated charcoal solid catalyst and method for preparing the same and the application in the aldehyde acetal/ketone building-up reactions |
| CN102040491A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Catalytic synthesis method for polyoxymethylene dimethyl ethers (PODE) by molecular sieves |
| CN102775284A (en) * | 2011-05-13 | 2012-11-14 | 南京大学 | Synthesis method of polyoxymethylene dimethyl ethers |
-
2012
- 2012-12-19 CN CN201210553952.7A patent/CN103880614B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999002626A1 (en) * | 1997-07-07 | 1999-01-21 | Southwest Research Institute | Diesel fuel having improved qualities and method of forming |
| US6160174A (en) * | 1998-11-12 | 2000-12-12 | Bp Amoco Corporation | Preparation of polyoxymethylene dimethyl ethers by catalytic conversion of dimethyl ether with formaldehyde formed by oxy-dehydrogenation of methanol |
| CN101116810A (en) * | 2007-07-24 | 2008-02-06 | 宁夏大学 | Modified coal-radicle activated charcoal solid catalyst and method for preparing the same and the application in the aldehyde acetal/ketone building-up reactions |
| CN102040491A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Catalytic synthesis method for polyoxymethylene dimethyl ethers (PODE) by molecular sieves |
| CN102775284A (en) * | 2011-05-13 | 2012-11-14 | 南京大学 | Synthesis method of polyoxymethylene dimethyl ethers |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104086380A (en) * | 2014-07-07 | 2014-10-08 | 中国科学院山西煤炭化学研究所 | Preparation method of polyoxymethylene dimethyl ethers |
| 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 |
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