CN102040491A - Catalytic synthesis method for polyoxymethylene dimethyl ethers (PODE) by molecular sieves - Google Patents
Catalytic synthesis method for polyoxymethylene dimethyl ethers (PODE) by molecular sieves Download PDFInfo
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Abstract
The invention relates to a catalytic synthesis method for polyoxymethylene dimethyl ethers (PODE) by molecular sieves, mainly solving the problem of relatively high cost in the conventional method which adopts trioxymethylene as a raw material. In the method, methanol, methylal and paraformaldehyde are adopted as raw materials based on the mass ratio of (0-10): (0-10):1, the raw materials contact with a catalyst to react and generate PODE, wherein the dosages of the methanol and the methylal can not be zero at the same time; the reaction temperature is 70-200 DEG C; the reaction pressure is 0.1-6MPa; and the adopted catalyst is selected from at least one of beta zeolite, X zeolite, Y zeolite, ZSM-5 molecular sieve, MCM-22, MCM-56, UZM-8 or SAPO-34 molecular sieve. The technical scheme adopted by the invention solves the above problem preferably, thus being applicable to industrialized production of the PODE.
Description
Technical field
The present invention relates to a kind of method of molecular sieve catalytic synthesizing polyoxymethylene dme.
Background technology
In recent years, along with Industrial Revolution influence day by day deeply and the resource general layout of China's distinctive " many coals, few oil, gas is arranged ", China's oil resource growing tension, the oil supply pressure unprecedentedly increases.Estimate following 10～20 years, China's oil supply rate has only～and 50%.How to utilize the energy dilemma of coal resources solution China of China's abundant just to become the researcher urgent problem.Therefore the oil product substitute by the coal-based methanol development of new is subject to people's attention day by day.
Dme is suggested the earliest as a kind of procetane, yet because himself cold starting performance is poor, vapour pressure height under the normal temperature, be easy to generate vapour lock and make dme obviously raise as the cost of vehicle alternative fuel.Polyoxymethylene dimethyl ether, promptly 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, have higher octane value (＞30) and oxygen level (42～51%).When the value of n was 2～10, its physical properties, combustionproperty and diesel oil were very approaching, preferably resolved the defective that dme exists as the 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 the tail gas
xAnd NO
xDischarging.It is reported, add 5～30% CH
3OCH
2OCH
3Can reduce NO
xDischarging 7～10%, PM reduces by 5～35%.Synthetic PODE not only can replace part diesel oil by coal-based methanol, can also improve the efficiency of combustion of diesel oil, reduces the harm of diesel combustion to environment, has important strategic meaning and good economic worth.
Polyoxymethylene dimethyl ether can exist down in the method preparation of 150～180 ℃ of heating low polymerization degree Paraformaldehyde 96s or paraformaldehyde and methyl alcohol reaction by trace sulfuric acid or hydrochloric acid in the laboratory.In recent years, the polyoxymethylene dimethyl ether synthetic technology has obtained progress.
CN 101182367A has introduced the employing acidic ionic liquid as catalyzer, is the method for reactant synthesizing polyoxymethylene dme by methyl alcohol and trioxymethylene.US5,746,785 with WO2006/045506A1 to have described with protonic acid (as formic acid, sulfuric acid and trifluoromethanesulfonic acid) be catalyzer, with methylal and trioxymethylene is the synthesis technique of the polyoxymethylene dimethyl ether of raw material, though this bronsted acid catalyst is cheap and easy to get, corrodibility is strong, is difficult to separate, environmental pollution is big, to the requirement height of equipment.We have also developed employing solid acid catalyst (molecular sieve CN 200910056820.1, solid super-strong acid CN200910056819.9) ourselves is the feedstock production polyoxymethylene dimethyl ether with methyl alcohol and trioxymethylene.
It is reaction raw materials that yet these technologies all adopt trioxymethylene, and according to market study as can be known, the price of trioxymethylene is 14000 yuan/ton; And the price of Paraformaldehyde 96 has only 5000 yuan/ton.We are not difficult to find, can greatly reduce production cost with the Paraformaldehyde 96 for the raw material production polyoxymethylene dimethyl ether.And be catalyzer with the solid molecular sieves, have product and be easy to separate, little to equipment corrosion, be beneficial to the round-robin advantage.
Summary of the invention
Technical problem to be solved by this invention is to be to exist in the raw material synthesizing polyoxymethylene dme technology because of raw material trioxymethylene price height causes the production cost problem of higher with methyl alcohol and trioxymethylene in the prior art, and a kind of method of new molecular sieve catalytic synthesizing polyoxymethylene dme is provided.It is cheap that this method has the raw material Paraformaldehyde 96, 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 96 are raw material, methyl alcohol wherein: methylal: the mass ratio of Paraformaldehyde 96 is 0～10: 0～10: 1, wherein methyl alcohol and methylal consumption can not be 0 simultaneously, in temperature of reaction is 70～200 ℃, reaction pressure is under 0.1～6MPa condition, raw material contacts with catalyzer, reaction generates polyoxymethylene dimethyl ether, wherein used catalyzer is selected from the β zeolite, X type zeolite, y-type zeolite, the ZSM-5 molecular sieve, MCM-22, MCM-56, at least a in UZM-8 or the SAPO-34 molecular sieve, catalyst levels is 0.05～10% of a raw material weight.
In the technique scheme, methyl alcohol: methylal: the quality of Paraformaldehyde 96 is 0.2～10: 0.5～10 than preferable range: 1, in the reactant quality of the consumption sum of methyl alcohol and methylal and Paraformaldehyde 96 than preferable range for being 0.4～5: 1.The catalyzer preferred version is selected from least a in β zeolite, ZSM-5 molecular sieve, MCM-22, MCM-56 or the UZM-8 molecular sieve; The catalyst levels preferable range is 0.5～10% of a raw material weight.The preferable range of temperature of reaction is 80～150 ℃, and the reaction pressure preferable range is 0.5～4.0MPa.Catalyzed reaction makes polyoxymethylene dimethyl ether, can be by filtering or centrifugal mode separating catalyst and liquid phase reaction thing.
Use solid molecular sieves to be catalyzer among the present invention, can realize methyl alcohol, methylal and Paraformaldehyde 96 catalyzed reaction synthesizing polyoxymethylene dme, replace the trioxymethylene in the traditional raw material.Because this method Paraformaldehyde 96 is inexpensive, so production cost is lower.Catalyst system therefor contains stronger acidity, from the reaction product of methyl alcohol and Paraformaldehyde 96, obtain methylal by the distillatory method, make by product methylal circulation enter the acid catalysis system once more 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 0.1～6MPa 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 with reaction product simply, adopt the distillatory way to make the by product circulating reaction, so the yield of product n=2～10 is good, has obtained better technical effect.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
Add 2 gram catalyzer ZSM-5 (Si/Al=49) in 300 milliliters of tank reactors, 100 ml methanol and 100 gram Paraformaldehyde 96s react 4h under 130 ℃ and 0.5MPa autogenous pressure, extract after the sample centrifugation by gas chromatographic analysis.Comprise polyoxymethylene dimethyl ether and unreacted material benzenemethanol and Paraformaldehyde 96 in the product, it forms distribution as table 1.
[embodiment 2]
Add 2 gram catalyzer MCM-56 (Si/Al=2.5) in 300 milliliters of tank reactors, 100 ml methanol and 50 gram Paraformaldehyde 96s react 4h under 130 ℃ and 0.6MPa autogenous pressure, extract after the sample centrifugation by gas chromatographic analysis.Comprise polyoxymethylene dimethyl ether and unreacted material benzenemethanol and Paraformaldehyde 96 in the product, it forms distribution as table 1.
[embodiment 3]
Add 2 gram catalyzer HY (Si/Al=3.3) in 300 milliliters of tank reactors, 100 ml methanol and 100 gram Paraformaldehyde 96s react 4h under 130 ℃ and 0.8MPa autogenous pressure, extract after the sample centrifugation by gas chromatographic analysis.Comprise polyoxymethylene dimethyl ether and unreacted material benzenemethanol and Paraformaldehyde 96 in the product, it forms distribution as table 1.
[embodiment 4]
Add 2 gram catalyzer β zeolites (Si/Al=56) in 300 milliliters of tank reactors, 100 milliliters of methylals and 100 gram Paraformaldehyde 96s react 4h under 130 ℃ and 0.6MPa autogenous pressure, extract after the sample centrifugation by gas chromatographic analysis.Comprise polyoxymethylene dimethyl ether and unreacted raw material first acetal and Paraformaldehyde 96 in the product, it forms distribution as table 1.
[embodiment 5]
In 300 milliliters of tank reactors, add 2 gram catalyzer UZM-8 (Si/Al=6.6), 100 milliliters are distilled sample (87% methylal, all the other are methyl alcohol) and 100 gram Paraformaldehyde 96s, at 130 ℃, 0.7MPa autogenous pressure is reaction 4h down, extracts after the sample centrifugation by through gas chromatographic analysis.Comprise polyoxymethylene dimethyl ether and unreacted material benzenemethanol, methylal and Paraformaldehyde 96 in the product, it forms distribution as table 1.
[embodiment 6]
Add 2 gram catalyzer ZSM-5 (Si/Al=49) in 300 milliliters of tank reactors, 100 ml methanol and 100 gram Paraformaldehyde 96s at 80 ℃ of reaction 12h, extract after the sample centrifugation by gas chromatographic analysis.Comprise polyoxymethylene dimethyl ether and unreacted material benzenemethanol and Paraformaldehyde 96 in the product, it forms distribution as table 1.
[embodiment 7]
Add 0.5 gram catalyzer ZSM-5 (Si/Al=49) in 300 milliliters of tank reactors, 50 ml methanol and 100 gram Paraformaldehyde 96s react 4h under 130 ℃ and 4MPa nitrogen pressure, extract after the sample centrifugation by gas chromatographic analysis.Comprise polyoxymethylene dimethyl ether and unreacted material benzenemethanol and Paraformaldehyde 96 in the product, it forms distribution as table 1.
[embodiment 8]
Add 1 gram catalyzer ZSM-5 (Si/Al=49) in 300 milliliters of tank reactors, 100 ml methanol and 100 gram Paraformaldehyde 96s react 4h under 150 ℃ and 4MPa nitrogen pressure, extract after the sample centrifugation by gas chromatographic analysis.Comprise polyoxymethylene dimethyl ether and unreacted material benzenemethanol and Paraformaldehyde 96 in the product, it forms distribution as table 1.
Table 1
| Represent with wt% | Paraformaldehyde 96 | Methyl alcohol | Methylal | n＝2 | n＝3 | n＝4 | n＝5～10 | ?n＞10 |
| Embodiment 1 | 3.2 | 6.5 | 21.5 | 22.9 | 19.5 | 8.4 | 18.0 | Surplus |
| Embodiment 2 | 10.3 | 33.2 | 25.6 | 10.7 | 5.9 | 1.6 | 5.1 | Surplus |
| Embodiment 3 | 49.4 | 15.0 | 7.2 | 5.7 | 3.8 | 1.6 | 10.2 | Surplus |
| Embodiment 4 | 13.5 | 0 | 25.3 | 19.2 | 17.5 | 11.1 | 7.8 | Surplus |
| Embodiment 5 | 22.6 | 0.5 | 19.7 | 20.3 | 15.4 | 10.7 | 7.1 | Surplus |
| Embodiment 6 | 1.0 | 7.6 | 23.8 | 22.8 | 19.0 | 7.7 | 14.6 | Surplus |
| Embodiment 7 | 22.6 | 0.5 | 19.7 | 20.3 | 15.4 | 10.7 | 7.1 | Surplus |
| Embodiment 8 | 4.7 | 7.6 | 27.3 | 22.1 | 17.8 | 12.5 | 6.6 | Surplus |
[comparative example 1]
As described in patent CN 200910056820.1, in 300 milliliters of tank reactors, add 2 gram catalyzer ZSM-5 (Si/Al=49), 100 ml methanol and 100 gram trioxymethylenes, inflated with nitrogen to pressure is 6MPa, be heated to 130 ℃ and stirred 4 hours, filtering separation catalyzer and reaction product are through gas chromatographic analysis, comprise methylal and polyoxymethylene dimethyl ether and unreacted raw material in the product, it forms distribution following (% represents with weight): methylal 36.7%, methyl alcohol 14.3%, trioxymethylene 4.2%, n=213.4%, n=312.7%, n=44.6%, n=5-10 14.1%, n＞10, surplus.
Use trioxymethylene and methyl alcohol to be raw material in the comparative example, the trioxymethylene price is higher, has caused the production cost height.And the selectivity of by product methylal is higher in the product, has the methylal of 36.7 weight % to generate.The production of resins complex process, and be raw material production cost height with the trioxymethylene.The embodiment of the invention 1 is compared with it, and the price of raw material Paraformaldehyde 96 will be far below trioxymethylene, and production cost significantly reduces.The transformation efficiency and product n=2～10 selectivity of reaction are higher, and product yield is higher, can obtain reaction result similar when being raw material to trioxymethylene.
Claims (5)
1. the synthetic method of a polyoxymethylene dimethyl ether, with methyl alcohol, methylal and Paraformaldehyde 96 are raw material, methyl alcohol wherein: methylal: the mass ratio of Paraformaldehyde 96 is 0～10: 0～10: 1, wherein methyl alcohol and methylal consumption can not be 0 simultaneously, in temperature of reaction is 70～200 ℃, reaction pressure is under 0.1～6MPa condition, raw material contacts with catalyzer, reaction generates polyoxymethylene dimethyl ether, wherein used catalyzer is selected from the β zeolite, X type zeolite, y-type zeolite, the ZSM-5 molecular sieve, MCM-22, MCM-56, at least a in UZM-8 or the SAPO-34 molecular sieve, catalyst levels is 0.05～10% of a raw material weight.
2. the synthetic method of polyoxymethylene dimethyl ether according to claim 1 is characterized in that catalyzer is selected from least a in β zeolite, ZSM-5 molecular sieve, MCM-22, MCM-56 or the UZM-8 molecular sieve; Catalyst levels is 0.5～10% of a raw material weight.
3. the synthetic method of polyoxymethylene dimethyl ether according to claim 1 is characterized in that methyl alcohol and the consumption sum of methylal and the mass ratio of Paraformaldehyde 96 are 0.4～5: 1 in the reactant; Methyl alcohol: methylal: the mass ratio of Paraformaldehyde 96 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 80～150 ℃.
5. the synthetic method of polyoxymethylene dimethyl ether according to claim 1 is characterized in that reaction pressure is 0.5～4.0MPa.
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| CN103121927A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Preparation method of polymethoxymethylal |
| CN103121926A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Preparation method of polymethoxy acetal |
| CN103360224A (en) * | 2013-07-31 | 2013-10-23 | 东营市润成碳材料科技有限公司 | Combined process for preparing poly methoxy-dimethyl ether |
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| CN103664546A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Method for preparing polyoxymethylene dimethylether |
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