CN103420946A - Separation method for epichlorohydrin - Google Patents

Separation method for epichlorohydrin Download PDF

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Publication number
CN103420946A
CN103420946A CN2012101565378A CN201210156537A CN103420946A CN 103420946 A CN103420946 A CN 103420946A CN 2012101565378 A CN2012101565378 A CN 2012101565378A CN 201210156537 A CN201210156537 A CN 201210156537A CN 103420946 A CN103420946 A CN 103420946A
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water
epoxy chloropropane
chlorallylene
organic solvent
methyl alcohol
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CN103420946B (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 separation method for epichlorohydrin comprises: mixing a solution containing epichlorohydrin, methanol, 3-chloropropene and water and an extraction agent, separating to obtain a liquid phase rich in epichlorohydrin and a liquid phase rich in methanol, distilling the obtained the liquid phase rich in epichlorohydrin to obtain epichlorohydrin, wherein the extraction agent comprises water and an organic solvent immiscible with water, and the density difference between the organic solvent and water is at least 10 Kg/m<3>, the organic solvent is lower in methanol extraction capability and higher in epichlorohydrin extraction capability than water, and the organic solvent has a boiling point different with that of epichlorohydrin. The method has short separation time (less than 3 min) during extraction, so that the requirement on extractive separation equipment and the difficulty in extraction operation are reduced; also during distillation, only part of the extraction agent needs evaporative recovery, so that energy consumption is effectively reduced; and therefore, the method is quite suitable for large-scale continuous production.

Description

A kind of separation method of epoxy chloropropane
Technical field
The present invention relates to a kind of separation method of epoxy chloropropane.
Background technology
Epoxy chloropropane is a kind of important basic organic chemical industry raw material and intermediate, is widely used in the multiple products such as synthetic epoxy resin, glycerine, chlorohydrin rubber, medicine, agricultural chemicals, tensio-active agent, softening agent.
It is catalyzer that epoxy chloropropane can adopt HTS, makes hydrogen peroxide and the preparation of chlorallylene initial ring oxidizing reaction.Because chlorallylene and hydrogen peroxide do not dissolve each other, cause speed of response slow, therefore, need to add a large amount of solvents as methyl alcohol, make chlorallylene and hydrogen peroxide initial ring oxidizing reaction in this solvent.In the epoxidation reaction product obtained after the HTS solid-liquid separation, usually contain water that excessive reactant chlorallylene, solvent methanol, purpose product epoxy chloropropane, hydrogen peroxide charging are brought into and that reaction generates, and the by products such as a small amount of propylene glycol of chlorine monomethyl ether and propylene glycol of chlorine.Therefore the reaction product epoxy chloropropane be need to isolate, and solvent methanol and excessive reactant chlorallylene reclaimed.
Existing method of separating epoxy chloropropane is generally the method for straight run distillation or the method extracted by extraction agent.For example, CN1534030A discloses a kind of straight run distillation method of epoxy chloropropane, and the method is directly distilled to separate epoxy chloropropane by the epoxidation reaction product by obtaining according to the height of component boiling point in distillation tower.Find when fractionation by distillation methyl alcohol and epoxy chloropropane, need to adopt to there is the distillation tower of very high theoretical plate number and very high reflux ratio, could be by epoxy chloropropane and methyl alcohol fractionation by distillation.Owing to containing a large amount of solvent methanols in the epoxidation reaction product, cause the facility investment of fractionation by distillation high, energy expenditure is large.And, when the first alcohol and water exists, in still-process epoxy chloropropane also can with first alcohol and water generation side reaction, generate the by products such as propylene glycol of chlorine monomethyl ether and propylene glycol of chlorine, reduce the yield of epoxy chloropropane.
US6350888B1 discloses a kind of method of carrying out the extracting and separating epoxy chloropropane by extraction agent, the method is by adding a kind of organic extractant extraction epoxy chloropropane, then distill out the extraction agent in the liquid phase that contains epoxy chloropropane obtained, separate and obtain epoxy chloropropane.Although this method can reach the purpose of separating epoxy chloropropane, but, not only need to use a large amount of extraction solvents while from the epoxidation reaction product, extracting epoxy chloropropane, and part methyl alcohol also can be extracted together with epoxy chloropropane, still need straight run distillation separation of methanol and epoxy chloropropane, cause the fractionation by distillation epoxy chloropropane and reclaim extraction solvent consuming a large amount of energy; In addition, in the process of straight run distillation separation of methanol and epoxy chloropropane, epoxy chloropropane also can with methyl alcohol generation side reaction, generate the by products such as propylene glycol of chlorine monomethyl ether, reduce the yield of epoxy chloropropane.
CN101293882A discloses a kind of method that simultaneously adopts two kinds of immiscible extraction agent A and extraction agent B extracting and separating epoxy chloropropane, and the extraction agent A that the method adopts is liquid halogenated hydrocarbon or monobasic ether, and extraction agent B is water or liquid polyol.When extraction agent A is chlorallylene, extraction agent B is water, and when fractionation by distillation extraction heavy phase and extraction gently obtain respectively mutually the epoxy chloropropane product and reclaim reaction solvent methyl alcohol, energy expenditure is minimum.But, there is the little and difficult problem that causes easily being separated in extraction process of the density of density ratio extraction agent water of extraction agent chlorallylene in this method, and due to the boiling point of extraction agent chlorallylene lower than epoxy chloropropane, after extraction, need first by distilling whole chlorallylenes from the distillation recovered overhead, and then the materials at bottom of tower of isolating after chlorallylene is distilled, obtain the epoxy chloropropane product from the distillation tower top again, whole chlorallylene extraction agents all needs could reclaim through pervaporation, the energy expenditure that causes separating epoxy chloropropane is still higher.
In sum, there is in extraction process the higher problem of energy expenditure in be separated difficulty and still-process in the separation method of existing epoxy chloropropane.
Summary of the invention
Difficulty and the higher problem of fractionation by distillation energy expenditure are separated in the extraction separation process that the objective of the invention is to exist in the separation method in order to overcome existing epoxy chloropropane, provide in a kind of extraction process and be separated easily and the separation method of the epoxy chloropropane that in still-process, energy expenditure is low, apply to facilitate in the large scale continuous prod process.
In order to realize purpose of the present invention, the invention provides a kind of separation method of epoxy chloropropane, the method comprises: the solution that will contain epoxy chloropropane, methyl alcohol, chlorallylene and water be separated after extraction agent mixes, the liquid phase that obtains being rich in the liquid phase of epoxy chloropropane and be rich in methyl alcohol, distill the resulting liquid phase that is rich in epoxy chloropropane, obtain epoxy chloropropane; Wherein, described extraction agent comprise water and with the immiscible organic solvent of water, the density of described organic solvent and water differs and is at least 10 kilograms per cubic meter, the ability of organic solvent extraction methyl alcohol is lower than the ability of water and extraction epoxy chloropropane higher than water, and organic solvent is different from the boiling point of epoxy chloropropane.
Because organic solvent and water in extraction agent of the present invention are immiscible, the ability of organic solvent extraction methyl alcohol lower than water and the extraction epoxy chloropropane ability higher than water, make organic solvent the most epoxy chloropropane in the solution that contains epoxy chloropropane, methyl alcohol, chlorallylene and water can be extracted into to organic solvent phase (being the liquid phase that is rich in epoxy chloropropane), and the most of methyl alcohol in the solution that contains epoxy chloropropane, methyl alcohol, chlorallylene and water is extracted to water (being the liquid phase that is rich in methyl alcohol).And the density of organic solvent and water differs and is at least 10 kilograms per cubic meter, and in the preferred case, the consumption of organic solvent and water makes has the organic solvent phase that comprises most epoxy chloropropane and the water that comprises most of methyl alcohol the above density difference of 70 kilograms per cubic meter, makes and be very easy to realize good being separated in extraction process.
In the present invention, described organic solvent phase and the water time that is separated in extraction process was no longer than 3 minutes, adopt method of the present invention to be separated, the time of extracting and separating is short, reduced the requirement of extraction and stripping apparatus and the difficulty of extracting operation, be conducive to reduce facility investment and reduce process cost.And the boiling point of organic solvent is different from the boiling point of epoxy chloropropane, under preferred condition, boiling point due to organic solvent A in organic solvent and halohydrocarbon under 1 normal atmosphere and the boiling point of epoxy chloropropane differ more than 20 ℃, obtain the epoxy chloropropane product and reclaim organic solvent by fractionation by distillation easily, organic solvent A in organic solvent does not need just can reclaim through pervaporation, compare than the method for the low-boiling extraction agent of epoxy chloropropane with employing, can effectively reduce energy expenditure.
Therefore, with the separation method of existing epoxy chloropropane, compare, the present invention has following advantage:
1, the time that is separated in extraction process short (being less than 3 minutes), reduced the requirement of extraction and stripping apparatus and the difficulty of extracting operation, be conducive to reduce facility investment and reduce process cost;
2, in a preferred embodiment, the boiling point of the organic solvent A in organic solvent and halohydrocarbon and epoxy chloropropane differs more than 20 ℃, make the fractionation by distillation process be very easy to realize, further reduced the requirement of fractionation by distillation equipment and the difficulty of distillation procedure, reduced facility investment and reduced process cost;
3, only need evaporation recovery part extraction agent in still-process, effectively reduced energy expenditure;
4, easily realize large scale continuous prod.
Other features and advantages of the present invention will partly be described in detail in embodiment subsequently.
The accompanying drawing explanation
Accompanying drawing is to be used to provide a further understanding of the present invention, and forms the part of specification sheets, is used from explanation the present invention with following embodiment one, but is not construed as limiting the invention.In the accompanying drawings:
The schema that Fig. 1 is distilled for separate the organic solvent phase that obtains (in figure referred to as the A phase) and water according to separation method of the present invention;
The schema that Fig. 2 is distilled for separate the chlorallylene phase that obtains and water according to the method for prior art.
Description of reference numerals
Within 1: the first, distillation tower 2: second column;
4: the four distillation towers of 3: the three distillation towers.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
The invention provides a kind of separation method of epoxy chloropropane, the method comprises: the solution that will contain epoxy chloropropane, methyl alcohol, chlorallylene and water be separated after extraction agent mixes, the liquid phase that obtains being rich in the liquid phase of epoxy chloropropane and be rich in methyl alcohol, distill the resulting liquid phase that is rich in epoxy chloropropane, obtain epoxy chloropropane; Wherein, described extraction agent comprise water and with the immiscible organic solvent of water, the density of described organic solvent and water differs and is at least 10 kilograms per cubic meter, the ability of organic solvent extraction methyl alcohol is lower than the ability of water and extraction epoxy chloropropane higher than water, and organic solvent is different from the boiling point of epoxy chloropropane.
In the present invention, if described organic solvent is mixed solvent, the boiling point of described organic solvent refers to the boiling point of various organic solvents in mixed solvent, if perhaps described mixed solvent can form azeotrope, the boiling point of described organic solvent refers to the azeotropic point of azeotrope, and what need to further illustrate is, if what described mixed organic solvents formed is minimum azeotropic mixture, described azeotropic point refers to minimum boiling point, if what described mixed organic solvents formed is the maximum azeotrope thing, described azeotropic point refers to the maximum boiling point of mixed solvent.
In the present invention, unless stated otherwise, density all refers to 20 ℃, 1 density that standard atmosphere is depressed.
In the present invention, according to the aforementioned techniques scheme, all can realize purpose of the present invention, for the present invention, further, under preferable case, under 20 ℃, the density of described organic solvent and water differs the 10-2000 kilograms per cubic meter.
In the present invention, as long as described organic solvent is different from the boiling point of epoxy chloropropane can realize purpose of the present invention, for the present invention, in order to realize more fully purpose of the present invention, the boiling point of preferred described organic solvent and the boiling-point difference of epoxy chloropropane are 20-300 ℃, more preferably 30-200 ℃.
The method according to this invention, further under preferable case, the liquid phase that is rich in epoxy chloropropane that described separation obtains (if not otherwise specified, be designated hereinafter simply as the organic solvent phase) and the liquid phase that is rich in methyl alcohol is (if not otherwise specified, being designated hereinafter simply as water) density difference under 20 ℃ is the 70-2000 kilograms per cubic meter, be preferably the 80-1000 kilograms per cubic meter, thereby two liquid phases are separated better.
The method according to this invention, optional a wider range as the consumption of the organic solvent of extraction agent and water, for the present invention, the solution that preferably with respect to 100 mass parts, contains epoxy chloropropane, methyl alcohol, chlorallylene and water, the consumption of described organic solvent is the 10-1000 mass parts, is preferably the 30-300 mass parts; The consumption of described water is the 10-1000 mass parts, is preferably the 20-200 mass parts.
The method according to this invention, all can realize purpose of the present invention according to the aforementioned techniques scheme, for the present invention, under preferable case, in order further to save disengaging time, to improve separation efficiency, in preferred described organic solvent, contain the organic solvent A that at least contains functional group's Sauerstoffatom.
The method according to this invention, meet the described organic solvent A of aforementioned requirement concrete can be for example one or more in liquid halogen ether, liquid halogenated carboxylic ester, liquid halo carbonyl compound and liquid nitrohalogen compound, under further preferable case, one or more in the liquid halo carbonyl compound (being generally halogenated ketone and/or halogenated aldehyde) of the liquid halogen ether that described organic solvent A is C4-C16, the liquid halogenated carboxylic ester of C4-C20, C4-C12 and the liquid nitrohalogen compound (being generally halogenated nitrobenzene) of C6-C12.Here be noted that aforementioned liquid nitrohalogen compound can realize purpose of the present invention as organic solvent, yet, because it has toxicity, therefore, preferably it does not use as described organic solvent in the present invention.
The method according to this invention, for light liquid phase and the heavy-fluid that extraction is obtained easily realizes being separated mutually, the large 10-2000 kilograms per cubic meter of the density of the density ratio water of preferred described organic solvent A, more preferably large 50-1000 kilograms per cubic meter.
The method according to this invention, in order to make organic solvent and the epoxy chloropropane easy fractionation by distillation of the heavy-fluid that obtains of extraction in mutually, thereby further reduce energy expenditure, the boiling point of preferred described organic solvent A under 1 normal atmosphere is than the high 20-300 ℃ of the boiling point of epoxy chloropropane, more preferably high 30-200 ℃.
The method according to this invention, the described organic solvent A that meets aforementioned requirement includes but not limited to: 2,2 '-dichloro-diethyl ether, dichloro-dipropyl ether, dichlorodiisopropyl ether, the dichloro dibutyl ether, the dichloro diisobutyl ether, 1,2-bis-(2-chloroethoxy) ethane, p-Fluoroanisole, adjacent fluoroanisole, 3-Fluoroanisole, to chloroneb, o-chloro-anisole, between chloroneb, para-bromoanisole, o-bromo-anisole, Meta Bromo Anisole, to chlorophenetole, adjacent chlorophenetole, between chlorophenetole, to Bromoethyl phenyl ether, adjacent Bromoethyl phenyl ether, between Bromoethyl phenyl ether, isopropyl chloracetate, butyl chloroacetate, the bromoacetic acid butyl ester, iso-butyl chloroacetate, n-amyl chloroacetate, ethyl trichloroacetate, the 2-chloropropionate, the 2 bromopropionic acid ethyl ester, the 4-neoprene acid ethyl ester, 2-bromo-butyric acid methyl esters, 4-bromo-butyric acid ethyl ester, ethyl bromoacetate, 2-chloro-benzoic 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-chloro-benzoic acid ethyl ester, the alpha-chloro phenylacrolein, the chloro-2 pentanone of 5-, the bromo-methyl-n-butyl ketone of 6-, o-chlorobenzaldehyde, m chlorobenzaldehyde, o-bromobenzaldehye, parachloroacetophenone, parabromoacetophenone, 2,5-dichloroacetophenone, DNF, 2,4-difluoro nitrobenzene and to one or more in the chlorine meta-nitrotoluene, be preferably dichloro-dipropyl ether, 1,2-bis-(2-chloroethoxy) ethane, to chloroneb, o-chloro-anisole, between chloroneb, to chlorophenetole, adjacent chlorophenetole, between chlorophenetole, butyl chloroacetate, ethyl trichloroacetate, one or more in parachloroacetophenone and 2,5-dichloroacetophenone.
The method according to this invention, further, under preferable case, also contain halohydrocarbon in described organic solvent.In order to make each material in the rear organic solvent of separation all can well realize separating, preferred described halohydrocarbon is different from the boiling point of organic solvent A.
The method according to this invention, optional a wider range of the ratio of organic solvent A and halohydrocarbon in described organic solvent, for the present invention, in preferred described organic solvent, the mass ratio of organic solvent A and halohydrocarbon is 1/50-50/1, more preferably 1/5-5/1.
The method according to this invention, one or more in the liquid halohydrocarbon that preferred described halohydrocarbon is C1-C16, easily realize fractionation by distillation in order to make halohydrocarbon and the epoxy chloropropane of heavy-fluid in mutually, thereby reduction energy expenditure, for the present invention, more preferably the boiling point of the boiling point of described halohydrocarbon and epoxy chloropropane differs more than 20 ℃, preferably differs more than 30 ℃.
The method according to this invention, the described halohydrocarbon that meets aforementioned requirement includes but not limited to: tetracol phenixin, 1, 1, 2, the 2-tetrachloroethane, pentaline, 1, 1, 2, the 2-tetrabromoethane, chlorallylene, 1, 2, the 3-trichloropropane, 1, 1, 1, 3-tetrachloro propane, 1, the 2-dibromopropane, 1, the 3-dibromopropane, 1, 2, the 3-tribromopropane, the bromo-3-chloropropane of 1-, 1, the 4-dichlorobutane, 1, the 4-dibromobutane, 1, the 5-dichloropentane, 1, pentamethylene bromide, 1, the 6-dibromo-hexane, the 1-bromo-dodecane, m-chlorotoluene, orthodichlorobenzene, Meta Dichlorobenzene, 2, the 4-toluene dichloride, 1, 2, the 4-trichlorobenzene, bromobenzene, o-dibromobenzene, m-dibromobenzene, adjacent bromochlorophene and 2, one or more in the 4-dichlor fluorbenzene, comprehensive cost is considered, chlorallylene more preferably.
The method according to this invention, optional a wider range of the condition that the described solution that will contain epoxy chloropropane, methyl alcohol, chlorallylene and water mixes with extraction agent, for the present invention, under preferable case, the temperature that the described solution that will contain epoxy chloropropane, methyl alcohol, chlorallylene and water mixes with extraction agent (being the temperature of extracting and separating) is 1-80 ℃, is preferably 5-40 ℃.Under aforementioned preferred extracting and separating condition, both can make the described solution that contains epoxy chloropropane, methyl alcohol, chlorallylene and water fully mix with extraction agent, reach the purpose of extraction, can reduce again epoxy chloropropane in the described solution that contains epoxy chloropropane, methyl alcohol, chlorallylene and water and the side reaction of first alcohol and water.
The method according to this invention, carry out extracting and separating according to aforementioned techniques scheme of the present invention, disengaging time is short, for example the described solution that will contain epoxy chloropropane, methyl alcohol, chlorallylene and water with separate after extraction agent is mixed be no more than 3 minutes total time and can separate and obtain organic solvent phase and water.This shows, method of the present invention is efficient and simple and easy to do.
The method according to this invention, the content that the content that the content that preferably in the described solution that contains epoxy chloropropane, methyl alcohol, chlorallylene and water, the content of epoxy chloropropane is 5-25 quality %, methyl alcohol is 35-65 quality %, chlorallylene is 4-35 quality % and water is 5-25 quality %.
The method according to this invention, the product that further preferably the described solution that contains epoxy chloropropane, methyl alcohol, chlorallylene and water is chlorallylene and hydrogen dioxide epoxidation reaction, concrete, the described solution that contains epoxy chloropropane, methyl alcohol, chlorallylene and water is: under titanium-silicon molecular sieve catalyst exists, take methyl alcohol as solvent, chlorallylene and product after hydrogen peroxide or aqueous hydrogen peroxide solution contact.
In order to make method of the present invention be more suitable in suitability for industrialized production, further under preferable case, method of the present invention also comprises: distill that the resulting liquid phase that is rich in methyl alcohol is contained or not containing methanol stream and the water logistics of chlorallylene, using described containing or containing the methanol stream of chlorallylene, partly or entirely do not return to the solvent that replaces methyl alcohol contact with hydrogen peroxide or aqueous hydrogen peroxide solution as described chlorallylene, using described water stream portions or all return as extraction agent for extraction (general need be returned to the water stream portions as extraction agent for extracting).
As previously mentioned, further under preferable case, when obtaining epoxy chloropropane, the resulting liquid phase that is rich in epoxy chloropropane of distillation obtains chlorallylene logistics and organic solvent logistics, using described chlorallylene stream portions or all return as the raw material contacted with hydrogen peroxide or aqueous hydrogen peroxide solution, by described organic solvent stream portions or all return for extraction.Here be noted that, contain halohydrocarbon in described organic solvent, and when described halohydrocarbon is chlorallylene, aforementioned organic solvent logistics is generally the logistics of the aforesaid organic solvent A of the present invention, and aforementioned chlorallylene logistics generally comprises chlorallylene in the solution that contains epoxy chloropropane, methyl alcohol, chlorallylene and water and as the chlorallylene of extraction agent, optionally, also can or all return for extraction described chlorallylene stream portions.
In the present invention, organic solvent and water as extraction agent both can join in the described solution that contains epoxy chloropropane, methyl alcohol, chlorallylene and water simultaneously, also can first a kind of extraction agent (organic solvent or water) be mixed with the described solution that contains epoxy chloropropane, methyl alcohol, chlorallylene and water, and then add another kind of extraction agent (organic solvent or water).
In the present invention, while in the ban a kind of extraction agent (organic solvent or water) being mixed with the described solution that contains epoxy chloropropane, methyl alcohol, chlorallylene and water, described can be the liquid contact mixing equipment such as the pipeline known, line mixer, stirring tank, mixing column for the equipment mixed.
In the present invention, when the organic solvent as extraction agent and water add fashionablely simultaneously, being blended in extraction equipment of extraction agent and the described solution that contains epoxy chloropropane, methyl alcohol, chlorallylene and water carried out.
The described equipment for extraction can be extraction equipment commonly used well-known to those skilled in the art, as steel basin, sieve-tray tower, packing tower, rotating disc contactor, valve tray column, spray tower etc., both can take the mode of periodical operation, also can adopt the mode of operate continuously, preferably adopt the operate continuously mode to realize large-scale industrial production to facilitate.While adopting the operate continuously mode, preferably adopt the continuous countercurrent extraction tower as extraction equipment.
In the present invention, the organic solvent liquid phase (referred to as heavy phase) of attaching most importance to mutually, water is light liquid phase (referred to as light phase).Separating of described organic solvent phase and water both can automatically complete and obtained respectively water and organic solvent phase at the bottom of tower top and tower in the extraction equipments such as continuous countercurrent extraction tower, also can in independent device for phase saparation, carry out.Described device for phase saparation can be the conventional device for phase saparation such as subsider, slurry tank, wet cyclone and whizzer.
According to the present invention, described HTS is the general name that titanium atom replaces a class zeolite of a part of Siliciumatom in the zeolite lattice framework.Described HTS is well known in the prior art, for example, can be to there is the titanium-containing zeolite TS-1 that is similar to ZSM-5 aluminosilicate zeolite MFI topological framework, there is the titanium-containing zeolite TS-2 that is similar to ZSM-11 aluminosilicate zeolite MEL topological framework, and there is molecular sieve containing titanium with the skeleton structure of mordenite, ZSM-12, MCM-22, MCM-41, MCM-48 and the beta-zeolite isomorphous etc., wherein, be preferably TS-1 and TS-2, be particularly preferably TS-1.The present invention's catalyzer used can be that the former powder of these zeolites is directly used, and also can after overmolding, be used by the former powder of these zeolites, specifically can be selected according to response situation.
According to the present invention, when described titanium-silicon molecular sieve catalyst adds fashionablely with slurry form, the described catalytic liquid phase of take is benchmark, and the content of described HTS is generally 0.5-30 quality %, is preferably 1-15 quality %, more preferably 1.5-10 quality %; When catalyzer is fixed in reactor, the charging quality space-time speed of hydrogen peroxide is (in the present invention, quality space-time speed generally also can be described as liquid hourly space velocity, refers to the ratio of the quality of the charging quality of unit time hydrogen peroxide and the catalyzer in reactor) be generally 0.01-100h -1, be preferably 0.02-10h -1, 0.02-1h more preferably -1.
According to the present invention, the temperature that described chlorallylene contacts with hydrogen peroxide or aqueous hydrogen peroxide solution (being the temperature of chlorallylene epoxidation reaction) is generally 10-120 ℃, is preferably 40-80 ℃; The time of contact is 0.01-100 hour, is preferably 0.1-10 hour; The raw materials components mole ratio of described chlorallylene and hydrogen peroxide is generally 1/1-10/1, is preferably 1.2/1-6/1; The charging mass ratio of described methyl alcohol and chlorallylene is generally 0.5/1-15/1, is preferably 0.5/1-5/1.
According to the present invention, described chlorallylene can be analytical reagent and/or chemically pure reagent, but considers preferably to use Industrial products from economic angle, and in Industrial products, the content of chlorallylene is generally 95-100 quality %, is preferably 97-99.9 quality %.
According to the present invention, can use hydrogen peroxide directly as oxygenant, but, for security consideration, general preferred employing aqueous hydrogen peroxide solution is as oxygenant, in aqueous hydrogen peroxide solution, the concentration of hydrogen peroxide can be generally 5-90 quality %, is preferably 20-60 quality %.
The method according to this invention, described organic solvent has comprised the most epoxy chloropropane in the described solution that contains epoxy chloropropane, methyl alcohol, chlorallylene and water, most of chlorallylene, a small amount of methyl alcohol and minor amount of water in mutually.The boiling point of depressing at 1 standard atmosphere due to chlorallylene is 45.0 ℃, and epoxy chloropropane boiling point under the same conditions is 116.1 ℃, and the two differs 71.1 ℃, is easy to realize separating by distillation; Equally, due to the boiling point of the organic solvent A in organic solvent, than the high 20-300 ℃ of the boiling point of epoxy chloropropane, also easily by simple distillation, realize separating, and organic solvent A can directly reclaim and not need through pervaporation from base product; And the boiling point of the boiling point of the halohydrocarbon in organic solvent and epoxy chloropropane differs more than 20 ℃, also easily by simple distillation, realize separating.A small amount of methyl alcohol wherein, because methyl alcohol is separated with epoxy chloropropane with chlorallylene at 40.0 ℃ of formation azeotropes (methyl alcohol that contains 10.0 quality % in azeotrope) at an easy rate with chlorallylene; As for minor amount of water wherein, because water can remove it at 88.0 ℃ of formation azeotropes (water that contains 25 quality % in azeotrope) with epoxy chloropropane at 43.0 ℃ of formation azeotropes (water that contains 2.2 quality % in azeotrope) and water easily with chlorallylene.
The method according to this invention, especially, when halohydrocarbon is chlorallylene, not only halohydrocarbon can save (the two can together with return to the raw material as aforementioned epoxy chloropropane epoxidation reaction) with the fractionation by distillation process of epoxy chloropropane, and compare as the situation of extraction agent with adopting single organic solvent A, because the boiling point of chlorallylene is low, make the temperature of base product in the time of can effectively reducing the fractionation by distillation chlorallylene, reduce the impact of high temperature on epoxy chloropropane and organic solvent A.
The method according to this invention, comprised the most of methyl alcohol in the described solution that contains epoxy chloropropane, methyl alcohol, chlorallylene and water, most of water and a small amount of chlorallylene in described extraction agent water.Because the boiling point of chlorallylene is lower than the boiling point of methyl alcohol (64.5 ℃), and can form than the low-boiling azeotrope of chlorallylene with the first alcohol and water, be easy to be separated with water when fractionation by distillation methyl alcohol.And the boiling point of methyl alcohol is lower 35.5 ℃ and do not form azeotrope with water than the boiling point of water (100 ℃), easily by simple distillation by methyl alcohol and moisture from, thereby realize Methanol Recovery, extraction agent water does not need to reclaim by evaporating yet.
Known by above description, utilize simple distillation can realize epoxy chloropropane being separated mutually from organic solvent and methyl alcohol and chlorallylene can being reclaimed, and do not need to reclaim extraction agent organic solvent and water by evaporating whole extraction agents, can effectively reduce the energy expenditure that epoxy chloropropane separates.Separation method than independent employing chlorallylene and water as extraction agent, the present invention is by adding organic solvent A as extraction agent, make separation method of the present invention both can realize being separated fast in extraction process, can reduce again the energy expenditure of fractionation by distillation.
The method according to this invention, described distillation can adopt the Distallation systm of normal pressure well known to those skilled in the art, decompression or the two combination.
For example, distillation organic solvent phase in atmospheric distillation tower, tower top obtains (containing epoxy chloropropane if described containing the chlorallylene logistics of a small amount of methyl alcohol and minor amount of water, methyl alcohol, the solution of chlorallylene and water is: under titanium-silicon molecular sieve catalyst exists, take methyl alcohol as solvent, chlorallylene and product after hydrogen peroxide contacts, the chlorallylene logistics containing a small amount of methyl alcohol and minor amount of water obtained can cyclically utilizing as the raw material contacted with hydrogen peroxide, when perhaps the halohydrocarbon in organic solvent is chlorallylene, the chlorallylene logistics containing a small amount of methyl alcohol and minor amount of water obtained can partly circulate and return to epoxidation reaction as the raw material contacted with hydrogen peroxide, the part circulation is returned as extraction agent), the described logistics containing epoxy chloropropane and organic solvent obtained at the bottom of tower, further fractionation by distillation in another normal pressure or vacuum still, the boiling point of the halohydrocarbon in organic solvent is during lower than epoxy chloropropane, obtain halohydrocarbon logistics circulation from tower top and return to extraction, obtain the logistics (when the halohydrocarbon in organic solvent is chlorallylene, just there is no described still-process) containing epoxy chloropropane and organic solvent A at the bottom of tower, the described logistics containing epoxy chloropropane and organic solvent A obtained at the bottom of tower, further fractionation by distillation in a normal pressure or vacuum still, obtain the epoxy chloropropane product stream from tower top, obtains organic solvent A logistics circulation at the bottom of tower and return to extraction.The water that distillation obtains in other atmospheric distillation tower, tower top obtains returning to containing the methanol stream circulation of a small amount of chlorallylene the solvent that epoxidation reaction contacts with hydrogen peroxide or aqueous hydrogen peroxide solution as described chlorallylene, extraction is returned in the water logistics part circulation obtained at the bottom of tower, and another part is as discharge of wastewater.
The present invention does not have concrete requirement to the condition of distillation, and the distillation condition of organic solvent phase and water is different and different with the composition of organic solvent, can be selected according to practical situation.
Describe in more detail the present invention below by embodiment, but the present invention is not limited to this.
Preparation Example
The preparation of the solution that contains epoxy chloropropane, methyl alcohol, chlorallylene and water (being the epoxidation reaction product):
Extracting epoxidation reaction product used carries out chlorallylene and aqueous hydrogen peroxide solution in fixed bed jacketed pipe type reactor epoxidation reaction according to the disclosed method of embodiment in CN101747296A 1 prepares.Be 50 ℃ at the jacket oil bath temperature, adopt under the reaction conditions of 30% aqueous hydrogen peroxide solution and 0.40MPa pressure, by changing chlorallylene and the raw materials components mole ratio of hydrogen peroxide and the charging mass ratio of methyl alcohol and chlorallylene, the epoxidation reaction product S 1-S5(that obtains respectively the difference composition shown in table 1 is following also referred to as the solution S 1-S5 that contains epoxy chloropropane, methyl alcohol, chlorallylene and water).
Embodiment 1
The present embodiment is for illustrating the separation method of epoxy chloropropane provided by the invention.
Under 28 ℃, 100 mass parts are formed to the known epoxy chloropropane that contains, methyl alcohol, first with the water of 49.9 mass parts, (density 20 ℃ the time is 998.2 kilograms per cubic meter to the solution S 1 of chlorallylene and water, boiling point is 100 ℃) the contact mixing, after stratification, collect lower floor's heavy phase, use again that (ladder is uncommon likes that (Shanghai) changes into industrial development company limited by the ethyl trichloroacetate of 70.0 mass parts, density in the time of 20 ℃ is 1383.6 kilograms per cubic meter, boiling point is 168 ℃) and chlorallylene (the industrial propenyl chloride of 34.8 mass parts, Ba Ling petrochemical complex limited liability company, the content of chlorallylene is 98 quality %, density in the time of 20 ℃ is 939.2 kilograms per cubic meter, boiling point is 45 ℃) mixed organic solvents that forms the quality such as be divided into extract the light phases in upper strata for five parts minute five times, merge all heavy phases and obtain the organic solvent phase, organic solvent is middle epoxy chloropropane mutually, methyl alcohol, the content of chlorallylene and water is respectively 11.92 quality %, 2.68 quality %, 31.96 quality % and 0.46 quality %, what finally obtain gently is water mutually, epoxy chloropropane in water, methyl alcohol, the content of chlorallylene and water is respectively 0.26 quality %, 40.50 quality %, 2.76 quality % and 55.08 quality %, organic solvent phase and the water density difference in the time of 20 ℃ is 254.4 kilograms per cubic meter.
According to flow process shown in Fig. 1, the water obtained is introduced in the first distillation tower 1 and carried out fractionation by distillation; Organic solvent phase (in figure referred to as the A phase) is introduced in second column 2 and carried out fractionation by distillation.
Water, under normal pressure, obtains returning to epoxidation reaction containing the methanol stream circulation of a small amount of chlorallylene via the tower top (64 ℃) of the first distillation tower 1, and at the bottom of tower, (104 ℃) obtain the water logistics; Extraction is returned in the water logistics part circulation of gained, and another part is as discharge of wastewater.
Organic solvent is under normal pressure, tower top (41 ℃) via second column 2 obtains the chlorallylene logistics containing methyl alcohol and minor amount of water, epoxidation reaction is returned in part circulation, extraction is returned in another part circulation, and at the bottom of tower, (149 ℃) obtain the ethyl trichloroacetate logistics containing epoxy chloropropane and minor amount of water, gained further separates the epoxy chloropropane that obtains tower top (88 ℃) and the azeotrope (water that contains 25 quality %) of water containing the ethyl trichloroacetate logistics of epoxy chloropropane and minor amount of water in the 3rd distillation tower 3, be separated into circulation containing 97.44 quality % epoxy chloropropane and return to the light phase logistics of the 3rd distillation tower 3 in proceeding the logistics (logistics that the heavy phase in turning back to the 3rd distillation tower 3 is partly separated) separated and returning to extraction tower containing the circulation of 92.58 quality % water in return tank (50 ℃), at the bottom of tower, (150 ℃) obtain the logistics of water-free epoxy chloropropane and ethyl trichloroacetate, by the logistics of the water-free epoxy chloropropane of gained at the bottom of tower and ethyl trichloroacetate further in the 4th distillation tower 4 fractionation by distillation obtain the epoxy chloropropane product stream of tower top (13 kPas, 60 ℃) and extraction is returned in the circulation of the ethyl trichloroacetate logistics at the bottom of tower.
In Solvent quantity (with respect to the epoxidation reaction product of 100 mass parts) and organic solvent, the mass ratio of organic solvent A and halohydrocarbon is as shown in table 2; The energy consumption of light phase (water) and the longest disengaging time, epoxy chloropropane yield and the fractionation by distillation of heavy phase (organic solvent phase) during extracting and separating, the distillation energy consumption is the water vapour that epoxy chloropropane product per ton that separation obtains consumes, unit is ton/ton, as shown in table 3.
Contained epoxy chloropropane in the epoxy chloropropane of the yield of epoxy chloropropane (%)=finally obtain/initial solution.
Comparative Examples 1
Under 23 ℃, 100 mass parts are formed to the known epoxy chloropropane that contains, methyl alcohol, first with the water of 60.0 mass parts, (density 20 ℃ the time is 998.2 kilograms per cubic meter to the solution S 1 of chlorallylene and water, 100 ℃ of boiling points) fully mix, after stratification, collect lower floor's heavy phase, use again chlorallylene (the industrial propenyl chloride of 80.0 mass parts, Ba Ling petrochemical complex limited liability company, the content of chlorallylene is 98 quality %, density in the time of 20 ℃ is 939.2 kilograms per cubic meter, boiling point is 45 ℃) the five parts minutes five times light phases in extraction upper strata of quality such as be divided into, merge all heavy phases and obtain the chlorallylene phase, chlorallylene is middle epoxy chloropropane mutually, methyl alcohol, the content of chlorallylene and water is respectively 14.68 quality %, 2.78 quality %, 81.62 quality % and 0.52 quality %, what finally obtain gently is water mutually, epoxy chloropropane in water, methyl alcohol, the content of chlorallylene and water is respectively 0.23 quality %, 37.91 quality %, 2.78 quality % and 58.58 quality %, chlorallylene phase and the water density difference in the time of 20 ℃ is 56.3 kilograms per cubic meter.
According to flow process shown in Fig. 2, the water obtained is introduced in the first distillation tower and carried out fractionation by distillation, chlorallylene is introduced mutually in second column 2 and carried out fractionation by distillation.
Water is under normal pressure, tower top (64 ℃) by the first distillation tower 1 obtains returning to epoxidation reaction containing the methanol stream circulation of a small amount of chlorallylene and minor amount of water, at the bottom of tower, (104 ℃) obtain moisture logistics, and wherein extraction is returned in part circulation, and another part is as discharge of wastewater.
Chlorallylene is under normal pressure, tower top (43 ℃) via second column 2 obtains the chlorallylene logistics containing a small amount of methyl alcohol and minor amount of water, epoxidation reaction is returned in part circulation, and extraction is returned in another part circulation, and at the bottom of tower, (121 ℃) obtain the logistics of water-free epoxy chloropropane; The water-free epoxy chloropropane logistics of gained further separates and obtains the epoxy chloropropane product stream of tower top (13 kPas, 60 ℃) and the heavy constituent logistics at the bottom of tower in the 3rd distillation tower 3.
The energy consumption of the longest disengaging time, epoxy chloropropane yield and the fractionation by distillation of light phase (water) and heavy phase (chlorallylene phase) when Solvent quantity (with respect to the epoxidation reaction product of 100 mass parts), extraction, the distillation energy consumption is that separation obtains the water vapour that epoxy chloropropane product per ton consumes, unit is ton/ton, as shown in table 4.
Contained epoxy chloropropane in the epoxy chloropropane of the yield of epoxy chloropropane (%)=finally obtain/initial solution.
Embodiment 2
The present embodiment is for illustrating the separation method of epoxy chloropropane provided by the invention.
Under 15 ℃, 100 mass parts are formed to the known epoxy chloropropane that contains, methyl alcohol, first with the water of 50.1 mass parts, (density 20 ℃ the time is 998.2 kilograms per cubic meter to the solution S 2 of chlorallylene and water, boiling point is 100 ℃) the contact mixing, after stratification, collect lower floor's heavy phase, use again that (ladder is uncommon likes that (Shanghai) changes into industrial development company limited by the ethyl trichloroacetate of 40.0 mass parts, density in the time of 20 ℃ is 1383.6 kilograms per cubic meter, boiling point is 168 ℃) and chlorallylene (the industrial propenyl chloride of 49.9 mass parts, Ba Ling petrochemical complex limited liability company, the content of chlorallylene is 98 quality %, density in the time of 20 ℃ is 939.2 kilograms per cubic meter, boiling point is 45 ℃) mixed organic solvents that forms the quality such as be divided into extract the light phases in upper strata for five parts minute five times, merge all heavy phases and obtain the organic solvent phase, organic solvent is middle epoxy chloropropane mutually, methyl alcohol, the content of chlorallylene and water is respectively 8.07 quality %, 2.46 quality %, 58.76 quality % and 0.38 quality %, what finally obtain gently is water mutually, epoxy chloropropane in water, methyl alcohol, the content of chlorallylene and water is respectively 0.12 quality %, 37.69 quality %, 3.78 quality % and 57.79 quality %, organic solvent phase and the water density difference in the time of 20 ℃ is 146.4 kilograms per cubic meter.
According to flow process shown in Fig. 1, the water obtained is introduced in the first distillation tower 1 and carried out fractionation by distillation, organic solvent is introduced mutually in second column 2 and carried out fractionation by distillation.
Water is under normal pressure, tower top (64 ℃) via the first distillation tower 1 obtains returning to epoxidation reaction containing the methanol stream circulation of a small amount of chlorallylene, at the bottom of tower, (104 ℃) obtain the water logistics, and extraction is returned in the water logistics part circulation of gained, and another part is as discharge of wastewater.
Organic solvent is under normal pressure, tower top (41 ℃) via second column 2 obtains the chlorallylene logistics containing methyl alcohol and minor amount of water, epoxidation reaction is returned in part circulation, extraction is returned in another part circulation, and at the bottom of tower, (147 ℃) obtain the ethyl trichloroacetate logistics containing the epoxy chloropropane of minor amount of water, gained further separates the epoxy chloropropane that obtains tower top (88 ℃) and the azeotrope (water that contains 25 quality %) of water containing the ethyl trichloroacetate logistics of epoxy chloropropane and minor amount of water in the 3rd distillation tower 3, be separated into circulation containing 97.44 quality % epoxy chloropropane and return to the logistics of the light phase of the 3rd distillation tower 3 in proceeding the logistics (logistics that the heavy phase in turning back to the 3rd distillation tower 3 is partly separated) separated and returning to extraction tower containing the circulation of 92.58 quality % water in return tank (50 ℃), at the bottom of tower, (147 ℃) obtain the logistics of water-free epoxy chloropropane and ethyl trichloroacetate, by the logistics of the water-free epoxy chloropropane of gained at the bottom of tower and ethyl trichloroacetate further in the 4th distillation tower 4 fractionation by distillation obtain the epoxy chloropropane product stream of tower top (13 kPas, 60 ℃) and extraction is returned in the circulation of the ethyl trichloroacetate logistics at the bottom of tower.
In Solvent quantity (with respect to the epoxidation reaction product of 100 mass parts) and organic solvent, the mass ratio of organic solvent A and halohydrocarbon is as shown in table 2; The energy consumption of light phase (water) and the longest disengaging time, epoxy chloropropane yield and the fractionation by distillation of heavy phase (organic solvent phase) during extracting and separating, the distillation energy consumption is the water vapour that epoxy chloropropane product per ton that separation obtains consumes, unit is ton/ton, as shown in table 3.
Contained epoxy chloropropane in the epoxy chloropropane of the yield of epoxy chloropropane (%)=finally obtain/initial solution.
Comparative Examples 2
Under 14 ℃, 100 mass parts are formed to the known epoxy chloropropane that contains, methyl alcohol, first with the water of 60.0 mass parts, (density 20 ℃ the time is 998.2 kilograms per cubic meter to the solution S 2 of chlorallylene and water, 100 ℃ of boiling points) fully mix, after stratification, collect lower floor's heavy phase, use again chlorallylene (the industrial propenyl chloride of 80.0 mass parts, Ba Ling petrochemical complex limited liability company, the content of chlorallylene is 98 quality %, density in the time of 20 ℃ is 939.2 kilograms per cubic meter, boiling point is 45 ℃) the five parts minutes five times light phases in extraction upper strata of quality such as be divided into, merge all heavy phases and obtain the chlorallylene phase, chlorallylene is middle epoxy chloropropane mutually, methyl alcohol, the content of chlorallylene and water is respectively 8.80 quality %, 2.00 quality %, 88.54 quality % and 0.42 quality %, what finally obtain gently is water mutually, epoxy chloropropane in water, methyl alcohol, the content of chlorallylene and water is respectively 0.10 quality %, 34.89 quality %, 3.86 quality % and 60.76 quality %, chlorallylene phase and the water density difference in the time of 20 ℃ is 40.0 kilograms per cubic meter.
The water and the chlorallylene that obtain are carried out to fractionation by distillation according to the method identical with Comparative Examples 1, obtain the epoxy chloropropane product.
The energy consumption of the longest disengaging time, epoxy chloropropane yield and the fractionation by distillation of light phase (water) and heavy phase (chlorallylene phase) when Solvent quantity (with respect to the epoxidation reaction product of 100 mass parts), extraction, the distillation energy consumption is that separation obtains the water vapour that epoxy chloropropane product per ton consumes, unit is ton/ton, as shown in table 4.
Contained epoxy chloropropane in the epoxy chloropropane of the yield of epoxy chloropropane (%)=finally obtain/initial solution.
Embodiment 3
The present embodiment is for illustrating the separation method of epoxy chloropropane provided by the invention.
Under 28 ℃, 100 mass parts are formed to the known epoxy chloropropane that contains, methyl alcohol, first with the water of 60.2 mass parts, (density 20 ℃ the time is 998.2 kilograms per cubic meter to the solution S 3 of chlorallylene and water, boiling point is 100 ℃) the contact mixing, after stratification, collect lower floor's heavy phase, use again by 50.0 mass parts to chloroneb, (ladder is uncommon likes that (Shanghai) changes into industrial development company limited, density in the time of 20 ℃ is 1160 kilograms per cubic meter, boiling point is 200 ℃) and chlorallylene (the industrial chlorallylene of 49.9 mass parts, Ba Ling petrochemical complex limited liability company, the content of chlorallylene is 98 quality %, density in the time of 20 ℃ is 939.2 kilograms per cubic meter, boiling point is 45 ℃) mixed organic solvents that forms the quality such as be divided into extract the light phases in upper strata for five parts minute five times, merge all heavy phases and obtain the organic solvent phase, organic solvent is middle epoxy chloropropane mutually, methyl alcohol, the content of chlorallylene and water is respectively 14.06 quality %, 2.42 quality %, 41.94 quality % and 0.46 quality %, what finally obtain gently is water mutually, epoxy chloropropane in water, methyl alcohol, the content of chlorallylene and water is respectively 0.31 quality %, 38.06 quality %, 2.50 quality % and 58.39 quality %, organic solvent phase and the water density difference in the time of 20 ℃ is 138.7 kilograms per cubic meter.
According to flow process shown in Fig. 1, the water obtained is introduced in the first distillation tower 1 and carried out fractionation by distillation; Organic solvent phase (in figure referred to as the A phase) is introduced in second column 2 and carried out fractionation by distillation.
Water, under normal pressure, obtains returning to epoxidation reaction containing the methanol stream circulation of a small amount of chlorallylene via the tower top (64 ℃) of the first distillation tower 1, and at the bottom of tower, (104 ℃) obtain the water logistics; Extraction is returned in the water logistics part circulation of gained, and another part is as discharge of wastewater.
Organic solvent is under normal pressure, tower top (41 ℃) via second column 2 obtains the chlorallylene logistics containing methyl alcohol and minor amount of water, epoxidation reaction is returned in part circulation, extraction is returned in another part circulation, at the bottom of tower (150 ℃) obtain containing epoxy chloropropane and minor amount of water to the chloroneb logistics, gained further separates the epoxy chloropropane that obtains tower top (88 ℃) and the azeotrope (water that contains 25 quality %) of water containing epoxy chloropropane and minor amount of water to the chloroneb logistics in the 3rd distillation tower 3, be separated into circulation containing 97.44 quality % epoxy chloropropane and return to the light phase logistics of the 3rd distillation tower 3 in proceeding the logistics (logistics that the heavy phase in turning back to the 3rd distillation tower 3 is partly separated) separated and returning to extraction tower containing the circulation of 92.58 quality % water in return tank (50 ℃), at the bottom of tower, (150 ℃) obtain water-free epoxy chloropropane and to the logistics of chloroneb, by the water-free epoxy chloropropane of gained at the bottom of tower and to the logistics of chloroneb further in the 4th distillation tower 4 fractionation by distillation obtain the epoxy chloropropane product stream of tower top (13 kPas, 60 ℃) and extraction is returned in the circulation to the chloroneb logistics at the bottom of tower.
In Solvent quantity (with respect to the epoxidation reaction product of 100 mass parts) and organic solvent, the mass ratio of organic solvent A and halohydrocarbon is as shown in table 2; The longest disengaging time, the yield of epoxy chloropropane and the energy consumption of fractionation by distillation of light phase (water) and heavy phase (organic solvent phase) during extraction, the distillation energy consumption is the water vapour that epoxy chloropropane product per ton that separation obtains consumes, unit is ton/ton, as shown in table 3.
Contained epoxy chloropropane in the epoxy chloropropane of the yield of epoxy chloropropane (%)=finally obtain/initial solution.
Comparative Examples 3
Under 22 ℃, 100 mass parts are formed to the known epoxy chloropropane that contains, methyl alcohol, first with the water of 60.0 mass parts, (density 20 ℃ the time is 998.2 kilograms per cubic meter to the solution S 3 of chlorallylene and water, 100 ℃ of boiling points) fully mix, after stratification, collect lower floor's heavy phase, use again chlorallylene (the industrial chlorallylene of 80.0 mass parts, Ba Ling petrochemical complex limited liability company, the content of chlorallylene is 98 quality %, density in the time of 20 ℃ is 939.2 kilograms per cubic meter, boiling point is 45 ℃) the five parts minutes five times light phases in extraction upper strata of quality such as be divided into, merge all heavy phases and obtain the chlorallylene phase, chlorallylene is middle epoxy chloropropane mutually, methyl alcohol, the content of chlorallylene and water is respectively 16.72 quality %, 2.78 quality %, 79.61 quality % and 0.48 quality %, what finally obtain gently is water mutually, epoxy chloropropane in water, methyl alcohol, the content of chlorallylene and water is respectively 0.28 quality %, 38.36 quality %, 2.11 quality % and 58.67 quality %, the density difference in the time of 20 ℃ of chlorallylene phase and water is 60.9 kilograms per cubic meter.
The water and the chlorallylene that obtain are carried out to fractionation by distillation according to the method identical with Comparative Examples 1, obtain the epoxy chloropropane product.
The energy consumption of the longest disengaging time, epoxy chloropropane yield and the fractionation by distillation of light phase (water) and heavy phase (chlorallylene phase) when Solvent quantity (with respect to the epoxidation reaction product of 100 mass parts), extraction, the distillation energy consumption is that separation obtains the water vapour that epoxy chloropropane product per ton consumes, unit is ton/ton, as shown in table 4.
Contained epoxy chloropropane in the epoxy chloropropane of the yield of epoxy chloropropane (%)=finally obtain/initial solution.
Embodiment 4
The present embodiment is for illustrating the separation method of epoxy chloropropane provided by the invention.
Under 29 ℃, 100 mass parts are formed to the known epoxy chloropropane that contains, methyl alcohol, first with the water of 53.0 mass parts, (density 20 ℃ the time is 998.2 kilograms per cubic meter to the solution S 4 of chlorallylene and water, boiling point is 100 ℃) the contact mixing, after stratification, collect lower floor's heavy phase, use again that (ladder is uncommon likes that (Shanghai) changes into industrial development company limited by the butyl chloroacetate of 30.0 mass parts, density in the time of 20 ℃ is 1070.4 kilograms per cubic meter, boiling point is 183 ℃) and chlorallylene (the industrial chlorallylene of 49.8 mass parts, Ba Ling petrochemical complex limited liability company, the content of chlorallylene is 98 quality %, density in the time of 20 ℃ is 939.2 kilograms per cubic meter, boiling point is 45 ℃) mixed organic solvents that forms the quality such as be divided into extract the light phases in upper strata for five parts minute five times, merge all heavy phases and obtain the organic solvent phase, organic solvent is middle epoxy chloropropane mutually, methyl alcohol, the content of chlorallylene and water is respectively 10.27 quality %, 4.22 quality %, 57.61 quality % and 0.83 quality %, what finally obtain gently is water mutually, epoxy chloropropane in water, methyl alcohol, the content of chlorallylene and water is respectively 0.22 quality %, 42.11 quality %, 3.66 quality % and 52.87 quality %, organic solvent phase and the water density difference in the time of 20 ℃ is 87.0 kilograms per cubic meter.
According to flow process shown in Fig. 1, the water obtained is introduced in the first distillation tower 1 and carried out fractionation by distillation; Organic solvent phase (in figure referred to as the A phase) is introduced in second column 2 and carried out fractionation by distillation.
Water, under normal pressure, obtains returning to epoxidation reaction containing the methanol stream circulation of a small amount of chlorallylene via the tower top (64 ℃) of the first distillation tower 1, and at the bottom of tower, (104 ℃) obtain the water logistics; Extraction is returned in the water logistics part circulation of gained, and another part is as discharge of wastewater.
Organic solvent is under normal pressure, tower top (41 ℃) via second column 2 obtains the chlorallylene logistics containing methyl alcohol and minor amount of water, epoxidation reaction is returned in part circulation, extraction is returned in another part circulation, and at the bottom of tower, (146 ℃) obtain the butyl chloroacetate logistics containing epoxy chloropropane and minor amount of water, gained further separates the epoxy chloropropane that obtains tower top (88 ℃) and the azeotrope (water that contains 25 quality %) of water containing the butyl chloroacetate logistics of epoxy chloropropane and minor amount of water in the 3rd distillation tower 3, be separated into circulation containing 97.44 quality % epoxy chloropropane and return to the logistics of the light phase of the 3rd distillation tower 3 in proceeding the logistics (logistics that the heavy phase in turning back to the 3rd distillation tower 3 is partly separated) separated and returning to extraction tower containing the circulation of 92.58 quality % water in return tank (50 ℃), at the bottom of tower, (147 ℃) obtain the logistics of water-free epoxy chloropropane and butyl chloroacetate, by the logistics of the water-free epoxy chloropropane of gained at the bottom of tower and butyl chloroacetate further in the 4th distillation tower 4 fractionation by distillation obtain the epoxy chloropropane product stream of tower top (13 kPas, 60 ℃) and extraction is returned in the circulation of the butyl chloroacetate logistics at the bottom of tower.
In Solvent quantity (with respect to the epoxidation reaction product of 100 mass parts) and organic solvent, the mass ratio of organic solvent A and halohydrocarbon is as shown in table 2; The energy consumption of light phase (water) and the longest disengaging time, epoxy chloropropane yield and the fractionation by distillation of heavy phase (extraction agent phase) during extracting and separating, the distillation energy consumption is the water vapour that epoxy chloropropane product per ton that separation obtains consumes, unit is ton/ton, as shown in table 3.
Contained epoxy chloropropane in the epoxy chloropropane of the yield of epoxy chloropropane (%)=finally obtain/initial solution.
Comparative Examples 4
Under 22 ℃, 100 mass parts are formed to the known epoxy chloropropane that contains, methyl alcohol, first with the water of 50.0 mass parts, (density 20 ℃ the time is 998.2 kilograms per cubic meter to the solution S 4 of chlorallylene and water, 100 ℃ of boiling points) fully mix, after stratification, collect lower floor's heavy phase, use again chlorallylene (the industrial chlorallylene of 70.0 mass parts, Ba Ling petrochemical complex limited liability company, the content of chlorallylene is 98 quality %, density in the time of 20 ℃ is 939.2 kilograms per cubic meter, boiling point is 45 ℃) the five parts minutes five times light phases in extraction upper strata of quality such as be divided into, merge all heavy phases and obtain the chlorallylene phase, chlorallylene is middle epoxy chloropropane mutually, methyl alcohol, the content of chlorallylene and water is respectively 11.28 quality %, 3.18 quality %, 84.78 quality % and 0.45 quality %, what finally obtain gently is water mutually, epoxy chloropropane in water, methyl alcohol, the content of chlorallylene and water is respectively 0.23 quality %, 44.34 quality %, 2.96 quality % and 52.07 quality %, chlorallylene phase and the water density difference in the time of 20 ℃ is 62.5 kilograms per cubic meter.
The water and the chlorallylene that obtain are distilled according to the method identical with Comparative Examples 1, obtained the epoxy chloropropane product.
The energy consumption of the longest disengaging time, epoxy chloropropane yield and the fractionation by distillation of light phase (water) and heavy phase (chlorallylene phase) when Solvent quantity (with respect to the epoxidation reaction product of 100 mass parts), extraction, the distillation energy consumption is that separation obtains the water vapour that epoxy chloropropane product per ton consumes, unit is ton/ton, as shown in table 4.
Contained epoxy chloropropane in the epoxy chloropropane of the yield of epoxy chloropropane (%)=finally obtain/initial solution.
Embodiment 5
The present embodiment is for illustrating the separation method of epoxy chloropropane provided by the invention.
Under 27 ℃, 100 mass parts are formed to the known epoxy chloropropane that contains, methyl alcohol, first with the water of 60.3 mass parts, (density 20 ℃ the time is 998.2 kilograms per cubic meter to the solution S 5 of chlorallylene and water, boiling point is 100 ℃) the contact mixing, after stratification, collect lower floor's heavy phase, use again that (ladder is uncommon likes that (Shanghai) changes into industrial development company limited by the parachloroacetophenone of 50.4 mass parts, density in the time of 20 ℃ is 1192 kilograms per cubic meter, boiling point is 232 ℃) and chlorallylene (the industrial chlorallylene of 55.5 mass parts, Ba Ling petrochemical complex limited liability company, the content of chlorallylene is 98 quality %, density in the time of 20 ℃ is 939.2 kilograms per cubic meter, boiling point is 45 ℃) mixed organic solvents that forms the quality such as be divided into extract the light phases in upper strata for five parts minute five times, merge all heavy phases and obtain the organic solvent phase, organic solvent is middle epoxy chloropropane mutually, methyl alcohol, the content of chlorallylene and water is respectively 11.89 quality %, 3.92 quality %, 45.85 quality % and 1.06 quality %, what finally obtain gently is water mutually, epoxy chloropropane in water, methyl alcohol, the content of chlorallylene and water is respectively 0.19 quality %, 37.21 quality %, 2.23 quality % and 59.38 quality %, organic solvent phase and the water density difference in the time of 20 ℃ is 129.3 kilograms per cubic meter.
According to flow process shown in Fig. 1, the water obtained is introduced in the first distillation tower 1 and carried out fractionation by distillation; Organic solvent phase (in figure referred to as the A phase) is introduced in second column 2 and carried out fractionation by distillation.
Water, under normal pressure, obtains returning to epoxidation reaction containing the methanol stream circulation of a small amount of chlorallylene via the tower top (64 ℃) of the first distillation tower 1, and at the bottom of tower, (104 ℃) obtain the water logistics; Extraction is returned in the water logistics part circulation of gained, and another part is as discharge of wastewater.
Organic solvent is under normal pressure, tower top (41 ℃) via second column 2 obtains the chlorallylene logistics containing methyl alcohol and minor amount of water, epoxidation reaction is returned in part circulation, extraction is returned in another part circulation, and at the bottom of tower, (153 ℃) obtain the parachloroacetophenone logistics containing epoxy chloropropane and a small amount of water, gained further separates the epoxy chloropropane that obtains tower top (88 ℃) and the azeotrope (water that contains 25 quality %) of water containing the parachloroacetophenone logistics of epoxy chloropropane and a small amount of water in the 3rd distillation tower 3, be separated into circulation containing 97.44 quality % epoxy chloropropane and return to the logistics of the light phase of the 3rd distillation tower 3 in proceeding the logistics (logistics that the heavy phase in turning back to the 3rd distillation tower 3 is partly separated) separated and returning to extraction tower containing the circulation of 92.58 quality % water in return tank (50 ℃), at the bottom of tower, (154 ℃) obtain the logistics of water-free epoxy chloropropane and parachloroacetophenone, by the logistics of the water-free epoxy chloropropane of gained at the bottom of tower and parachloroacetophenone further in the 4th distillation tower 4 fractionation by distillation obtain the epoxy chloropropane product stream of tower top (13 kPas, 60 ℃) and extraction is returned in the circulation of the parachloroacetophenone logistics at the bottom of tower.
In Solvent quantity (with respect to the epoxidation reaction product of 100 mass parts) and organic solvent, the mass ratio of organic solvent A and halohydrocarbon is as shown in table 2; The energy consumption of light phase (water) and the longest disengaging time, epoxy chloropropane yield and the fractionation by distillation of heavy phase (organic solvent phase) during extracting and separating, the distillation energy consumption is the water vapour that epoxy chloropropane product per ton that separation obtains consumes, unit is ton/ton, as shown in table 3.
Contained epoxy chloropropane in the epoxy chloropropane of the yield of epoxy chloropropane (%)=finally obtain/initial solution.
Comparative Examples 5
Under 22 ℃, 100 mass parts are formed to the known epoxy chloropropane that contains, methyl alcohol, first with the water of 60.0 mass parts, (density 20 ℃ the time is 998.2 kilograms per cubic meter to the solution S 5 of chlorallylene and water, 100 ℃ of boiling points) fully mix, after stratification, collect lower floor's heavy phase, use again chlorallylene (the industrial chlorallylene of 80.0 mass parts, Ba Ling petrochemical complex limited liability company, the content of chlorallylene is 98 quality %, density in the time of 20 ℃ is 939.2 kilograms per cubic meter, boiling point is 45 ℃) the five parts minutes five times light phases in extraction upper strata of quality such as be divided into, merge all heavy phases and obtain the chlorallylene phase, chlorallylene is middle epoxy chloropropane mutually, methyl alcohol, the content of chlorallylene and water is respectively 15.10 quality %, 2.84 quality %, 81.12 quality % and 0.53 quality %, what finally obtain gently is water mutually, epoxy chloropropane in water, methyl alcohol, the content of chlorallylene and water is respectively 0.24 quality %, 38.06 quality %, 2.72 quality % and 58.46 quality %, chlorallylene phase and the water density difference in the time of 20 ℃ is 57.4 kilograms per cubic meter.
The water and the chlorallylene that obtain are distilled according to the method identical with Comparative Examples 1, obtained the epoxy chloropropane product.
The energy consumption of the longest disengaging time, epoxy chloropropane yield and the fractionation by distillation of light phase (water) and heavy phase (chlorallylene phase) when Solvent quantity (with respect to the epoxidation reaction product of 100 mass parts), extraction, the distillation energy consumption is that separation obtains the water vapour that epoxy chloropropane product per ton consumes, unit is ton/ton, as shown in table 4.
Contained epoxy chloropropane in the epoxy chloropropane of the yield of epoxy chloropropane (%)=finally obtain/initial solution.
Table 1
Figure BDA00001656148800251
Table 2
Figure BDA00001656148800261
Table 3
Figure BDA00001656148800262
Table 4
Figure BDA00001656148800263
Known by embodiments of the invention, the separation method of epoxy chloropropane provided by the invention is compared with Comparative Examples, when extracting and separating, heavy phase shortens significantly with the maximum duration gently be separated, reduce widely the requirement to extraction equipment and extracting operation, can effectively save facility investment and process cost; In addition, when the epoxy chloropropane separation yield is basic identical, the energy consumption of fractionation by distillation also has obvious reduction.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, in technical conceive scope of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition each the concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.
In addition, between various embodiment of the present invention, also can carry out arbitrary combination, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.

Claims (21)

1. the separation method of an epoxy chloropropane, the method comprises: the solution that will contain epoxy chloropropane, methyl alcohol, chlorallylene and water be separated after extraction agent mixes, the liquid phase that obtains being rich in the liquid phase of epoxy chloropropane and be rich in methyl alcohol, distill the resulting liquid phase that is rich in epoxy chloropropane, obtain epoxy chloropropane; It is characterized in that, described extraction agent comprise water and with the immiscible organic solvent of water, the density of described organic solvent and water differs and is at least 10 kilograms per cubic meter, the ability of organic solvent extraction methyl alcohol is lower than the ability of water and extraction epoxy chloropropane higher than water, and organic solvent is different from the boiling point of epoxy chloropropane.
2. method according to claim 1, wherein, the density of described organic solvent and water differs the 10-2000 kilograms per cubic meter, and the boiling-point difference of organic solvent and epoxy chloropropane is 20-300 ℃.
3. method according to claim 1, wherein, the liquid phase that is rich in epoxy chloropropane that described separation obtains and the density difference of liquid phase under 20 ℃ that is rich in methyl alcohol are the 70-2000 kilograms per cubic meter.
4. according to the described method of any one in claim 1-3, wherein, with respect to the described solution that contains epoxy chloropropane, methyl alcohol, chlorallylene and water of 100 mass parts, the consumption of described water is the 10-1000 mass parts, and the consumption of described organic solvent is the 10-1000 mass parts.
5. according to the described method of any one in claim 1-3, wherein, contain the organic solvent A that at least contains functional group's Sauerstoffatom in described organic solvent.
6. method according to claim 5, wherein, one or more in the liquid halo carbonyl compound of the liquid halogen ether that described organic solvent A is C4-C16, the liquid halogenated carboxylic ester of C4-C20, C4-C12 and the liquid nitrohalogen compound of C6-C12.
7. method according to claim 6, wherein, under 20 ℃, the large 10-2000 kilograms per cubic meter of the density of the density ratio water of described organic solvent A.
8. method according to claim 6, wherein, the boiling point of described organic solvent A under 1 normal atmosphere is than the high 20-300 ℃ of the boiling point of epoxy chloropropane.
9. according to the described method of any one in claim 6-8, wherein, described organic solvent A is 2,2 '-dichloro-diethyl ether, dichloro-dipropyl ether, dichlorodiisopropyl ether, the dichloro dibutyl ether, the dichloro diisobutyl ether, 1,2-bis-(2-chloroethoxy) ethane, p-Fluoroanisole, adjacent fluoroanisole, 3-Fluoroanisole, to chloroneb, o-chloro-anisole, between chloroneb, para-bromoanisole, o-bromo-anisole, Meta Bromo Anisole, to chlorophenetole, adjacent chlorophenetole, between chlorophenetole, to Bromoethyl phenyl ether, adjacent Bromoethyl phenyl ether, between Bromoethyl phenyl ether, isopropyl chloracetate, butyl chloroacetate, iso-butyl chloroacetate, n-amyl chloroacetate, ethyl trichloroacetate, the 2-chloropropionate, the 4-neoprene acid ethyl ester, 2-chloro-benzoic acid ethyl ester, ethyl bromoacetate, the bromoacetic acid butyl ester, the 2 bromopropionic acid ethyl ester, 2-bromo-butyric acid methyl esters, 4-bromo-butyric 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, the chloro-2 pentanone of 5-, the bromo-methyl-n-butyl ketone of 6-, o-chlorobenzaldehyde, m chlorobenzaldehyde, o-bromobenzaldehye, the alpha-chloro phenylacrolein, parachloroacetophenone, parabromoacetophenone, 2,5-dichloroacetophenone, DNF, 2,4-difluoro nitrobenzene and to one or more in the chlorine meta-nitrotoluene.
10. method according to claim 5, wherein, also contain halohydrocarbon in described organic solvent, and described halohydrocarbon is different from the boiling point of organic solvent A.
11. method according to claim 10, wherein, in described organic solvent, the mass ratio of organic solvent A and halohydrocarbon is 1/50-50/1.
12. method according to claim 10, wherein, one or more in the liquid halohydrocarbon that described halohydrocarbon is C1-C16.
13. method according to claim 12, wherein, the boiling point of described halohydrocarbon and the boiling point of epoxy chloropropane differ more than 20 ℃.
14. according to the described method of any one in claim 10-13, wherein, described halohydrocarbon is tetracol phenixin, 1, 1, 2, the 2-tetrachloroethane, pentaline, 1, 1, 2, the 2-tetrabromoethane, chlorallylene, 1, 2, the 3-trichloropropane, 1, 1, 1, 3-tetrachloro propane, 1, the 2-dibromopropane, 1, the 3-dibromopropane, 1, 2, the 3-tribromopropane, the bromo-3-chloropropane of 1-, 1, the 4-dichlorobutane, 1, the 4-dibromobutane, 1, the 5-dichloropentane, 1, pentamethylene bromide, 1, the 6-dibromo-hexane, the 1-bromo-dodecane, m-chlorotoluene, orthodichlorobenzene, Meta Dichlorobenzene, 2, the 4-toluene dichloride, 1, 2, the 4-trichlorobenzene, bromobenzene, o-dibromobenzene, m-dibromobenzene, adjacent bromochlorophene and 2, one or more in the 4-dichlor fluorbenzene.
15. method according to claim 14, wherein, described halohydrocarbon is chlorallylene.
16. method according to claim 1, wherein, the temperature that the described solution that will contain epoxy chloropropane, methyl alcohol, chlorallylene and water mixes with extraction agent is 1-80 ℃.
17. method according to claim 16, wherein, the described solution that will contain epoxy chloropropane, methyl alcohol, chlorallylene and water be separated after extraction agent mixes be no more than 3 minutes total time.
18. method according to claim 1, wherein, the content that the content that the content that in the described solution that contains epoxy chloropropane, methyl alcohol, chlorallylene and water, the content of epoxy chloropropane is 5-25 quality %, methyl alcohol is 35-65 quality %, chlorallylene is 4-35 quality % and water is 5-25 quality %.
19. method according to claim 18, wherein, the described solution that contains epoxy chloropropane, methyl alcohol, chlorallylene and water is: under titanium-silicon molecular sieve catalyst exists, take methyl alcohol as solvent, chlorallylene and product after hydrogen peroxide or aqueous hydrogen peroxide solution contact.
20. method according to claim 19, wherein, the method also comprises: distill that the resulting liquid phase that is rich in methyl alcohol is contained or not containing methanol stream and the water logistics of chlorallylene, the described methanol stream that contains or do not contain chlorallylene is partly or entirely returned to the solvent that replaces methyl alcohol to contact with hydrogen peroxide or aqueous hydrogen peroxide solution as described chlorallylene, described water stream portions is returned for extraction.
21. method according to claim 19, wherein, when obtaining epoxy chloropropane, the resulting liquid phase that is rich in epoxy chloropropane of distillation obtains chlorallylene logistics and organic solvent logistics, using described chlorallylene stream portions or all return as the raw material contacted with hydrogen peroxide or aqueous hydrogen peroxide solution, by described organic solvent stream portions or all return for extraction.
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