CN102372611A - Method for preparing polyoxymethylene dimethyl ether - Google Patents
Method for preparing polyoxymethylene dimethyl ether Download PDFInfo
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- CN102372611A CN102372611A CN2010102608723A CN201010260872A CN102372611A CN 102372611 A CN102372611 A CN 102372611A CN 2010102608723 A CN2010102608723 A CN 2010102608723A CN 201010260872 A CN201010260872 A CN 201010260872A CN 102372611 A CN102372611 A CN 102372611A
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- dimethyl ether
- polyoxymethylene dimethyl
- catalytic distillation
- trioxymethylene
- methylal
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention relates to a method for preparing polyoxymethylene dimethyl ether, which mainly solves the problems of low conversion rate of trioxymethylene and low selectivity of DMM 3-8 in current polyoxymethylene dimethyl ether production. According to the invention, under the effective reaction condition, methylal and trioxymethylene are reacted in a catalytic distillation tower, a components separation is performed simultaneously, steam at the top of the tower is condensed and then reflowed, a first part of the materials at the bottom of the tower is vaporized by a reboiler and returned back to the catalytic distillation tower, a second part of the materials is taken as produced liquid, the mass ratio of the first part to the second part is 1-10:1, wherein the trioxymethylene enters from the top of the tower, methylal can enter from any position from a stripping section to the tower top. The technical scheme of catalyst capable of being a heterogeneous phase acidic catalyst can effectively solve the problem, and the catalyst can be used for industrial production of polyoxymethylene dimethyl ether.
Description
Technical field
The present invention relates to a kind of method for preparing polyoxymethylene dimethyl ether.
Background technology
Over year, international community increases the diesel oil demand day by day, and limited diesel oil resource reduces day by day, has occurred that diesel oil is under-supply, the trend of price increase.Because the alkane molecule amount of diesel component is bigger, and rate of combustion is not high enough, and combustionproperty is good inadequately, this has not only increased oil consumption, and has deepened the pollution level of exhaust to environment in addition.In order to reach energy-conservation and purpose environmental protection, the numerous and confused increasing of fuel oil scientific and technological industry circle both at home and abroad is to the research and development dynamics of diesel-dope.(skeleton symbol is CH to polyoxymethylene dimethyl ether
3O (CH
2O)
nCH
3), abbreviate DMMn as, have very high cetane value and oxygen level, in diesel oil, add 10%～20%, can improve the combustioncharacteristics of diesel oil significantly, effectively improve thermo-efficiency, significantly reduce NO
xDischarging with particulate matter.Consider its vp, boiling point and the solubleness in oil product, the suitable polyoxymethylene dimethyl ether (DMM that is generally 3≤n≤8 that does the oil product interpolation
n).
In the laboratory, polyoxymethylene dimethyl ether can through trace sulfuric acid or hydrochloric acid in the presence of under 150～180 ℃, heat low polymerization degree Paraformaldehyde 96 or paraformaldehyde and methyl alcohol and prepare, the reaction times is 12～15 hours.Cause forming carbonic acid gas and the decomposition reaction that forms dme like this.Ratio at paraformaldehyde or low polymerization degree Paraformaldehyde 96 and methyl alcohol is 6: 1 o'clock, obtains wherein n＞100, usually the polymkeric substance of n=300～500.Product is used the sodium sulphite solution washing, separates through fractional crystallization then.US2449469 has described the method that a kind of wherein methylal and paraformaldehyde or concentrated methylal solution heat in the presence of sulfuric acid.This method provides per molecule to have the polyoxymethylene dimethyl ether of 2～4 formaldehyde units.US5746785 has described molar mass to be 80～350 and to be equivalent to the preparation method of the polyoxymethylene dimethyl ether of n=1～10; This method exists fourth 150～240 ℃ of reactions down through 1 part of methylal and 5 parts of paraformaldehydes at 0.1 weight % formic acid, perhaps reacts down at 150～240 ℃ through 1 part of methyl alcohol and 3 parts of paraformaldehydes.The polyoxymethylene dimethyl ether that is obtained adds in the diesel-fuel with the amount of 5～30 weight %.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.Above several 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; Adopt anionite-exchange resin as catalyzer; Gas-solid phase reaction obtains polyoxymethylene dimethyl ether, though this method has the catalyzer separate easily, helps advantages such as circulation; But exist reaction conversion ratio low, selectivity is hanged down the shortcoming with complex process.CN101665414A has introduced the employing acidic ion liquid as catalyzer; Through methylal and trioxymethylene is the method for reactant synthesizing polyoxymethylene dme; But this method exists the catalyzer cost higher; To equipment corrosion, the catalyzer its separate reclaims and purifies, and trioxymethylene reaction conversion ratio and DMM
3～8The problem that selectivity is low.
Summary of the invention
Technical problem to be solved by this invention is trioxymethylene transformation efficiency and DMM during present polyoxymethylene dimethyl ether is produced
3～8The problem that selectivity is not high provides a kind of new method for preparing polyoxymethylene dimethyl ether.This method has trioxymethylene transformation efficiency height and DMM
3～8The characteristics that selectivity 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 for preparing polyoxymethylene dimethyl ether; Methylal and trioxymethylene react in catalytic distillation tower under the effecting reaction condition, carry out component in the time of reaction and separate; Overhead vapours refluxes after condensation, and bottoms material first part turns back to catalytic distillation tower after the reboiler vaporization, and second section is as extraction liquid; First part and second section mass ratio are 1～10: 1; Wherein trioxymethylene gets into from cat head, and methylal can get into from stripping section to the cat head optional position, and the catalyzer in the catalytic distillation tower is a heterogeneous acid catalyst.
In technique scheme; The stripping section number of theoretical plate of described catalytic distillation tower is 5～50; It is 5～50 that the conversion zone of effecting reaction condition is equivalent to number of theoretical plate; The working pressure of catalytic distillation tower is 0.1～4MPa, total reflux after the overhead vapours condensation, and the controlled temperature of conversion zone is 50～200 ℃; The mass ratio of trioxymethylene and methylal is 0.1～10: 1; Heterogeneous acid catalyst is selected from least a in acidic ion exchange resin, zeolite, silico-aluminate, aluminum oxide, titanium oxide or the Indian red; The stripping section number of theoretical plate of described catalytic distillation tower is preferably 10～30, and conversion zone is equivalent to number of theoretical plate and is preferably 10～30, and the controlled temperature of conversion zone is preferably 90～150 ℃; The mass ratio of trioxymethylene and methylal is preferably 0.5～5: 1.
The present invention has given full play to the advantage of catalytic distillation, because distillment makes tower internal reaction section temperature be difficult for fluctuation, it is wayward to have overcome on-catalytic distil process temperature in the catalytic distillation tower; The shortcoming that catalyst life is short; The more important thing is that separate while reactant reacts in catalytic distillation tower with reaction product, the polyoxymethylene dimethyl ether of generation constantly shifts out from conversion zone; Reach the purpose that promotes reaction through isolating effect, thereby improved the transformation efficiency and the selectivity of reaction.Use the inventive method condition under to carry out the catalytic distillation reaction at pressure 0.5MPa, catalyzer at 1: 2 as the mass ratio of SAPO-34,100～110 ℃ of temperature of reaction, methylal and trioxymethylene, the trioxymethylene transformation efficiency reaches 100%, DMM
3～8Selectivity reaches 58.6%, has obtained better technical effect.
Description of drawings
Fig. 1 is the process flow diagram of preparation polyoxymethylene dimethyl ether.
Among Fig. 1, I is a catalytic distillation tower, and II is a stripping section, and III is a catalyst reaction section, the IV condensing surface, and the V reboiler, 1 is methylal, and 2 is trioxymethylene, and 3 for containing the still liquid of polyoxymethylene dimethyl ether.
As shown in Figure 1; Methylal 1 gets into catalytic distillation tower with trioxymethylene 2; Trioxymethylene and methylal generate polyoxymethylene dimethyl ether in the catalyst reaction section III; Overhead vapours refluxes after the condensation of condensing surface IV, and a bottoms material part turns back to the catalytic distillation tower I after the vaporization of reboiler V, and all the other extraction are the still liquid 3 that contains polyoxymethylene dimethyl ether.
Through specific embodiment the present invention is further described below, still, scope of the present invention has more than and is limited to the scope that embodiment covers.
Embodiment
[embodiment 1]
By shown in Figure 1, catalytic distillation tower working pressure 0.5MPa, wherein the stripping section number of theoretical plate is 20; It is 25 that the catalyst reaction section separation efficiency is equivalent to number of theoretical plate, and catalyzer is the SAPO-34 molecular sieve, and trioxymethylene gets into the 1st theoretical stage with 2 gram/minute flows and (counts from top to bottom; As follows), methylal gets into the cat head total reflux with 1 gram/minute flow from the catalyst reaction section bottom; Tower still first part is 3: 1 with the ratio of second section material; The catalyst reaction section TR of effecting reaction condition is 100～120 ℃, and with 3 gram/minute flow extraction, the catalytic distillation result sees table 1 at the bottom of the tower.
[embodiment 2～5]
Other conditions are identical with embodiment 1, just change the kind of catalyzer, and catalyzer is respectively Su Qing board 001 * semi-finals acidic resins, ZSM-5, SO
4 -2/ Fe
2O
3, Cl
-1/ TiO
2And SO
4 -2/ Fe
2O
3, the catalytic distillation result sees table 1.
[embodiment 6]
By shown in Figure 1, catalytic distillation tower working pressure 4.0MPa, wherein the stripping section number of theoretical plate is 5; It is 5 that the catalyst reaction section separation efficiency is equivalent to number of theoretical plate; Catalyzer is the MCM-22 molecular sieve, and trioxymethylene gets into the 1st theoretical stage, cat head total reflux with 1 gram/minute flow and methylal with 10 gram/minute flows; Tower still first part is 10:1 with the ratio of second section material; The catalyst reaction section TR of effecting reaction condition is 180～200 ℃, and with 11 gram/minute flow extraction, the catalytic distillation result sees table 1 at the bottom of the tower.
[embodiment 7]
By shown in Figure 1, catalytic distillation tower working pressure normal pressure, wherein the stripping section number of theoretical plate is 50; It is 50 that the catalyst reaction section separation efficiency is equivalent to number of theoretical plate, and catalyzer is an X type zeolite, and trioxymethylene gets into the 1st theoretical stage with 1 gram/minute flow; Methylal gets into from the catalyst reaction section bottom with 3 gram/minute flows; The cat head total reflux, tower still first part is 1: 1 with the ratio of second section material, the catalyst reaction section TR of effecting reaction condition is 50～70 ℃; With 4 gram/minute flow extraction, the catalytic distillation result sees table 1 at the bottom of the tower.
[embodiment 8]
By shown in Figure 1, catalytic distillation tower working pressure 1.0MPa, wherein the stripping section number of theoretical plate is 25; It is 30 that the catalyst reaction section separation efficiency is equivalent to number of theoretical plate, and catalyzer is the ZSM-5 molecular sieve, and trioxymethylene gets into the 1st theoretical stage with 3 gram/minute flows; Methylal gets into from the catalyst reaction section bottom with 1 gram/minute flow; The cat head total reflux, tower still first part is 5: 1 with the ratio of second section material, the catalyst reaction section TR of effecting reaction condition is 130～150 ℃; With 4 gram/minute flow extraction, the catalytic distillation result sees table 1 at the bottom of the tower.
[embodiment 9]
Other conditions are identical with embodiment 8; Trioxymethylene gets into the 1st theoretical stage with 10 gram/minute flows, and methylal gets into the cat head total reflux with 1 gram/minute flow from the catalyst reaction section bottom; Tower still first part is 2: 1 with the ratio of second section material; The catalyst reaction section TR of effecting reaction condition is 120～130 ℃, and with 11 gram/minute flow extraction, the catalytic distillation result sees table 1 at the bottom of the tower.
[comparative example 1]
According to the described method of patent CN101665414A; The cationic moiety of functionalization acidic ionic liquid body selects 1-methyl-3-(4-sulfonic group butyl) imidazol ion, anionicsite to select bisulfate ion; Methylal and trioxymethylene add 4.0 moles and 2.0 moles respectively, and reaction conditions is 115 ℃ of temperature, pressure 1.0MPa; 40 minutes time, reaction result is seen table 1.
Table 1 catalytic distillation result
| Embodiment | Trioxymethylene transformation efficiency/% | DMM 3～8Selectivity/% |
| Embodiment 1 | 100.0 | 58.6 |
| Embodiment 2 | 100.0 | 52.5 |
| |
100.0 | 53.4 |
| Embodiment 4 | 100.0 | 55.7 |
| Embodiment 5 | 100.0 | 58.2 |
| Embodiment 6 | 100.0 | 48.2 |
| Embodiment 7 | 100.0 | 51.7 |
| Embodiment 8 | 100.0 | 60.5 |
| Embodiment 9 | 100.0 | 62.7 |
| Comparative example 1 | 94.0 | 45.4 |
Claims (6)
1. method for preparing polyoxymethylene dimethyl ether, methylal and trioxymethylene react in catalytic distillation tower under the effecting reaction condition; Carrying out component in the time of reaction separates; Overhead vapours refluxes after condensation, and bottoms material first part turns back to catalytic distillation tower after the reboiler vaporization, and second section is as extraction liquid; First part and second section mass ratio are 1～10: 1; Wherein trioxymethylene gets into from cat head, and methylal can get into from stripping section to the cat head optional position, and the catalyzer in the catalytic distillation tower is a heterogeneous acid catalyst.
2. according to the said method for preparing polyoxymethylene dimethyl ether of claim 1; The stripping section number of theoretical plate that it is characterized in that described catalytic distillation tower is 5～50; It is 5～50 that conversion zone is equivalent to number of theoretical plate; The working pressure of catalytic distillation tower is 0.1～4MPa, total reflux after the overhead vapours condensation, and the controlled temperature of conversion zone is 50～200 ℃.
3. according to the said method for preparing polyoxymethylene dimethyl ether of claim 1, the mass ratio that it is characterized in that trioxymethylene and methylal is 0.1～10: 1.
4. according to the said method for preparing polyoxymethylene dimethyl ether of claim 1, it is characterized in that heterogeneous acid catalyst is selected from least a in acidic ion exchange resin, zeolite, silico-aluminate, aluminum oxide, titanium oxide or the Indian red.
5. according to the said method for preparing polyoxymethylene dimethyl ether of claim 2; The stripping section number of theoretical plate that it is characterized in that described catalytic distillation tower is 10～30; It is 10～30 that the conversion zone of effecting reaction condition is equivalent to number of theoretical plate, and the controlled temperature of conversion zone is 90～150 ℃.
6. according to the said method for preparing polyoxymethylene dimethyl ether of claim 3, the mass ratio that it is characterized in that trioxymethylene and methylal is 0.5～5: 1.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701923A (en) * | 2012-06-11 | 2012-10-03 | 北京科尔帝美工程技术有限公司 | System device and process for preparing polymethoxy dimethyl ether |
| CN103333059A (en) * | 2013-06-09 | 2013-10-02 | 北京东方红升新能源应用技术研究院有限公司 | Method for catalytically hydrofining polyformaldehyde dialkyl ether on fixed bed |
| CN103420817A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Method for synthesizing polyformaldehyde dimethyl ether from methylal and paraformaldehyde |
| CN103664544A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Method for synthesizing polyformaldehyde dimethyl ether by methanol and trioxymethylene |
| CN103755535A (en) * | 2014-01-03 | 2014-04-30 | 中国科学院山西煤炭化学研究所 | Preparation method of polyformaldehyde dimethyl ether |
| CN105061165A (en) * | 2015-08-04 | 2015-11-18 | 青岛迈特达新材料有限公司 | Reaction apparatus for preparing polyoxymethylene dimethyl ether |
| CN106397142A (en) * | 2016-09-05 | 2017-02-15 | 沈阳化工大学 | High-selectivity preparation method of single DMM2 |
| CN107285999A (en) * | 2017-07-13 | 2017-10-24 | 湖北三里枫香科技有限公司 | A kind of alkyl polyoxyether DMMn reaction tower and manufacturing technique method |
| CN107827719A (en) * | 2017-11-22 | 2018-03-23 | 厦门大学 | A kind of application of metal oxide catalyst in polymethoxy dimethyl ether is prepared |
| CN109232516A (en) * | 2018-11-08 | 2019-01-18 | 凯瑞环保科技股份有限公司 | A kind of multifunctional membrane synthesizing triformol and DMM3-8Device and method |
| CN110372477A (en) * | 2018-04-13 | 2019-10-25 | 中国科学院大连化学物理研究所 | A kind of continuous catalysis extracting process preparing polymethoxy dimethyl ether |
| CN110559678A (en) * | 2019-10-21 | 2019-12-13 | 无锡赫利邦化工科技有限公司 | rectifying tower for synthesizing and separating polymethoxy dimethyl ether and use method thereof |
| CN113939493A (en) * | 2019-05-23 | 2022-01-14 | 弗劳恩霍夫应用研究促进协会 | Method for producing polyoxymethylene dimethyl ethers |
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| CN103420817A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Method for synthesizing polyformaldehyde dimethyl ether from methylal and paraformaldehyde |
| CN103420817B (en) * | 2012-05-16 | 2016-05-18 | 中国石油化工股份有限公司 | By the method for dimethoxym ethane and paraformaldehyde synthesizing polyoxymethylene dimethyl ether |
| CN102701923A (en) * | 2012-06-11 | 2012-10-03 | 北京科尔帝美工程技术有限公司 | System device and process for preparing polymethoxy dimethyl ether |
| CN102701923B (en) * | 2012-06-11 | 2014-09-24 | 北京科尔帝美工程技术有限公司 | System device and process for preparing polymethoxy dimethyl ether |
| CN103664544A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Method for synthesizing polyformaldehyde dimethyl ether by methanol and trioxymethylene |
| CN103664544B (en) * | 2012-09-05 | 2016-02-10 | 中国石油化工股份有限公司 | By the method for methyl alcohol and trioxymethylene synthesizing polyoxymethylene dme |
| CN103333059A (en) * | 2013-06-09 | 2013-10-02 | 北京东方红升新能源应用技术研究院有限公司 | Method for catalytically hydrofining polyformaldehyde dialkyl ether on fixed bed |
| CN103755535A (en) * | 2014-01-03 | 2014-04-30 | 中国科学院山西煤炭化学研究所 | Preparation method of polyformaldehyde dimethyl ether |
| CN103755535B (en) * | 2014-01-03 | 2016-01-20 | 中国科学院山西煤炭化学研究所 | A kind of preparation method of polyoxymethylene dimethyl ether |
| CN105061165A (en) * | 2015-08-04 | 2015-11-18 | 青岛迈特达新材料有限公司 | Reaction apparatus for preparing polyoxymethylene dimethyl ether |
| CN106397142A (en) * | 2016-09-05 | 2017-02-15 | 沈阳化工大学 | High-selectivity preparation method of single DMM2 |
| CN106397142B (en) * | 2016-09-05 | 2019-06-21 | 沈阳化工大学 | A kind of highly selective method for preparing single dimerization dimethoxym ethane |
| CN107285999A (en) * | 2017-07-13 | 2017-10-24 | 湖北三里枫香科技有限公司 | A kind of alkyl polyoxyether DMMn reaction tower and manufacturing technique method |
| CN107827719A (en) * | 2017-11-22 | 2018-03-23 | 厦门大学 | A kind of application of metal oxide catalyst in polymethoxy dimethyl ether is prepared |
| CN107827719B (en) * | 2017-11-22 | 2019-12-20 | 厦门大学 | Application of metal oxide catalyst in preparation of poly (methoxy dimethyl ether) |
| CN110372477A (en) * | 2018-04-13 | 2019-10-25 | 中国科学院大连化学物理研究所 | A kind of continuous catalysis extracting process preparing polymethoxy dimethyl ether |
| CN110372477B (en) * | 2018-04-13 | 2022-07-15 | 中国科学院大连化学物理研究所 | Continuous catalytic extraction method for preparing poly-methoxy-dimethyl ether |
| CN109232516A (en) * | 2018-11-08 | 2019-01-18 | 凯瑞环保科技股份有限公司 | A kind of multifunctional membrane synthesizing triformol and DMM3-8Device and method |
| CN109232516B (en) * | 2018-11-08 | 2024-03-19 | 凯瑞环保科技股份有限公司 | Multifunctional membrane synthesis trioxymethylene and DMM 3-8 Apparatus and method of (2) |
| CN113939493A (en) * | 2019-05-23 | 2022-01-14 | 弗劳恩霍夫应用研究促进协会 | Method for producing polyoxymethylene dimethyl ethers |
| CN110559678A (en) * | 2019-10-21 | 2019-12-13 | 无锡赫利邦化工科技有限公司 | rectifying tower for synthesizing and separating polymethoxy dimethyl ether and use method thereof |
| CN110559678B (en) * | 2019-10-21 | 2024-02-27 | 无锡赫利邦化工科技有限公司 | Rectifying tower for synthesizing and separating polymethoxy dimethyl ether and application method thereof |
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