CN103420947A - Separation method for epichlorohydrin - Google Patents
Separation method for epichlorohydrin Download PDFInfo
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- CN103420947A CN103420947A CN2012101568802A CN201210156880A CN103420947A CN 103420947 A CN103420947 A CN 103420947A CN 2012101568802 A CN2012101568802 A CN 2012101568802A CN 201210156880 A CN201210156880 A CN 201210156880A CN 103420947 A CN103420947 A CN 103420947A
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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. The separation method is characterized in that: the extraction agent comprises water and an carbonyl-containing no-halogen-containing organic solvent immiscible with water, the organic solvent is lower in methanol extraction capability and higher in epichlorohydrin extraction capability than water, the organic solvent has a boiling point different with that of epichlorohydrin, and the organic solvent is higher in density that water. Good separation is easy to realize during extraction by using the separation method of the invention; the organic solvent can be recovered without evaporation; compared with methods in which an extraction agent with a boiling point lower than that of epichlorohydrin is employed, the separation method of the invention helps to effectively reduce energy consumption.
Description
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
The objective of the invention is the higher problem of energy expenditure existed in the separation method in order to overcome existing epoxy chloropropane, a kind of separation method of epoxy chloropropane of less energy-consumption is provided, in order to apply 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 immiscible carbonyl and the organic solvent of halogen atom-containing not of containing of water, the ability of organic solvent extraction methyl alcohol lower than water and the extraction epoxy chloropropane ability higher than water, and organic solvent is different from the boiling point of epoxy chloropropane, the density ratio water of organic solvent is large.
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 ratio water of organic solvent is large, in the preferred case, adding of organic solvent and water has the organic solvent phase that comprises most epoxy chloropropane that makes extracting and separating obtain and the water that comprises most of methyl alcohol the above density difference of 60 kilograms per cubic meter, makes and be very easy to realize good being separated in extraction process.And, in a preferred embodiment, because the boiling point of organic solvent under 1 normal atmosphere is higher more than 20 ℃ than the boiling point of epoxy chloropropane, thereby can obtain the epoxy chloropropane product from the distillation tower top by simple distillation, reclaim organic solvent from base product, organic solvent does not need just can reclaim through pervaporation, with employing, than the method for the low-boiling extraction agent of epoxy chloropropane, compares, and can effectively reduce energy expenditure.
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 immiscible carbonyl and the organic solvent of halogen atom-containing not of containing of water, the ability of organic solvent extraction methyl alcohol lower than water and the extraction epoxy chloropropane ability higher than water, and organic solvent is different from the boiling point of epoxy chloropropane, the density ratio water of organic solvent is large.
The method according to this invention, be separated fast in order to make easy realization in extraction process, the large 10-2000 kilograms per cubic meter of the density of the density ratio water of preferred described organic solvent, more preferably large 20-1000 kilograms per cubic meter.
In the present invention, can realize purpose of the present invention as long as described organic solvent is different from the boiling point of epoxy chloropropane, for the present invention, for example, in order to realize more fully purpose of the present invention (reducing follow-up distillation energy consumption), the boiling point of preferred described organic solvent is higher than the boiling point of epoxy chloropropane, more preferably the boiling point of described organic solvent under 1 normal atmosphere is than the high 20-300 ℃ of the boiling point of epoxy chloropropane, more preferably high 30-200 ℃.
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.
The method according to this invention, can realize purpose of the present invention according to the aforementioned techniques scheme, for the present invention, under preferable case, the ketone compounds that described organic solvent is not halogen atom-containing and/or aldehyde compound, be preferably the aromatic ketone of C8-C14 and/or the aromatic aldehyde of C7-C11.
The method according to this invention, the described organic solvent that meets aforementioned requirement includes but not limited to: phenyl aldehyde, phenylacetic aldehyde, phenylpropyl aldehyde, cinnamic aldehyde, the 2-tolyl aldehyde, the 4-tolyl aldehyde, aubepine, the 1-naphthaldehyde, methyl phenyl ketone, Propiophenone, 2, the 4-dimethyl acetophenone, the 3-methoxyacetophenone, to one or more in anisole acetone and 2 methyl benzophenone, be preferably phenylacetic aldehyde, the 2-tolyl aldehyde, the 1-naphthaldehyde, methyl phenyl ketone, the 3-methoxyacetophenone, to one or more in anisole acetone and 2 methyl benzophenone.
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, be designated hereinafter simply as water) density difference be the 60-2000 kilograms per cubic meter, be preferably the 100-1000 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, 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, 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, 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.
As previously mentioned, further under preferable case, method of the present invention also is included in when the resulting liquid phase that is rich in epoxy chloropropane of distillation obtains epoxy chloropropane and 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.
In the present invention, described extraction agent comprise water and with water immiscible contain carbonyl and not the organic solvent of halogen atom-containing refer to that water and described organic solvent are as extraction agent.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 propenyl chloride contacts with hydrogen peroxide or aqueous hydrogen peroxide solution (being the temperature of chloro propylene epoxidation reaction) is generally 10-120 ℃, is preferably 40-80 ℃; The time of contact is generally 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 described epoxidation reaction product, 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 organic solvent, than the high 20-300 ℃ of the boiling point of epoxy chloropropane, also easily by simple distillation, realize separating, and organic solvent can directly reclaim and not need through pervaporation from base product.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, can form azeotrope (water that contains 2.2 quality % in azeotrope) and water and epoxy chloropropane at 43.0 ℃ by water and chlorallylene and remove at 88.0 ℃ of formation azeotropes (water that contains 25 quality % in azeotrope).
The most of methyl alcohol in described epoxidation reaction product, most of water and a small amount of chlorallylene have been comprised in described 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.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, reclaim methanol loop and be used for described epoxidation reaction, 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 the evaporation extraction agent, can effectively reduce the energy expenditure that epoxy chloropropane separates.
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.
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 aqueous hydrogen peroxide solution that concentration is 30 quality % and the reaction conditions of 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-S2(that obtains respectively the difference composition shown in table 1 is following also referred to as the solution S 1-S2 that contains epoxy chloropropane, methyl alcohol, chlorallylene and water).
The present embodiment is for illustrating the separation method of epoxy chloropropane provided by the invention.
Under 24 ℃, 100 mass parts are formed to the known epoxy chloropropane that contains, methyl alcohol, first with the water of 50 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 3-methoxyacetophenone (the lark prestige Science and Technology Ltd. of 150 mass parts, density in the time of 20 ℃ is 1090 kilograms per cubic meter, boiling point is 240 ℃) 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 3-methoxyacetophenone phase, the 3-methoxyacetophenone is middle epoxy chloropropane mutually, methyl alcohol, the content of chlorallylene and water is respectively 6.97 quality %, 1.19 quality %, 11.37 quality % and 0.21 quality %, what finally obtain gently is water mutually, epoxy chloropropane in water, methyl alcohol, the content of chlorallylene and water is respectively 0.15 quality %, 41.29 quality %, 0.00 quality % and 57.51 quality %, 3-methoxyacetophenone phase and the water density difference in the time of 20 ℃ is 169.1 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 (be also 3-methoxyacetophenone 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 the methanol stream circulation via the tower top (65 ℃) of the first distillation tower 1 and returns to epoxidation reaction, 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.
The 3-methoxyacetophenone is under normal pressure, tower top (41 ℃) via second column 2 obtains returning to epoxidation reaction containing the chlorallylene logistics circulation of methyl alcohol and minor amount of water, and at the bottom of tower, (194 ℃) obtain the 3-methoxyacetophenone 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 3-methoxyacetophenone 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, (197 ℃) obtain the logistics of water-free epoxy chloropropane and 3-methoxyacetophenone, the logistics of the water-free epoxy chloropropane of gained and 3-methoxyacetophenone further separates the epoxy chloropropane product stream and the circulation of the 3-methoxyacetophenone logistics at the bottom of tower that obtain tower top (13 kPas, 60 ℃) and returns to extraction in the 4th distillation tower 4.
The energy consumption of Solvent quantity (with respect to the epoxidation reaction product of 100 mass parts) and epoxy chloropropane yield and fractionation by distillation, the distillation energy consumption is the water vapour that epoxy chloropropane product per ton that separation obtains consumes, unit be ton/ton, as shown in table 2.
Contained epoxy chloropropane in the epoxy chloropropane of the yield of epoxy chloropropane (%)=finally obtain/initial solution.
Comparative Examples 1
Under 22 ℃, 100 mass parts are formed to the known epoxy chloropropane that contains, methyl alcohol, first with the water of 60 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 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 11.51 quality %, 2.40 quality %85.30 quality % and 0.47 quality %, what finally obtain gently is water mutually, epoxy chloropropane in water, methyl alcohol, the content of chlorallylene and water is respectively 0.15 quality %, 36.41 quality %, 3.99 quality % and 59.00 quality %, chlorallylene phase and the water density difference in the time of 20 ℃ is 48.1 kilograms per cubic meter.
According to flow process shown in Fig. 2, the water obtained is introduced in the first distillation tower 1 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 Solvent quantity (with respect to the epoxidation reaction product of 100 mass parts) and epoxy chloropropane yield and fractionation by distillation, 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 2.
Contained epoxy chloropropane in the epoxy chloropropane of the yield of epoxy chloropropane (%)=finally obtain/initial solution.
The present embodiment is for illustrating the separation method of epoxy chloropropane provided by the invention.
Under 13 ℃, 100 mass parts are formed to the known epoxy chloropropane that contains, methyl alcohol, first with the water of 60 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, (ladder is uncommon likes that (Shanghai) changes into industrial development company limited to use the 2-tolyl aldehyde of 100 mass parts again, density in the time of 20 ℃ is 1040 kilograms per cubic meter, boiling point is 200 ℃) the five parts minutes five times light phases in extraction upper strata of quality such as be divided into, merging all heavy phases, to obtain 2-tolyl aldehyde phase (be the phase of organic solvent described in the present invention, below also like this), epoxy chloropropane in the 2-tolyl aldehyde, methyl alcohol, the content of chlorallylene and water is respectively 7.90 quality %, 1.60 quality %, 19.91 quality % and 0.32 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 %, 36.75 quality %, 0.12 quality % and 61.85 quality %, 2-tolyl aldehyde phase and the water density difference in the time of 20 ℃ is 110.0 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 (be also 2-tolyl aldehyde 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.
The 2-tolyl aldehyde is under normal pressure, tower top (41 ℃) via second column 2 obtains returning to epoxidation reaction containing the chlorallylene logistics circulation of methyl alcohol and minor amount of water, and at the bottom of tower, (176 ℃) obtain the 2-tolyl aldehyde 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 2-tolyl aldehyde 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, (177 ℃) obtain the logistics of water-free epoxy chloropropane and 2-tolyl aldehyde, the logistics of the water-free epoxy chloropropane of gained and 2-tolyl aldehyde further separates the epoxy chloropropane product stream and the circulation of the 2-tolyl aldehyde logistics at the bottom of tower that obtain tower top (13 kPas, 60 ℃) and returns to extraction in the 4th distillation tower 4.
The energy consumption of Solvent quantity (with respect to the epoxidation reaction product of 100 mass parts) and epoxy chloropropane yield and fractionation by distillation, the distillation energy consumption is the water vapour that epoxy chloropropane product per ton that separation obtains consumes, unit be ton/ton, as shown in table 2.
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 50 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 70 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 10.41 quality %, 2.30 quality %, 86.66 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 0.24 quality %, 38.52 quality %, 4.48 quality % and 56.30 quality %, the density difference in the time of 20 ℃ of chlorallylene phase and water is 50.6 kilograms per cubic meter.
According to the method identical with Comparative Examples 1, the water obtained is introduced to the first distillation tower 1, chlorallylene is introduced to second column 2 mutually, according to the flow process shown in Fig. 2, distilled, obtain the epoxy chloropropane product.
The energy consumption of Solvent quantity (with respect to the epoxidation reaction product of 100 mass parts) and epoxy chloropropane yield and fractionation by distillation, 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 2.
Contained epoxy chloropropane in the epoxy chloropropane of the yield of epoxy chloropropane (%)=finally obtain/initial solution.
Table 1
Table 2
Known by embodiments of the invention, the separation method of epoxy chloropropane provided by the invention is compared with Comparative Examples, and when the epoxy chloropropane separation yield is basic identical, the energy consumption of fractionation by distillation significantly reduces, and method of the present invention is very suitable for industrial applications.
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 (11)
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 immiscible carbonyl and the organic solvent of halogen atom-containing not of containing of water, the ability of organic solvent extraction methyl alcohol lower than water and the extraction epoxy chloropropane ability higher than water, and organic solvent is different from the boiling point of epoxy chloropropane, the density ratio water of organic solvent is large.
2. method according to claim 1, wherein, described organic solvent is than the large 10-2000 kilograms per cubic meter of the density of water, and the boiling point of organic solvent under 1 normal atmosphere is than the high 20-300 ℃ of the boiling point of epoxy chloropropane.
3. method according to claim 2, wherein, the aromatic ketone that described organic solvent is C8-C14 and/or the aromatic aldehyde of C7-C11.
4. method according to claim 3, wherein, described organic solvent is phenyl aldehyde, phenylacetic aldehyde, phenylpropyl aldehyde, cinnamic aldehyde, 2-tolyl aldehyde, 4-tolyl aldehyde, aubepine, 1-naphthaldehyde, methyl phenyl ketone, Propiophenone, 2,4-dimethyl acetophenone, 3-methoxyacetophenone, to one or more in anisole acetone and 2 methyl benzophenone.
5. according to the described method of any one in claim 1-4, wherein, the liquid phase that is rich in epoxy chloropropane that described separation obtains is the 60-2000 kilograms per cubic meter with the density difference of liquid phase under 20 ℃ that is rich in methyl alcohol.
6. according to the described method of any one in claim 1-4, 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.
7. according to the described method of any one in claim 1-4, wherein, the temperature that the described solution that will contain epoxy chloropropane, methyl alcohol, chlorallylene and water mixes with extraction agent is 1-80 ℃.
8. according to the described method of any one in claim 1-4, 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 %.
9. method according to claim 8, 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.
10. method according to claim 9, 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.
11. method according to claim 9, wherein, the method also is included in when the resulting liquid phase that is rich in epoxy chloropropane of distillation obtains epoxy chloropropane and 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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| US6350888B1 (en) * | 1997-09-18 | 2002-02-26 | Solvay (Societe Anonyme) | Method for making an oxirane |
| WO2008087657A2 (en) * | 2007-01-15 | 2008-07-24 | Aditya Birla Science & Technology Limited | A process for preparing epichlorohydrin |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6350888B1 (en) * | 1997-09-18 | 2002-02-26 | Solvay (Societe Anonyme) | Method for making an oxirane |
| WO2008087657A2 (en) * | 2007-01-15 | 2008-07-24 | Aditya Birla Science & Technology Limited | A process for preparing epichlorohydrin |
| 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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