CN106631720A - Method for directly synthesizing polyoxymethylene dimethyl ether by taking dilute formaldehyde and methylal as raw materials - Google Patents
Method for directly synthesizing polyoxymethylene dimethyl ether by taking dilute formaldehyde and methylal as raw materials Download PDFInfo
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- CN106631720A CN106631720A CN201610943861.2A CN201610943861A CN106631720A CN 106631720 A CN106631720 A CN 106631720A CN 201610943861 A CN201610943861 A CN 201610943861A CN 106631720 A CN106631720 A CN 106631720A
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- formaldehyde
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- dimethoxym ethane
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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
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Abstract
The invention discloses a method for directly synthesizing polyoxymethylene dimethyl ether by taking dilute formaldehyde and methylal as raw materials. The method comprises the following steps: directly mixing dilute formaldehyde and methylal, removing the moisture through a membrane separation process, and carrying out a condensation reaction, thereby obtaining the polyoxymethylene dimethyl ether. According to the method disclosed by the invention, the membrane separation dehydration process and the catalytic condensation reaction are efficiently coupled, the polyoxymethylene dimethyl ether is directly synthesized by taking the dilute formaldehyde and methylal as raw materials, and the method achieves the effects of investment conservation and low cost and has high comprehensive benefits in technical economy.
Description
Technical field
The present invention provides a kind of new polymethoxy dimethyl ether synthetic process, and specifically one kind is with dilute formaldehyde and first
The method that acetal is directly synthesized polymethoxy dimethyl ether for raw material, belongs to methyl alcohol derived energy chemical technical field.
Background technology
Polymethoxy dimethyl ether (Polyoxymethylene dimethyl ethers, abbreviation PODE or DMMn) it is one
The low-molecular-weight acetal polymer with methylene epoxide as main chain is planted, its structural formula is CH3(OCH2)nOCH3.Put down when n=3～8
Cetane number reaches more than 76, oxygen content up to 47～50%, 65.6 DEG C of flash-point, 160～280 DEG C of boiling point, the thing with diesel oil
Property is very close, is the diesel oil blending component of a kind of cleaning, high cetane number.The DMM of addition 15% in diesel oil3-8, it is not necessary to
Diesel vehicle engine oil supply system is transformed, the combustion characteristics of diesel oil is can obviously improve, be greatly reduced nitrogen oxides,
PM2.5Deng the discharge of particulate pollutant in combustion tail gas.Additionally, compared with numerous coal derived energy chemical technology paths, methyl alcohol Jing first
Aldehyde prepares DMMnIt is efficiency is higher on a Coal Chemical Industry and methanol industry chain, the three wastes are less technology path.It is initial with methyl alcohol
Raw material, Jing formaldehyde, dimethoxym ethane, metaformaldehyde（Paraformaldehyde）Deng preparation DMMnDevelopment to China's methanol industry and formaldehyde industry
It is once great strategic opportunity.
BP、BASF（CN101048357, CN101193948, CN10119830 etc.）With Chinese Academy of Sciences's Lanzhou Chemical Physics
Research institute（CN101182367A, CN1016654148, CN102249868A etc.）It is to research and develop DMM earliest both at home and abroadnSynthetic technology
Unit, and applied for multinomial Chinese invention patent.Methyl alcohol or dimethoxym ethane and trimerization first have nearly all been selected in the research of early stage
Aldehyde prepares DMM for raw materialnAlthough reaction conversion ratio and selectivity of product are preferable, the technology of preparing complexity of metaformaldehyde,
Long flow path, equipment material is had high demands, product yield it is relatively low, cause and adopt metaformaldehyde for waste DMMnThe investment of device
Very high, cost is also very high（So far the market price of China's metaformaldehyde still is about 1.2～1.6 ten thousand yuan/ton）, as diesel oil
Addition blend component, is unacceptable from technological economics evaluation.
In addition, red liter of new forms of energy application technical research institute of Beijing Orient and China University Of Petroleum Beijing（East China）Cooperation one-up innovation
Adopt dimethoxym ethane with paraformaldehyde for raw material, using many kettle consecutive reactions DMM is preparednObtain successfully（CN101898943A、
CN104926627A etc.）.Compared with metaformaldehyde, dimethoxym ethane prepares DMM with paraformaldehydenWith larger cost advantage, skill
Art economic evaluation is feasible.But due to paraformaldehyde, [its structural formula is HO- (CH2O)n- H, n=8～100] it mostly is aqueous 5
～8% polymer/solid, during the course of the reaction firstly the need of catalytic degradation into formaldehyde, while it is poly to discharge concentrated formaldehyde condensation
The end-blocking free radical (OH-, H+) of formaldehyde, that is, discharge and could participate in after moisture reaction；Research both domestic and external is pointed out：In raw material
The moisture for containing is very big to the impact for generating the reaction of polymethoxy dimethyl ether！Paraformaldehyde is degraded on acidic catalyst
Reaction speed for formaldehyde is very slow ,-as need just can complete within 2～3 hours, so slurry bed system autoclave successive reaction can only be adopted.
Setting solid powder conveying, metering device, many kettle consecutive reaction devices, catalyst is needed finely to divide in technological process
From and filter etc., although the product quality of this technical process is preferable, feasible in safety and ambient influnence, in technology Jing
The upper economic benefit of Ji assessment also preferably, and is domestic and international first technology for completing commerical test and obtaining expert's favorable comment, but
Still suffer from the shortcomings of technological process length, equipment are more, investment is higher, energy consumption is higher.
In recent years patent adopts dimethoxym ethane（Purity >=99%）Concentrated formaldehyde with 85% is that raw material prepares DMMn
（CN104591984A）, this technology path eliminated in mist projection granulating, drying and the paraformaldehyde synthesis procedure of paraformaldehyde
The process such as material conveying, metering, many kettle consecutive reactions, catalyst filtration, simplifies FF, hence it is evident that reduce investment,
It is feasible in Technological Economy.But from synthesis DMMnFrom the point of view of chemical reaction, containing non-to technical process compared with juicy in system
Chang Buli's.
Moreover, the dehydration concentration of dilute formaldehyde is the process of high energy consumption, and equipment is also more complicated, particularly when concentration of formaldehyde is higher
When formaldehyde is easily spontaneous carries out condensation reaction, the formalin for being concentrated to 85% concentration is highly difficult, but still restricts
Generation DMMnThe further optimization of condensation reaction.The presence of a large amount of water causes reaction speed to slow down, side reaction increase, one way turn
The once through yield of rate and target product declines to a great extent, and its result is that unreacted recycle stock increases in synthetic reaction device
Many, energy consumption increases, relevant device investment increases；Refinement treatment dehydration device is larger, and not only energy consumption increases, corresponding investment also increases
Plus.Experiment shows, when the water content of formaldehyde is reduced to below 5% from 15%, DMM in condensation product3-8Once through yield can be with
Improve 35～40%；More importantly when adopting the formalin for being concentrated to 85% concentration for raw material, technical process is obtained
Product in contain many hemiacetals, their molecular weight and similar DMMnProduct is similar, and boiling point also complies with requirement, but Ban is Shrink
The presence of aldehyde can cause that the stability of product declines, acidity rises to the level that quality standard is not allowed.These products will be not
Qualified products.
All clearly propose that this course of reaction requires feed moisture content in the research of BASF AG and BP companies etc. and patent
Should≤0.5～1% strict demand.We through Technological Economy comprehensive assessment, as preparing DMMnRaw material formaldehyde it is dense
Degree should reach about 95%（I.e. water content is～5%）It is advisable, but remains current insoluble technical barrier.
The content of the invention
It is an object of the invention to overcome the problems referred to above that prior art is present, there is provided one kind is with dilute formaldehyde and dimethoxym ethane
The method that raw material is directly synthesized polymethoxy dimethyl ether.The present invention is efficient by UF membrane dehydration and catalyzing and condensing course of reaction
Coupling, DMM is directly synthesized with dilute formaldehyde and dimethoxym ethane as raw materialn。
For achieving the above object, the technical solution used in the present invention is as follows：
One kind is directly synthesized DMM with dilute formaldehyde and dimethoxym ethane as raw materialnMethod, it is characterised in that：By dilute formaldehyde and dimethoxym ethane
After directly mixing, first pass through membrane separating process and remove moisture therein, then carry out condensation reaction and obtain DMMn。
Methods described detailed process is：After dilute formaldehyde and dimethoxym ethane are directly mixed, pass through in the case where temperature is for 85～110 DEG C
Membrane separating process removes moisture therein, and at 80～120 DEG C, 0.3～1.5MPa is reacted the feed liquid after dehydration using multi-floating bodies
Catalyst concn 1～5% during device, or when adopting fixed bed catalytic reactor air speed for 1～10h-1Under the conditions of carry out condensation reaction
Obtain polymethoxy dimethyl ether.
Described dilute formaldehyde refers to the formalin that concentration is 37～85%.
The molar ratio of formaldehyde and dimethoxym ethane in dilute formaldehyde is 0.5～5:1, preferably 0.6～2:1.
The membrane separating process is seepage slope or Steam soak process, adopts film for hydrophilic organic polymer
Film, inorganic ceramic membrane or other composite separating films.
After the membrane separating process in material, the moisture in terms of formaldehyde is reduced to≤5%, preferably≤1%, further preferably
≤ 0.5%.
Dilute formaldehyde is dehydrated concentration process, it would however also be possible to employ the concentration of traditional dehydration by evaporation and UF membrane are carried out into integrated coupling
Method.
In the synthetic method, the concentration in dilute formaldehyde can be adopted to be concentrated to for 50～65% stages using tradition from 37%
Dehydration by evaporation is concentrated；UF membrane is then adopted when dilute concentration of formaldehyde is from 50～65% further Nong Shrink to >=95%.
Condensation reaction can adopt multi-continuous stirred tank reactor, it would however also be possible to employ fixed bed catalytic reactor.
The catalyst that condensation reaction is adopted for storng-acid cation exchange resin, solid acid catalyst, molecular sieve catalyst,
One or more in ionic-liquid catalyst composite catalyst in any proportion.
Using it is an advantage of the current invention that：
First, the present invention carries out the integrated method for coupling using by the concentration of traditional dehydration by evaporation with UF membrane, it will acquisition reduced investment,
The effect of low cost, Technological Economy comprehensive benefit is higher.
2nd, because the water content in system can be reduced to less than 5% by the present invention using UF membrane dewatering（With formaldehyde
Meter）Such that it is able to the yield of polymethoxy dimethyl ether is increased substantially, the generation of accessory substance is reduced.
3rd, the present invention shortens technological process directly with dilute formaldehyde and dimethoxym ethane as Material synthesis polymethoxy dimethyl ether,
Reduce the energy consumption of formaldehyde concentration and separation and purification of products.
4th, the present invention directly mixes dilute formaldehyde and dimethoxym ethane, then is dehydrated by UF membrane, both can effectively prevent formaldehyde
Generation self-polymerization, can improve the efficiency of UF membrane dehydration again.
Specific embodiment
Embodiment 1
With 37% formalin and dimethoxym ethane mixture Jing microporous silica membranes series connection film（Total membrane area is 0.21m2）It is de-
Synthesize DMM after watern。
By 37% formalin and dimethoxym ethane according to formaldehyde and dimethoxym ethane 1:1 mixed in molar ratio, then into two
Silicon oxide ceramics film cascade film（Total membrane area is 0.15m2）, film infiltration evaporation is dehydrated at being installed on 85 DEG C.Dehydration
The water content of middle analysis feed liquid.
When water content is 15.1% [water content=m water/(m water+m formaldehyde) × 100%], about 105g dehydration feed liquids are put into
To in the 150mL reactors of preset 4.2g HZSM-5 catalyst and nitrogen displacement, it is then heated to 120 DEG C and is reacted.Reaction
Less than 10 DEG C are cooled to after 60min, press filtration is carried out using 0.2 μm of poly tetrafluoroethylene, separating catalyst obtains product.Take product
Chromatography is carried out, target product content, wherein DMM is determined3～8Content is 20.65%.
The present embodiment is used to simulate conventional 85% concentration formaldehyde and dimethoxym ethane reaction prepares the reaction of polymethoxy dimethyl ether.
Embodiment 2
DMM is synthesized Jing after microporous silica membrane series connection film dehydration with 37% formalin and dimethoxym ethane mixturen。
By 37% formalin and dimethoxym ethane according to formaldehyde and dimethoxym ethane 1:1 mixed in molar ratio, then into two
Silicon oxide ceramics film cascade film（Total membrane area is 0.15m2）, film infiltration evaporation is dehydrated at being installed on 100 DEG C.Dehydration
The water content of middle analysis feed liquid.
When water content is 4.7% [water content=m water/(m water+m formaldehyde) × 100%], it is put into about 105g dehydrations feed liquid and arrives
In the 150mL reactors of preset 4.2g HZSM-5 catalyst and nitrogen displacement, it is then heated to 120 DEG C and is reacted.Reaction
Less than 10 DEG C are cooled to after 60min, press filtration is carried out using 0.2 μm of poly tetrafluoroethylene, separating catalyst obtains product.Take product
Chromatography is carried out, target product content, wherein DMM is determined3～8Content is 28.40%.
Embodiment 3
DMM is synthesized Jing after microporous silica membrane series connection film dehydration with 37% formalin and dimethoxym ethane mixturen。
By 37% formalin and dimethoxym ethane according to formaldehyde and dimethoxym ethane 1:1 mixed in molar ratio, then into two
Silicon oxide ceramics film cascade film（Total membrane area is 0.15m2）Film infiltration evaporation is dehydrated at being installed on 110 DEG C.Dehydration
The water content of middle analysis feed liquid.
When water content is 1.0% [water content=m water/(m water+m formaldehyde) × 100%], it is put into about 105g dehydrations feed liquid and arrives
In the 150mL reactors of preset 4.2g HZSM-5 catalyst and nitrogen displacement, it is then heated to 120 DEG C and is reacted.Reaction
Less than 10 DEG C are cooled to after 60min, press filtration is carried out using 0.2 μm of poly tetrafluoroethylene, separating catalyst obtains product.Take product
Chromatography is carried out, target product content, wherein DMM is determined3～8Content is 35.30%.
Embodiment 4
DMM is synthesized Jing after microporous silica membrane series connection film dehydration with 37% formalin and dimethoxym ethane mixturen。
By 37% formalin and dimethoxym ethane according to formaldehyde and dimethoxym ethane 1:1 mixed in molar ratio, then into two
Silicon oxide ceramics film cascade film（Total membrane area is 0.15m2）, film infiltration evaporation is dehydrated at being installed on 110 DEG C.Dehydration
The water content of middle analysis feed liquid.
When water content is 0.92% [water content=m water/(m water+m formaldehyde) × 100%], about 105g dehydration feed liquids are put into
To in the 150mL reactors of preset 4.2g storng-acid cation exchange resins DF-6 catalyst and nitrogen displacement, it is then heated to
110 DEG C are reacted.Less than 10 DEG C are cooled to after reaction 90min, press filtration is carried out using 0.2 μm of poly tetrafluoroethylene, separation is urged
Agent obtains product.Taking product carries out chromatography, determines target product content, wherein DMM3～8Content is 34.92%.
Embodiment 5
With 50% formalin and dimethoxym ethane mixture Jing after microporous silica membrane series connection film dehydration Jing fixed bed reactors
Synthesis DMMn。
By 50% formalin and dimethoxym ethane according to formaldehyde and dimethoxym ethane 1:1 mixed in molar ratio, then into two
Silicon oxide ceramics film cascade film（Total membrane area is 0.21m2）, film infiltration evaporation is dehydrated at being installed on 105 DEG C.Dehydration
The water content of middle analysis feed liquid.
Fixed bed reactors（Internal diameter is 20mm）Install HZSM-5 catalyst（20～40 mesh）15mL, use high pure nitrogen leak test
Afterwards, replaced 5 times with high pure nitrogen, and be forced into 1.0MPa.It is 3.0% [water by water content when reactor is warming up to 115 DEG C
Content=m water/(m water+m formaldehyde) × 100%] microporous silica membrane dehydration feed liquid be passed into fixed bed reactors, liquid
Air speed is 3.0h-1.Product enters after cooling knockout drum and product storage tank, from product storage tank sample analysis.Wherein
DMM3～8Content is 32.16%.
Embodiment 6
One kind is directly synthesized DMM with dilute formaldehyde and dimethoxym ethane as raw materialnMethod dilute formaldehyde and dimethoxym ethane are directly mixed after, first
Moisture therein is removed by membrane separating process, then carries out condensation reaction and obtain DMMn。
Methods described detailed process is：After dilute formaldehyde and dimethoxym ethane are directly mixed, pass through in the case where temperature is for 85～110 DEG C
Membrane separating process removes moisture therein, and at 80～120 DEG C, 0.3～1.5MPa is reacted the feed liquid after dehydration using multi-floating bodies
Catalyst concn 1～5% during device, or when adopting fixed bed catalytic reactor air speed for 1～10h-1Under the conditions of carry out condensation reaction
Obtain polymethoxy dimethyl ether.
Described dilute formaldehyde refers to the formalin that concentration is 37～85%.
The molar ratio of formaldehyde and dimethoxym ethane in dilute formaldehyde is 0.5～5:1, preferably 0.6～2:1.
The membrane separating process is seepage slope or Steam soak process, adopts film for hydrophilic organic polymer
Film, inorganic ceramic membrane or other composite separating films.
After the membrane separating process in material, the moisture in terms of formaldehyde is reduced to≤5%, preferably≤1%, further preferably
≤ 0.5%.
Dilute formaldehyde is dehydrated concentration process, it would however also be possible to employ the concentration of traditional dehydration by evaporation and UF membrane are carried out into integrated coupling
Method.
In the synthetic method, the concentration in dilute formaldehyde can be adopted to be concentrated to for 50～65% stages using tradition from 37%
Dehydration by evaporation is concentrated；UF membrane is then adopted when dilute concentration of formaldehyde is from 50～65% further Nong Shrink to >=95%.
Condensation reaction can adopt multi-continuous stirred tank reactor, it would however also be possible to employ fixed bed catalytic reactor.
The catalyst that condensation reaction is adopted for storng-acid cation exchange resin, solid acid catalyst, molecular sieve catalyst,
One or more in ionic-liquid catalyst composite catalyst in any proportion.
Claims (10)
1. a kind of method that polymethoxy dimethyl ether is directly synthesized as raw material with dilute formaldehyde and dimethoxym ethane, it is characterised in that：Will be dilute
After formaldehyde and dimethoxym ethane directly mix, first pass through membrane separating process and remove moisture therein, then carry out condensation reaction and obtain poly- first
Epoxide dimethyl ether.
2. the method that polymethoxy dimethyl ether is directly synthesized as raw material with dilute formaldehyde and dimethoxym ethane according to claim 1,
It is characterized in that：Methods described detailed process is：After dilute formaldehyde and dimethoxym ethane are directly mixed, in the case where temperature is for 85～110 DEG C
Moisture therein is removed by membrane separating process, the feed liquid after dehydration at 80～120 DEG C, 0.3～1.5MPa, using multi-floating bodies
Catalyst concn 1～5% during reactor, or when adopting fixed bed catalytic reactor air speed for 1～10h-1Under the conditions of be condensed
Reaction obtains polymethoxy dimethyl ether.
3. the side for being directly synthesized polymethoxy dimethyl ether as raw material with dilute formaldehyde and dimethoxym ethane according to claim 1 and 2
Method, it is characterised in that：Described dilute formaldehyde refers to the formalin that concentration is 37～85%.
4. the method that polymethoxy dimethyl ether is directly synthesized as raw material with dilute formaldehyde and dimethoxym ethane according to claim 3,
It is characterized in that：The molar ratio of formaldehyde and dimethoxym ethane in dilute formaldehyde is 0.5～5:1, preferably 0.6～2:1.
5. polymethoxy dimethyl ether is directly synthesized as raw material with dilute formaldehyde and dimethoxym ethane according to claim 1,2 or 4
Method, it is characterised in that：The membrane separating process is seepage slope or Steam soak process, adopts film for hydrophilic organic
Polymeric membrane, inorganic ceramic membrane or other composite separating films.
6. the method that polymethoxy dimethyl ether is directly synthesized as raw material with dilute formaldehyde and dimethoxym ethane according to claim 5,
It is characterized in that：After the membrane separating process in material, the moisture in terms of formaldehyde is reduced to≤5%, preferably≤1%, further
It is preferred that≤0.5%.
7. polymethoxy dimethyl ether is directly synthesized as raw material with dilute formaldehyde and dimethoxym ethane according to claim 1,2,4 or 6
Method, it is characterised in that：Dilute formaldehyde is dehydrated concentration process, and integrated coupling is carried out with UF membrane using by the concentration of traditional dehydration by evaporation
The method of conjunction.
8. the method that polymethoxy dimethyl ether is directly synthesized as raw material with dilute formaldehyde and dimethoxym ethane according to claim 7,
It is characterized in that：In the synthetic method, 50～65% stages were concentrated to using tradition from 37% using the concentration in dilute formaldehyde
Dehydration by evaporation is concentrated；UF membrane is then adopted when dilute concentration of formaldehyde is from 50～65% further Nong Shrink to >=95%.
9. polymethoxy diformazan is directly synthesized as raw material with dilute formaldehyde and dimethoxym ethane according to claim 1,2,4,6 or 8
The method of ether, it is characterised in that：Condensation reaction adopts multi-continuous stirred tank reactor, or adopts fixed bed catalytic reactor.
10. the method that polymethoxy dimethyl ether is directly synthesized as raw material with dilute formaldehyde and dimethoxym ethane according to claim 9,
It is characterized in that：The catalyst that condensation reaction is adopted is storng-acid cation exchange resin, solid acid catalyst, molecular sieve catalytic
One or more in agent, ionic-liquid catalyst composite catalyst in any proportion.
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| CN107413386A (en) * | 2017-08-21 | 2017-12-01 | 中国科学院成都有机化学有限公司 | A kind of catalyst of methanol liquid phase one-step oxidation to methylal and preparation method thereof and application method |
| CN108383696A (en) * | 2018-04-24 | 2018-08-10 | 中国科学院成都有机化学有限公司 | The method for preparing polymethoxy dimethyl ether |
| CN109384652A (en) * | 2017-08-07 | 2019-02-26 | 中国石化扬子石油化工有限公司 | The synthetic method and application of polyethoxy dimethyl ether |
| CN110054550A (en) * | 2019-04-09 | 2019-07-26 | 天津大学 | A kind of process system and method for gaseous formaldehyde method production polymethoxy dimethyl ether |
| CN110156575A (en) * | 2019-04-17 | 2019-08-23 | 天津大学 | Reactive distillation-Steam soak coupling technique for polymethoxy dimethyl ether synthesis |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109384652A (en) * | 2017-08-07 | 2019-02-26 | 中国石化扬子石油化工有限公司 | The synthetic method and application of polyethoxy dimethyl ether |
| CN107413386A (en) * | 2017-08-21 | 2017-12-01 | 中国科学院成都有机化学有限公司 | A kind of catalyst of methanol liquid phase one-step oxidation to methylal and preparation method thereof and application method |
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| CN110054550A (en) * | 2019-04-09 | 2019-07-26 | 天津大学 | A kind of process system and method for gaseous formaldehyde method production polymethoxy dimethyl ether |
| CN110054550B (en) * | 2019-04-09 | 2022-03-29 | 天津大学 | Process system and method for producing polymethoxy dimethyl ether by gas-phase formaldehyde method |
| CN110156575A (en) * | 2019-04-17 | 2019-08-23 | 天津大学 | Reactive distillation-Steam soak coupling technique for polymethoxy dimethyl ether synthesis |
| CN110156575B (en) * | 2019-04-17 | 2023-06-06 | 天津大学 | Reactive distillation-vapor permeation coupling process for polymethoxy dimethyl ether synthesis |
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