CN110372479A - A kind of continuous catalysis extracting process preparing more polymethoxy dimethyl ethers - Google Patents
A kind of continuous catalysis extracting process preparing more polymethoxy dimethyl ethers Download PDFInfo
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- CN110372479A CN110372479A CN201810333173.3A CN201810333173A CN110372479A CN 110372479 A CN110372479 A CN 110372479A CN 201810333173 A CN201810333173 A CN 201810333173A CN 110372479 A CN110372479 A CN 110372479A
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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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
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Abstract
This application discloses a kind of continuous catalysis extracting process that more polymethoxy dimethyl ethers are prepared by methanol and formalin, the following steps are included: the material B of the material A containing formaldehyde and the polymethoxy dimethyl ether containing circular response, which a) is introduced into pre-reactor, carries out pre-reaction, prereacted material I is obtained;B) prereacted material I that step a) is obtained and raw material C containing methanol are introduced into catalytic extraction tower or multistage catalytic extraction reactor, with extractant counter current contacting, carry out catalysis reaction and extraction, obtains extraction phase materials II and raffinate phase materials III;Wherein, the raw material C containing methanol is in the middle part of catalytic extraction tower or the centre grade of multistage catalytic extraction reactor is fed.Method of the invention can be improved the concentration of the polymethoxy dimethyl ether from the extraction phase that catalytic extraction tower or multistage catalytic extraction reactor obtain, and have the advantages that cost of material is low, product separation is easy.
Description
Technical field
This application involves the continuous catalysis that a kind of methanol and formalin prepare the above polymethoxy dimethyl ether of more dimerization
Extracting process.
Background technique
Polymethoxy dimethyl ether, also known as polymethoxy methylal, polyoxymethylene dimethyl ether, abbreviation PODEn
(polyoxymethylene dimethyl ethers)。
PODE1As dimethoxym ethane, also known as dimethoxymethane, abbreviation DMM are a kind of colourless, nontoxic while to environment friend
Good industrial chemicals, generallys use methanol and formalin through aldol reaction to prepare.Due to existing in reaction process
A large amount of water (water that the water and reaction brought into including formalin generate), makes the reaction by the limitation of chemical balance, mesh
Break the limitation of chemical balance as previous using catalytic rectification process.
PODE3-4Have the characteristics that high cetane number, rich oxygen content, can dissolve each other with diesel oil, performance indexes and bavin
Oil is close, it is considered to be ideal diesel fuel additives.Although there is the higher PODE of the degree of polymerization potential low temperature to solidify risk,
It is PODE in general synthesis polymethoxy dimethyl ether product5-8Content it is very low, be not sufficient to cause fuel oil low temperature to solidify, thus
Also it is believed that the PODE containing a small amount of high polymerization degree component3-5Or PODE3-8It is also suitable diesel oil addO-on therapy.
PODE3+Generally by the compound of offer paraformaldehyde (formalin, metaformaldehyde or paraformaldehyde etc.) and mention
Compound (methanol, dimethyl ether or dimethoxym ethane etc.) for blocking methyl synthesizes in the presence of acidic, while having a large amount of
PODE1-2It generates.PODE2It is also a kind of potential industrial chemicals, there are certain market prospects.
Japanese Asahi Kasei Corporation discloses a kind of raw by formalin and methanol in 1020450 C of Chinese patent CN
The catalytic rectification method for producing dimethoxym ethane, using the auxiliary reactor form being arranged in outside catalytic rectifying tower, with macropore or gel-type
Cation exchange resin is catalyst.
102351666 A of Chinese patent CN discloses one kind by formalin and methanol continuous production of high-concentration methylal
Catalytic rectification method, also use auxiliary reactor form.
100344596 C of Chinese patent Authorization Notice No. CN discloses a kind of continuous reaction rectification and liquid-liquid extraction combines
The method for preparing high-purity methylal, the dimethoxym ethane obtained after reactive distillation, methanol, water mixture extract in liquid-liquid extraction tower
High-purity methylal is obtained, extractant is glycerine or dimethanolamine.
102070417 A of Chinese patent CN discloses a kind of catalytic distillation by formalin and methanol production dimethoxym ethane
Technique and its production equipment, using cation exchange resin as catalyst, using the catalytic rectifying tower for being filled with Catalyst capsule.
It is catalysis that Chinese patent CN 101182367, which discloses one kind using methanol and metaformaldehyde as reactant, ionic liquid,
The method that agent prepares polymethoxy dimethyl ether, with reaction condition is mild, catalyst activity is high, the letter of high conversion rate, reaction process
Just, easy to operate, the features such as distribution of reaction products is good.
Chinese patent CN 101665414 disclose it is a kind of using dimethoxym ethane and metaformaldehyde as reactant, functionalization acidity from
Sub- liquid is the method for catalyst preparation polymethoxy dimethyl ether, with reaction condition is mild, catalyst activity is high, conversion ratio
High, the features such as reaction process is easy, easy to operate, distribution of reaction products is good.
Chinese patent CN 101768057 discloses one kind and prepares polymethoxy using methanol and metaformaldehyde as reaction raw materials
The method of dimethyl ether, using solid super acid catalyst, 70-200 DEG C of reaction temperature, 0.5-6MPa of reaction pressure.
Chinese patent CN 102040488 is disclosed a kind of prepared using methanol, dimethoxym ethane and metaformaldehyde as reaction raw materials and gathered
The method of methoxyl group dimethyl ether, using molecular sieve catalyst, 50-200 DEG C of reaction temperature, 0.1-10MPa of reaction pressure.
Chinese patent CN 102040490 is disclosed a kind of prepared using methanol, dimethoxym ethane and paraformaldehyde as reaction raw materials and gathered
The method of methoxyl group dimethyl ether, using solid super acid catalyst, 70-200 DEG C of reaction temperature, 0.2-6MPa of reaction pressure.
Chinese patent CN 102372611 and 102372612 individually discloses one kind with dimethoxym ethane and metaformaldehyde as reaction
Raw material carries out the method that reaction prepares polymethoxy dimethyl ether in catalytic rectifying tower.
PODE made above3-8Patent use metaformaldehyde or paraformaldehyde to provide the raw material of paraformaldehyde, reactant
Not aqueous or water content is very low in system, PODEnHigh income, PODE in product3-8Selectivity it is also higher, but metaformaldehyde or
Paraformaldehyde price is higher, therefore production cost is higher.
Use cheap methanol and formalin by the main problem that faces of raw material production polymethoxy dimethyl ether it
First is that contain a large amount of water in the reaction system, the water that the water and reaction brought into including formalin generate.By a large amount of water
It influences, methanol and formaldehyde reaction generate PODEnEquilibrium conversion substantially reduce, while generate PODEnProduct is mainly
PODE1-2, PODE3-8Selectivity it is very low.
Under the conditions of another problem is existing for the liquid water and methanol, only few part formaldehyde is with formaldehyde monomers molecule
Form exist, most formaldehyde reacted with water generation methylene glycol and its polymer poly Oxymethylene glycol or anti-with methanol
The hemiacetal of different polymerization degree should be generated;These reactions are reversible reaction and are not required to catalyst and can carry out, and are separated in distillation
It is easy to mutually convert in the process, so that purpose product PODEnIt is difficult to divide completely using general distillating method with these substances
From.
Chinese patent CN 106542977 discloses a kind of method for preparing polymethoxy dimethyl ether, draws in the reaction system
Enter extractant, under the catalysis of acidic catalyst, reaction and extraction are merged, separate organic phase and water phase after the reaction was completed, it will
Organic phase is refining to obtain polymethoxy dimethyl ether.The invention by introduce extractant, by reaction raw materials be extracted into extraction phase into
Row reaction, effectively prevents reaction product and side reaction occurs for water, can effectively improve the conversion ratio of raw material and the selectivity of product
And yield.But formaldehyde cannot react completely, still will cause very big difficulty, the separation including water in reaction mixture to later separation
With the recycling of formaldehyde etc..
Summary of the invention
The purpose of the present invention is to provide one kind to prepare more polymethoxy dimethyl ether (PODE by methanol and formalin2+)
Continuous catalysis extracting process, have the advantages that cost of material is low, product separation is easy.This method can both individually produce
PODE2, diesel fuel additives component (PODE3-4、PODE3-5Or PODE3-8One of) two kinds of products, it can also be with arbitrary proportion simultaneously
Produce both products.
As an implementation, the method that more polymethoxy dimethyl ethers are prepared by methanol and formalin,
It is characterized in that, comprising the following steps:
A) the material B of the material A containing formaldehyde and the polymethoxy dimethyl ether containing circular response is introduced into pre-reaction
Device carries out pre-reaction, obtains prereacted material I;
B) prereacted material I that step a) is obtained and material C containing methanol are introduced into catalytic extraction tower or multistage is urged
Change in extraction reactor, with extractant counter current contacting, carries out catalysis reaction and extraction, obtain extraction phase materials II and raffinate phase object
Expect III;
Wherein, the material C containing methanol is in the middle part of catalytic extraction tower or the centre of multistage catalytic extraction reactor
Grade charging.
As another embodiment, the method that more polymethoxy dimethyl ethers are prepared by methanol and formalin,
It is characterized in that, being arranged alternately catalyst bed and separating member in catalytic extraction tower, the separating member includes separation
Tower tray and/or filler;
The material B of material A containing formaldehyde and the polymethoxy dimethyl ether containing circular response is introduced together into catalysis
Extraction tower is introduced into one of catalyst bed and carries out catalysis reaction, then extracts with extractant counter current contacting, and alternately
Catalysis reaction and extraction process obtain extraction phase materials II and raffinate phase materials III;
Material C containing methanol charging in the middle part of catalytic extraction tower.
In all embodiments noted earlier,
Optionally, the catalytic extraction tower is the extraction tower containing at least one catalyst bed.Catalysis can be made to react
Journey and extraction process carry out simultaneously or in tower repeatedly alternately.
Optionally, the multistage catalytic extraction reactor is the multitple extraction equipment containing at least one catalyst bed.
Optionally, the catalyst bed is arranged in the water phase channel of catalytic extraction tower or multistage catalytic extraction reactor
The two-phase mixtures region and/or.
The extraction phase materials II mainly contains extractant, dimethoxym ethane and more polymethoxy dimethyl ethers.
Optionally, the material A containing formaldehyde is the aqueous solution containing formaldehyde.
Optionally, the material C containing methanol is methanol.
Polymethoxy dimethyl ether in the material B of the polymethoxy dimethyl ether containing circular response comes from the extraction
The isolate of phase materials II and/or the dimethoxym ethane of fresh addition.
Optionally, the polymethoxy dimethyl ether in the material B all is from the isolate of the extraction phase materials II.
Optionally, the inlet amount of the extractant and (material A containing the formaldehyde+material C containing methanol) inlet amount
Weight ratio is 0.3~12:1.The inlet amount of extractant is bigger, required catalytic extraction tower or multistage catalytic extraction reactor
Theoretical stage is fewer, but the energy consumption for recycling extractant increases.
Optionally, the extractant is selected from least one of halogenated hydrocarbons, aromatic hydrocarbons, alkane, cycloalkane.
Optionally, the halogenated hydrocarbons is selected from least one of dichloroethanes, dichloropropane, chlorobenzene, bromobenzene.
Optionally, the aromatic hydrocarbons is in benzene, toluene, ethylbenzene, dimethylbenzene, n-proplbenzene, isopropylbenzene, the first and second benzene, butylbenzene
It is at least one.
Optionally, in the isoparaffin that the alkane is 5~10 selected from carbon number n-alkane, carbon number are 5~10
It is at least one.
Optionally, the cycloalkane in hexamethylene, methyl cyclopentane, hexahydrotoluene, ethyl cyclohexane at least
It is a kind of.
Optionally, the extractant is dimethylbenzene.
Optionally, the extractant is isopropylbenzene.
Optionally, the extractant is the mixture of toluene and ethylbenzene.
Optionally, the extractant is the mixture of 1,2- dichloroethanes, 1,2- dichloropropane.
Optionally, the extractant is benzene.
Optionally, the extractant is the mixture of chlorobenzene and bromobenzene.
Optionally, the extractant is the mixture of n-hexane, normal heptane, isoheptane, normal octane and isooctane.
Optionally, the extractant is the mixture of n-proplbenzene, the first and second benzene, butylbenzene.
Optionally, the extractant is the mixture of hexamethylene, methyl cyclopentane, hexahydrotoluene, ethyl cyclohexane.
The catalyst of the catalysis reaction is selected from least one of solid acid catalyst.
Optionally, the solid acid catalyst is selected from storng-acid cation exchange resin and/or hydrogen molecular sieve catalyst.
Optionally, the hydrogen type molecular sieve catalyst contains HZSM-5 molecular sieve and/or H beta-molecular sieve.
The catalyst loaded in pre-reactor and catalytic extraction tower or multistage catalytic extraction reactor can it is identical, can also be with
It is different.
Optionally, the reaction temperature of the pre-reactor is 40~140 DEG C.
Optionally, the upper limit of the reaction temperature of the pre-reaction is selected from 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C, 130
DEG C or 140 DEG C;Lower limit is selected from 40 DEG C, 50 DEG C, 60 DEG C or 70 DEG C.
Optionally, the reaction temperature in the catalytic extraction tower or multistage catalytic extraction reactor is 40~140 DEG C.
Optionally, the upper limit of the catalytic extraction tower or the reaction temperature in multistage catalytic extraction reactor be selected from 80 DEG C,
90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C or 140 DEG C;Lower limit is selected from 40 DEG C, 50 DEG C, 60 DEG C or 70 DEG C.
Reaction temperature in the reaction temperature and catalytic extraction tower or multistage catalytic extraction reactor of the pre-reaction can be with
Identical to can also be different, the reaction temperature of pre-reaction can be higher than, be equal to or less than catalytic extraction tower or multistage catalytic extraction instead
The reaction temperature in device is answered, in above-mentioned range of reaction temperature.
Optionally, it is stripped out formaldehyde from extraction phase materials II with water or methanol, obtains the aqueous solution containing formaldehyde or contains first
The methanol solution of aldehyde;The aqueous solution containing formaldehyde or the methanol solution containing formaldehyde return to catalytic extraction tower or multistage catalytic extraction
The reaction was continued in reactor.
Optionally, using extract phase materials II removing extractant after at least part as reflux return catalytic extraction tower or
Multistage catalytic extraction reactor.It can be improved the concentration of more polymethoxy dimethyl ethers in extraction phase.
Specifically, when using catalytic extraction tower, the method in the case where water phase is heavy phase, extractant is light phase,
The material I or material A, B of the pre-reactor outflow are fed from the tower top of catalytic extraction tower, tower of the extractant from catalytic extraction tower
Bottom charging is obtained mainly organizing the extraction phase materials for becoming extractant and polymethoxy dimethyl ether from tower top, be obtained mainly from tower bottom
Group becomes the raffinate phase materials of water.
The method is in the case where water phase is light phase, extractant is heavy phase, the material I or object of the pre-reactor outflow
Expect that A, B are fed from the tower bottom of catalytic extraction tower, extractant is fed from the tower top of catalytic extraction tower, and obtaining main group from tower bottom becomes
The extraction phase materials of extractant and polymethoxy dimethyl ether obtain mainly organizing the raffinate phase materials for becoming water from tower top.
Methanol and formaldehyde can occur condensation reaction in aqueous solution under suitable catalyst action and generate different polymerizations
The polymethoxy dimethyl ether of degree, the reaction are a reversible reactions, and conversion ratio is limited very big by chemical balance, and product is poly-
It is right higher, selective lower, therefore it is suitable as the PODE of diesel fuel additives3-8Yield it is lower.The influence of water is non-in the reaction
Chang great, water content is higher in reaction system, and the conversion ratio of formaldehyde and methanol is lower, reaction product distribution more concentrates on dimethoxym ethane
Equal low polymerization degrees product.And methanol, formaldehyde ratio are higher, formaldehyde conversion is higher, methanol conversion is lower, simultaneous reactions product
Distribution more concentrates on the low polymerization degrees product such as dimethoxym ethane.
In the inventive solutions, in the presence of the suitable extractant immiscible with water, methanol and formaldehyde are main
It is present in water phase, and reaction product polymethoxy dimethyl ether is then enriched in extraction phase.By Catalyst packing in raffinate phase (water
Phase) in channel, only water phase material is enabled to contact with catalyst, diffuse into inside its particle and carry out reaction and generate poly- first
Oxygroup dimethyl ether;Extraction phase is not contacted with catalyst, because connecing inside its particle with its Active sites without entering simultaneously
Touching, i.e., the polymethoxy dimethyl ether in extraction phase will not decompose under the effect of the catalyst.In this way, although the condensation in water phase is anti-
It should still be limited by chemical balance, but catalysis reaction will not occur in extraction phase, the content of polymethoxy dimethyl ether is not changed
The limitation of balance is learned, thus the conversion ratio of methanol and formaldehyde can substantially exceed equilibrium conversion.Or by Catalyst packing two
It mixes in region, since catalyst has stronger hydrophily, only water phase material is able to enter hair inside catalyst granules
Raw catalysis reaction, and extracting phase materials cannot enter inside catalyst granules, is same because can also obtain without catalysis reaction occurs
The effect of sample.
In the first embodiment of the invention, at first the PODE mono- of formalin and circular response is introduced into pre- anti-
Answer in device and sufficiently reacted, become water, formaldehyde, methanol, the various degree of polymerization PODEnThe mixture of (n=1,2,3, etc.),
Composition is formed close to chemical balance.Wherein methanol is this reaction process consumption one from the PODE hydrolysis of circular response
Quantitative water, and the reaction that the PODE of circular response is converted into other degree of polymerization PODE does not generate water, this reduces anti-
The water content in system is answered, keeps chemical balance mobile to the direction for being conducive to formaldehyde conversion and generation higher degrees of polymerization PODE, it can
To improve formaldehyde conversion and target product (PODE2Or be suitable as the PODE of diesel oil addO-on therapy) concentration.Then should
Reaction mixture is introduced into catalytic extraction tower or multistage catalytic extraction reactor with extractant counter current contacting, can be made from catalysis
The concentration of target product reaches highest in the extraction phase that extraction tower or multistage catalytic extraction reactor obtain, to improve production effect
Rate.
If the PODE of formalin and circular response is directly entered catalytic extraction tower or multistage catalytic extraction reactor
It is in contact with extraction, due to being substantially free of target product in water phase at this time, a part of the target product in extraction phase can enter
Water phase causes the concentration of the target product from the extraction phase that catalytic extraction tower or multistage catalytic extraction reactor obtain to reduce.Using
The method that pre-reactor is arranged described in the first embodiment above can be to avoid the generation of this rough sledding.
In the second embodiment, when the PODE of formalin and circular response is introduced together into catalytic extraction tower,
It is introduced into catalyst bed to be reacted, then the extraction that is in contact with extraction can also obtain and similar effect described above.
In catalytic extraction tower or multistage catalytic extraction reactor, water phase material (methanol and formalin) and extraction phase
Material counter current contacting either simultaneously or alternately carries out catalysis reaction and extraction process.In the water phase of water phase material entrance, water is dense
Spend lower and reactant concentration of formaldehyde is higher, thus the concentration of polymethoxy dimethyl ether is higher (limitation of chemical balance is smaller);
And extraction phase carries the polymethoxy dimethyl ether (concentration is lower) for extracting and from the water phase of downstream and contacts and further extracted
It takes, polymethoxy dimethyl ether therein is up to higher concentration.Concentration of formaldehyde has been in water phase material near exit, water phase
Very low, after contacting with fresh extractant, extracting polymethoxy dimethyl ether therein, the condensation reaction of formaldehyde and methanol is obtained
Promote, in the excessive situation of methanol, the formaldehyde in water phase can be converted substantially completely, to can avoid the difficulty of separating formaldehyde.
The basic demand of slective extraction agent is PODEnDistribution ratio (PODE in extraction phasenPODE in concentration and water phasenIt is dense
The ratio between degree) be greater than methanol, formaldehyde distribution ratio (methanol in the concentration and water phase of methanol, formaldehyde in extraction phase, formaldehyde concentration it
Than).Meeting this requirement i.e. can reach the effect for breaking Equilibrium limit, and the two difference is bigger, effect is more obvious.PODEn
Distribution ratio it is bigger, the effect that reaction product polymethoxy dimethyl ether is enriched in extraction phase is better, and Solvent quantity is fewer, return
Energy consumption required for receipts extractant is lower, and production cost is lower.Methanol, the distribution ratio of formaldehyde are smaller, methanol in water phase, formaldehyde
Concentration is higher, reacts easier progress, and the methanol, concentration of formaldehyde in extraction phase are lower, recycling is easier.
The PODE of partial extraction agentnDistribution ratio increases with the increase of n, is conducive to improve PODE in product3-8Ratio.
Methanol is in the middle part of catalytic extraction tower or the charging of the centre grade of multistage catalytic extraction reactor is conducive to improve from urging
Change the reaction product PODE that extraction tower or multistage catalytic extraction reactor obtainnThe ratio of middle higher degrees of polymerization PODE is reduced and is followed
The internal circulating load of ring reaction PODE.Under this methanol feeding mode, in the downstream of catalytic extraction tower or multistage catalytic extraction reactor
(pressing water phase flow direction of material), methanol can excessively ensure formaldehyde fully reacting, and key reaction product is dimethoxym ethane;At its upstream
(pressing water phase flow direction of material) then keeps higher formaldehyde group and sealing end methyl ratio, while it is anti-with formaldehyde condensation to reduce methanol
At once the water generated is conducive to more generate high polymerization degree PODE;The dimethoxym ethane wherein generated in the water phase of downstream enters extraction
It mutually returns to water phase upstream, partially enter the PODE that water phase reacts generation higher degrees of polymerization with formaldehyde.
Main group of obtained extraction phase become extractant and polymethoxy dimethyl ether, formaldehyde, methanol, water content very
It is low.Wherein formaldehyde mainly in the form of methylene glycol, polyoxymethylene glycol, hemiacetal exist and be readily decomposed to monomer formaldehyde and
Water, methanol are difficult to effectively remove using common rectificating method, and a small amount of formaldehyde contained therein can be first stripped out with water or methanol
After separate other components.Being stripped the obtained strip liquor containing formaldehyde can return in catalytic extraction tower or multistage catalytic extraction reactor
The reaction was continued, and feed entrance point is the centre grade of catalytic extraction tower middle part or multistage catalytic extraction reactor.
Extraction phase extractant obtained after separation can be recycled, and product polymethoxy dimethyl ether can be divided into dimethoxym ethane
(DMM), two polymethoxy dimethyl ether (PODE2), diesel fuel additives component (PODE3-4, PODE3-5Or PODE3-8), heavy constituent it is (poly-
The right PODE higher than diesel fuel additives component) etc. components.
PODE2, diesel fuel additives component all can serve as final products, can both individually produce any of them production
Product with arbitrary proportion while can also produce both products, and remaining PODEn(i.e. circular response PODE) then returns to catalysis
Extraction reaction system circular response is reacted into reactor set in addition, is converted into required final products.
Circular response PODE includes DMM, heavy constituent;When with PODE2It further include diesel fuel additives when for primary end product
Component;It further include PODE when using diesel fuel additives component as primary end product2。
Heavy constituent under the action of catalyst can be with methanol or PODE1-2The compound of equal offers sealing end methyl reacts, and turns
Turn to the PODE of low degree.Two kinds of reactive modes can be taken, returns and urges one is a part as circular response PODE
Change extraction tower or multistage catalytic extraction reactor circular response, one is with proper amount of methanol or DMM and/or PODE2Into independent
Reactor reacted.
Reaction raw materials formalin can use concentration of formaldehyde for the aqueous solution of 10-80wt%, wherein can be containing few
Methanol is measured, concentration of formaldehyde is higher, the internal circulating load of circular response PODE is smaller, production efficiency is higher.PODEnSelectivity (be based on
Carbon number calculates) up to 96-99.5%, mainly metaformaldehyde in by-product, selectivity < 1% of other by-products.Metaformaldehyde
It can be isolated as a kind of product, catalytic extraction reaction system circular response or the individual reactor of setting can also be returned
With methanol or DMM and/or PODE2Reaction generates PODEn。
It is below that a kind of of technical solution of the present invention uses ethylbenzene to produce PODE for extractant3-8Specific embodiment.
As shown in Fig. 1, the PODE of formalin (S1) and circular response1-2(S11)、PODE9+(S16) in mixer
(M1) (S4) enters the pre-reactor (R1) that strong acid cation exchange resin catalyst is housed after mixing in, sufficiently after reaction
(S5) from the catalytic extraction tower or multistage catalytic extraction reactor for being filled with strong acid cation exchange resin catalyst catalyst
(T1) top feed, methanol (S2) are fed in the middle part of tower, and extractant ethylbenzene (S3) is fed from tower bottom;Raffinate phase (S6) i.e. water phase
It is produced from catalytic extraction tower or multistage catalytic extraction reactor (T1) tower bottom, is substantially free of the organic matters such as formaldehyde, can be directly as
Wastewater treatment feeds from the back extraction tower bottom (T2) from extraction phase (S7) the i.e. organic phase of overhead extraction, is fed from the top of tower
Water (S8) be stripped out after formaldehyde therein, methanol from overhead extraction (back extraction organic phase S10), tower bottom produces formaldehyde, methanol
Aqueous solution (strip aqueous S9) returns to catalytic extraction tower or multistage catalytic extraction reactor (T1), and the reaction was continued, because of wherein water content
The higher therefore charging in the middle part of tower;It is stripped organic phase (S10) and enters lightness-removing column (T3) progress rectifying separation, tower top obtains light component
PODE1-2(S11), tower bottoms (S12) enters ethylbenzene recovery tower (T4) recycling extractant ethylbenzene;Ethylbenzene recovery tower (T4) tower top obtains
The recycling ethylbenzene (S13) arrived returns to catalytic extraction tower or (i.e. S3) is recycled in multistage catalytic extraction reactor (T1), when necessary
The fresh ethylbenzene in part can be supplemented, tower bottoms (S14) enters PODE tower (T5) and carries out rectifying separation;PODE tower (T5) tower top is produced
Product PODE3-8(S15), the PODE that tower bottom obtains9+(S16) and the PODE of formalin (S1), circular response1-2(S11) mixed
Enter pre-reactor (R1) after mixing in clutch (M1).
In the application, " more polymethoxy dimethyl ethers " refers to the target product of technical scheme, is PODE2, diesel oil
Additive component (PODE3-4、PODE3-5Or PODE3-8One of) two kinds of products, both can also be produced simultaneously with arbitrary proportion
Product.
The polymethoxy dimethyl ether of circular response refers to the dimethoxym ethane except target product, such as when target product is
PODE2When, the polymethoxy dimethyl ether of circular response is PODE1、PODE3-4、PODE3-5、PODE3-8Deng;Such as work as target product
For PODE3-4、PODE3-5Or PODE3-8When, the polymethoxy dimethyl ether of circular response is PODE1、PODE2Deng.
In the application, storng-acid cation exchange resin is the common knowledge of those skilled in the art, is not done herein specific
Description.
The beneficial effect that the present invention can generate includes: that cheap formalin can be used for raw material, low cost,
Expeditiously produce PODE2And/or diesel fuel additives component.
Detailed description of the invention
Fig. 1 is that the application uses ethylbenzene to produce PODE for extractant3-8Process flow diagram.
Component and appended drawing reference:
S1: formalin, S2: methanol, S3: ethylbenzene, S4:R1 charging,
S5:R1 discharging, S6: raffinate phase, S7: extraction phase, S8: water, S9: strip aqueous, S10: back extraction organic phase, S11:
PODE1-2, S12:T3 tower bottoms, S13: recycling ethylbenzene, S14:T4 tower bottoms, S15:PODE3-8, S16:PODE9+
M1: mixer, R1: pre-reactor, T1: catalytic extraction tower, T2: back extraction tower,
T3: lightness-removing column, T4: ethylbenzene recovery tower, T5:PODE tower
Specific embodiment
The present invention is described in detail below by embodiment, but the invention is not limited to these embodiments.
In following embodiment and comparative example, methanol used, formalin, paraformaldehyde, dimethoxym ethane are the pure examination of analysis
Agent;Wherein, the content of formaldehyde of formalin is 38wt%, and 3wt% containing methanol.The above polymethoxy dimethyl ether of dimerization
(PODE2+) it is to recycle to obtain from reaction solution, purity 99wt%.
Strong acidic ion resin catalyst used in embodiment is D006 resin catalyst, is purchased from triumphant auspiciousization in Hebei
Work Co., Ltd.
The molecular sieves such as HZSM-5 and H β used in embodiment are purchased from Catalyst Factory, Nankai Univ.
Embodiment 1
Pre-reactor is the stainless steel fixed bed reactors of internal diameter 14mm high 0.3m, loads storng-acid cation exchange resin
40 milliliters of catalyst, the heavy phase feed pipe of pre-reactor outlet connection catalytic extraction reactor.
Loaded in the stainless steel catalytic extraction reactor of internal diameter 20mm high 1.3m 160 milliliters of uniformly mixed highly acid sun from
Sub-exchange resin catalyst and 200 milliliters of Φ 3 × 3mm stainless steel Dixon rings load 1.2 meters of height, thereon a height of blank pipe of 10cm.
Heavy phase feed pipe is set at the top of reactor 1.2m eminence, that is, catalyst and Dixon ring bed, and reactor head is arranged light phase and discharges
Light phase feed pipe is arranged in the counterbalance valve of pipe connection control reaction pressure, reactor bottom, and reactor bottom connects heat resisting and pressure resisting glass
Glass pipe connects heavy phase discharge nozzle for observing two phase stratification situation.
The formalin (containing methanol 3wt%) and PODE of 38wt%1-2Enter pre-reaction after (DMM accounts for 60wt%) mixing
Device, inlet amount are respectively 11.7ml/min, 8.2ml/min;Methanol is fed from catalytic extraction reactor 0.3m eminence, inlet amount
3.1ml/min;It uses mixed xylenes for extractant, is fed from reactor bottom, inlet amount 56ml/min;Pre-reactor reaction
Temperature 60 C, catalytic extraction reactor reaction temperature 60 C, reaction pressure 0.3MPa.
Reactor head light phase load be 63.6g/min, wherein formaldehyde 2.7wt%, methanol 1wt%, water 0.2wt%,
DMM 6.4wt%, PODE24.6wt%, PODE3+7wt%, remaining is mixed xylenes and micro by-product.
Reactor bottom heavy phase load is 7.8g/min, wherein methanol 3.1wt%, formaldehyde 0.01wt%, mixing diformazan
Benzene 0.4wt%, remaining is water.
Embodiment 2
Using pre-reactor same as Example 1, catalytic extraction reactor, catalyst, catalyst loading pattern and dress
The amount of filling out.
The formalin (containing methanol 3wt%) and PODE of 38wt%1-2Enter pre-reaction after (DMM accounts for 60wt%) mixing
Device, inlet amount are respectively 7ml/min, 6ml/min;Methanol is fed from catalytic extraction reactor 0.5m eminence, inlet amount 2ml/
min;It uses isopropylbenzene for extractant, is fed from reactor bottom, inlet amount 37ml/min;60 DEG C of pre-reactor reaction temperature,
Catalytic extraction reactor reaction temperature 50 C, reaction pressure 0.3MPa.
Reactor head light phase load is 41.2g/min, wherein formaldehyde 1.8wt%, methanol 0.74wt%, water
0.16wt%, DMM 7.2wt%, PODE25.1wt%, PODE3+7.5wt%, remaining is isopropylbenzene and micro by-product.
Reactor bottom heavy phase load is 4.9g/min, wherein methanol 2.8wt%, formaldehyde 0.01wt%, isopropylbenzene
0.24wt%, remaining is water.
Embodiment 3
Using pre-reactor same as Example 1, catalytic extraction reactor and catalyst loading pattern.The difference is that pre-
Bar shaped HZSM-5 molecular sieve catalyst (the wherein salic binder of 40 milliliters of 2 × 3-5mm of Φ is loaded in reactor
20wt%, the silicoaluminophosphate molecular ratio of molecular sieve are 38), 160 milliliters of uniformly mixed 2 × 3- of Φ to be loaded in catalytic extraction reactor
60) and 200 (wherein salic binder 20wt%, the silicoaluminophosphate molecular ratio of molecular sieve are to the bar shaped H beta-molecular sieve catalyst of 5mm
Milliliter Φ 3 × 3mm stainless steel Dixon ring.
The formalin (from being diluted by 38wt% formalin, containing methanol 2.4wt%) and PODE of 30wt%1-2
Enter pre-reactor after (DMM accounts for 55wt%) mixing, inlet amount is respectively 8.3ml/min, 5ml/min;Methanol is from catalytic extraction
The charging of reactor 0.3m eminence, inlet amount 2.4ml/min;Use toluene and ethyl benzene mixtures (weight ratio 1:1) for extractant, from
Reactor bottom charging, inlet amount 37.2ml/min;110 DEG C of pre-reactor reaction temperature, catalytic extraction reactor reaction temperature
120 DEG C, reaction pressure 1.2MPa.
Reactor head light phase load be 41.6g/min, wherein formaldehyde 2.2wt%, methanol 1wt%, water 0.2wt%,
DMM 6.2wt%, PODE24.6wt%, PODE3+6.7wt%, remaining is toluene, ethylbenzene and micro by-product.
Reactor bottom heavy phase load is 6.7g/min, wherein methanol 2.6wt%, formaldehyde 0.01wt%, toluene and second
Benzene 0.3wt%, remaining is water.
Embodiment 4
Using pre-reactor same as Example 1, catalytic extraction reactor, catalyst, catalyst loading pattern and dress
The amount of filling out.The difference is that the light phase feed pipe of pre-reactor outlet connection catalytic extraction reactor.
Paraformaldehyde reagent and suitable quantity of water are mixed and heated to the formalin that content of formaldehyde 50wt% is made after dissolution,
With PODEn(DMM accounts for 50wt%, PODE2Account for 40wt%, PODE5+Account for 10wt%) mixing after enter pre-reactor, inlet amount difference
For 8.4ml/min, 11.4ml/min;Methanol is fed from 0.9m eminence, inlet amount 3.9ml/min;Using 1,2- dichloroethanes and
1,2- dichloropropane mixture (weight ratio 1:1) is extractant, from the heavy phase feed tube of 1.2m eminence, inlet amount
12.4ml/min;55 DEG C of pre-reactor reaction temperature, 40 DEG C of catalytic extraction reactor reaction temperature, reaction pressure 0.3MPa.
Reactor bottom heavy phase load be 32g/min, wherein formaldehyde 5.8wt%, methanol 3.2wt%, water 0.6wt%,
DMM 13.9wt%, PODE211.6wt%, PODE3+18.2wt%, metaformaldehyde 0.2wt%, remaining is 1,2- dichloroethanes
With 1,2- dichloropropane and micro by-product.
Reactor head light phase load is 5.4g/min, wherein methanol 1.6wt%, formaldehyde 0.01wt%, 1,2- dichloro
Ethane and 1,2- dichloropropane 3wt%, remaining is water.
Embodiment 5
Using pre-reactor same as Example 1, catalytic extraction reactor, catalyst, catalyst loading pattern and dress
The amount of filling out.
Paraformaldehyde reagent and suitable quantity of water are mixed and heated to the formalin that content of formaldehyde 60wt% is made after dissolution
With PODE1-2Enter pre-reactor after (DMM accounts for 50wt%) mixing, inlet amount is respectively 10.4ml/min, 8.4ml/min;Methanol
It is fed from 0.3m eminence, inlet amount 5.7ml/min;It uses benzene for extractant, is fed from reactor bottom, inlet amount 10ml/
min;80 DEG C of pre-reactor reaction temperature, catalytic extraction reactor reaction temperature 60 C, reaction pressure 0.5MPa.
Reactor head light phase load be 26.5g/min, wherein formaldehyde 3.8wt%, methanol 3wt%, water 0.1wt%,
DMM 13.6wt%, PODE213.1wt%, PODE3+32.6wt%, metaformaldehyde 0.5wt%, remaining is benzene and micro by-product
Object.
Reactor bottom heavy phase load is 6.2g/min, wherein methanol 1.8wt%, formaldehyde 0.01wt%, benzene
0.1wt%, remaining is water.
Embodiment 6
Using pre-reactor same as Example 1, catalytic extraction reactor, catalyst, catalyst loading pattern and dress
The amount of filling out.The difference is that the light phase feed pipe of pre-reactor outlet connection catalytic extraction reactor.
The formalin (containing methanol 3wt%) and PODE of 38wt%1-2Enter pre-reaction after (DMM accounts for 60wt%) mixing
Device, inlet amount are respectively 8.2ml/min, 6ml/min;Methanol is fed from 0.9m eminence, inlet amount 2.6ml/min;Using chlorobenzene
It is extractant with bromobenzene (weight ratio 9:1) mixture, from the heavy phase feed tube of 1.2m eminence, inlet amount 30ml/min;In advance
80 DEG C of reactor reaction temperature, 80 DEG C of catalytic extraction reactor reaction temperature, reaction pressure 0.5MPa.
Reactor bottom heavy phase load be 43.8g/min, wherein formaldehyde 2wt%, methanol 0.6wt%, water 0.16wt%,
DMM 6.7wt%, PODE25.3wt%, PODE3+8.2wt%, remaining is chlorobenzene, bromobenzene and micro by-product.
Reactor head light phase load is 5.7g/min, wherein methanol 1.8wt%, formaldehyde 0.01wt%, chlorobenzene and bromine
Benzene 1wt%, remaining is water.
Embodiment 7
Using pre-reactor same as Example 1, catalytic extraction reactor and catalyst loading pattern, pre-reactor
Same 40 milliliters of strong acid cation exchange resin catalyst of filling.Unlike, filling mixing is equal in catalytic extraction reactor
Bar shaped HMCM-22 molecular sieve catalyst (wherein salic binder 30wt%, the molecule of 160 milliliters of even 2 × 3-5mm of Φ
28) and 200 milliliters of Φ 3 × 3mm stainless steel Dixon rings the silicoaluminophosphate molecular ratio of sieve is.
The formalin (containing methanol 3wt%) and PODE of 38wt%1-2Enter pre-reaction after (DMM accounts for 60wt%) mixing
Device, inlet amount are respectively 6ml/min, 8.5ml/min;Methanol is fed from 0.3m eminence, inlet amount 2ml/min;It is mixed using alkane
Closing object (n-hexane, normal heptane, isoheptane, normal octane and isooctane respectively account for 20wt%) is extractant, is fed from reactor bottom,
Inlet amount 108ml/min;80 DEG C of pre-reactor reaction temperature, 120 DEG C of catalytic extraction reactor reaction temperature, reaction pressure
1.2MPa。
Reactor head light phase load is 84.4g/min, wherein formaldehyde 0.4wt%, methanol 0.3wt%, water
0.1wt%, DMM 5.1wt%, PODE23.5wt%, PODE3+3.7wt%, remaining is paraffins mixture and micro by-product.
Reactor bottom heavy phase load is 4.3g/min, wherein methanol 1.2wt%, formaldehyde 0.01wt%, alkane mixing
Object 0.1wt%, remaining is water.
Embodiment 8
Using pre-reactor same as Example 1, catalytic extraction reactor, catalyst, catalyst loading pattern and dress
The amount of filling out.
The formalin (containing methanol 3wt%) and PODE of 38wt%1-2Enter pre-reaction after (DMM accounts for 55wt%) mixing
Device, inlet amount are respectively 7.4ml/min, 6ml/min;Methanol is fed from catalytic extraction reactor 0.3m eminence, inlet amount
2.4ml/min;Use aromatic hydrocarbons mixture (n-proplbenzene, the first and second benzene, butylbenzene account for 40wt%, 30wt%, 30wt% respectively) for extraction
Agent is fed, inlet amount 37ml/min from reactor bottom;60 DEG C of pre-reactor reaction temperature, catalytic extraction reactor reaction temperature
50 DEG C of degree, reaction pressure 0.3MPa.
Reactor head light phase load flow is 41.3g/min, wherein formaldehyde 1wt%, methanol 0.8wt%, water
0.1wt%, DMM 7.2wt%, PODE25.6wt%, PODE3+9.3wt%, remaining is BTX aromatics and micro by-product.
Reactor bottom heavy phase load is 5.4g/min, wherein methanol 1.8wt%, formaldehyde 0.01wt%, BTX aromatics
0.1wt%, remaining is water.
Embodiment 9
Using pre-reactor same as Example 1, catalytic extraction reactor, catalyst, catalyst loading pattern and dress
The amount of filling out.
Paraformaldehyde reagent and suitable quantity of water are mixed and heated to the formalin that content of formaldehyde 80wt% is made after dissolution
With PODE1-2Enter pre-reactor after (DMM accounts for 50wt%) mixing, inlet amount is respectively 10.3ml/min, 10.6ml/min;First
Alcohol is fed from 0.3m eminence, inlet amount 7.5ml/min;Using using cycloalkanes hydrocarbon mixture (hexamethylene, methyl cyclopentane, methyl
Hexamethylene, ethyl cyclohexane respectively account for 25wt%) it is extractant, it is fed from reactor bottom, inlet amount 14.5ml/min;Pre-reaction
80 DEG C of device reaction temperature, catalytic extraction reactor reaction temperature 60 C, reaction pressure 0.5MPa.
Reactor head light phase load be 36g/min, wherein formaldehyde 0.8wt%, methanol 0.9wt%, water 0.1wt%,
DMM 13.1wt%, PODE212wt%, PODE3+37.3wt%, metaformaldehyde 0.3wt%, remaining is cycloalkane and micro pair
Product.
Reactor bottom heavy phase load is 4.5g/min, wherein methanol 1.5wt%, formaldehyde 0.01wt%, cycloalkane
0.06wt%, remaining is water.
Embodiment 10
2 × 2mm of Φ stainless steel Dixon ring is loaded in the glass tube of internal diameter 15mm high 1.2m as back extraction tower, filling height 1
Heavy phase and light phase feed inlet, glass tube is respectively set in Dixon ring bed upper and lower ends position in rice, upper and lower Ge Liu 10cm high blank pipe
Upper and lower ends are respectively light phase and heavy phase discharge port.
By extract liquor obtained in embodiment 2, (group becomes formaldehyde 1.8wt%, methanol 0.74wt%, water 0.16wt%, DMM
7.2wt%, PODE25.1wt%, PODE3+7.5wt%, remaining is isopropylbenzene and micro by-product) from light phase throat-fed,
Inlet amount 15ml/min;Water (heavy phase) is used as strippant from heavy phase throat-fed, inlet amount 0.6ml/min;It is stripped temperature
26 DEG C, operating pressure is normal pressure.
Back extraction top of tower light phase (organic phase) load be 12.7g/min, wherein formaldehyde < 0.005wt%, methanol <
0.005wt%, water 0.5wt%, DMM 7.2wt%, PODE25.1wt%, PODE3+7.6wt%, remaining is isopropylbenzene and micro
By-product.
Back extraction tower bottom heavy phase (water phase) load be 0.9g/min, wherein methanol 10.6wt%, formaldehyde 25.7wt%,
DMM 2.3wt%, PODE21.6wt%, PODE3+1.4wt%, isopropylbenzene 0.3wt%, remaining is water.
Embodiment 11
Using back extraction experimental provision same as in Example 10.
By extract liquor obtained in embodiment 4, (group becomes formaldehyde 5.8wt%, methanol 3.2wt%, water 0.6wt%, DMM
13.9wt%, PODE211.6wt%, PODE3+18.2wt%, metaformaldehyde 0.2wt%, remaining is 1,2- dichloroethanes and 1,
2- dichloropropane and micro by-product) from heavy phase throat-fed, inlet amount 15ml/min;Methanol (light phase) is used as strippant
From light phase throat-fed, inlet amount 4.4ml/min;26 DEG C of temperature of back extraction, operating pressure is normal pressure.
Back extraction tower bottom heavy phase load is 17.6g/min, wherein formaldehyde < 0.005wt%, water < 0.005wt%, methanol
12.2wt%, DMM 13.1wt%, PODE211wt%, PODE3+17.5wt%, metaformaldehyde 0.19wt%, remaining is 1,2-
Dichloroethanes and 1,2- dichloropropane and micro by-product.
Back extraction top of tower light phase load is 3.2g/min, wherein water 3.3wt%, formaldehyde 31.4wt%, DMM
3.4wt%, PODE22.3wt%, PODE3+2.6wt%, metaformaldehyde 0.06wt%, 1,2- dichloroethanes and 1,2- dichloro third
Alkane 2.8wt%, remaining is methanol.
Comparative example 1
Loaded in the stainless steel catalytic extraction reactor of internal diameter 20mm high 1.3m 160 milliliters of uniformly mixed highly acid sun from
Sub-exchange resin catalyst and 200 milliliters of Φ 3 × 3mm stainless steel Dixon rings load 1.2 meters of height, thereon a height of blank pipe of 10cm.
Heavy phase feed pipe is set at the top of reactor 1.2m eminence, that is, catalyst and Dixon ring bed, and reactor head is arranged light phase and discharges
Light phase feed pipe is arranged in the counterbalance valve of pipe connection control reaction pressure, reactor bottom, and reactor bottom connects heat resisting and pressure resisting glass
Glass pipe connects heavy phase discharge nozzle for observing two phase stratification situation.
Do not set pre-reactor, the formalin (containing methanol 3wt%) of 38wt% is from catalytic extraction reactor 1.2m eminence
Heavy phase feed tube, inlet amount 10.7ml/min;PODE1-2(DMM accounts for 60wt%) is from catalytic extraction reactor 0.9m eminence
Charging, inlet amount 8.2ml/min;Methanol is fed from catalytic extraction reactor 0.3m eminence, inlet amount 2.6ml/min;Using
Mixed xylenes is extractant, is fed from reactor bottom, inlet amount 62ml/min;60 DEG C of reaction temperature, reaction pressure
0.3MPa。
Reactor head light phase load is 67.6g/min, wherein formaldehyde 3.2wt%, methanol 0.8wt%, water
0.2wt%, DMM 6.2wt%, PODE24.2wt%, PODE3+4.8wt%, remaining is mixed xylenes and micro by-product.
Reactor bottom heavy phase load is 7.8g/min, wherein methanol 3.1wt%, formaldehyde 0.03wt%, mixing diformazan
Benzene 0.4wt%, remaining is water.
Comparative example 1 compared with Example 1 compared with, when illustrating not set pre-reactor, other conditions as close possible to the case where
Under, the concentration for extracting PODE in phase materials is substantially reduced, and wherein PODE3+Shared ratio is obviously reduced.
The above is only several embodiments of the application, not does any type of limitation to the application, although this Shen
Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off
In the range of technical scheme, a little variation or modification are made using the technology contents of the disclosure above and is equal to
Case study on implementation is imitated, is belonged in technical proposal scope.
Claims (10)
1. a kind of method for preparing more polymethoxy dimethyl ethers by methanol and formalin, which is characterized in that including following step
It is rapid:
A) by the material B of the material A containing formaldehyde and the polymethoxy dimethyl ether containing circular response be introduced into pre-reactor into
Row pre-reaction obtains prereacted material I;
B) prereacted material I that step a) is obtained and material C containing methanol are introduced into catalytic extraction tower or multistage catalytic extracts
It takes in reactor, with extractant counter current contacting, carries out catalysis reaction and extraction, obtain extraction phase materials II and raffinate phase materials
III;
Wherein, the material C containing methanol is in the middle part of catalytic extraction tower or the centre of multistage catalytic extraction reactor is grading
Material.
2. a kind of method for preparing more polymethoxy dimethyl ethers by methanol and formalin, which is characterized in that in catalytic extraction
Catalyst bed and separating member are arranged alternately in tower, the separating member includes separation tray and/or filler;
The material B of material A containing formaldehyde and the polymethoxy dimethyl ether containing circular response is introduced together into catalytic extraction
Tower is introduced into one of catalyst bed and carries out catalysis reaction, then extracts with extractant counter current contacting, and be alternately catalyzed
Reaction and extraction process obtain extraction phase materials II and raffinate phase materials III;
Material C containing methanol charging in the middle part of catalytic extraction tower.
3. preparing the method for more polymethoxy dimethyl ethers according to claim 1 or described in 2, which is characterized in that described to contain
Isolate of the polymethoxy dimethyl ether from the extraction phase materials II in the material B of the polymethoxy dimethyl ether of circular response
And/or the polymethoxy dimethyl ether of fresh addition.
4. the method according to claim 1 or 2 for preparing more polymethoxy dimethyl ethers, which is characterized in that the extractant
Inlet amount and (material A containing the formaldehyde+material C containing methanol) inlet amount weight ratio be 0.3~12:1.
5. the method according to claim 1 or 2 for preparing more polymethoxy dimethyl ethers, which is characterized in that the extractant
Selected from least one of halogenated hydrocarbons, aromatic hydrocarbons, alkane, cycloalkane;
Preferably, the halogenated hydrocarbons is selected from least one of dichloroethanes, dichloropropane, chlorobenzene, bromobenzene;
Preferably, the aromatic hydrocarbons in benzene, toluene, ethylbenzene, dimethylbenzene, n-proplbenzene, isopropylbenzene, the first and second benzene, butylbenzene at least
It is a kind of;
Preferably, the alkane is 5-10 selected from carbon number n-alkane, carbon number are at least one in the isoparaffin of 5-10
Kind;
Preferably, the cycloalkane is selected from least one of hexamethylene, methyl cyclopentane, hexahydrotoluene, ethyl cyclohexane;
Preferably, the extractant is dimethylbenzene;
Preferably, the extractant is isopropylbenzene;
Preferably, the extractant is the mixture of toluene and ethylbenzene;
Preferably, the extractant is the mixture of 1,2- dichloroethanes, 1,2- dichloropropane;
Preferably, the extractant is benzene;
Preferably, the extractant is the mixture of chlorobenzene and bromobenzene;
Preferably, the extractant is the mixture of n-hexane, normal heptane, isoheptane, normal octane and isooctane;
Preferably, the extractant is the mixture of n-proplbenzene, the first and second benzene, butylbenzene;
Preferably, the extractant is the mixture of hexamethylene, methyl cyclopentane, hexahydrotoluene, ethyl cyclohexane.
6. the method according to claim 1 or 2 for preparing more polymethoxy dimethyl ethers, which is characterized in that the catalysis is anti-
The catalyst answered is selected from least one of solid acid catalyst;
Preferably, the solid acid catalyst is selected from storng-acid cation exchange resin and/or hydrogen type molecular sieve catalyst;
It is further preferred that the hydrogen type molecular sieve catalyst contains HZSM-5 molecular sieve and/or H beta-molecular sieve.
7. the method according to claim 1 for preparing more polymethoxy dimethyl ethers, which is characterized in that the reaction of pre-reactor
Temperature is 40~140 DEG C.
8. the method according to claim 1 or 2 for preparing more polymethoxy dimethyl ethers, which is characterized in that catalytic extraction tower
Or the reaction temperature in multistage catalytic extraction reactor is 40~140 DEG C.
9. the method according to claim 1 or 2 for preparing more polymethoxy dimethyl ethers, which is characterized in that use water or methanol
It is stripped out formaldehyde from extraction phase materials II, obtains the aqueous solution containing formaldehyde or the methanol solution containing formaldehyde;It is described containing formaldehyde
Aqueous solution or methanol solution containing formaldehyde return in catalytic extraction tower or multistage catalytic extraction reactor that the reaction was continued.
10. the method according to claim 1 or 2 for preparing more polymethoxy dimethyl ethers, which is characterized in that by extraction phase object
At least part after expecting II removing extractant returns to catalytic extraction tower or multistage catalytic extraction reactor as reflux.
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