CN106220481B - A kind of technique of continuous production polyoxymethylene dimethyl ether - Google Patents
A kind of technique of continuous production polyoxymethylene dimethyl ether Download PDFInfo
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- CN106220481B CN106220481B CN201610598952.7A CN201610598952A CN106220481B CN 106220481 B CN106220481 B CN 106220481B CN 201610598952 A CN201610598952 A CN 201610598952A CN 106220481 B CN106220481 B CN 106220481B
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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
Abstract
A kind of technique of continuous production polyoxymethylene dimethyl ether is to be completely dissolved and to form stable mixed raw material dimethoxym ethane and metaformaldehyde or paraformaldehyde, mixed raw material is pumped into equipped with being reacted in solid catalyst reactor, it is consistent with feed rate to control discharge velocity, the mixture that reaction product and unreacting material form is imported in collection of products tank, mixture is separated with catalyst by the stainless steel cylinder of reactor exit；Mixture in collection of products tank is pumped into separator, reaction product PODE is isolated2‑8And unreacted raw material, unreacted raw material enter head tank and recycle.The present invention has the advantages of preparation is simple, the continuous production that low energy consumption.
Description
Technical field
The present invention relates to a kind of techniques of continuous production polyoxymethylene dimethyl ether.
Background technique
Polyoxymethylene dimethyl ether (CH3-O-(CH2-O)n-CH3, n>1, abbreviation PODEn) it is that the novel polyether class methanol of one kind spreads out
Biology, wherein PODE2-8Due to oxygen content with higher and Cetane number, diesel oil can significantly improve as diesel fuel additives
Combustion position in engine, effectively reduces CO, NOxAnd the discharge of particulate pollutant.PODE2-8It can be by methanol or dimethoxym ethane
(DMM) with formaldehyde (FA), metaformaldehyde (TOM) or paraformaldehyde (PFn) etc. pass through polymerization reaction synthesize.Therefore, by methanol and
Its derivative efficiently prepares PODE2-8Alleviate superfluous current methanol production, Development of Novel coal chemical industry and improves motor-vehicle tail-gas dirt
Dye etc. has important research value and wide application prospect.
At present about PODEnSynthesis had a large amount of document report.BASF AG reports in patent US7999140B2
Road uses sulfuric acid for catalyst, and dimethyl ether and metaformaldehyde are raw material, and product is reached by catalytic distillation post separation, reaction 8h
It balances, PODE in product2-4Mass fraction be 92%；US2449469 and US5746785 individually discloses one kind with dimethoxym ethane
It is raw material with paraformaldehyde, using sulfuric acid and formic acid as catalyst, the method for preparing polyoxymethylene dimethyl ether series of products.Liquid acid is urged
Agent is low in cost, but there is a problem of that catalytic erosion is serious, and environmental pollution is big, and catalyst is asked with what product was difficult to separate
Topic.
101768058 B of CN, which is disclosed, to be used using methanol and metaformaldehyde as raw material, catalyst be selected from β zeolite, ZSM-5,
The method as catalyst preparation polyoxymethylene dimethyl ether such as MCM-22, MCM-56 zeolite molecular sieve.Wherein, anti-in 300ML autoclave
Addition 2g catalyst HY, 100mL methanol and 100g metaformaldehyde, nitrogen in device is answered to purge and keep 1MPa pressure, be heated to 150
DEG C stirring 4h, is separated by filtration catalyst and liquid composition, through gas chromatographic analysis, PODE in component2-10Account for constituent content
62.5%.
104045530 A of CN discloses one kind using methanol and concentrated formaldehyde as initial reaction raw material, with support type ionic liquid
Body is that the continuous acetalation of catalyst prepares reaction system and technique that polymethoxy dimethyl ether prepares polymethoxy dimethyl ether.
The ionic liquid of support type has preferable stability, but the case where still remain loss by dissolution during the reaction, it is clear that steady
The solid acid of order one is more suitable for the technical process.
When with methanol and metaformaldehyde or polyformaldehyde reaction, it may occur that aldol condensation and generate a certain amount of water, water meeting
With product PODE2-8Effect generates by-product hemiacetal, inhibits long-chain PODE2-8Generation, reduce reaction-ure conversion-age, and half contracts
Aldehyde physical property and PODE2-8It is similar, it is difficult to from PODE2-8It separates, seriously reduces PODE2-8Performance.And carbinol derivatives
Dimethoxym ethane can be used as excellent basic material and metaformaldehyde or paraformaldehyde effect synthesis PODE2-8.On the one hand, first contracts
Aldehyde can provide the capped species such as sufficient methyl and methoxyl group；On the other hand, dimethoxym ethane good dissolubility energy can be abundant
Metaformaldehyde and paraformaldehyde are dissolved, polyformaldehyde and catalyst is promoted to come into full contact with depolymerization.It in addition to this, is original with dimethoxym ethane
Expect there is no the generation of water in reaction process, can effectively inhibit by-product hemiacetal to generate, improve conversion ratio and the production of reactant
Object PODE2-8Selectivity.
Although about PODE2-8Synthesis there are many reports, but most of reaction process is all by intermittent reaction reality
Existing, process is cumbersome, and energy consumption is higher, while report focuses primarily upon the improvement aspect of catalyst.And about PODE2-8Continuous conjunction
It is less at technique report, not yet realize industrialized production.
Summary of the invention
Simple, the technique for the continuous production polyoxymethylene dimethyl ether that low energy consumption is prepared the object of the present invention is to provide a kind of.
The present invention is to use dimethoxym ethane (DMM) and metaformaldehyde (TOM) or paraformaldehyde (PF) as reaction raw materials, it is ensured that
There is no the generation of hemiacetal and water in reaction product, the mixing for obtaining stable homogeneous using the efficient solubility property of dimethoxym ethane is former
Material, it is ensured that reaction feed continuous uniform.Catalyst is isolated using membrane separation process simultaneously with reaction mass and product, is not necessarily to pair
Catalyst carries out being separately separated processing, and reaction product can be directly entered collection of products tank, and mix products are in rectifying separator
It realizes that efficient separation, this process flow significantly reduce industrial cost and energy consumption, there is extensive prospects for commercial application.Tool
Body includes the following steps：
(1) dimethoxym ethane is added to raw material with metaformaldehyde or paraformaldehyde to mix in filling, is allowed to be completely dissolved to be formed
Stable mixed raw material, wherein dimethoxym ethane：The molar ratio of metaformaldehyde or paraformaldehyde is 3-10：1, mixed raw material is continued to pump
Enter to have been loaded into the stirring for keeping continual and steady in solid catalyst reactor, so that catalyst and reaction raw materials are uniformly mixed
Under the conditions of reacted, volume space velocity control in 0.24h-1-1.2h-1Between, reaction temperature is 70-160 DEG C, and reaction pressure is
0.5-3.0MPa；
(2) control discharge velocity is consistent with feed rate, and the mixture that reaction product and unreacting material form is imported
In collection of products tank, mixture is separated with catalyst by the stainless steel cylinder of reactor exit；
(3) mixture in collection of products tank is pumped into separator, isolates reaction product PODE2-8And unreacted
Raw material, unreacted raw material enters head tank and recycles.
Reactor as described above is the stainless steel cauldron containing polytetrafluoroethyllining lining, and with lasting agitating device.
Catalyst as described above is at least one in the solid acid catalysts such as molecular sieve, ion exchange resin, heteropoly acid
Kind.Molecular sieve is one of ZSM-5, MCM-22, the molecular sieves such as H β, MOR, USY；Ion exchange resin is Purolite
One of resins such as CT175, Amberlyst 46, NKC-9, D001-CC；Heteropoly acid is H3PW12O40, SO4 2-/Fe2O3-
SiO2, H3+nPVnMo12-nO40(n=3-12) one such.
Stainless steel cylinder as described above is by stainless steel bowl wall 9, and mixture discharge port 11 forms, in stainless steel
Micropore 10 is provided on bowl wall 9.
The pore size of micropore 10 is between 200nm-500nm in stainless steel cylinder as described above.
The present invention mainly has following advantage:
(1) heterogeneous reaction is carried out using solid acid catalyst, realizes product and catalyst using membrane separation device
Separate；
(2) technique can effectively avoid intermittent reaction timing replacement raw material, the disadvantage of repeated isolation catalyst；
(3) catalyst meets under good mechanical strength, it can be achieved that prolonged continuous operation；
(4) the synthesis PODE of the device2-8It is close with intermittent reaction result, even better than intermittent reaction；
(5) target product PODE can be achieved at the same time in the technique2-8Synthesis with separate.
Detailed description of the invention
Fig. 1 is flow chart of the invention.As shown, 1 is dimethoxym ethane storage tank；2 be that raw material mixing fills；3 be feed pump；
4 be reactor；5 be collection of products tank；6 refer to product separator；7 be PODE2-8Storage tank；8 be stainless steel cylinder.
In reaction process, first a certain proportion of dimethoxym ethane and metaformaldehyde or paraformaldehyde are uniformly mixed in 2, by 3
Mixed raw material is imported in 4 and (loads a certain amount of solid catalyst in advance), under pressure itself, liquid phase mix products pass through 8
It enters in 5, then the mix products in 5 is imported and carry out rectifying separation in 6, isolate target product PODE2-8It is placed in 7, not
The DMM of reaction is imported in 1.
Fig. 2 is stainless steel cylinder structural schematic diagram in the present invention.As shown, 9 be stainless steel bowl wall；10 be not
Micro channel in steel seperation film of becoming rusty, between 200-500nm；11 be mixture discharge port.
Specific embodiment
Embodiment 1
Stainless steel cylinder of the invention is by stainless steel bowl wall 9, and mixture discharge port 11 forms, in stainless steel point
From being provided with micropore 10 on barrel 9.The aperture of micropore 10 is 500nm in stainless steel cylinder.
(1) dimethoxym ethane is added to raw material with paraformaldehyde to mix in filling, is allowed to be completely dissolved to form stable mixing
Raw material, wherein dimethoxym ethane：The molar ratio of paraformaldehyde is 5：1, mixed raw material is persistently pumped into and has been loaded into 20g amberlite
In rouge Purolite CT175 catalyst and the reactor of 479g mixed raw material, reactor assembly size is 900mL, keeps holding
Continue stable stirring, so that catalyst and reaction raw materials are reacted under the conditions of being uniformly mixed, volume space velocity is controlled in 0.24h-1,
Reaction temperature is by electric jacket computer heating control at 70 DEG C, reaction pressure 0.5Mpa, and discharge velocity is consistent with feed rate is for control
2mL/min.The mixture that reaction product and unreacting material form is imported in collection of products tank, mixture passes through with catalyst
The stainless steel cylinder of reactor exit separates.Mixture in mixture collecting tank is pumped into separator, target is isolated
Product PODE2-8And unreacted raw material, unreacted raw material, which enters in dimethoxym ethane storage tank, to be recycled.
Continuous operation 20h is reacted, every two hours sampling is primary, weighs and internal standard analysis is added.The conversion ratio mean value of DMM is
62%, TOM conversion ratio mean value are 99%, PODE2-8Selectivity then mean value be 59%, concrete analysis result it is as follows：
Embodiment 2
Dimethoxym ethane is added to raw material with paraformaldehyde to mix in filling, is allowed to be completely dissolved to form stable mixing original
Expect, wherein dimethoxym ethane：The molar ratio of metaformaldehyde is 10：1, it is 200 that mixed raw material, which is persistently pumped into, and has been loaded into 20g silica alumina ratio
MCM-22 molecular sieve catalyst and 479g mixed raw material reactor in, reactor assembly size be 900mL, keep continue
Stable stirring, so that catalyst and reaction raw materials are reacted under the conditions of being uniformly mixed, volume space velocity is controlled in 0.48h-1, instead
Answer temperature by electric jacket computer heating control at 90 DEG C, reaction pressure 0.8Mpa, discharge velocity is consistent with feed rate is for control
4mL/min.The mixture that reaction product and unreacting material form is imported in collection of products tank, mixture passes through with catalyst
The stainless steel cylinder of reactor exit separates, and the aperture of micropore 10 is 200nm in stainless steel cylinder.It will be in mixture collecting tank
Mixture be pumped into separator, isolate target product PODE2-8And unreacted raw material, unreacted raw material enter first
It is recycled in acetal storage tank.
Continuous operation 20h is reacted, every two hours sampling is primary, weighs and internal standard analysis is added.The conversion ratio mean value of DMM is
67%, TOM conversion ratio mean value are 96%, PODE2-8Selectivity then mean value be 89%, concrete analysis result it is as follows：
Embodiment 3
Dimethoxym ethane is added to raw material with metaformaldehyde to mix in filling, is allowed to be completely dissolved to form stable mixing original
Expect, wherein dimethoxym ethane：The molar ratio of metaformaldehyde is 3：1, mixed raw material is persistently pumped into and has been loaded into 20g H6PV3Mo9O40It urges
In the reactor of agent and 479g mixed raw material, reactor assembly size is 900mL, keeps continual and steady stirring, so that
Catalyst and reaction raw materials are reacted under the conditions of being uniformly mixed, and volume space velocity is controlled in 0.72h-1, reaction temperature passes through electric heating
Computer heating control is covered at 150 DEG C, reaction pressure 3.0Mpa, and control discharge velocity consistent with feed rate is 6mL/min.Reaction is produced
The mixture of object and unreacting material composition imports in collection of products tank, and mixture and catalyst pass through reactor exit not
The steel cylinder that becomes rusty separates, and the aperture of micropore 10 is 500nm in stainless steel cylinder.Mixture in mixture collecting tank is pumped into separation
In device, target product PODE is isolated2-8And unreacted raw material, unreacted raw material, which enters in dimethoxym ethane storage tank, to be recycled
It utilizes.
Continuous operation 20h is reacted, every two hours sampling is primary, weighs and internal standard analysis is added.The conversion ratio mean value of DMM is
65%, TOM conversion ratio mean value are 97%, PODE2-8Selective mean value be 69%, concrete analysis result it is as follows：
Embodiment 4
Dimethoxym ethane is added to raw material with metaformaldehyde to mix in filling, is allowed to be completely dissolved to form stable mixing original
Expect, wherein dimethoxym ethane：The molar ratio of metaformaldehyde is 3：1, it is 110 that mixed raw material, which is persistently pumped into, and has been loaded into 10g silica alumina ratio
ZSM-5 molecular sieve and 46 mixed catalyst of 10g acid-exchange resin Amberlyst and 479g mixed raw material it is anti-
It answers in device, reactor assembly size is 900mL, keeps being reacted under continual and steady stirring condition, so that catalyst and anti-
Raw material is answered to be uniformly mixed, volume space velocity is controlled in 0.96h-1, reaction temperature controlled by oil bath heating at 110 DEG C, reaction pressure
1.0Mpa, control discharge velocity consistent with feed rate is 8mL/min.The mixture that reaction product and unreacting material are formed
It imports in collection of products tank, mixture is separated with catalyst by the stainless steel cylinder of reactor exit, in stainless steel cylinder
The aperture of micropore 10 is 400nm.Mixture in mixture collecting tank is pumped into separator, target product is isolated
PODE2-8And unreacted raw material, unreacted raw material, which enters in dimethoxym ethane storage tank, to be recycled.
Continuous operation 20h is reacted, every two hours sampling is primary, weighs and internal standard analysis is added.The conversion ratio mean value of DMM is
69%, TOM conversion ratio mean value are 97%, PODE2-8Selectivity then mean value be 91%, concrete analysis result it is as follows：
Embodiment 5
Dimethoxym ethane is added to raw material with metaformaldehyde to mix in filling, is allowed to be completely dissolved to form stable mixing original
Expect, wherein dimethoxym ethane：The molar ratio of metaformaldehyde is 3：1, mixed raw material is persistently pumped into have been loaded into it is by 10g silica alumina ratio
110 ZSM-5 molecular sieve and 5g acid-exchange resin Amberlyst 46 and 5g heteropoly acid H5PV2Mo10O40Composition mixes
It closes in catalyst and the reactor of 479g mixed raw material, reactor assembly size is 900mL, continual and steady stirring is kept,
So that catalyst and reaction raw materials are reacted under the conditions of being uniformly mixed, volume space velocity is controlled in 1.2h-1, reaction temperature passes through oil
Computer heating control is bathed at 130 DEG C, reaction pressure 1.5Mpa, control discharge velocity consistent with feed rate is 10mL/min.It will reaction
Product imports in collection of products tank, and product is separated with catalyst by the stainless steel cylinder of reactor exit, stainless steel cylinder
The aperture of middle micropore 10 is 300nm.Mixture in mixture collecting tank is pumped into separator, target product is isolated
PODE2-8And unreacted raw material, unreacted raw material, which enters in dimethoxym ethane storage tank, to be recycled.
Continuous operation 20h is reacted, every two hours sampling is primary, weighs and internal standard analysis is added.The conversion ratio mean value of DMM is
75%, TOM conversion ratio mean value are 98%, PODE2-8Selectivity then mean value be 89%, concrete analysis result it is as follows：
Above description only describes section Example of the invention, it should be understood that the present invention is not limited to defined herein
Form, for the Enlargement Design of reaction unit, the big minor adjustment of reaction feed rate, the increase and decrease of catalyst amount, different film
The various preferred modifications such as the use of separator are related to embodiment and belong to scope, should all weigh in protection of the invention
In sharp range.
Claims (5)
1. a kind of technique of continuous production polyoxymethylene dimethyl ether, it is characterised in that include the following steps：
（1）Dimethoxym ethane and metaformaldehyde or paraformaldehyde are added to raw material to mix in filling, be allowed to be completely dissolved to be formed it is stable
Mixed raw material, wherein dimethoxym ethane：The molar ratio of metaformaldehyde or paraformaldehyde is 3-10：1, mixed raw material is persistently pumped into
It is fitted into solid catalyst reactor, keeps continual and steady stirring, so that catalyst and reaction raw materials are uniformly mixed condition
Under reacted, volume space velocity control in 0.24h-1-1.2h-1Between, reaction temperature is 70-160 DEG C, reaction pressure 0.5-
3.0MPa, the catalyst are at least one of molecular sieve, ion exchange resin and heteropoly acid solid acid catalyst；
（2）Control the mixture importing product that discharge velocity is consistent with feed rate, and reaction product and unreacting material are formed
In collecting tank, mixture is separated with catalyst by the stainless steel cylinder of reactor exit, the stainless steel cylinder be by
Stainless steel bowl wall (9), mixture discharge port (11) composition, is provided with micropore (10) on stainless steel bowl wall (9), described
Micropore (10) pore size between 200nm-500nm；
（3）Mixture in collection of products tank is pumped into separator, reaction product PODE is isolated2-8And unreacted original
Material, unreacted raw material enter head tank and recycle.
2. a kind of technique of continuous production polyoxymethylene dimethyl ether as described in claim 1, it is characterised in that molecular sieve ZSM-
5, one of MCM-22, H β, MOR and USY molecular sieve.
3. a kind of technique of continuous production polyoxymethylene dimethyl ether as described in claim 1, it is characterised in that ion exchange resin
For one of Purolite CT175,46 Amberlyst, NKC-9, D001-CC resin.
4. a kind of technique of continuous production polyoxymethylene dimethyl ether as described in claim 1, it is characterised in that heteropoly acid is
H3PW12O40、SO4 2−/Fe2O3-SiO2Or H3+nPVnMo12-nO40, one of n=3-12.
5. a kind of technique of continuous production polyoxymethylene dimethyl ether as described in claim 1, it is characterised in that the reactor
For the stainless steel cauldron containing polytetrafluoroethyllining lining, and there is lasting agitating device.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107011130A (en) * | 2017-04-19 | 2017-08-04 | 天津大学 | The device and operating method of a kind of synthesizing polymethoxy methylal |
| CN107011491B (en) * | 2017-04-28 | 2020-02-07 | 湖南师范大学 | Method for preparing polymethyleneoxy dimethyl ether |
| CN111454134A (en) * | 2019-01-21 | 2020-07-28 | 中信国安化工有限公司 | Device and method for adjusting yield of target product of polymethoxy dimethyl ether |
| CN110156576B (en) * | 2019-04-29 | 2021-11-02 | 中国科学院山西煤炭化学研究所 | Process for continuously producing polyformaldehyde dimethyl ether at low temperature |
| CN110180470B (en) * | 2019-04-29 | 2024-01-26 | 中国科学院山西煤炭化学研究所 | Kettle type continuous slurry bed reactor and use method thereof |
| CN112239397A (en) * | 2019-07-17 | 2021-01-19 | 南京凯旋化学科技有限公司 | Preparation method of polyformaldehyde dimethyl ether |
| CN112724000B (en) * | 2019-10-14 | 2022-12-09 | 中国石油化工股份有限公司 | Production method of polymethoxy dimethyl ether |
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| 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 |
| CN104292084A (en) * | 2014-09-05 | 2015-01-21 | 中国科学院山西煤炭化学研究所 | Method for preparing polyoxymethylene dimethyl ether under catalysis of molecular sieve with high silica-alumina ratio |
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| US6534685B1 (en) * | 1999-07-22 | 2003-03-18 | Snamprogetti S.P.A. | Liquid mixture consisting of diesel gas oils and oxygenated compounds |
| CN101048357A (en) * | 2004-10-25 | 2007-10-03 | 巴斯福股份公司 | Method for producing polyoxymethylene dimethyl ethers |
| 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 |
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