CN103420946B - A kind of separation method of epoxychloropropane - Google Patents

A kind of separation method of epoxychloropropane Download PDF

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CN103420946B
CN103420946B CN201210156537.8A CN201210156537A CN103420946B CN 103420946 B CN103420946 B CN 103420946B CN 201210156537 A CN201210156537 A CN 201210156537A CN 103420946 B CN103420946 B CN 103420946B
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epoxychloropropane
water
chlorallylene
organic solvent
methanol
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CN103420946A (en
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张永强
刘易
杜泽学
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

A kind of separation method of epoxychloropropane, including: it is separated after the solution containing epoxychloropropane, methanol, 3 chloropropenes and water is mixed with extractant, obtain the liquid phase rich in epoxychloropropane and the liquid phase rich in methanol, the liquid phase rich in epoxychloropropane obtained by distillation, obtains epoxychloropropane；Wherein, described extractant includes water and organic solvent immiscible with water, described organic solvent is at least 10 kilograms per cubic meter with the density difference of water, and the ability of organic solvent extraction methanol is higher than water less than the ability of water and extraction epoxychloropropane, and organic solvent is different from the boiling point of epoxychloropropane.The method of the present invention, the separated time in extraction process is short (less than 3 minutes), reduces the difficulty of the requirement to extraction and stripping apparatus and extracting operation；And still-process has only to evaporate recovery section extractant, significantly reduce energy expenditure；As can be seen here, the method for the present invention is very suitable for large-scale continuous production.

Description

A kind of separation method of epoxychloropropane
Technical field
The present invention relates to the separation method of a kind of epoxychloropropane.
Background technology
Epoxychloropropane is a kind of important basic organic chemical industry raw material and intermediate, is widely used in synthesis The multiple products such as epoxy resin, glycerol, chlorohydrin rubber, medicine, pesticide, surfactant, plasticizer.
Epoxychloropropane can use HTS to be catalyst, makes hydrogen peroxide occur with chlorallylene Prepared by epoxidation reaction.Owing to chlorallylene and hydrogen peroxide are immiscible, cause response speed slow, because of This, need to add a large amount of solvent such as methanol, makes chlorallylene and hydrogen peroxide that epoxy to occur in this solvent Change reaction.With the epoxidation reaction product obtained after HTS solid-liquid separation, usually contain excess Reactant chlorallylene, solvent methanol, purpose product epoxychloropropane, hydrogen peroxide charge bring into The water generated with reaction, and the by-product such as a small amount of propylene glycol of chlorine monomethyl ether and propylene glycol of chlorine.Therefore need To be separated go out product epoxychloropropane, and recycling design methanol and excess reactant chlorallylene.
The method of the method generally straight run distillation of existing separation epoxychloropropane or carried out by extractant The method of extraction.Such as, CN1534030A discloses a kind of straight run distillation method of epoxychloropropane, The method is direct the most in a distillation column according to the height of component boiling point by the epoxidation reaction product that will obtain Carry out distilling to separate epoxychloropropane.Find when separated methanol and epoxychloropropane, need to adopt With having the distillation column of the highest theoretical cam curve and the highest reflux ratio, could be by epoxychloropropane and first Alcohol separated.Owing to epoxidation reaction product containing substantial amounts of solvent methanol, cause separated Equipment investment is high, energy expenditure is big.And, in the presence of first alcohol and water, epoxy chlorine in still-process Propane also can generate the by-product such as propylene glycol of chlorine monomethyl ether and propylene glycol of chlorine with first alcohol and water generation side reaction Thing, reduces the yield of epoxychloropropane.
US6350888B1 discloses a kind of method carrying out extract and separate epoxychloropropane by extractant, The method by adding a kind of organic extractant extraction epoxychloropropane, then distill out obtain containing ring Extractant in the liquid phase of oxygen chloropropane, isolated epoxychloropropane.Although the method can reach point From the purpose of epoxychloropropane, but, not only need when extracting epoxychloropropane from epoxidation reaction product Use substantial amounts of extractant, and part methanol also can be extracted together with epoxychloropropane, still Need straight run distillation separation methanol and epoxychloropropane, cause separated epoxychloropropane and reclaim extraction Solvent needs to consume substantial amounts of energy；It addition, in straight run distillation separation methanol and the process of epoxychloropropane In, epoxychloropropane also can generate the by-products such as propylene glycol of chlorine monomethyl ether, fall with methanol generation side reaction The yield of low epoxychloropropane.
CN101293882A discloses one and uses two kinds of immiscible extractant A and extractant B simultaneously The method of extract and separate epoxychloropropane, the extractant A that the method uses is liquid halogenated hydrocarbon or unitary Ether, extractant B is water or liquid polyol.When extractant A is chlorallylene, and extractant B is Water, separated extraction heavy phase and extraction are light phase to be respectively obtained epoxychloropropane product and reclaims reaction dissolvent During methanol, energy expenditure is minimum.But, there is the density of extractant chlorallylene and compare extractant in the method The density of water is little and causes the problem being susceptible to separated difficulty in extraction process, and due to extraction The boiling point of agent chlorallylene is less than epoxychloropropane, needs after the extraction to first pass through distillation by whole 3-chlorine third Materials at bottom of tower after isolating chlorallylene, from distillation recovered overhead, is distilled by alkene the most again, then from Distillation tower top obtains epoxychloropropane product, and whole chlorallylene extractants is required for through pervaporation ability Reclaim, cause the energy expenditure separating epoxychloropropane the highest.
In sum, there is be separated in extraction process difficulty and steaming in the separation method of existing epoxychloropropane The problem that during evaporating, energy expenditure is higher.
Summary of the invention
The invention aims to overcome and extract present in the separation method of existing epoxychloropropane The problem that the difficulty that is separated in separation process is higher with separated energy expenditure, it is provided that one extracted Journey is separated easily and the separation method of the epoxychloropropane that energy expenditure is low in still-process, to facilitate Apply during large-scale continuous production.
In order to realize the purpose of the present invention, the invention provides the separation method of a kind of epoxychloropropane, should Method includes: after being mixed with extractant by the solution containing epoxychloropropane, methanol, chlorallylene and water It is separated, obtains the liquid phase rich in epoxychloropropane and the liquid phase rich in methanol, obtained by distillation Rich in the liquid phase of epoxychloropropane, obtain epoxychloropropane；Wherein, described extractant includes water and and water Immiscible organic solvent, described organic solvent is at least 10 kilograms per cubic meter with the density difference of water, The ability of organic solvent extraction methanol is higher than water and organic molten less than the ability of water and extraction epoxychloropropane Agent is different from the boiling point of epoxychloropropane.
Owing in the extractant of the present invention, organic solvent and water are immiscible, the energy of organic solvent extraction methanol Power is higher than water less than the ability of water and extraction epoxychloropropane so that organic solvent can be containing epoxy chlorine Most epoxychloropropane in the solution of propane, methanol, chlorallylene and water are extracted into organic solvent Phase (is the liquid phase rich in epoxychloropropane), and containing epoxychloropropane, methanol, chlorallylene and Most of methanol in the solution of water is extracted to aqueous phase (being the liquid phase rich in methanol).And it is organic molten The density difference of agent and water is at least 10 kilograms per cubic meter, and in the preferred case, organic solvent and The consumption of water makes the organic solvent comprising overwhelming majority epoxychloropropane and comprises major part methanol Aqueous phase has the density contrast of more than 70 kilograms per cubic meter so that be very easy to realize good in extraction process Good is separated.
In the present invention, described organic solvent phase and the aqueous phase separated time in extraction process is the longest not to be surpassed Spending 3 minutes, i.e. use the method for the present invention to separate, the time of extract and separate is short, reduces extraction Take the requirement of separation equipment and the difficulty of extracting operation, advantageously reduce equipment investment and reduce operating cost With.And the boiling point of organic solvent is different from the boiling point of epoxychloropropane, under still more preferential conditions, due to The boiling point phase of organic solvent A and halogenated hydrocarbons boiling point under 1 atmospheric pressure and epoxychloropropane in organic solvent Differ from more than 20 DEG C, obtain epoxychloropropane product by separated easily and reclaim organic molten Agent, the organic solvent A in organic solvent needs not move through evaporation and just can reclaim, compares epoxy chloropropionate with employing The method of the low-boiling extractant of alkane is compared, and can be effectively reduced energy expenditure.
Therefore, compared with the separation method of existing epoxychloropropane, the present invention has the advantage that
1, the separated time in extraction process short (less than 3 minutes), reduces extraction and stripping apparatus Requirement and the difficulty of extracting operation, advantageously reduce equipment investment and reduce operating cost；
2, in a preferred embodiment, the organic solvent A in organic solvent and halogenated hydrocarbons and epoxy chlorine The boiling point of propane differs more than 20 DEG C so that separated process is very easy to realize, and reduce further Requirement and the difficulty of distillation procedure to separated equipment, decreases equipment investment and reduces operating cost With；
3, still-process has only to evaporate recovery section extractant, significantly reduce energy expenditure；
4, large-scale continuous production is easily realized.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, with Detailed description below is used for explaining the present invention together, but is not intended that limitation of the present invention.? In accompanying drawing:
Fig. 1 is the organic solvent phase (being referred to as A phase in figure) of the separation method isolated according to the present invention The flow chart that distills is carried out with aqueous phase；
Fig. 2 is the chlorallylene phase of the method isolated according to prior art and aqueous phase carries out the stream that distills Cheng Tu.
Description of reference numerals
1: the first distillation column 2: after-fractionating tower；
3: the three distillation column 4: the four distillation column.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides the separation method of a kind of epoxychloropropane, the method includes: will be containing epoxy chlorine The solution of propane, methanol, chlorallylene and water is separated after mixing with extractant, obtains rich in ring The liquid phase of oxygen chloropropane and the liquid phase rich in methanol, the liquid phase rich in epoxychloropropane obtained by distillation, Obtain epoxychloropropane；Wherein, described extractant includes water and organic solvent immiscible with water, described Organic solvent is at least 10 kilograms per cubic meter, the ability of organic solvent extraction methanol with the density difference of water It is higher than water less than the ability of water and extraction epoxychloropropane, and the boiling point of organic solvent and epoxychloropropane is not With.
In the present invention, if described organic solvent is mixed solvent, the boiling point of the most described organic solvent refers to The boiling point of various organic solvents in mixed solvent, if or described mixed solvent can form azeotropic mixture, then The boiling point of described organic solvent refers to the azeotropic point of azeotropic mixture, and if needing it is further noted that institute State that mixed organic solvents formed for minimum azeotropic mixture, the most described azeotropic point refers to minimum boiling point, if Described mixed organic solvents formed for maximum azeotrope thing, the most described azeotropic point refers to mixed solvent High azeotropic point.
In the present invention, unless stated otherwise, density refers both to the density of 20 DEG C, 1 standard atmosphere pressures.
In the present invention, all can realize the purpose of the present invention according to preceding solution, for the present invention, enter Under one step preferable case, at 20 DEG C, density difference 10-2000 kilogram of described organic solvent and water/ Cubic meter.
In the present invention, as long as described organic solvent is different from the boiling point of epoxychloropropane can realize the present invention Purpose, for the present invention, in order to realize the purpose of the present invention more fully, the most described organic solvent The boiling-point difference of boiling point and epoxychloropropane be 20-300 DEG C, more preferably 30-200 DEG C.
The method according to the invention, further preferably in the case of, described isolated rich in epoxy chloropropionate The liquid phase of alkane (if not otherwise specified, hereinafter referred to as organic solvent phase) and rich in methanol liquid phase (as Not specified, hereinafter referred to as aqueous phase) density contrast at 20 DEG C is 70-2000 kilograms per cubic meter, It is preferably 80-1000 kilograms per cubic meter, so that two liquid phases are preferably separated.
The method according to the invention, as the organic solvent of extractant and the consumption of water optional scope relatively Width, for the present invention, contains epoxychloropropane, methanol, chlorallylene preferably with respect to 100 mass parts With the solution of water, the consumption of described organic solvent is 10-1000 mass parts, preferably 30-300 mass parts； The consumption of described water is 10-1000 mass parts, preferably 20-200 mass parts.
The method according to the invention, all can realize the purpose of the present invention according to preceding solution, for this Invention, under preferable case, in order to save further disengaging time, improve separation efficiency, preferably described in have Containing the organic solvent A at least containing functional group's oxygen atom in machine solvent.
The method according to the invention, meet the described organic solvent A of aforementioned claim concrete can be such as Liquid halogen ether, liquid halogenated carboxylic ester, liquid halo carbonyl compounds and liquid nitrohalogen compound In one or more, further preferably in the case of, described organic solvent A is the liquid of C4-C16 Halogen ether, the liquid halogenated carboxylic ester of C4-C20, C4-C12 liquid halo carbonyl compounds (general For halogenated ketone and/or halogenated aldehyde) and liquid nitrohalogen compound (the generally halonitro of C6-C12 Benzene) in one or more.It will be clear that aforementioned liquid nitrohalogen compound is as having Machine solvent can realize the purpose of the present invention, has toxicity yet with it, and therefore, the present invention is the most preferred It uses as described organic solvent.
The method according to the invention, in order to make the light liquid phase being obtained by extraction and heavy-fluid the most easily realize dividing mutually From, density 10-2000 bigger than the density of the water kilograms per cubic meter of the most described organic solvent A, more excellent Select big 50-1000 kilograms per cubic meter.
The method according to the invention, for the organic solvent in making the heavy-fluid that is obtained by extraction mutually and epoxy chloropropionate The easy separated of alkane, thus reduce energy expenditure further, the most described organic solvent A is at 1 air The boiling point of pressure is higher than the boiling point of epoxychloropropane 20-300 DEG C, the highest 30-200 DEG C.
The method according to the invention, the described organic solvent A meeting aforementioned claim includes but not limited to: 2,2 '-dichlorodiethyl ether, dichloro-dipropyl ether, dichlorodiisopropyl ether, dichloro butyl oxide, dichloro diisobutyl ether, 1,2-bis-(2-chloroethoxy) ethane, p-Fluoroanisole, adjacent fluoroanisole, 3-Fluoroanisole, to chlorobenzene first Ether, o-chloro-anisole, m-chloroanisole, para-bromoanisole, o-bromo-anisole, Meta Bromo Anisole, right Chlorophenetole, adjacent chlorophenetole, a chlorophenetole, to Bromoethyl phenyl ether, bromophenyl ether, a bromobenzene second Ether, isopropyl chloracetate, butyl chloroacetate, bromoacetic acid butyl ester, iso-butyl chloroacetate, n-amyl chloroacetate, Ethyl trichloroacetate, 2-chloropropionate, 2 bromopropionic acid ethyl ester, 4-neoprene acid ethyl ester, 2-bromo-butyric acid first Ester, 4-bromobutyrate, bromoacetate, 2-chlorobenzoic acid ethyl ester, acetic acid-2-chloroethene ester, acetic acid-3- Chlorine propyl ester, acetic acid-4-neoprene ester, acetic acid-2-bromine ethyl ester, 2-chlorobenzoic acid ethyl ester, alpha-chloro cinnamic aldehyde, The chloro-2 pentanone of 5-, the bromo-methyl-n-butyl ketone of 6-, o-chlorobenzaldehyde, m chlorobenzaldehyde, o-bromobenzaldehye, to chlorobenzene Ethyl ketone, parabromoacetophenone, 2,5-dichloroacetophenone, 2,4-dinitrofluorobenzene, 2,4-difluoro nitrobenzene and right One or more in chlorine meta-nitrotoluene, preferably dichloro-dipropyl ether, 1,2-bis-(2-chloroethoxy) ethane, To chloroanisole, o-chloro-anisole, m-chloroanisole, to chlorophenetole, adjacent chlorophenetole, a chlorobenzene One in ether, butyl chloroacetate, ethyl trichloroacetate, parachloroacetophenone and 2,5-dichloroacetophenone Or it is multiple.
The method according to the invention, further preferably in the case of, possibly together with halogenated hydrocarbons in described organic solvent. So that after Fen Liing in organic solvent each material all can well realize separate, the most described halogenated hydrocarbons with The boiling point of organic solvent A is different.
The method according to the invention, in described organic solvent, organic solvent A and the ratio of halogenated hydrocarbons is optional Wider range, for the present invention, organic solvent A and the mass ratio of halogenated hydrocarbons in the most described organic solvent For 1/50-50/1, more preferably 1/5-5/1.
With the method for the invention it is preferred to the one in the liquid halogenated hydrocarbons that described halogenated hydrocarbons is C1-C16 Or multiple, in order to the halogenated hydrocarbons in making heavy-fluid mutually and epoxychloropropane easily realize separated, thus drop Low-energy-consumption, for the present invention, the boiling point phase of the boiling point of the most described halogenated hydrocarbons and epoxychloropropane Differ from more than 20 DEG C, preferably difference more than 30 DEG C.
The method according to the invention, the described halogenated hydrocarbons meeting aforementioned claim includes but not limited to: four chlorinations Carbon, 1,1,2,2-sym-tetrachloroethane, Pentalin., 1,1,2,2-tetrabromoethane, chlorallylene, 1,2,3-trichlorine Propane, 1,1,1,3-tetra-chloropropane, 1,2-dibromopropane, 1,3-dibromopropane, 1,2,3-tribromopropane, 1- Bromo-3-chloropropane, 1,4-dichloroetane, 1,4-dibromobutane, 1,5-dichloropentane, pentamethylene bromide, 1,6-dibromo-hexane, 1-bromo-dodecane, m-chlorotoluene, o-dichlorohenzene, m-dichlorobenzene, 2,4 di chloro toluene, In 1,2,4-trichloro-benzenes, bromobenzene, o-dibromobenzene, m-dibromobenzene, adjacent bromochlorobenzene and 2,4 dichloro fluorobenzene one Planting or multiple, integrated cost considers, more preferably chlorallylene.
The method according to the invention, described molten by containing epoxychloropropane, methanol, chlorallylene and water The optional wider range of the condition that liquid mixes with extractant, for the present invention, under preferable case, described general The temperature that solution containing epoxychloropropane, methanol, chlorallylene and water mixes with extractant (i.e. extracts The temperature separated) it is 1-80 DEG C, preferably 5-40 DEG C.Under the conditions of aforementioned preferred extract and separate, both The described solution containing epoxychloropropane, methanol, chlorallylene and water can be made to be sufficiently mixed with extractant, Reach the purpose of extraction, can reduce again described containing epoxychloropropane, methanol, chlorallylene and water Epoxychloropropane in solution and the side reaction of first alcohol and water.
The method according to the invention, carries out extract and separate, during separation according to the preceding solution of the present invention Between short, the most described will enter with extractant containing the solution of epoxychloropropane, methanol, chlorallylene and water The total time separated after row mixing is less than 3 minutes i.e. can be with isolated organic solvent phase and aqueous phase.By This is it can be seen that the method for the present invention is efficient and simple and easy to do.
With the method for the invention it is preferred to it is described containing epoxychloropropane, methanol, chlorallylene and water The content of solution in ethylene chloropropane be 5-25 mass %, the content of methanol be 35-65 mass %, 3-chlorine The content of propylene be the content of 4-35 mass % and water be 5-25 mass %.
The method according to the invention, the most described containing epoxychloropropane, methanol, chlorallylene With the product that solution is chlorallylene and hydrogen dioxide epoxidation reaction of water, concrete, described containing ring The solution of oxygen chloropropane, methanol, chlorallylene and water is: in the presence of titanium-silicon molecular sieve catalyst, with Methanol is solvent, chlorallylene contact with hydrogen peroxide or aqueous hydrogen peroxide solution after product.
So that the method for the present invention is more suitable for industrialized production, further preferably in the case of, this Bright method also includes: the liquid phase rich in methanol obtained by distillation obtains the first with or without chlorallylene Alcohol logistics and water logistics, partly or entirely return the described methanol stream with or without chlorallylene to replacement The solvent that methanol contacts with hydrogen peroxide or aqueous hydrogen peroxide solution as described chlorallylene, by described water Stream portions or all return as extractant be used for extracting (general only water stream portions need to be returned as Extractant is used for extracting).
As it was previously stated, the liquid phase rich in epoxychloropropane in the case of Jin Yibuyouxuan, obtained by distillation Chlorallylene logistics and organic solvent logistics is obtained, by described chlorallylene while obtaining epoxychloropropane Stream portions or whole return are as the raw material contacted with hydrogen peroxide or aqueous hydrogen peroxide solution, by described Organic solvent stream portions or all return are used for extracting.It will be clear that when described organic solvent In containing halogenated hydrocarbons, and when described halogenated hydrocarbons is chlorallylene, aforementioned organic solvents logistics is generally this The logistics of bright aforesaid organic solvent A, and aforementioned chlorallylene logistics generally comprises containing epoxy chloropropionate Chlorallylene in the solution of alkane, methanol, chlorallylene and water and the chlorallylene as extractant, Optionally, it is also possible to be used for extracting by described chlorallylene stream portions or whole return.
In the present invention, organic solvent and water as extractant both can be added simultaneously to described containing epoxy In the solution of chloropropane, methanol, chlorallylene and water, it is also possible to first by one extractant (organic solvent Or water) mix with the described solution containing epoxychloropropane, methanol, chlorallylene and water, add the most again Enter another kind of extractant (organic solvent or water).
In the present invention, in the ban by one extractant (organic solvent or water) with described containing epoxychloropropane, Methanol, chlorallylene and water solution mixing time, described for mixing equipment can be known to pipeline, The liquid contact mixing apparatus such as pipe-line mixer, stirred tank, mixing column.
In the present invention, when being simultaneously introduced as the organic solvent of extractant and water, extractant contains with described Being blended in extraction equipment of solution having epoxychloropropane, methanol, chlorallylene and water is carried out.
The described equipment for extraction can be conventional extraction equipment well-known to those skilled in the art, as Agitator tank, sieve-plate tower, packed tower, rotating disc column, valve tower, spray tower etc., both can take interval to grasp The mode made, it would however also be possible to employ the mode of continuous operation, it is preferred to use continuous operation mode is to facilitate realization Large-scale commercial production.When using continuous operation mode, it is preferred to use continuous countercurrent extraction tower is as extraction Taking equipment.
In the present invention, organic solvent is attached most importance to liquid phase (referred to as heavy phase) mutually, and aqueous phase is that light liquid phase (is called for short For light phase).Described organic solvent phase and the separation of aqueous phase, both can extract at continuous countercurrent extraction tower etc. Taking equipment is automatically performed and from respectively obtaining aqueous phase and organic solvent phase at the bottom of tower top and tower, it is also possible at list Only device for phase saparation is carried out.Described device for phase saparation can be that subsider, settling tank, spinning liquid divide From the device for phase saparation that device and centrifuge etc. are conventional.
According to the present invention, described HTS is that in titanium atom replacement zeolite lattice skeleton, a part of silicon is former The general name of one class zeolite of son.Described HTS is well known in the prior art, for example, it may be Have and be similar to the titanium-containing zeolite TS-1 of ZSM-5 aluminosilicate zeolite MFI topological structure, have and be similar to The titanium-containing zeolite TS-2 of ZSM-11 aluminosilicate zeolite MEL topological structure, and have with modenite, The titaniferous of the framing structure of ZSM-12, MCM-22, MCM-41, MCM-48 and the beta-zeolite isomorphous divides Sub-sieve etc., wherein, preferably TS-1 and TS-2, particularly preferably TS-1.Catalysis used by the present invention Agent can be that the former powder of these zeolites directly uses, it is also possible to is made after overmolding by the former powder of these zeolites With, specifically can select according to response situation.
According to the present invention, when described titanium-silicon molecular sieve catalyst adds fashionable in from of a slurry, with described contact On the basis of the liquid phase of reaction, the content of described HTS is generally 0.5-30 mass %, preferably 1-15 Quality %, more preferably 1.5-10 mass %；When catalyst is fixed in the reactor, peroxidating The null-rate during feedstock quality of hydrogen (in the present invention, during quality, null-rate is typically alternatively referred to as liquid hourly space velocity (LHSV), Refer to the feedstock quality of unit interval hydrogen peroxide and the ratio of the quality of the catalyst in reactor) general For 0.01-100h-1, preferably 0.02-10h-1, more preferably 0.02-1h-1。
According to the present invention, the temperature that described chlorallylene contacts with hydrogen peroxide or aqueous hydrogen peroxide solution (i.e. the temperature of chlorallylene epoxidation reaction) generally 10-120 DEG C, preferably 40-80 DEG C；Contact Time be 0.01-100 hour, preferably 0.1-10 hour；Described chlorallylene enters with hydrogen peroxide Material mol ratio is generally 1/1-10/1, preferably 1.2/1-6/1；Described methanol and the charging matter of chlorallylene Amount ratio generally 0.5/1-15/1, preferably 0.5/1-5/1.
According to the present invention, described chlorallylene can be analytical reagent and/or chemically pure reagent, but from Being preferably used industrial products from the point of view of economy, in industrial products, the content of chlorallylene is generally 95-100 mass %, preferably 97-99.9 mass %.
According to the invention, it is possible to use hydrogen peroxide is directly as oxidant, but for security consideration, one As preferably employ aqueous hydrogen peroxide solution as oxidant, the concentration of hydrogen peroxide in aqueous hydrogen peroxide solution Can be typically 5-90 mass %, preferably 20-60 mass %.
The method according to the invention, described organic solvent mutually in contain described containing epoxychloropropane, first Most epoxychloropropane in the solution of alcohol, chlorallylene and water, major part chlorallylene, a small amount of Methanol and minor amount of water.Owing to chlorallylene is 45.0 DEG C at the boiling point that 1 standard atmosphere is depressed, epoxy chlorine Propane boiling point under the same conditions is 116.1 DEG C, the two difference 71.1 DEG C, it is easy to real by distillation Now separate；Similarly, since the boiling point of organic solvent A in organic solvent is higher than the boiling point of epoxychloropropane 20-300 DEG C, also realize separating easily by simple distillation, and organic solvent A can be directly from distillation Reclaim without through pervaporation at the bottom of tower；And the boiling point of the halogenated hydrocarbons in organic solvent and epoxychloropropane Boiling point differs more than 20 DEG C, also realizes separating easily by simple distillation.A small amount of methanol therein, then because of For methanol with chlorallylene 40.0 DEG C of formation azeotropic mixtures (containing the methanol of 10.0 mass % in azeotropic mixture) Separate with epoxychloropropane with chlorallylene easily；As for minor amount of water therein, then by In water can with chlorallylene 43.0 DEG C formed the azeotropic mixtures water of 2.2 mass % (in the azeotropic mixture containing) with And water can form azeotropic mixture (containing the water of 25 mass % in azeotropic mixture) with epoxychloropropane at 88.0 DEG C And removed easily.
The method according to the invention, especially, when halogenated hydrocarbons is chlorallylene, not only halogenated hydrocarbons and ring The separated process of oxygen chloropropane can save that (the two can return together as aforementioned epoxy chloropropane The raw material of epoxidation reaction), and with use single organic solvent A as compared with the situation of extractant, Owing to the boiling point of chlorallylene is low so that base product when can be effectively reduced separated chlorallylene Temperature, reduce high temperature on epoxychloropropane and the impact of organic solvent A.
The method according to the invention, contains described containing epoxychloropropane, first in described extractant aqueous phase Most of methanol, major part water and a small amount of chlorallylene in the solution of alcohol, chlorallylene and water.By Lower than the boiling point of methanol (64.5 DEG C) in the boiling point of chlorallylene, and ratio can be formed with first alcohol and water The low-boiling azeotropic mixture of chlorallylene, it is easy to separate with water when separated methanol.And methanol Boiling point lower than the boiling point of water (100 DEG C) 35.5 DEG C and be formed without azeotropic mixture with water, easily by simply Distillation methanol is separated from water, thus realize Methanol Recovery, extractant water comes also without by evaporation Reclaim.
By above description, utilize simple distillation can realize epoxychloropropane from organic molten Agent mutually is separated and methanol and chlorallylene can be reclaimed, and need not by evaporation all Extractant reclaim extractant organic solvent and water, can be effectively reduced epoxychloropropane separate energy Amount consumes.Compared to individually using chlorallylene and water as the separation method of extractant, the present invention passes through Add organic solvent A as extractant so that the separation method of the present invention both can realize in extraction process Be quickly separated, the energy expenditure of separated can be reduced again.
The method according to the invention, described distillation can use normal pressure well known to those skilled in the art, subtract Pressure or the Distallation systm of the two combination.
Such as, distilling organic solvent phase in atmospheric distillation tower, tower top obtains containing a small amount of methanol and minor amount of water Chlorallylene logistics (if the described solution containing epoxychloropropane, methanol, chlorallylene and water is: In the presence of titanium-silicon molecular sieve catalyst, with methanol as solvent, after chlorallylene contacts with hydrogen peroxide Product, then the chlorallylene logistics containing a small amount of methanol and minor amount of water obtained can using circulating and recovering as with mistake The raw material of hydrogen oxide contact, or when the halogenated hydrocarbons in organic solvent is chlorallylene, then obtain contains The chlorallylene logistics of a small amount of methanol and minor amount of water can be partially recycled back to epoxidation reaction as with mistake The raw material of hydrogen oxide contact, is partially recycled back to as extractant)；Obtain at the bottom of tower is described containing epoxy chlorine Propane and the logistics of organic solvent, further separated in another normal pressure or vacuum distillation tower, When the boiling point of the halogenated hydrocarbons in organic solvent is less than epoxychloropropane, obtains halogenated hydrocarbons logistics from tower top and follow Ring returns extraction, obtains the logistics containing epoxychloropropane and organic solvent A (when in organic solvent at the bottom of tower When halogenated hydrocarbons is chlorallylene, just there is no described still-process)；Obtain at the bottom of tower is described containing epoxy chloropropionate Alkane and the logistics of organic solvent A, further separated in a normal pressure or vacuum distillation tower, from Tower top obtains epoxychloropropane product stream, obtains organic solvent A logistics and be recycled back into extraction at the bottom of tower.? The aqueous phase that in other atmospheric distillation tower, distillation obtains, tower top obtains the methanol stream containing a small amount of chlorallylene It is recycled back into epoxidation reaction to contact with hydrogen peroxide or aqueous hydrogen peroxide solution as described chlorallylene Solvent, the water logistics part obtained at the bottom of tower be recycled back into extraction, another part is as discharge of wastewater.
The present invention to distillation condition there is no concrete requirement, the distillation condition of organic solvent phase and aqueous phase with The composition of organic solvent is different and different, can select according to practical situation.
It is more fully described the present invention below by embodiment, but the present invention is not limited to this.
Preparation embodiment
Solution (i.e. epoxidation reaction product) containing epoxychloropropane, methanol, chlorallylene and water Preparation:
Epoxidation reaction product used by extraction is according to method disclosed in embodiment in CN101747296A 1 The epoxidation reaction of chlorallylene and aqueous hydrogen peroxide solution is carried out in fixed bed jacketed pipe type reactor Prepare.It is 50 DEG C, the aqueous hydrogen peroxide solution of employing 30% and 0.40MPa at jacket oil bath temperature Under the reaction condition of pressure, by change the raw materials components mole ratio of chlorallylene and hydrogen peroxide and methanol with The charge-mass ratio of chlorallylene, respectively obtains the epoxidation reaction product of the different compositions shown in table 1 S1-S5(hereinafter also referred to contains solution S 1-S5 of epoxychloropropane, methanol, chlorallylene and water).
Embodiment 1
The separation method of the epoxychloropropane that the present embodiment provides for the present invention is described.
At 28 DEG C, by known containing epoxychloropropane, methanol, chlorallylene for 100 mass parts compositions With the solution S 1 of water first with the water of 49.9 mass parts (density when 20 DEG C is 998.2 kilograms per cubic meter, Boiling point is 100 DEG C) contact mixing, after stratification, collect lower floor's heavy phase, then with by 70.0 mass parts Ethyl trichloroacetate (ladder is uncommon likes (Shanghai) chemical conversion industrial development company limited, and density when 20 DEG C is 1383.6 kilograms per cubic meter, boiling point is 168 DEG C) and chlorallylene (the industry chlorine third of 34.8 mass parts Alkene, Ba Ling petrochemical industry Co., Ltd, the content of chlorallylene is 98 mass %, when 20 DEG C Density is 939.2 kilograms per cubic meter, and boiling point is 45 DEG C) mixed organic solvents that forms the quality such as is divided into Five parts in five times extraction upper strata light phase, merge all of heavy phase and obtain organic solvent phase, organic solvent mutually in The content of epoxychloropropane, methanol, chlorallylene and water be respectively 11.92 mass %, 2.68 mass %, 31.96 mass % and 0.46 mass %, the light phase aqueous phase that is finally obtained, epoxychloropropane in aqueous phase, The content of methanol, chlorallylene and water be respectively 0.26 mass %, 40.50 mass %, 2.76 mass % and 55.08 mass %, organic solvent phase and the aqueous phase density contrast when 20 DEG C is 254.4 kilograms per cubic meter.
According to flow process shown in Fig. 1, the aqueous phase obtained is introduced in the first distillation column 1 and carry out separated； Organic solvent phase (being referred to as A phase in figure) is introduced in after-fractionating tower 2 and carries out separated.
Aqueous phase at ambient pressure, obtains containing a small amount of chlorallylene via the tower top (64 DEG C) of the first distillation column 1 Methanol stream be recycled back into epoxidation reaction, at the bottom of tower, (104 DEG C) obtain water logistics；The water thing of gained A stream part is recycled back into extraction, and another part is as discharge of wastewater.
Organic solvent mutually the most at ambient pressure, obtain containing methanol via the tower top (41 DEG C) of after-fractionating tower 2 and The chlorallylene logistics of minor amount of water, a part is recycled back into epoxidation reaction, and another part is recycled back into extraction Taking, at the bottom of tower, (149 DEG C) obtain the ethyl trichloroacetate logistics containing epoxychloropropane and minor amount of water；Gained Ethyl trichloroacetate logistics containing epoxychloropropane and minor amount of water separates further in the 3rd distillation column 3 To epoxychloropropane and the azeotropic mixture (containing the water of 25 mass %) of water of tower top (88 DEG C), at return tank (50 DEG C) are separated into the 3rd distillation column 3 that is recycled back into containing 97.44 mass % epoxychloropropane continue Carry out the logistics (i.e. returning to the logistics that the heavy phase portion in the 3rd distillation column 3 carries out separating) that separates and The light phase logistics being recycled back in extraction tower containing 92.58 mass % water, at the bottom of tower, (150 DEG C) are not contained The epoxychloropropane of water and the logistics of ethyl trichloroacetate；By water-free for gained at the bottom of tower epoxychloropropane and The logistics of ethyl trichloroacetate further in the 4th distillation column 4 separated obtain tower top (13 kPas, 60 DEG C) epoxychloropropane product stream and tower at the bottom of ethyl trichloroacetate logistics be recycled back into extraction.
In Solvent quantity (relative to the epoxidation reaction product of 100 mass parts) and organic solvent organic Solvent orange 2 A is as shown in table 2 with the mass ratio of halogenated hydrocarbons；During extract and separate light phase (aqueous phase) with heavy phase ( Organic solvent phase) the longest disengaging time, epoxychloropropane yield and the energy consumption of separated, distill energy The steam that consumption is consumed by the epoxychloropropane product per ton of isolated, unit is ton/ton, such as table 3 Shown in.
Contained epoxy in the solution of the epoxychloropropane of the yield (%) of epoxychloropropane=finally give/initially Chloropropane.
Comparative example 1
At 23 DEG C, by known containing epoxychloropropane, methanol, chlorallylene for 100 mass parts compositions With the solution S 1 of water first with the water of 60.0 mass parts (density when 20 DEG C is 998.2 kilograms per cubic meter, Boiling point 100 DEG C) it is sufficiently mixed, after stratification, collect lower floor's heavy phase, then the 3-by 80.0 mass parts (industry chloropropene, Ba Ling petrochemical industry Co., Ltd, the content of chlorallylene is 98 to chloropropene Quality %, density when 20 DEG C is 939.2 kilograms per cubic meter, and boiling point is 45 DEG C) the five of the quality such as it is divided into Part extraction upper strata in five times is light phase, merges all of heavy phase and obtains chlorallylene phase, chlorallylene phase medium ring The content of oxygen chloropropane, methanol, chlorallylene and water be respectively 14.68 mass %, 2.78 mass %, 81.62 Quality % and 0.52 mass %, the light phase aqueous phase that is finally obtained, epoxychloropropane in aqueous phase, methanol, The content of chlorallylene and water is respectively 0.23 mass %, 37.91 mass %, 2.78 mass % and 58.58 Quality %, chlorallylene phase and the aqueous phase density contrast when 20 DEG C are 56.3 kilograms per cubic meter.
According to flow process shown in Fig. 2, the aqueous phase obtained is introduced in the first distillation column and carry out separated, will Chlorallylene introduces mutually and carries out separated in after-fractionating tower 2.
Aqueous phase at ambient pressure, the tower top (64 DEG C) of the first distillation column 1 obtain containing a small amount of chlorallylene and The methanol stream of minor amount of water is recycled back into epoxidation reaction, and at the bottom of tower, (104 DEG C) obtain aqueous logistics, A portion is recycled back into extraction, and another part is as discharge of wastewater.
Chlorallylene the most at ambient pressure, obtains containing a small amount of first via the tower top (43 DEG C) of after-fractionating tower 2 The chlorallylene logistics of alcohol and minor amount of water, a part is recycled back into epoxidation reaction, and another part circulation is returned Returning extraction, at the bottom of tower, (121 DEG C) obtain the logistics of water-free epoxychloropropane；Gained water-free Epoxychloropropane logistics isolated tower top (13 kPas, 60 DEG C) in the 3rd distillation column 3 further Heavy constituent logistics at the bottom of epoxychloropropane product stream and tower.
Solvent quantity (relative to the epoxidation reaction product of 100 mass parts), extraction time light phase ( Aqueous phase) and the longest disengaging time of heavy phase (i.e. chlorallylene phase), epoxychloropropane yield and distillation point From energy consumption, the distillation steam that consumed by isolated epoxychloropropane per ton product of energy consumption, unit For ton/ton, as shown in table 4.
Contained epoxy in the solution of the epoxychloropropane of the yield (%) of epoxychloropropane=finally give/initially Chloropropane.
Embodiment 2
The separation method of the epoxychloropropane that the present embodiment provides for the present invention is described.
At 15 DEG C, by known containing epoxychloropropane, methanol, chlorallylene for 100 mass parts compositions With the solution S 2 of water first with the water of 50.1 mass parts (density when 20 DEG C is 998.2 kilograms per cubic meter, Boiling point is 100 DEG C) contact mixing, after stratification, collect lower floor's heavy phase, then with by 40.0 mass parts Ethyl trichloroacetate (ladder is uncommon likes (Shanghai) chemical conversion industrial development company limited, and density when 20 DEG C is 1383.6 kilograms per cubic meter, boiling point is 168 DEG C) and chlorallylene (the industry chlorine third of 49.9 mass parts Alkene, Ba Ling petrochemical industry Co., Ltd, the content of chlorallylene is 98 mass %, when 20 DEG C Density is 939.2 kilograms per cubic meter, and boiling point is 45 DEG C) mixed organic solvents that forms the quality such as is divided into Five parts in five times extraction upper strata light phase, merge all of heavy phase and obtain organic solvent phase, organic solvent mutually in The content of epoxychloropropane, methanol, chlorallylene and water be respectively 8.07 mass %, 2.46 mass %, 58.76 mass % and 0.38 mass %, the light phase aqueous phase that is finally obtained, epoxychloropropane in aqueous phase, The content of methanol, chlorallylene and water be respectively 0.12 mass %, 37.69 mass %, 3.78 mass % and 57.79 mass %, organic solvent phase and the aqueous phase density contrast when 20 DEG C is 146.4 kilograms per cubic meter.
According to flow process shown in Fig. 1, the aqueous phase obtained is introduced in the first distillation column 1 and carries out separated, Organic solvent is introduced mutually in after-fractionating tower 2 and carry out separated.
Aqueous phase at ambient pressure, obtains containing a small amount of chlorallylene via the tower top (64 DEG C) of the first distillation column 1 Methanol stream be recycled back into epoxidation reaction, at the bottom of tower, (104 DEG C) obtain water logistics, the water thing of gained A stream part is recycled back into extraction, and another part is as discharge of wastewater.
Organic solvent mutually the most at ambient pressure, obtain containing methanol via the tower top (41 DEG C) of after-fractionating tower 2 and The chlorallylene logistics of minor amount of water, a part is recycled back into epoxidation reaction, and another part is recycled back into extraction Taking, at the bottom of tower, (147 DEG C) obtain the ethyl trichloroacetate logistics of the epoxychloropropane containing minor amount of water；Gained Ethyl trichloroacetate logistics containing epoxychloropropane and minor amount of water separates further in the 3rd distillation column 3 To epoxychloropropane and the azeotropic mixture (containing the water of 25 mass %) of water of tower top (88 DEG C), at return tank (50 DEG C) are separated into the 3rd distillation column 3 that is recycled back into containing 97.44 mass % epoxychloropropane continue Carry out the logistics (i.e. returning to the logistics that the heavy phase portion in the 3rd distillation column 3 carries out separating) that separates and The light phase logistics being recycled back in extraction tower containing 92.58 mass % water, at the bottom of tower, (147 DEG C) obtain not Aqueous epoxychloropropane and the logistics of ethyl trichloroacetate；By water-free for gained at the bottom of tower epoxychloropropane Logistics with ethyl trichloroacetate further in the 4th distillation column 4 separated obtain tower top (13,000 Handkerchief, 60 DEG C) epoxychloropropane product stream and tower at the bottom of ethyl trichloroacetate logistics be recycled back into extraction.
In Solvent quantity (relative to the epoxidation reaction product of 100 mass parts) and organic solvent organic Solvent orange 2 A is as shown in table 2 with the mass ratio of halogenated hydrocarbons；During extract and separate light phase (aqueous phase) with heavy phase ( Organic solvent phase) the longest disengaging time, epoxychloropropane yield and the energy consumption of separated, distill energy The steam that consumption is consumed by the epoxychloropropane product per ton of isolated, unit is ton/ton, such as table 3 Shown in.
Contained epoxy in the solution of the epoxychloropropane of the yield (%) of epoxychloropropane=finally give/initially Chloropropane.
Comparative example 2
At 14 DEG C, by known containing epoxychloropropane, methanol, chlorallylene for 100 mass parts compositions With the solution S 2 of water first with the water of 60.0 mass parts (density when 20 DEG C is 998.2 kilograms per cubic meter, Boiling point 100 DEG C) it is sufficiently mixed, after stratification, collect lower floor's heavy phase, then the 3-by 80.0 mass parts (industry chloropropene, Ba Ling petrochemical industry Co., Ltd, the content of chlorallylene is 98 to chloropropene Quality %, density when 20 DEG C is 939.2 kilograms per cubic meter, and boiling point is 45 DEG C) the five of the quality such as it is divided into Part extraction upper strata in five times is light phase, merges all of heavy phase and obtains chlorallylene phase, chlorallylene phase medium ring The content of oxygen chloropropane, methanol, chlorallylene and water be respectively 8.80 mass %, 2.00 mass %, 88.54 Quality % and 0.42 mass %, the light phase aqueous phase that is finally obtained, epoxychloropropane in aqueous phase, methanol, The content of chlorallylene and water is respectively 0.10 mass %, 34.89 mass %, 3.86 mass % and 60.76 Quality %, chlorallylene phase and the aqueous phase density contrast when 20 DEG C are 40.0 kilograms per cubic meter.
The aqueous phase obtained is carried out separated with chlorallylene according to the method identical with comparative example 1, Obtain epoxychloropropane product.
Solvent quantity (relative to the epoxidation reaction product of 100 mass parts), extraction time light phase ( Aqueous phase) and the longest disengaging time of heavy phase (i.e. chlorallylene phase), epoxychloropropane yield and distillation point From energy consumption, the distillation steam that consumed by isolated epoxychloropropane per ton product of energy consumption, unit For ton/ton, as shown in table 4.
Contained epoxy in the solution of the epoxychloropropane of the yield (%) of epoxychloropropane=finally give/initially Chloropropane.
Embodiment 3
The separation method of the epoxychloropropane that the present embodiment provides for the present invention is described.
At 28 DEG C, by known containing epoxychloropropane, methanol, chlorallylene for 100 mass parts compositions With the solution S 3 of water first with the water of 60.2 mass parts (density when 20 DEG C is 998.2 kilograms per cubic meter, Boiling point is 100 DEG C) contact mixing, after stratification, collect lower floor's heavy phase, then with by 50.0 mass parts To chloroanisole, (ladder is uncommon likes (Shanghai) chemical conversion industrial development company limited, and density when 20 DEG C is 1160 Kilograms per cubic meter, boiling point is 200 DEG C) and 49.9 mass parts chlorallylene (industry chlorallylene, Ba Ling petrochemical industry Co., Ltd, the content of chlorallylene is 98 mass %, density when 20 DEG C Being 939.2 kilograms per cubic meter, boiling point is 45 DEG C) mixed organic solvents that forms five parts of quality such as is divided into Extraction upper strata is light phase in five times, merges all of heavy phase and obtains organic solvent phase, organic solvent middle epoxy mutually The content of chloropropane, methanol, chlorallylene and water be respectively 14.06 mass %, 2.42 mass %, 41.94 Quality % and 0.46 mass %, the light phase aqueous phase that is finally obtained, epoxychloropropane in aqueous phase, methanol, The content of chlorallylene and water is respectively 0.31 mass %, 38.06 mass %, 2.50 mass % and 58.39 Quality %, organic solvent phase and the aqueous phase density contrast when 20 DEG C is 138.7 kilograms per cubic meter.
According to flow process shown in Fig. 1, the aqueous phase obtained is introduced in the first distillation column 1 and carry out separated； Organic solvent phase (being referred to as A phase in figure) is introduced in after-fractionating tower 2 and carries out separated.
Aqueous phase at ambient pressure, obtains containing a small amount of chlorallylene via the tower top (64 DEG C) of the first distillation column 1 Methanol stream be recycled back into epoxidation reaction, at the bottom of tower, (104 DEG C) obtain water logistics；The water thing of gained A stream part is recycled back into extraction, and another part is as discharge of wastewater.
Organic solvent mutually the most at ambient pressure, obtain containing methanol via the tower top (41 DEG C) of after-fractionating tower 2 and The chlorallylene logistics of minor amount of water, a part is recycled back into epoxidation reaction, and another part is recycled back into extraction Take, (150 DEG C) at the bottom of tower obtain containing epoxychloropropane and minor amount of water to chloroanisole logistics；Gained contains The isolated tower in the 3rd distillation column 3 further to chloroanisole logistics of epoxychloropropane and minor amount of water The epoxychloropropane on top (88 DEG C) and the azeotropic mixture (containing the water of 25 mass %) of water, at return tank (50 DEG C) In be separated into containing 97.44 mass % epoxychloropropane be recycled back into the 3rd distillation column 3 proceed separate Logistics (i.e. returning to the logistics that the heavy phase portion in the 3rd distillation column 3 carries out separating) and containing 92.58 The light phase logistics being recycled back in extraction tower of quality % water, at the bottom of tower, (150 DEG C) obtain water-free ring Oxygen chloropropane and the logistics to chloroanisole；By water-free for gained at the bottom of tower epoxychloropropane with to chlorobenzene first The logistics of ether further in the 4th distillation column 4 separated obtain the ring of tower top (13 kPas, 60 DEG C) Being recycled back into chloroanisole logistics at the bottom of oxygen chloropropane product stream and tower extracts.
In Solvent quantity (relative to the epoxidation reaction product of 100 mass parts) and organic solvent organic Solvent orange 2 A is as shown in table 2 with the mass ratio of halogenated hydrocarbons；During extraction, light phase (aqueous phase) and heavy phase (has Machine solvent phase) the longest disengaging time, the yield of epoxychloropropane and the energy consumption of separated, distill energy The steam that consumption is consumed by the epoxychloropropane product per ton of isolated, unit is ton/ton, such as table 3 Shown in.
Contained epoxy in the solution of the epoxychloropropane of the yield (%) of epoxychloropropane=finally give/initially Chloropropane.
Comparative example 3
At 22 DEG C, by known containing epoxychloropropane, methanol, chlorallylene for 100 mass parts compositions With the solution S 3 of water first with the water of 60.0 mass parts (density when 20 DEG C is 998.2 kilograms per cubic meter, Boiling point 100 DEG C) it is sufficiently mixed, after stratification, collect lower floor's heavy phase, then the 3-by 80.0 mass parts (industry chlorallylene, Ba Ling petrochemical industry Co., Ltd, the content of chlorallylene is 98 to chloropropene Quality %, density when 20 DEG C is 939.2 kilograms per cubic meter, and boiling point is 45 DEG C) the five of the quality such as it is divided into Part extraction upper strata in five times is light phase, merges all of heavy phase and obtains chlorallylene phase, chlorallylene phase medium ring The content of oxygen chloropropane, methanol, chlorallylene and water be respectively 16.72 mass %, 2.78 mass %, 79.61 Quality % and 0.48 mass %, the light phase aqueous phase that is finally obtained, epoxychloropropane in aqueous phase, methanol, The content of chlorallylene and water is respectively 0.28 mass %, 38.36 mass %, 2.11 mass % and 58.67 Quality %, chlorallylene phase is 60.9 kilograms per cubic meter with the density contrast when 20 DEG C of aqueous phase.
The aqueous phase obtained is carried out separated with chlorallylene according to the method identical with comparative example 1, Obtain epoxychloropropane product.
Solvent quantity (relative to the epoxidation reaction product of 100 mass parts), extraction time light phase ( Aqueous phase) and the longest disengaging time of heavy phase (i.e. chlorallylene phase), epoxychloropropane yield and distillation point From energy consumption, the distillation steam that consumed by isolated epoxychloropropane per ton product of energy consumption, unit For ton/ton, as shown in table 4.
Contained epoxy in the solution of the epoxychloropropane of the yield (%) of epoxychloropropane=finally give/initially Chloropropane.
Embodiment 4
The separation method of the epoxychloropropane that the present embodiment provides for the present invention is described.
At 29 DEG C, by known containing epoxychloropropane, methanol, chlorallylene for 100 mass parts compositions With the solution S 4 of water first with the water of 53.0 mass parts (density when 20 DEG C is 998.2 kilograms per cubic meter, Boiling point is 100 DEG C) contact mixing, after stratification, collect lower floor's heavy phase, then with by 30.0 mass parts Butyl chloroacetate (ladder is uncommon likes (Shanghai) chemical conversion industrial development company limited, and density when 20 DEG C is 1070.4 Kilograms per cubic meter, boiling point is 183 DEG C) and 49.8 mass parts chlorallylene (industry chlorallylene, Ba Ling petrochemical industry Co., Ltd, the content of chlorallylene is 98 mass %, density when 20 DEG C Being 939.2 kilograms per cubic meter, boiling point is 45 DEG C) mixed organic solvents that forms five parts of quality such as is divided into Extraction upper strata is light phase in five times, merges all of heavy phase and obtains organic solvent phase, organic solvent middle epoxy mutually The content of chloropropane, methanol, chlorallylene and water be respectively 10.27 mass %, 4.22 mass %, 57.61 Quality % and 0.83 mass %, the light phase aqueous phase that is finally obtained, epoxychloropropane in aqueous phase, methanol, The content of chlorallylene and water is respectively 0.22 mass %, 42.11 mass %, 3.66 mass % and 52.87 Quality %, organic solvent phase and the aqueous phase density contrast when 20 DEG C is 87.0 kilograms per cubic meter.
According to flow process shown in Fig. 1, the aqueous phase obtained is introduced in the first distillation column 1 and carry out separated； Organic solvent phase (being referred to as A phase in figure) is introduced in after-fractionating tower 2 and carries out separated.
Aqueous phase at ambient pressure, obtains containing a small amount of chlorallylene via the tower top (64 DEG C) of the first distillation column 1 Methanol stream be recycled back into epoxidation reaction, at the bottom of tower, (104 DEG C) obtain water logistics；The water thing of gained A stream part is recycled back into extraction, and another part is as discharge of wastewater.
Organic solvent mutually the most at ambient pressure, obtain containing methanol via the tower top (41 DEG C) of after-fractionating tower 2 and The chlorallylene logistics of minor amount of water, a part is recycled back into epoxidation reaction, and another part is recycled back into extraction Taking, at the bottom of tower, (146 DEG C) obtain the butyl chloroacetate logistics containing epoxychloropropane and minor amount of water；Gained contains The butyl chloroacetate logistics of epoxychloropropane and minor amount of water isolated tower in the 3rd distillation column 3 further The epoxychloropropane on top (88 DEG C) and the azeotropic mixture (containing the water of 25 mass %) of water, at return tank (50 DEG C) In be separated into containing 97.44 mass % epoxychloropropane be recycled back into the 3rd distillation column 3 proceed separate Logistics (i.e. returning to the logistics that the heavy phase portion in the 3rd distillation column 3 carries out separating) and containing 92.58 The light phase logistics being recycled back in extraction tower of quality % water, at the bottom of tower, (147 DEG C) obtain water-free Epoxychloropropane and the logistics of butyl chloroacetate；By water-free for gained at the bottom of tower epoxychloropropane and monoxone The logistics of butyl ester further in the 4th distillation column 4 separated obtain tower top (13 kPas, 60 DEG C) Butyl chloroacetate logistics at the bottom of epoxychloropropane product stream and tower is recycled back into extraction.
In Solvent quantity (relative to the epoxidation reaction product of 100 mass parts) and organic solvent organic Solvent orange 2 A is as shown in table 2 with the mass ratio of halogenated hydrocarbons；During extract and separate light phase (aqueous phase) with heavy phase ( Extractant phase) the longest disengaging time, epoxychloropropane yield and the energy consumption of separated, distill energy consumption The steam consumed by the epoxychloropropane product per ton of isolated, unit is ton/ton, such as table 3 Shown in.
Contained epoxy in the solution of the epoxychloropropane of the yield (%) of epoxychloropropane=finally give/initially Chloropropane.
Comparative example 4
At 22 DEG C, by known containing epoxychloropropane, methanol, chlorallylene for 100 mass parts compositions With the solution S 4 of water first with the water of 50.0 mass parts (density when 20 DEG C is 998.2 kilograms per cubic meter, Boiling point 100 DEG C) it is sufficiently mixed, after stratification, collect lower floor's heavy phase, then the 3-by 70.0 mass parts (industry chlorallylene, Ba Ling petrochemical industry Co., Ltd, the content of chlorallylene is 98 to chloropropene Quality %, density when 20 DEG C is 939.2 kilograms per cubic meter, and boiling point is 45 DEG C) the five of the quality such as it is divided into Part extraction upper strata in five times is light phase, merges all of heavy phase and obtains chlorallylene phase, chlorallylene phase medium ring The content of oxygen chloropropane, methanol, chlorallylene and water be respectively 11.28 mass %, 3.18 mass %, 84.78 Quality % and 0.45 mass %, the light phase aqueous phase that is finally obtained, epoxychloropropane in aqueous phase, methanol, The content of chlorallylene and water is respectively 0.23 mass %, 44.34 mass %, 2.96 mass % and 52.07 Quality %, chlorallylene phase and the aqueous phase density contrast when 20 DEG C are 62.5 kilograms per cubic meter.
The aqueous phase obtained is distilled according to the method identical with comparative example 1 with chlorallylene, obtains Epoxychloropropane product.
Solvent quantity (relative to the epoxidation reaction product of 100 mass parts), extraction time light phase ( Aqueous phase) and the longest disengaging time of heavy phase (i.e. chlorallylene phase), epoxychloropropane yield and distillation point From energy consumption, the distillation steam that consumed by isolated epoxychloropropane per ton product of energy consumption, unit For ton/ton, as shown in table 4.
Contained epoxy in the solution of the epoxychloropropane of the yield (%) of epoxychloropropane=finally give/initially Chloropropane.
Embodiment 5
The separation method of the epoxychloropropane that the present embodiment provides for the present invention is described.
At 27 DEG C, by known containing epoxychloropropane, methanol, chlorallylene for 100 mass parts compositions With the solution S 5 of water first with the water of 60.3 mass parts (density when 20 DEG C is 998.2 kilograms per cubic meter, Boiling point is 100 DEG C) contact mixing, after stratification, collect lower floor's heavy phase, then with by 50.4 mass parts Parachloroacetophenone (ladder is uncommon likes (Shanghai) chemical conversion industrial development company limited, and density when 20 DEG C is 1192 Kilograms per cubic meter, boiling point is 232 DEG C) and 55.5 mass parts chlorallylene (industry chlorallylene, Ba Ling petrochemical industry Co., Ltd, the content of chlorallylene is 98 mass %, density when 20 DEG C Being 939.2 kilograms per cubic meter, boiling point is 45 DEG C) mixed organic solvents that forms five parts of quality such as is divided into Extraction upper strata is light phase in five times, merges all of heavy phase and obtains organic solvent phase, organic solvent middle epoxy mutually The content of chloropropane, methanol, chlorallylene and water be respectively 11.89 mass %, 3.92 mass %, 45.85 Quality % and 1.06 mass %, the light phase aqueous phase that is finally obtained, epoxychloropropane in aqueous phase, methanol, The content of chlorallylene and water is respectively 0.19 mass %, 37.21 mass %, 2.23 mass % and 59.38 Quality %, organic solvent phase and the aqueous phase density contrast when 20 DEG C is 129.3 kilograms per cubic meter.
According to flow process shown in Fig. 1, the aqueous phase obtained is introduced in the first distillation column 1 and carry out separated； Organic solvent phase (being referred to as A phase in figure) is introduced in after-fractionating tower 2 and carries out separated.
Aqueous phase at ambient pressure, obtains containing a small amount of chlorallylene via the tower top (64 DEG C) of the first distillation column 1 Methanol stream be recycled back into epoxidation reaction, at the bottom of tower, (104 DEG C) obtain water logistics；The water thing of gained A stream part is recycled back into extraction, and another part is as discharge of wastewater.
Organic solvent mutually the most at ambient pressure, obtain containing methanol via the tower top (41 DEG C) of after-fractionating tower 2 and The chlorallylene logistics of minor amount of water, a part is recycled back into epoxidation reaction, and another part is recycled back into extraction Taking, at the bottom of tower, (153 DEG C) obtain the parachloroacetophenone logistics containing epoxychloropropane and a small amount of water；Gained contains The parachloroacetophenone logistics of epoxychloropropane and a small amount of water isolated tower in the 3rd distillation column 3 further The epoxychloropropane on top (88 DEG C) and the azeotropic mixture (containing the water of 25 mass %) of water, at return tank (50 DEG C) In be separated into containing 97.44 mass % epoxychloropropane be recycled back into the 3rd distillation column 3 proceed separate Logistics (i.e. returning to the logistics that the heavy phase portion in the 3rd distillation column 3 carries out separating) and containing 92.58 The light phase logistics being recycled back in extraction tower of quality % water, at the bottom of tower, (154 DEG C) obtain water-free Epoxychloropropane and the logistics of parachloroacetophenone；By water-free for gained at the bottom of tower epoxychloropropane with to chlorobenzene The logistics of ethyl ketone further in the 4th distillation column 4 separated obtain tower top (13 kPas, 60 DEG C) Parachloroacetophenone logistics at the bottom of epoxychloropropane product stream and tower is recycled back into extraction.
In Solvent quantity (relative to the epoxidation reaction product of 100 mass parts) and organic solvent organic Solvent orange 2 A is as shown in table 2 with the mass ratio of halogenated hydrocarbons；During extract and separate light phase (aqueous phase) with heavy phase ( Organic solvent phase) the longest disengaging time, epoxychloropropane yield and the energy consumption of separated, distill energy The steam that consumption is consumed by the epoxychloropropane product per ton of isolated, unit is ton/ton, such as table 3 Shown in.
Contained epoxy in the solution of the epoxychloropropane of the yield (%) of epoxychloropropane=finally give/initially Chloropropane.
Comparative example 5
At 22 DEG C, by known containing epoxychloropropane, methanol, chlorallylene for 100 mass parts compositions With the solution S 5 of water first with the water of 60.0 mass parts (density when 20 DEG C is 998.2 kilograms per cubic meter, Boiling point 100 DEG C) it is sufficiently mixed, after stratification, collect lower floor's heavy phase, then the 3-by 80.0 mass parts (industry chlorallylene, Ba Ling petrochemical industry Co., Ltd, the content of chlorallylene is 98 to chloropropene Quality %, density when 20 DEG C is 939.2 kilograms per cubic meter, and boiling point is 45 DEG C) the five of the quality such as it is divided into Part extraction upper strata in five times is light phase, merges all of heavy phase and obtains chlorallylene phase, chlorallylene phase medium ring The content of oxygen chloropropane, methanol, chlorallylene and water be respectively 15.10 mass %, 2.84 mass %, 81.12 Quality % and 0.53 mass %, the light phase aqueous phase that is finally obtained, epoxychloropropane in aqueous phase, methanol, The content of chlorallylene and water is respectively 0.24 mass %, 38.06 mass %, 2.72 mass % and 58.46 Quality %, chlorallylene phase and the aqueous phase density contrast when 20 DEG C are 57.4 kilograms per cubic meter.
The aqueous phase obtained is distilled according to the method identical with comparative example 1 with chlorallylene, obtains Epoxychloropropane product.
Solvent quantity (relative to the epoxidation reaction product of 100 mass parts), extraction time light phase ( Aqueous phase) and the longest disengaging time of heavy phase (i.e. chlorallylene phase), epoxychloropropane yield and distillation point From energy consumption, the distillation steam that consumed by isolated epoxychloropropane per ton product of energy consumption, unit For ton/ton, as shown in table 4.
Contained epoxy in the solution of the epoxychloropropane of the yield (%) of epoxychloropropane=finally give/initially Chloropropane.
Table 1
Table 2
Table 3
Table 4
By embodiments of the invention, the separation method of the epoxychloropropane that the present invention provides and contrast Example is compared, and when extract and separate, heavy phase is significantly reduced with the light phase maximum duration separated, and is greatly reduced To extraction equipment and the requirement of extracting operation, equipment investment and operating cost can be effectively saved；Separately Outward, when epoxychloropropane separation yield is essentially identical, the energy consumption of separated also has significantly reduction.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special Levy, in the case of reconcilable, can be combined by any suitable means.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as its Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.

Claims (10)

1. a separation method for epoxychloropropane, the method includes: will be containing epoxychloropropane, first The solution of alcohol, chlorallylene and water is separated after mixing with extractant, obtains rich in epoxychloropropane Liquid phase and rich in the liquid phase of methanol, the liquid phase rich in epoxychloropropane obtained by distillation, obtain epoxy Chloropropane；It is characterized in that, described extractant includes water and organic solvent immiscible with water, described in have Machine solvent is at least 10 kilograms per cubic meter with the density difference of water, and the ability of organic solvent extraction methanol is low Ability in water and extraction epoxychloropropane is higher than water, and the boiling point of organic solvent and epoxychloropropane is not With, described organic solvent contains organic solvent A and the halogenated hydrocarbons at least containing functional group's oxygen atom, institute State halogenated hydrocarbons different from the boiling point of organic solvent A, wherein, in described organic solvent organic solvent A with The mass ratio of halogenated hydrocarbons is 1/50-50/1, wherein, at 20 DEG C, and the density ratio of described organic solvent A The density big 10-2000 kilograms per cubic meter of water, wherein, described organic solvent A is at 1 atmosphere pressure Boiling point higher than the boiling point of epoxychloropropane 20-300 DEG C；
Described organic solvent A be 2,2 '-dichlorodiethyl ether, dichloro-dipropyl ether, dichlorodiisopropyl ether, two Chlorine butyl oxide, dichloro diisobutyl ether, 1,2-bis-(2-chloroethoxy) ethane, p-Fluoroanisole, adjacent fluorobenzene first Ether, 3-Fluoroanisole, to chloroanisole, o-chloro-anisole, m-chloroanisole, para-bromoanisole, neighbour Bromoanisole, Meta Bromo Anisole, to chlorophenetole, adjacent chlorophenetole, a chlorophenetole, to bromobenzene second Ether, bromophenyl ether, a Bromoethyl phenyl ether, isopropyl chloracetate, butyl chloroacetate, iso-butyl chloroacetate, N-amyl chloroacetate, ethyl trichloroacetate, 2-chloropropionate, 4-neoprene acid ethyl ester, 2-chlorobenzoic acid second Ester, bromoacetate, bromoacetic acid butyl ester, 2 bromopropionic acid ethyl ester, 2-bromo butyric acid methyl ester, 4-bromo-butyric acid second Ester, acetic acid-2-chloroethene ester, acetic acid-3-chlorine propyl ester, acetic acid-4-neoprene ester, acetic acid-2-bromine ethyl ester, 5-chlorine The bromo-methyl-n-butyl ketone of-2 pentanone, 6-, o-chlorobenzaldehyde, m chlorobenzaldehyde, o-bromobenzaldehye, alpha-chloro Cortex Cinnamomi Aldehyde, parachloroacetophenone, parabromoacetophenone, 2,5-dichloroacetophenone, 2,4-dinitrofluorobenzene, 2,4-difluoro Nitrobenzol and to one or more in chlorine meta-nitrotoluene, described halogenated hydrocarbons is chlorallylene.
Method the most according to claim 1, wherein, described organic solvent and the density difference of water 10-2000 kilograms per cubic meter, organic solvent is 20-300 DEG C with the boiling-point difference of epoxychloropropane.
Method the most according to claim 1, wherein, described isolated rich in epoxy chloropropionate The liquid phase of alkane and be 70-2000 kilograms per cubic meter rich in the liquid phase of the methanol density contrast at 20 DEG C.
4. according to the method described in any one in claim 1-3, wherein, relative to 100 mass Containing epoxychloropropane, methanol, chlorallylene and the solution of water described in part, the consumption of described water is 10-1000 Mass parts, the consumption of described organic solvent is 10-1000 mass parts.
Method the most according to claim 1, wherein, described will containing epoxychloropropane, methanol, The temperature that the solution of chlorallylene and water mixes with extractant is 1-80 DEG C.
Method the most according to claim 5, wherein, described will containing epoxychloropropane, methanol, The total time that the solution of chlorallylene and water carries out after mixing with extractant being separated was less than 3 minutes.
Method the most according to claim 1, wherein, described containing epoxychloropropane, methanol, The content of the solution in ethylene chloropropane of chlorallylene and water be 5-25 mass %, the content of methanol be 35-65 Quality %, the content that content is 4-35 mass % and water of chlorallylene are 5-25 mass %.
Method the most according to claim 7, wherein, described containing epoxychloropropane, methanol, The solution of chlorallylene and water is: in the presence of titanium-silicon molecular sieve catalyst, with methanol as solvent, 3-chlorine Propylene contact with hydrogen peroxide or aqueous hydrogen peroxide solution after product.
Method the most according to claim 8, wherein, the method also includes: obtained by distillation Liquid phase rich in methanol obtains the methanol stream with or without chlorallylene and water logistics, by described containing or not Methanol stream containing chlorallylene partly or entirely returns replacement methanol as described chlorallylene and peroxide Change hydrogen or the solvent of aqueous hydrogen peroxide solution contact, described water stream portions is returned and is used for extracting.
Method the most according to claim 8, wherein, distillation obtained by rich in epoxy chloropropionate The liquid phase of alkane obtains the logistics of chlorallylene logistics and organic solvent A while obtaining epoxychloropropane, Described chlorallylene stream portions or whole return are connect as with hydrogen peroxide or aqueous hydrogen peroxide solution The raw material touched, is used for extracting by stream portions or whole return of described organic solvent A.
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CN101293882A (en) * 2007-04-24 2008-10-29 中国石油化工股份有限公司 Process for the separation of epoxychloropropane
CN102190636A (en) * 2010-03-03 2011-09-21 中国石油化工股份有限公司 Method for preparing epoxy chloropropane by cyclizing chloropropene

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CN101293882A (en) * 2007-04-24 2008-10-29 中国石油化工股份有限公司 Process for the separation of epoxychloropropane
CN102190636A (en) * 2010-03-03 2011-09-21 中国石油化工股份有限公司 Method for preparing epoxy chloropropane by cyclizing chloropropene

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