CN102295734B - Method for synthesizing polyoxymethylene dimethyl ether - Google Patents
Method for synthesizing polyoxymethylene dimethyl ether Download PDFInfo
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- CN102295734B CN102295734B CN201010208137A CN201010208137A CN102295734B CN 102295734 B CN102295734 B CN 102295734B CN 201010208137 A CN201010208137 A CN 201010208137A CN 201010208137 A CN201010208137 A CN 201010208137A CN 102295734 B CN102295734 B CN 102295734B
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- dimethyl ether
- paraformaldehyde
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Abstract
The invention relates to a method for synthesizing polyoxymethylene dimethyl ether, which mainly solves the problems of low reaction efficiency of a solid superacid catalyst, high cost of raw material trioxymethylene and more byproducts after reaction during synthesis of polyoxymethylene dimethyl ether existing in the prior art. In the method, dimethoxymethane and paraformaldehyde are used as raw materials, wherein the mass ratio of the dimethoxymethane to the paraformaldehyde is 0.5-10:1; the raw materials are in contact with the catalyst to generate catalytic reaction to prepare the polyoxymethylene dimethyl ether under the conditions of reaction temperature of 70-200 DEG C and reaction pressure of 0.2-6MPa; the amount of the used catalyst is 0.1-5.0 percent; and the used catalyst comprises the following components in percentage by weight: (a) 30-80 parts of molecular sieve carrier; and (b) 20-70 parts of solid superacid. Due to the technical scheme, the problems are solved well; and the method can be used for industrial production of the polyoxymethylene dimethyl ether.
Description
Technical field
The present invention relates to a kind of method of synthesizing polyoxymethylene dme.
Background technology
In recent years, along with International Crude Oil continue day by day being becoming tight of soaring and resource, the oil supply pressure unprecedentedly increases.Utilize the coal resources advantage of China's abundant, receive people's attention by the oil product substitute of coal-based methanol development of new day by day.
Polyoxymethylene dimethyl ether, promptly Polyoxymethylene dimethyl ethers (PODE) is the common name of one type of 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.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 mover, improves thermo-efficiency, reduces PM for 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, has strategic importance and good economic worth.
WO2006/045506A1 has introduced BASF AG and has used sulfuric acid, trifluoromethanesulfonic acid as catalyzer, is the series product that raw material has obtained n=1～10 with methylal, paraformaldehyde, trioxymethylene.
This method all adopts protonic acid as catalyzer, and this catalyzer is cheap and easy to get, but corrodibility is strong, is difficult to separate, and environmental pollution is big, to the demanding shortcoming of equipment.
It is raw material that US6160174 and US62655284 have introduced BP company employing methyl alcohol, formaldehyde, dme and methylal, adopts anionite-exchange resin as catalyzer, and gas-solid phase reaction obtains polyoxymethylene dimethyl ether.Though but this method has the catalyzer separate easily, is beneficial to advantages such as circulation, reaction conversion ratio is low, and productive rate is not high, complex process.
CN 101182367A has introduced the employing acidic ionic liquid as catalyzer, is the method for reactant synthesizing polyoxymethylene dme through methyl alcohol and trioxymethylene.But it is higher that this method also exists the catalyzer cost, and to equipment corrosion, and the catalyzer its separate reclaims and the problem of purification.
CN 200910056819.9 with methyl alcohol and trioxymethylene be raw material with solid super-strong acid as catalyst synthesizing polyoxymethylene dme; Though obtained feed stock conversion preferably; Yet because solid super-strong acid is acid strong; Irregular pore structure makes the selectivity of by product methylal in the product 20～50%, and a large amount of existence of methylal can reduce the flash-point of diesel fuel mixtures and therefore damage its quality, make product not too be suitable as procetane; There is the cost problem of higher in used trioxymethylene, has influenced it and has transformed into industrialized possibility.
In sum; At present about all there being the low problem of utilising efficiency of catalyzer in the technology of synthesizing polyoxymethylene dme--under the equal conditions; In temperature of reaction is 100～150 ℃, and reaction pressure is under 0.5～4MPa condition, reaction 4h; Conversion of raw material is reached more than 80%, and required catalyzer and raw material ratio are more than 1%.
Summary of the invention
Technical problem to be solved by this invention be prior art in the process of synthesizing polyoxymethylene dme solid super-strong acid low and raw material trioxymethylene cost is high as catalyst reaction efficient; The problem that reaction back by product is many provides a kind of method of new synthesizing polyoxymethylene dme.It is high that this method has catalyst reaction efficient, and raw materials cost is low, and product n=2～10 selectivity are good, the advantage that yield is high.
For solving the problems of the technologies described above; The technical scheme that the present invention adopts is following: a kind of method of synthesizing polyoxymethylene dme is a raw material with methylal and Paraformaldehyde 96, methylal: the mass ratio 0.5～10: 1 of Paraformaldehyde 96; In temperature of reaction is 70～200 ℃; Reaction pressure is under 0.2～6MPa condition, and raw material contacts the generation catalyzed reaction and makes polyoxymethylene dimethyl ether with catalyzer, and catalyst levels is 0.1～5.0% of a raw material weight; Wherein used catalyzer comprises following component in weight fraction: a) 30～80 parts carrier, carrier are selected from least a in SBA-15, MCM-41, the MCM-22 molecular sieve; With the b that carries on it) 20～70 parts be selected from SO
4 2-/ ZrO
2, SO
4 2-/ Fe
2O
3, Cl
-/ TiO
2Or Cl
-/ Fe
2O
3In at least a solid super-strong acid.
In the technique scheme, the quality optimization scope of reactant methylal and Paraformaldehyde 96 is than 1.0～5.0: 1, and the preferable range of temperature of reaction is 100～150 ℃.The reaction pressure preferable range is 0.5～4.0MPa.Catalyzed reaction makes polyoxymethylene dimethyl ether, can be through filtering or centrifugal mode separating catalyst and liquid phase reaction thing.
Catalyzer is the mesoporous material of modification among the present invention, has very regular mesopore orbit, high-specific surface area and less relatively diffusional resistance, can help long chain polymer molecule turnover catalyzer duct, has reduced micromolecular selectivity; The mesoporous material of this modification has simultaneously kept the strongly-acid of solid super-strong acid, and effectively raises the distribution of acidic site, has significantly improved the utilising efficiency of catalyzer, owing to being raw material with methylal and Paraformaldehyde 96, greatly reduces raw materials cost in addition.Use the inventive method; Use methylal and polyformaldehyde reaction; In temperature of reaction is 70～200 ℃, and reaction pressure is to react under 0.2～6MPa condition, and conversion of raw material is reached more than 80%; The quality of catalyzer and raw material only than being can reach equal effect at 0.1% o'clock, has obtained better technical effect.
Through embodiment the present invention is done further elaboration below.
Embodiment
[embodiment 1]
In 300 milliliters of tank reactors, add 0.2 gram catalyst S O
4 2-/ ZrO
2/ SBA-15,100 milliliters of methylals and 100 gram Paraformaldehyde 96s, 130 ℃ with 0.7MPa autogenous pressure reaction 4h down, after the spinning of extraction sample by gas chromatographic analysis.Comprise polyoxymethylene dimethyl ether and unreacted raw material in the product, it forms distribution like table 1.
[embodiment 2]
In 300 milliliters of tank reactors, add 0.2 gram catalyzer Cl
-/ Fe
2O
3/ MCM-22,45 milliliters of methylals and 100 gram Paraformaldehyde 96s, 130 ℃ with 0.5MPa autogenous pressure reaction 4h down, after the spinning of extraction sample by gas chromatographic analysis.Comprise polyoxymethylene dimethyl ether and unreacted raw material in the product, it forms distribution like table 1.
[embodiment 3]
In 300 milliliters of tank reactors, add 0.1 gram catalyst S O
4 2-/ ZrO
2/ SBA-15,100 milliliters of methylals and 100 gram Paraformaldehyde 96s at 150 ℃, are 4MPa reaction 8h towards nitrogen to pressure, extract after the sample spinning by gas chromatographic analysis.Comprise polyoxymethylene dimethyl ether and unreacted raw material in the product, it forms distribution like table 1.
[embodiment 4]
In 300 milliliters of tank reactors, add 0.5 gram catalyst S O
4 2-/ Fe
2O
3/ MCM-22,100 milliliters of methylals and 100 gram Paraformaldehyde 96s at 130 ℃, are 2MPa reaction 4h towards nitrogen to pressure, extract after the sample spinning by gas chromatographic analysis.Comprise polyoxymethylene dimethyl ether and unreacted raw material in the product, it forms distribution like table 1.
[embodiment 5]
In 300 milliliters of tank reactors, add 0.5 gram catalyzer Cl
-/ TiO
2/ MCM-41 and 0.2 gram Al
2O
3, 100 milliliters of methylals and 44 gram Paraformaldehyde 96s, 100 ℃ with 0.7MPa autogenous pressure reaction 4h down, after the spinning of extraction sample by gas chromatographic analysis.Comprise polyoxymethylene dimethyl ether and unreacted raw material in the product, it forms distribution like table 1.
[embodiment 6]
In 300 milliliters of tank reactors, add 0.5 gram catalyzer Cl
-/ TiO
2/ MCM-41,100 milliliters of distillation appearance (87% methylal, all the other be methyl alcohol) and 100 gram Paraformaldehyde 96s, at 130 ℃, the 0.7MPa autogenous pressure reacts 4h down, after the spinning of extraction sample by through gas chromatographic analysis.Comprise polyoxymethylene dimethyl ether and unreacted raw material methylal and Paraformaldehyde 96 in the product, it forms distribute (% representes with weight) as follows: methyl alcohol, 0.7%; Methylal, 13.1%; Paraformaldehyde 96,5.1%; N=2,10.2%; N=3,33.9%; N=4,24.0%; N=5～10,13.4%; N＞10, surplus.
[embodiment 7]
Used modified mesoporous material SO among the embodiment 1
4 2-/ ZrO
2/ SBA-15 method for preparing catalyst:
Take by weighing 100 gram ZrOCl
2Place 400 milliliters beaker, process the aqueous solution of 15 quality %, add 200 gram SBA-15, the back drips the NH of 12.5 quality %
3H
2O regulates pH=9, ageing 3h, and suction filtration, washing is to there not being Cl
-Detect.With 100 ℃ of oven dry of above-mentioned filter cake, grind.The above-mentioned powder of 10 grams is joined the H of 150 milliliters of 0.5mol/L
2SO
4In the solution, dipping 2h, oven dry, 600 ℃ of roastings.
SBA-15, MCM-41, MCM-22 related among the embodiment 1～6 are conventional mesoporous material.
Table 1
| Represent with wt% | Paraformaldehyde 96 | Methylal | n＝2 | n＝3 | n＝4 | n＝5～10 | n＞10 |
| Embodiment 1 | 2.7 | 20.3 | 18.8 | 17..9 | 22.4 | 17.5 | Surplus |
| Embodiment 2 | 21.2 | 8.7 | 13.9 | 16.5 | 17.9 | 19.5 | Surplus |
| Embodiment 3 | 7.2 | 12.5 | 15.6 | 15.5 | 21.8 | 25.4 | Surplus |
| Embodiment 4 | 7.3 | 15.5 | 14.6 | 18.3 | 20.6 | 22.3 | Surplus |
| Embodiment 5 | 0 | 27.9 | 21.8 | 25.3 | 12.4 | 10.2 | Surplus |
[comparative example 1]
CN200910201662.4 is said like patent, in 300 milliliters of tank reactors, adds 1 gram catalyst S O
4 2-/ Fe
2O
3, 100 milliliters of methylals and 100 gram Paraformaldehyde 96s, 130 ℃ with 4MPa nitrogen pressure reaction 4h down, after the spinning of extraction sample by gas chromatographic analysis.Comprise polyoxymethylene dimethyl ether and unreacted raw material methylal and Paraformaldehyde 96 in the product, the trioxymethylene transformation efficiency is 82.4%, the product relative content, and methylal 52.3%, n=2,24.2%, n=3～8,23.5%, n＞8 do not detect.
[comparative example 2]
In 300 milliliters of tank reactors, add 0.1 gram catalyst S O
4 2-/ ZrO
2, 100 milliliters of methylals and 100 gram Paraformaldehyde 96s, 130 ℃ with 0.5MPa autogenous pressure reaction 4h down, after the spinning of extraction sample by gas chromatographic analysis.Comprise polyoxymethylene dimethyl ether and unreacted raw material methylal and Paraformaldehyde 96 in the product, Paraformaldehyde 96 content 34.7%, methanol content 28.4%, the product relative content, methylal 17.4%, n=2,14.9%, n=3～8,5.1%, n＞8 do not detect.
Solid super acid catalyst unit catalyzer utilising efficiency in the process of synthesizing polyoxymethylene dme is low; Invention technical scheme 1 is compared with comparative example 1, uses methylal and polyformaldehyde reaction, is 100～150 ℃ in temperature of reaction; Reaction pressure is under 0.5～4MPa condition; Reaction 4h will make conversion of raw material reach more than 80%, and the mass ratio of catalyzer and raw material is can reach equal technique effect at 0.1% o'clock.Compare under identical catalyzer and proportioning raw materials with comparative example 2, conversion of raw material is high, good product selectivity.
Claims (4)
1. the method for a synthesizing polyoxymethylene dme; With methylal and Paraformaldehyde 96 is raw material; Methylal: the mass ratio 0.5～10: 1 of Paraformaldehyde 96 is 70～200 ℃ in temperature of reaction, and reaction pressure is under 0.2～6MPa condition; Raw material contacts the generation catalyzed reaction and makes polyoxymethylene dimethyl ether with catalyzer; Catalyst levels is 0.1～5.0% of a raw material weight, and wherein used catalyzer comprises following component in weight fraction: a) 30～80 parts carrier, carrier are selected from least a in SBA-15, MCM-41, the MCM-22 molecular sieve; With the b that carries on it) 20～70 parts be selected from SO
4 2-/ ZrO
2, SO
4 2-/ Fe
2O
3, Cl
-/ TiO
2Or Cl
-/ Fe
2O
3In at least a solid super-strong acid.
2. according to the method for claims 1 described synthesizing polyoxymethylene dme, the mol ratio that it is characterized in that reactant methylal and Paraformaldehyde 96 is 1.0～5.0: 1.
3. according to the method for claims 1 described synthesizing polyoxymethylene dme, it is characterized in that temperature of reaction is 100～150 ℃.
4. according to the method for claims 1 described synthesizing polyoxymethylene dme, it is characterized in that reaction pressure is 0.5～4.0MPa.
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|---|---|---|---|---|
| US9057034B2 (en) | 2013-06-09 | 2015-06-16 | Dongfang Hongsheng New Energy Application Technology Research Institute Co., Ltd | Method for synthesizing polyoxymethylene dimethyl ethers |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103420815B (en) * | 2012-05-16 | 2016-02-10 | 中国石油化工股份有限公司 | By the method for methylal and trioxymethylene synthesizing polyoxymethylene dme |
| CN102786397A (en) * | 2012-07-30 | 2012-11-21 | 中国海洋石油总公司 | Method for continuous production of polyformaldehyde dimethyl ether |
| CN103664549B (en) * | 2012-09-05 | 2015-08-12 | 中国石油化工股份有限公司 | The synthetic method of polyoxymethylene dimethyl ether |
| CN104151147B (en) * | 2013-05-16 | 2016-05-18 | 中国石油化工股份有限公司 | With the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers |
| CN104557483B (en) * | 2013-10-28 | 2017-01-04 | 中国石油化工股份有限公司 | The process of synthesizing polyoxymethylene dimethyl ether |
| CN103848730B (en) * | 2014-01-09 | 2015-06-17 | 东营市润成碳材料科技有限公司 | Production device system and production process for polymethoxy dimethyl ether (PODE) |
| CN105439830B (en) * | 2014-08-27 | 2018-02-13 | 中国石油化工股份有限公司 | In the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers |
| CN106928036B (en) * | 2017-04-19 | 2021-01-15 | 四川达兴能源股份有限公司 | Method for preparing polymethoxy butyl ether by using butyral |
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| 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 |
| CN101048357A (en) * | 2004-10-25 | 2007-10-03 | 巴斯福股份公司 | Method for producing polyoxymethylene dimethyl ethers |
| CN101665414B (en) * | 2008-09-04 | 2012-12-12 | 中国科学院兰州化学物理研究所 | Method for catalytically synthesizing polymethoxy methylal by using ionic liquid |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9057034B2 (en) | 2013-06-09 | 2015-06-16 | Dongfang Hongsheng New Energy Application Technology Research Institute Co., Ltd | Method for synthesizing polyoxymethylene dimethyl ethers |
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