CN105085196A - Synthesis method of polyoxymethylene dimethyl ether from paraformaldehyde - Google Patents
Synthesis method of polyoxymethylene dimethyl ether from paraformaldehyde Download PDFInfo
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- CN105085196A CN105085196A CN201410201904.0A CN201410201904A CN105085196A CN 105085196 A CN105085196 A CN 105085196A CN 201410201904 A CN201410201904 A CN 201410201904A CN 105085196 A CN105085196 A CN 105085196A
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Abstract
The present invention relates to a synthesis method of polyoxymethylene dimethyl ether from paraformaldehyde, and mainly solves the problems of conventional catalyst low reaction efficiency and higher costs of trioxymethylene as a raw material. The polyoxymethylene dimethyl ether is prepared from methanol, methylal and the paraformaldehyde as raw materials, the mass ratio of methanol: methylal: paraformaldehyde is (0-10): (0-10) :1, wherein methanol and methylal cannot be used simultaneously in an amount of 0, under the conditions of reaction temperature of 70-200 DEG C, and reaction pressure of 0.2-6MPa, the raw materials are contacted with a catalyst for reaction to produce the polyoxymethylene dimethyl ether, the amount of the catalyst is 0.05 to 10% of the amount of the raw materials, the catalyst comprises, by weight, a) 30-80 parts of a metal-organic aggregate carrier (IRMOFs series); and b) 20 to 70 parts of a solid super acid, and by the technical scheme, the problem can be better solved, and the method can be used for polyoxymethylene dimethyl ether industrial production.
Description
Technical field
The present invention relates to a kind of with the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, particularly about a kind of take paraformaldehyde as the method for Material synthesis 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 supplies pressure and unprecedentedly increases.Estimate following 10 ~ 20 years, China's oil supply rate only has ~ and 50%.The energy dilemma how utilizing the coal resources of China's abundant to solve China just becomes 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, but high, the easy generation vapour lock of vapour pressure makes dme obviously raise as the cost of vehicle alternative fuel because himself cold starting performance is poor, under normal temperature.Polyoxymethylene dimethyl ether, i.e. Polyoxymethylenedimethylethers (PODE), be 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%).When the value of n is 2 ~ 10, its physical properties, combustionproperty and diesel oil closely, 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 diesel oil combustion position within the engine, improves thermo-efficiency, reduces the particulate matter in tail gas and CO
xand NO
xdischarge.It is reported, add the CH of 5 ~ 30%
3oCH
2oCH
3nO can be reduced
xdischarge 7 ~ 10%, PM reduces by 5 ~ 35%.Synthesize PODE by coal-based methanol and not only can replace part diesel oil, the efficiency of combustion of diesel oil can also be improved, reduce diesel combustion to the harm of environment, there is important strategic importance and good economic worth.
IRMOFs material is mainly by [Zn
4o]
6+bunch with organic carboxyl acid part with the ligand polymer of octahedra perforate bridging.These organic carboxyl acid parts have the following advantages constructing in porous MOFs material: can synthesize the molecular sieve analog material with large aperture and pore volume; Carboxylic acid ligand easily and metal ion or metal oxide to be formed bunch, decrease the possibility running through phenomenon and line style part and occur low dimensional structures to a certain extent.In a series of MOF-n material, the structure of MOF-5, MOF-74, MOF-177 is the most typical.
Prepared by the method that in laboratory, polyoxymethylene dimethyl ether is reacted in 150 ~ 180 DEG C of heating low polymerization degree paraformaldehyde or paraformaldehyde and methyl alcohol under can being existed by trace sulfuric acid or hydrochloric acid.In recent years, polyoxymethylene dimethyl ether synthetic technology achieves progress.
CN102040491A describes and adopts β zeolite, ZSM-5 molecular sieve, MCM-22, MCM-56 or UZM-8 molecular sieve etc. as catalyzer, is the method for reactant synthesizing polyoxymethylene dme by methyl alcohol, methylal and paraformaldehyde.CN102040490A describes employing solid super acid catalyst, and temperature of reaction 90 ~ 130 DEG C, during reaction pressure 0.4 ~ 4.0MPa, transformation efficiency and selectivity are all not as good as sour as catalyzer using metallic organic framework IRMOFs serial carrier supported solid superacid.
Although more than adopt methyl alcohol, methylal and paraformaldehyde to be reaction raw materials in report, molecular sieve and solid super-strong acid are as these synthesis techniques of catalyzer, but the zeolite catalyst adopted and solid super acid catalyst separation difficulty, feed stock conversion is low, selectivity of product is poor.Especially, IRMOFs series metal organic backbone carrier has high-specific surface area (the Langmuir specific surface area as MOF-177 can reach 4500m2g-1) and very high voidage, modulation metal ion and organism part can also be passed through in addition, its texture character (expansion or compression as aperture) and surface functional group can be regulated and controled flexibly and easily, having homogeneous controlled aperture size makes it have " selecting shape " characteristic of picture molecular sieve to reactant and product, and these advantages are that traditional catalytic material can not be compared.
Summary of the invention
Technical problem to be solved by this invention be prior art with methyl alcohol, methylal and paraformaldehyde in order to exist in reaction raw materials synthesizing polyoxymethylene dme technique, catalyst reaction efficiency is low, trioxymethylene for the higher problem of raw materials cost, provide a kind of newly with the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers.The method has the advantage that catalyst low-temperature activity is high, selectivity is high, reaction conditions is gentle.
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 with the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, 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 and catalyst exposure, reaction generates polyoxymethylene dimethyl ether, catalyst levels is 0.05 ~ 10% of raw material weight, catalyzer wherein used comprises following component with weight parts: a) carrier of 30 ~ 80 parts, carrier is selected from MOF-5 in IRMOFs series, MOF-74, at least one in MOF-177 metallic organic framework, with carry b thereon) 20 ~ 70 parts be selected from SO
4 2-, Cl
-, S
2o
8 2-in at least one solid super-strong acid.
In technique scheme, catalyst levels preferable range is 0.1 ~ 5% of raw material weight.Methyl alcohol in raw material: methylal: the quality of paraformaldehyde is (0.2 ~ 10) than preferable range: (0.5 ~ 10): 1.The preferable range of temperature of reaction is 90 ~ 130 DEG C.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 obtains polyoxymethylene dimethyl ether, by filtering or centrifugal mode separating catalyst and liquid phase reaction thing.
In technique scheme, from inventing the 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, usually will control in the reaction times is 1 to 20 hour.The reaction times adopted in the embodiment of the present invention is 4 ~ 12 hours.
In technique scheme, SO
4 2-/ MOF-5, SO
4 2-/ MOF-74, SO
4 2-/ MOF-177, Cl
-/ MOF-5, Cl
-/ MOF-74, Cl
-/ MOF-177, S
2o
8 2-/ MOF-5, S
2o
8 2-/ MOF-74, S
2o
8 2-/ MOF-177 is known substance, can be used for the present invention and solve the technology of the present invention problem.Metal ion wherein in metal-organic framework materials IRMOFs series and the mol ratio of part are preferably between 1: 10 to 10: 1.
The polymerization degree of paraformaldehyde adopts Arbiso process or iodometric determination, method comes from: Chen Yongjie, Zhao Hui, Shao Yong wait so long. the polymerization degree measurement of industrial paraformaldehyde and the preparation of low polymerization degree paraformaldehyde, Shenyang Institute of Chemical Technology journal, 15 (2): 2001.
Owing to using metal-organic framework materials IRMOFs load series solid super-strong acid to be catalyzer in the present invention, methyl alcohol, methylal and paraformaldehyde catalyzed reaction synthesizing polyoxymethylene dme can be realized, replace the trioxymethylene in traditional raw material.Because the method can paraformaldehyde be raw material, the inexpensive production cost that makes is lower, and distribution of reaction products is even.With metal-organic framework materials IRMOFs load series solid super-strong acid for catalyzer, metal-organic framework materials IRMOFs serial carrier has higher physical strength while catalyzer can be made to have very big specific surface area and porosity, thus improve the productive rate of polyoxymethylene dimethyl ether, extend the work-ing life of catalyzer.Used catalyst contains extremely strong acidity, from the reaction product of methyl alcohol and paraformaldehyde, methylal is obtained by the method for distillation, make by product methylal circulate enter acid catalytic systems again with polyformaldehyde reaction, therefore can keep higher reaction conversion ratio and product yield.Use the inventive method, be 70 ~ 200 DEG C in temperature of reaction, reaction pressure is under 0.2 ~ 6MPa condition, and use methyl alcohol, methylal and polyformaldehyde reaction, the yield of product n=2 ~ 10 is good, and selectivity of product, up to 76.3%, achieves good technique effect.
Below by embodiment, the present invention is further elaborated, and the polymerization degree of the raw material paraformaldehyde adopted in embodiment and comparative example is 5, selectivity of product to take paraformaldehyde as benchmark with the polymerization degree be 2 ~ 10 polyoxymethylene dimethyl ether calculate for target product.
Embodiment
[embodiment 1]
2 grams of catalyst S O are added in 300 milliliters of tank reactors
4 2-/ MOF-5 (mol ratio of metal ion and part is 0.1), wherein solid super-strong acid and the massfraction of MOF-5 carrier are than being 20:80,100 grams of methyl alcohol and 100 grams of paraformaldehydes, 4h is reacted, by gas chromatographic analysis after the centrifugation of extraction sample under 130 DEG C and 0.8MPa autogenous pressure.Comprise polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde in product, its composition distribution is as table 1.
[embodiment 2]
2 grams of catalyst S O are added in 300 milliliters of tank reactors
4 2-/ MOF-74 (mol ratio of metal ion and part is 0.1), wherein solid super-strong acid and the massfraction of MOF-74 carrier are than being 20:80,100 grams of methyl alcohol and 100 grams of paraformaldehydes, 4h is reacted, by gas chromatographic analysis after the centrifugation of extraction sample under 130 DEG C and 0.6MPa autogenous pressure.Comprise polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde in product, its composition distribution is as table 1.
[embodiment 3]
2 grams of catalyst S O are added in 300 milliliters of tank reactors
4 2-/ MOF-177 (mol ratio of metal ion and part is 0.1), wherein solid super-strong acid and the massfraction of MOF-177 carrier are than being 20:80,100 grams of methylals and 100 grams of paraformaldehydes, 4h is reacted, by gas chromatographic analysis after the centrifugation of extraction sample under 130 DEG C and 0.6MPa autogenous pressure.Comprise polyoxymethylene dimethyl ether and unreacted raw material methylal and paraformaldehyde in product, its composition distribution is as table 1.
[embodiment 4]
2 grams of catalyzer Cl are added in 300 milliliters of tank reactors
-/ MOF-5 (mol ratio of metal ion and part is 0.1), wherein solid super-strong acid and the massfraction of MOF-5 carrier are than being 20:80,100 grams of distillation sample (methylals of 87wt%, all the other are methyl alcohol) and 100 grams of paraformaldehydes, at 130 DEG C, react 4h under 0.7MPa autogenous pressure, extract after sample centrifugation by through gas chromatographic analysis.Comprise polyoxymethylene dimethyl ether and unreacted raw material methylal and paraformaldehyde in product, its composition distribution is as table 1.
[embodiment 5]
2 grams of catalyzer Cl are added in 300 milliliters of tank reactors
-/ MOF-74 (mol ratio of metal ion and part is 0.1), wherein solid super-strong acid and the massfraction of MOF-74 carrier are than being 20:80,100 grams of methyl alcohol and 50 grams of paraformaldehydes, at 130 DEG C, react 4h under 0.7MPa autogenous pressure, extract after sample centrifugation by through gas chromatographic analysis.Comprise polyoxymethylene dimethyl ether and unreacted raw material methylal and paraformaldehyde in product, its composition distribution is as table 1.
[embodiment 6]
2 grams of catalyst S are added in 300 milliliters of tank reactors
2o
8 2-/ MOF-177 (mol ratio of metal ion and part is 0.1), wherein solid super-strong acid and the massfraction of MOF-177 carrier are than being 20:80,100 grams of methyl alcohol and 100 grams of paraformaldehydes, at 130 DEG C, 4h is reacted, by gas chromatographic analysis after the centrifugation of extraction sample under 0.7MPa autogenous pressure.Comprise polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde in product, its composition distribution is as table 1.
[embodiment 7]
2 grams of catalyst S O are added in 300 milliliters of tank reactors
4 2-/ MOF-5 (mol ratio of metal ion and part is 10), wherein solid super-strong acid and the massfraction of MOF-5 carrier are than being 20:80,100 grams of methyl alcohol and 100 grams of paraformaldehydes, react 12h under 130 DEG C and 2MPa autogenous pressure, by gas chromatographic analysis after the centrifugation of extraction sample.Comprise polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde in product, its composition distribution is as table 1.
[embodiment 8]
2 grams of catalyst S O are added in 300 milliliters of tank reactors
4 2-/ MOF-5 (mol ratio of metal ion and part is 0.1), wherein solid super-strong acid and the massfraction of MOF-5 carrier are than being 70:30,100 grams of methylals and 100 grams of paraformaldehydes, 4h is reacted, by gas chromatographic analysis after the centrifugation of extraction sample under 130 DEG C and 4MPa nitrogen pressure.Comprise polyoxymethylene dimethyl ether and unreacted raw material methylal and paraformaldehyde in product, its composition distribution is as table 1.
[embodiment 9]
0.5 gram of catalyst S O is added in 300 milliliters of tank reactors
4 2-/ MOF-5 (mol ratio of metal ion and part is 0.1), wherein solid super-strong acid and the massfraction of MOF-5 carrier are than being 20:80,100 grams of methylals and 100 grams of paraformaldehydes, 4h is reacted, by gas chromatographic analysis after the centrifugation of extraction sample under 130 DEG C and 4MPa nitrogen pressure.Comprise polyoxymethylene dimethyl ether and unreacted raw material methylal and paraformaldehyde in product, its composition distribution is as table 1.
[embodiment 10]
2 grams of catalyst S O are added in 300 milliliters of tank reactors
4 2-/ MOF-5 (mol ratio of metal ion and part is 0.1), wherein solid super-strong acid and the massfraction of MOF-5 carrier are than being 20:80,100 grams of methylals and 100 grams of paraformaldehydes, 4h is reacted, by gas chromatographic analysis after the centrifugation of extraction sample under 90 DEG C and 4MPa nitrogen pressure.Comprise polyoxymethylene dimethyl ether and unreacted raw material methylal and paraformaldehyde in product, its composition distribution is as table 1.
[embodiment 11]
2 grams of catalyst S O are added in 300 milliliters of tank reactors
4 2-/ MOF-5/SBA-15 (mol ratio of metal ion and part is 0.1), the weight ratio that wherein solid super-strong acid and the massfraction ratio of carrier are 20:80, MOF-5 and molecular sieve carrier SBA-15 is 50:50.100 grams of methylals and 100 grams of paraformaldehydes, react 4h under 130 DEG C and 4MPa nitrogen pressure, by gas chromatographic analysis after the centrifugation of extraction sample.Comprise polyoxymethylene dimethyl ether and unreacted raw material methylal and paraformaldehyde in product, its composition distribution is as table 1.
[comparative example 1]
According to patent " synthetic method of polyoxymethylene dimethyl ether ", (number of patent application: 201210325102.1) described method, adds 2 grams of catalyst S O in 300 milliliters of tank reactors
4 2-/ ZrO
2/ SBA-15 (wherein solid super-strong acid SO
4 2-with carrier (ZrO
2and molecular sieve carrier SBA-15) total mass ratio be 20:80, wherein ZrO
2be 50:50 with the mass ratio of SBA-15), 100 ml methanol and 100 grams of paraformaldehydes, reaction 4 hours under 130 DEG C and 0.8MPa autogenous pressure, extracts after sample centrifugation by gas chromatographic analysis.Polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde is comprised in product, its composition distribution following (representing with % by weight): methylal is 22.2%, methyl alcohol is 5.1%, and paraformaldehyde is 2.1%, n=2 is 25.1%, n=3 is 18.4%, n=4 is 17.5%, n=5-10 is 9.6%, n>10, surplus, to product n=2 ~ 10 optionally selectivity be 70.6%.
Use methyl alcohol, methylal and paraformaldehyde for raw material in comparative example, under equal conditions selectivity of product is lower as catalyzer for molecular sieve carried solid super-strong acid.In contrast, transformation efficiency and product n=2 ~ 10 selectivity of reaction are higher, be 76.3%, and in product, paraformaldehyde content are lower for the embodiment of the present invention 1.Can obtain with zeolite molecular sieve as reaction result better during catalyzer.
Table 1
N is the polymerization degree, and product is CH
3o (CH
2o)
ncH
3
Claims (9)
1. one kind with the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, 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 and catalyst exposure, reaction generates polyoxymethylene dimethyl ether, catalyst levels is 0.05 ~ 10% of raw material weight, catalyzer wherein used comprises following component in weight fraction: a) carrier of 30 ~ 80 parts, carrier is selected from MOF-5 in metal-organic framework materials IRMOFs series, MOF-74, at least one in MOF-177 metallic organic framework, with carry b thereon) 20 ~ 70 parts be selected from SO
4 2-, Cl
-, S
2o
8 2-in at least one solid super-strong acid.
2. according to claim 1 with the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, it is characterized in that catalyst levels is 0.1 ~ 5% of raw material weight.
3. according to claim 1 with the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, it is characterized in that methyl alcohol in raw material: methylal: the mass ratio of paraformaldehyde is (0.2 ~ 10): (0.5 ~ 10): 1.
4. according to claim 1 with the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, it is characterized in that temperature of reaction is 90 ~ 130 DEG C.
5. according to claim 1 with the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, it is characterized in that reaction pressure is 0.4 ~ 4.0MPa.
6. according to claim 1 with the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, it is characterized in that the polymerization degree of described paraformaldehyde is 2 ~ 8.
7. according to claim 6 with the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, it is characterized in that the polymerization degree of described paraformaldehyde is 4 ~ 6.
8. according to claim 1 with the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, it is characterized in that the reaction times is 1 to 20 hour.
9. according to claim 8 with the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, it is characterized in that the reaction times is 4 to 12 hours.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107337591A (en) * | 2016-05-03 | 2017-11-10 | 南京大学 | A kind of synthetic method of polyoxymethylene dimethyl ethers |
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2014
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| WO2000029364A1 (en) * | 1998-11-12 | 2000-05-25 | Bp Amoco Corporation | Preparation of polyoxymethylene dimethyl ethers by reaction of dimethylether with formaldehyde over heterogeneous catalysts |
| CN101768057A (en) * | 2009-01-07 | 2010-07-07 | 中国石油化工股份有限公司 | Method for synthesizing polyoxymethylene dimethyl ether |
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