CN103420947B - A kind of separation method of epoxychloropropane - Google Patents
A kind of separation method of epoxychloropropane Download PDFInfo
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Abstract
A kind of separation method of epoxychloropropane, including: it is separated after the solution containing epoxychloropropane, methanol, chlorallylene and water is mixed with extractant, obtain the liquid phase rich in epoxychloropropane and the liquid phase rich in methanol, distill the obtained liquid phase rich in epoxychloropropane, obtain epoxychloropropane；It is characterized in that, described extractant includes water and organic solvent containing carbonyl and not halogen atom-containing immiscible with water, the ability of organic solvent extraction methanol is higher than water lower than the ability of water and extraction epoxychloropropane, and organic solvent is different from the boiling point of epoxychloropropane, the density ratio water of organic solvent is big.Being very easy to realize good being separated in the method extraction process of the present invention, organic solvent needs not move through evaporation and just can reclaim, with employing than compared with the method for the low-boiling extractant of epoxychloropropane, it is possible to be effectively reduced energy expenditure.
Description
Technical field
The present invention relates to the separation method of a kind of epoxychloropropane.
Background technology
Epoxychloropropane is a kind of important basic organic chemical industry raw material and intermediate, is widely used in the multiple products such as synthetic epoxy resin, glycerol, chlorohydrin rubber, medicine, pesticide, surfactant, plasticizer.
Epoxychloropropane can adopt HTS to be catalyst, makes hydrogen peroxide and chlorallylene initial ring oxidation reaction prepare.Owing to chlorallylene and hydrogen peroxide do not dissolve each other, cause that response speed is slow, accordingly, it would be desirable to add a large amount of solvent such as methanol, make chlorallylene and hydrogen peroxide initial ring oxidation reaction in this solvent.With in the epoxidation reaction product obtained after HTS solid-liquid separation, usually contain excessive reactant chlorallylene, solvent methanol, purpose product epoxychloropropane, hydrogen peroxide charge is brought into and reaction generates water and the by-product such as a small amount of propylene glycol of chlorine monomethyl ether and propylene glycol of chlorine.It is thus desirable to isolate product epoxychloropropane, and recycling design methanol and excessive reactant chlorallylene.
Method that the method for existing separation epoxychloropropane is generally straight run distillation or the method being undertaken extracting by extractant.Such as, CN1534030A discloses a kind of straight run distillation method of epoxychloropropane, and the method is by directly carrying out in a distillation column distilling to separate epoxychloropropane according to the height of component boiling point by the epoxidation reaction product obtained.Find when separated methanol and epoxychloropropane, it is necessary to adopt and there is the distillation column of significantly high theoretical cam curve and significantly high reflux ratio, could by epoxychloropropane and methanol separated.Owing to epoxidation reaction product containing substantial amounts of solvent methanol, cause that the equipment investment of separated is high, energy expenditure is big.And, when first alcohol and water exists, in still-process, epoxychloropropane also with first alcohol and water generation side reaction, can generate the by-product such as propylene glycol of chlorine monomethyl ether and propylene glycol of chlorine, reduces the yield of epoxychloropropane.
US6350888B1 discloses a kind of method carrying out extract and separate epoxychloropropane by extractant, the method extracts epoxychloropropane by adding a kind of organic extractant, then distill out the extractant in the liquid phase containing epoxychloropropane obtained, separate and obtain epoxychloropropane.Although the method can reach to separate the purpose of epoxychloropropane, but, not only need to use substantial amounts of extractant when extracting epoxychloropropane from epoxidation reaction product, and part methanol also can be extracted together with epoxychloropropane, need nonetheless remain for straight run distillation separation methanol and epoxychloropropane, cause that separated epoxychloropropane and recovery extractant need to consume substantial amounts of energy；It addition, in the process of straight run distillation separation methanol and epoxychloropropane, epoxychloropropane also with methanol generation side reaction, can generate the by-products such as propylene glycol of chlorine monomethyl ether, reduces the yield of epoxychloropropane.
CN101293882A discloses a kind of method simultaneously adopting two kinds of immiscible extractant A and extractant B extract and separate epoxychloropropane, and the extractant A that the method adopts is liquid halogenated hydrocarbon or unitary ether, and extractant B is water or liquid polyol.When extractant A is chlorallylene, extractant B is water, and separated extracts heavy phase and extracts the light phase epoxychloropropane product that respectively obtains with when reclaiming reaction dissolvent methanol, and energy expenditure is minimum.But, the method exists that the density of the density ratio extractant water of extractant chlorallylene is little and the problem of the difficulty that causes being susceptible in extraction process being separated, and owing to the boiling point of extractant chlorallylene is lower than epoxychloropropane, need after the extraction to first pass through distillation by whole chlorallylenes from distilling recovered overhead, then again the materials at bottom of tower after isolating chlorallylene is distilled, epoxychloropropane product is obtained again from distillation tower top, whole chlorallylene extractants is required for could reclaiming through pervaporation, cause that the energy expenditure separating epoxychloropropane is still higher.
In sum, there is the problem that in be separated in extraction process difficulty and still-process, energy expenditure is higher in the separation method of existing epoxychloropropane.
Summary of the invention
The problem that the invention aims to overcome the energy expenditure existed in the separation method of existing epoxychloropropane higher, it is provided that the separation method of the epoxychloropropane of a kind of low energy consumption, in order to apply in large-scale continuous production process.
In order to realize the purpose of the present invention, the invention provides the separation method of a kind of epoxychloropropane, the method includes: be separated after being mixed with extractant by the solution containing epoxychloropropane, methanol, chlorallylene and water, obtain the liquid phase rich in epoxychloropropane and the liquid phase rich in methanol, distill the obtained liquid phase rich in epoxychloropropane, obtain epoxychloropropane；Wherein, described extractant includes water and organic solvent containing carbonyl and not halogen atom-containing immiscible with water, the ability of organic solvent extraction methanol is higher than water lower than the ability of water and extraction epoxychloropropane, and organic solvent is different from the boiling point of epoxychloropropane, and the density ratio water of organic solvent is big.
Owing in the extractant of the present invention, organic solvent and water are immiscible, the ability of organic solvent extraction methanol is higher than water lower than the ability of water and extraction epoxychloropropane, make organic solvent that the most epoxychloropropane in the solution containing epoxychloropropane, methanol, chlorallylene and water can be extracted into organic solvent phase (being the liquid phase rich in epoxychloropropane), and the most of methanol in the solution containing epoxychloropropane, methanol, chlorallylene and water is extracted to aqueous phase (being the liquid phase rich in methanol).And, the density ratio water of organic solvent is big, in the preferred case, the addition of organic solvent and water makes the organic solvent comprising overwhelming majority epoxychloropropane that extract and separate obtains and the aqueous phase that comprises major part methanol have the density contrast of more than 60 kilograms per cubic meter so that be very easy to realize good being separated in extraction process.And, in a preferred embodiment, owing to organic solvent boiling point under 1 atmospheric pressure is higher than the boiling point of epoxychloropropane more than 20 DEG C, such that it is able to obtain epoxychloropropane product by simple distillation from distillation tower top, organic solvent is reclaimed from base product, organic solvent needs not move through evaporation and just can reclaim, with employing than compared with the method for the low-boiling extractant of epoxychloropropane, it is possible to be effectively reduced energy expenditure.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, is used for explaining the present invention, but is not intended that limitation of the present invention together with detailed description below.In the accompanying drawings:
Fig. 1 separates, according to the separation method of the present invention, the organic solvent phase (referred to as A phase in figure) that obtains and aqueous phase carries out the flow chart that distills；
Fig. 2 separates, according to the method for prior art, the chlorallylene phase that obtains and aqueous phase carries out the flow chart that distills.
Description of reference numerals
1: the first distillation column 2: after-fractionating tower；
3: the three distillation column 4: the four distillation column.
Detailed description of the invention
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that detailed description of the invention described herein is merely to illustrate and explains the present invention, it is not limited to the present invention.
The invention provides the separation method of a kind of epoxychloropropane, the method includes: be separated after being mixed with extractant by the solution containing epoxychloropropane, methanol, chlorallylene and water, obtain the liquid phase rich in epoxychloropropane and the liquid phase rich in methanol, distill the obtained liquid phase rich in epoxychloropropane, obtain epoxychloropropane；Wherein, described extractant includes water and organic solvent containing carbonyl and not halogen atom-containing immiscible with water, the ability of organic solvent extraction methanol is higher than water lower than the ability of water and extraction epoxychloropropane, and organic solvent is different from the boiling point of epoxychloropropane, and the density ratio water of organic solvent is big.
The method according to the invention, in order to make easy realization in extraction process quickly be separated, it is preferable that the big 10-2000 kilograms per cubic meter of density of the density ratio water of described organic solvent, more preferably big 20-1000 kilograms per cubic meter.
In the present invention, as long as described organic solvent is different from the boiling point of epoxychloropropane can realize the purpose of the present invention, for the present invention, in order to realize the purpose of the present invention (such as reducing follow-up distillation energy consumption) more fully, the boiling point of preferred described organic solvent is higher than the boiling point of epoxychloropropane, more preferably described organic solvent boiling point under 1 atmospheric pressure is higher than the boiling point of epoxychloropropane 20-300 DEG C, more preferably high 30-200 DEG C.
In the present invention, if described organic solvent is mixed solvent, then the boiling point of described organic solvent refers to the boiling point of various organic solvents in mixed solvent, if or described mixed solvent can form azeotropic mixture, then the boiling point of described organic solvent refers to the azeotropic point of azeotropic mixture, and need further illustrate be, if what described mixed organic solvents was formed is minimum azeotropic mixture, then described azeotropic point refers to minimum boiling point, if what described mixed organic solvents was formed is maximum azeotrope thing, then described azeotropic point refers to the maximum boiling point of mixed solvent.
In the present invention, unless stated otherwise, density refers both to the density of 20 DEG C, 1 standard atmosphere pressure.
The method according to the invention, the purpose of the present invention can be realized, for the present invention, it is preferable that in situation according to preceding solution, described organic solvent is ketone compounds and/or the aldehyde compound of not halogen atom-containing, it is preferred to the aromatic ketone of C8-C14 and/or the aromatic aldehyde of C7-C11.
The method according to the invention, the described organic solvent meeting aforementioned claim includes but not limited to: benzaldehyde, hyacinthin, benzenpropanal, cinnamaldehyde, 2-tolyl aldehyde, 4-tolyl aldehyde, P-methoxybenzal-dehyde, 1-naphthaldehyde, 1-Phenylethanone., propiophenone, 2,4-dimethyl acetophenone, 3-methoxyacetophenone, to one or more in methoxybenzene acetone and 2 methyl benzophenone, it is preferred to hyacinthin, 2-tolyl aldehyde, 1-naphthaldehyde, 1-Phenylethanone., 3-methoxyacetophenone, to one or more in methoxybenzene acetone and 2 methyl benzophenone.
The method according to the invention, it is preferred that in situation, the liquid phase rich in epoxychloropropane that described separation obtains is (if not otherwise specified, hereinafter referred to as organic solvent phase) and rich in methanol liquid phase (if not otherwise specified, hereinafter referred to as aqueous phase) density contrast be 60-2000 kilograms per cubic meter, it is preferably 100-1000 kilograms per cubic meter, so that two liquid phases are separated better.
The method according to the invention, optional wider range as the organic solvent of extractant and the consumption of water, for the present invention, the solution of epoxychloropropane, methanol, chlorallylene and water is contained preferably with respect to 100 mass parts, the consumption of described organic solvent is 10-1000 mass parts, it is preferred to 30-300 mass parts；The consumption of described water is 10-1000 mass parts, it is preferred to 20-200 mass parts.
The method according to the invention, optional wider range of the described condition that the solution containing epoxychloropropane, methanol, chlorallylene and water is mixed with extractant, for the present invention, under preferable case, the described temperature (i.e. the temperature of extract and separate) mixed with extractant by the solution containing epoxychloropropane, methanol, chlorallylene and water is for 1-80 DEG C, it is preferred to 5-40 DEG C.When aforementioned preferred extract and separate, both the described solution containing epoxychloropropane, methanol, chlorallylene and water can have been made to be sufficiently mixed with extractant, reach the purpose extracted, the side reaction of the epoxychloropropane in the described solution containing epoxychloropropane, methanol, chlorallylene and water and first alcohol and water can be reduced again.
With the method for the invention it is preferred to the content of the described solution in ethylene chloropropane containing epoxychloropropane, methanol, chlorallylene and water be 5-25 mass %, methanol content be 35-65 mass %, chlorallylene the content that content is 4-35 mass % and water be 5-25 mass %.
The method according to the invention, it is preferred that the product that the described solution containing epoxychloropropane, methanol, chlorallylene and water is chlorallylene and hydrogen dioxide epoxidation reaction, concrete, the described solution containing epoxychloropropane, methanol, chlorallylene and water is: under titanium-silicon molecular sieve catalyst exists, with methanol for solvent, chlorallylene contact with hydrogen peroxide or aqueous hydrogen peroxide solution after product.
So that the method for the present invention is more suitable for industrialized production, it is preferred that in situation, the method of the present invention also includes: distill the obtained liquid phase rich in methanol obtain containing or methanol stream without chlorallylene and water logistics, using described containing or methanol stream without chlorallylene partly or entirely return the solvent replacing methanol to contact with hydrogen peroxide or aqueous hydrogen peroxide solution as described chlorallylene, be used for extracting by the return of described water stream portions.
As previously mentioned, it is preferred that in situation, the method of the present invention is additionally included in while the obtained liquid phase rich in epoxychloropropane of distillation obtains epoxychloropropane and obtains chlorallylene logistics and organic solvent logistics, using described chlorallylene stream portions or all return as raw material contact with hydrogen peroxide or aqueous hydrogen peroxide solution, by described organic solvent stream portions or all return be used for extracting.
In the present invention, described extractant includes water and organic solvent containing carbonyl and not halogen atom-containing immiscible with water refers to that water and described organic solvent are used as extractant.In the present invention, organic solvent and water as extractant both can be added simultaneously in the described solution containing epoxychloropropane, methanol, chlorallylene and water, first a kind of extractant (organic solvent or water) can also be mixed with the described solution containing epoxychloropropane, methanol, chlorallylene and water, then add another kind of extractant (organic solvent or water).
In the present invention, when a kind of extractant (organic solvent or water) being mixed with the described solution containing epoxychloropropane, methanol, chlorallylene and water in the ban, the described equipment for mixing can be that the pipeline known, pipe-line mixer, stirred tank, the liquid such as mixing column contact mixing apparatus.
In the present invention, when being simultaneously introduced as the organic solvent of extractant and water, extractant and the described solution containing epoxychloropropane, methanol, chlorallylene and water be blended in extraction equipment to carry out.
The described equipment for extracting can be conventional extraction equipment well-known to those skilled in the art, such as agitator tank, sieve-plate tower, packed tower, rotating disc column, valve tower, spray tower etc., both the mode of intermittently operated can have been taked, the mode of continuous operation can also be adopted, it is preferred to use continuous operation mode realizes large-scale commercial production to facilitate.When adopting continuous operation mode, it is preferred to use continuous countercurrent extraction tower is as extraction equipment.
In the present invention, organic solvent is attached most importance to liquid phase (referred to as heavy phase) mutually, and aqueous phase is light liquid phase (referred to as light phase).Described organic solvent phase and the separation of aqueous phase, both can be automatically performed and from respectively obtaining aqueous phase and organic solvent phase at the bottom of tower top and tower, it is also possible to carry out in independent device for phase saparation in the extraction equipments such as continuous countercurrent extraction tower.Described device for phase saparation can be the device for phase saparation that subsider, settling tank, cyclone hydraulic separators and centrifuge etc. are conventional.
According to the present invention, described HTS is that titanium atom replaces the general name of a class zeolite of a part of silicon atom in zeolite lattice skeleton.Described HTS is well known in the prior art, such as, can be have and be similar to ZSM-5 aluminosilicate zeolite MFI topological structure titanium-containing zeolite TS-1, there is the titanium-containing zeolite TS-2 being similar to ZSM-11 aluminosilicate zeolite MEL topological structure, and there is the molecular sieve containing titanium etc. of framing structure with modenite, ZSM-12, MCM-22, MCM-41, MCM-48 and the beta-zeolite isomorphous, wherein, it is preferably TS-1 and TS-2, it is particularly preferred to for TS-1.The former powder that catalyst used by the present invention can be these zeolites directly uses, it is also possible to is used after overmolding by the former powder of these zeolites, specifically can select according to response situation.
According to the present invention, when described titanium-silicon molecular sieve catalyst adds fashionable in from of a slurry, with described catalytic liquid phase for benchmark, the content of described HTS is generally 0.5-30 mass %, it is preferred to 1-15 mass %, more preferably 1.5-10 mass %；When catalyst is fixed in the reactor, the feedstock quality space-time speed of hydrogen peroxide is (in the present invention, quality space-time speed is generally alternatively referred to as liquid hourly space velocity (LHSV), refers to the feedstock quality of unit interval hydrogen peroxide and the ratio of the quality of the catalyst in reactor) it is generally 0.01-100h-1, it is preferred to 0.02-10h-1, more preferably 0.02-1h-1。
According to the present invention, the temperature (temperature that namely chloro propylene epoxidation reacts) that described chloropropene contacts with hydrogen peroxide or aqueous hydrogen peroxide solution is generally 10-120 DEG C, it is preferred to 40-80 DEG C；The time of contact is generally 0.01-100 hour, it is preferred to 0.1-10 hour；The raw materials components mole ratio of described chlorallylene and hydrogen peroxide is generally 1/1-10/1, it is preferred to 1.2/1-6/1；The charge-mass ratio of described methanol and chlorallylene is generally 0.5/1-15/1, it is preferred to 0.5/1-5/1.
According to the present invention, described chlorallylene can be analytical reagent and/or chemically pure reagent, but considers to be preferably used industrial products from economic angle, and in industrial products, the content of chlorallylene is generally 95-100 mass %, it is preferred to 97-99.9 mass %.
According to the present invention, hydrogen peroxide can be used directly as oxidant, but for security consideration, it is generally preferable to adopt aqueous hydrogen peroxide solution as oxidant, in aqueous hydrogen peroxide solution, the concentration of hydrogen peroxide can be generally 5-90 mass %, it is preferred to 20-60 mass %.
The method according to the invention, described organic solvent mutually in contain the most epoxychloropropane in described epoxidation reaction product, major part chlorallylene, a small amount of methanol and minor amount of water.Owing to chlorallylene is 45.0 DEG C at the boiling point that 1 standard atmosphere is depressed, epoxychloropropane boiling point under the same conditions is 116.1 DEG C, the two difference 71.1 DEG C, it is easy to realize separating by distilling；Similarly, since organic solvent is higher than the boiling point of epoxychloropropane 20-300 DEG C, also realize separating easily by simple distillation, and organic solvent can directly reclaim without through pervaporation from base product.A small amount of methanol therein, then because methanol is easily separated with epoxychloropropane with chlorallylene 40.0 DEG C of formation azeotropic mixture (containing the methanol of 10.0 mass % in azeotropic mixture) easily with chlorallylene；As for minor amount of water therein, then can form azeotropic mixture (in azeotropic mixture containing the water of 2.2 mass %s) and water and epoxychloropropane with chlorallylene at 43.0 DEG C by water and remove 88.0 DEG C of formation azeotropic mixture (containing the water of 25 mass % in azeotropic mixture).
Described aqueous phase contains the most of methanol in described epoxidation reaction product, major part water and a small amount of chlorallylene.Owing to the boiling point of chlorallylene is lower than the boiling point of methanol (64.5 DEG C), and can be formed more low-boiling azeotropic mixture than chlorallylene with first alcohol and water, it is easy to be easily separated with water when separated methanol.The boiling point of methanol is lower than the boiling point of water (100 DEG C) 35.5 DEG C and be formed without azeotropic mixture with water, it is easy to be separated from water by methanol by simply distilling, and reclaims methanol loop for described epoxidation reaction, and extractant water is also without reclaiming by evaporating.
By above description, utilize simple distillation can realize by epoxychloropropane from organic solvent mutually separate and methanol and chlorallylene can be reclaimed, and extractant organic solvent and water need not be reclaimed by evaporation agent, it is possible to it is effectively reduced the energy expenditure that epoxychloropropane separates.
The method according to the 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 condition of distillation is not had concrete requirement, organic solvent phase and the distillation condition of aqueous phase different and different with the composition of organic solvent by the present invention, it is possible to select according to practical situation.
It is more fully described the present invention by the examples below, but the present invention is not limited to this.
Preparation embodiment
The preparation of the solution (i.e. epoxidation reaction product) containing epoxychloropropane, methanol, chlorallylene and water:
Epoxidation reaction product method disclosed in embodiment in CN101747296A 1 used by extracting carries out the epoxidation reaction of chlorallylene and aqueous hydrogen peroxide solution in fixing bed jacketed pipe type reactor and prepares.Jacket oil bath temperature be 50 DEG C, the reaction condition of the aqueous hydrogen peroxide solution that adopts concentration to be 30 mass % and 0.40MPa pressure, by changing the charge-mass ratio of the chlorallylene raw materials components mole ratio with hydrogen peroxide and methanol and chlorallylene, respectively obtain the epoxidation reaction product S1-S2(of the different compositions shown in table 1 hereinafter also referred to the solution S 1-S2 containing epoxychloropropane, methanol, chlorallylene and water).
Embodiment 1
The present embodiment is for illustrating the separation method of epoxychloropropane provided by the invention.
nullAt 24 DEG C，Known for 100 mass parts compositions is contained epoxychloropropane、Methanol、First (density when 20 DEG C is 998.2 kilograms per cubic meter to the solution S 1 of chlorallylene and water with the water of 50 mass parts，Boiling point is 100 DEG C) contact mixing，After stratification，Collect lower floor's heavy phase，Again with the 3-methoxyacetophenone of 150 mass parts (lark prestige Science and Technology Ltd.，Density when 20 DEG C is 1090 kilograms per cubic meter，Boiling point is 240 DEG C) being divided into etc. five parts points of quality, to extract upper stratas five times light phase，Merge all of heavy phase and obtain 3-methoxyacetophenone phase，3-methoxyacetophenone is middle epoxychloropropane mutually、Methanol、The content of chlorallylene and water respectively 6.97 mass %、1.19 mass %、11.37 quality % and 0.21 mass %，What finally obtain light phase is aqueous phase，Epoxychloropropane in aqueous phase、Methanol、The content of chlorallylene and water respectively 0.15 mass %、41.29 quality %、0.00 mass % and 57.51 mass %，3-methoxyacetophenone phase and the aqueous phase density contrast when 20 DEG C are 169.1 kilograms per cubic meter.
Flow process shown in Fig. 1, introduces the aqueous phase obtained in the first distillation column 1 and carries out separated, organic solvent phase (namely 3-methoxyacetophenone phase, referred to as A phase in figure) is introduced and carries out separated in after-fractionating tower 2；
Aqueous phase at ambient pressure, obtains methanol stream via the tower top (65 DEG C) of the first distillation column 1 and is recycled back into epoxidation reaction, and at the bottom of tower, (104 DEG C) obtain water logistics；A water logistics part for gained is recycled back into extracting, and another part is as discharge of wastewater.
3-methoxyacetophenone is mutually at ambient pressure, the chlorallylene logistics obtained containing methanol and minor amount of water via the tower top (41 DEG C) of after-fractionating tower 2 is recycled back into epoxidation reaction, and (194 DEG C) at the bottom of tower obtain the 3-methoxyacetophenone logistics containing epoxychloropropane and minor amount of water；The gained 3-methoxyacetophenone logistics containing epoxychloropropane and minor amount of water separates in the 3rd distillation column 3 further and obtains the epoxychloropropane of tower top (88 DEG C) and the azeotropic mixture (water containing 25 mass %) of water, being separated into the 3rd distillation column 3 that is recycled back into containing 97.44 mass % epoxychloropropane in return tank (50 DEG C) and proceed logistics (namely returning to the logistics that the heavy phase portion in the 3rd distillation column 3 is easily separated) and the light phase logistics being recycled back in extraction tower containing 92.58 mass % water of separation, at the bottom of tower, (197 DEG C) obtain water-free epoxychloropropane and the logistics of 3-methoxyacetophenone；The logistics of the water-free epoxychloropropane of gained and 3-methoxyacetophenone separates the 3-methoxyacetophenone logistics obtained at the bottom of the epoxychloropropane product stream of tower top (13 kPas, 60 DEG C) and tower further in the 4th distillation column 4 and is recycled back into extracting.
The energy consumption of Solvent quantity (the epoxidation reaction products relative to 100 mass parts) and epoxychloropropane yield and separated, distillation energy consumption is the steam that the epoxychloropropane product per ton that separation obtains consumes, and unit is ton/ton, as shown in table 2.
Contained epoxychloropropane in the epoxychloropropane of the yield (%) of epoxychloropropane=finally give/initial solution.
Comparative example 1
nullAt 22 DEG C，Known for 100 mass parts compositions is contained epoxychloropropane、Methanol、First (density when 20 DEG C is 998.2 kilograms per cubic meter to the solution S 1 of chlorallylene and water with the water of 60 mass parts，Boiling point 100 DEG C) it is sufficiently mixed，After stratification，Collect lower floor's heavy phase，Again with chlorallylene (the industry chloropropene of 80 mass parts，Ba Ling petrochemical industry Co., Ltd，The content of chlorallylene is 98 mass %，Density when 20 DEG C is 939.2 kilograms per cubic meter，Boiling point is 45 DEG C) being divided into etc. five parts points of quality, to extract upper stratas five times light phase，Merge all of heavy phase and obtain chlorallylene phase，Chlorallylene is middle epoxychloropropane mutually、Methanol、The content of chlorallylene and water respectively 11.51 mass %、2.40 mass %85.30 mass % and 0.47 mass %，What finally obtain light phase is aqueous phase，Epoxychloropropane in aqueous phase、Methanol、The content of chlorallylene and water respectively 0.15 mass %、36.41 quality %、3.99 mass % and 59.00 mass %，Chlorallylene phase and the aqueous phase density contrast when 20 DEG C are 48.1 kilograms per cubic meter.
Flow process shown in Fig. 2, introduces the aqueous phase obtained in the first distillation column 1 and carries out separated, is introduced mutually by chlorallylene and carries out separated in after-fractionating tower 2.
Aqueous phase is at ambient pressure, obtained being recycled back into epoxidation reaction containing the methanol stream of a small amount of chlorallylene and minor amount of water by the tower top (64 DEG C) of the first distillation column 1, at the bottom of tower, (104 DEG C) obtain moisture logistics, and a portion is recycled back into extracting, and another part is as discharge of wastewater.
Chlorallylene is mutually at ambient pressure, the chlorallylene logistics containing a small amount of methanol and minor amount of water is obtained via the tower top (43 DEG C) of after-fractionating tower 2, a part is recycled back into epoxidation reaction, and another part is recycled back into extracting, and at the bottom of tower, (121 DEG C) obtain the logistics of water-free epoxychloropropane；The water-free epoxychloropropane logistics of gained separates the heavy constituent logistics at the bottom of the epoxychloropropane product stream obtaining tower top (13 kPas, 60 DEG C) and tower further in the 3rd distillation column 3.
The energy consumption of Solvent quantity (the epoxidation reaction products relative to 100 mass parts) and epoxychloropropane yield and separated, distillation energy consumption is the steam that separation obtains that epoxychloropropane product per ton consumes, and unit is ton/ton, as shown in table 2.
Contained epoxychloropropane in the epoxychloropropane of the yield (%) of epoxychloropropane=finally give/initial solution.
Embodiment 2
The present embodiment is for illustrating the separation method of epoxychloropropane provided by the invention.
nullAt 13 DEG C，Known for 100 mass parts compositions is contained epoxychloropropane、Methanol、First (density when 20 DEG C is 998.2 kilograms per cubic meter to the solution S 2 of chlorallylene and water with the water of 60 mass parts，Boiling point is 100 DEG C) contact mixing，After stratification，Collect lower floor's heavy phase，With the 2-tolyl aldehyde of 100 mass parts, (ladder is uncommon likes that (Shanghai) is melted into industrial development company limited again，Density when 20 DEG C is 1040 kilograms per cubic meter，Boiling point is 200 DEG C) being divided into etc. five parts points of quality, to extract upper stratas five times light phase，Merge all of heavy phase and obtain 2-tolyl aldehyde phase (i.e. heretofore described organic solvent phase，Below also such)，Epoxychloropropane in 2-tolyl aldehyde、Methanol、The content of chlorallylene and water respectively 7.90 mass %、1.60 mass %、19.91 quality % and 0.32 mass %，What finally obtain light phase is aqueous phase，Epoxychloropropane in aqueous phase、Methanol、The content of chlorallylene and water respectively 0.24 mass %、36.75 quality %、0.12 mass % and 61.85 mass %，2-tolyl aldehyde phase and the aqueous phase density contrast when 20 DEG C are 110.0 kilograms per cubic meter.
Flow process shown in Fig. 1, introduces the aqueous phase obtained in the first distillation column 1 and carries out separated；Organic solvent phase (namely 2-tolyl aldehyde phase, referred to as A phase in figure) is introduced after-fractionating tower 2 carries out separated；
Aqueous phase at ambient pressure, obtains being recycled back into epoxidation reaction containing the methanol stream of a small amount of chlorallylene via the tower top (64 DEG C) of the first distillation column 1, and at the bottom of tower, (104 DEG C) obtain water logistics；A water logistics part for gained is recycled back into extracting, and another part is as discharge of wastewater.
Mutually at ambient pressure, the chlorallylene logistics obtained containing methanol and minor amount of water via the tower top (41 DEG C) of after-fractionating tower 2 is recycled back into epoxidation reaction to 2-tolyl aldehyde, and (176 DEG C) at the bottom of tower obtain the 2-tolyl aldehyde logistics containing epoxychloropropane and minor amount of water；The gained 2-tolyl aldehyde logistics containing epoxychloropropane and minor amount of water separates in the 3rd distillation column 3 further and obtains the epoxychloropropane of tower top (88 DEG C) and the azeotropic mixture (water containing 25 mass %) of water, being separated into the 3rd distillation column 3 that is recycled back into containing 97.44 mass % epoxychloropropane in return tank (50 DEG C) and proceed logistics (namely returning to the logistics that the heavy phase portion in the 3rd distillation column 3 is easily separated) and the light phase logistics being recycled back in extraction tower containing 92.58 mass % water of separation, at the bottom of tower, (177 DEG C) obtain water-free epoxychloropropane and the logistics of 2-tolyl aldehyde；The logistics of the water-free epoxychloropropane of gained and 2-tolyl aldehyde separates the 2-tolyl aldehyde logistics obtained at the bottom of the epoxychloropropane product stream of tower top (13 kPas, 60 DEG C) and tower further in the 4th distillation column 4 and is recycled back into extracting.
The energy consumption of Solvent quantity (the epoxidation reaction products relative to 100 mass parts) and epoxychloropropane yield and separated, distillation energy consumption is the steam that the epoxychloropropane product per ton that separation obtains consumes, and unit is ton/ton, as shown in table 2.
Contained epoxychloropropane in the epoxychloropropane of the yield (%) of epoxychloropropane=finally give/initial solution.
Comparative example 2
nullAt 14 DEG C，Known for 100 mass parts compositions is contained epoxychloropropane、Methanol、First (density when 20 DEG C is 998.2 kilograms per cubic meter to the solution S 2 of chlorallylene and water with the water of 50 mass parts，Boiling point 100 DEG C) it is sufficiently mixed，After stratification，Collect lower floor's heavy phase，Again with chlorallylene (the industry chloropropene of 70 mass parts，Ba Ling petrochemical industry Co., Ltd，The content of chlorallylene is 98 mass %，Density when 20 DEG C is 939.2 kilograms per cubic meter，Boiling point is 45 DEG C) being divided into etc. five parts points of quality, to extract upper stratas five times light phase，Merge all of heavy phase and obtain chlorallylene phase，Chlorallylene is middle epoxychloropropane mutually、Methanol、The content of chlorallylene and water respectively 10.41 mass %、2.30 mass %、86.66 quality % and 0.38 mass %，What finally obtain light phase is aqueous phase，Epoxychloropropane in aqueous phase、Methanol、The content of chlorallylene and water respectively 0.24 mass %、38.52 quality %、4.48 mass % and 56.30 mass %，The density contrast when 20 DEG C of chlorallylene phase and aqueous phase is 50.6 kilograms per cubic meter.
According to the method identical with comparative example 1, the aqueous phase obtained introducing the first distillation column 1, chlorallylene introduces after-fractionating tower 2 mutually, the flow process shown in Fig. 2 is distilled, and obtains epoxychloropropane product.
The energy consumption of Solvent quantity (the epoxidation reaction products relative to 100 mass parts) and epoxychloropropane yield and separated, distillation energy consumption is the steam that separation obtains that epoxychloropropane product per ton consumes, and unit is ton/ton, as shown in table 2.
Contained epoxychloropropane in the epoxychloropropane of the yield (%) of epoxychloropropane=finally give/initial solution.
Table 1
Table 2
By embodiments of the invention it can be seen that the separation method of epoxychloropropane provided by the invention is compared with comparative example, when epoxychloropropane separation yield is essentially identical, the energy consumption of separated significantly reduces, and namely the method for the present invention is very suitable for industrial applications.
The preferred embodiment of the present invention described in detail above; but, the present invention is not limited to the detail in above-mentioned embodiment, in the technology concept of the present invention; technical scheme can being carried out multiple simple variant, these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, it is possible to be combined by any suitable mode.
Additionally, can also carry out combination in any between the various different embodiment of the present invention, as long as it is without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (8)
1. the separation method of an epoxychloropropane, the method includes: be separated after being mixed with extractant by the solution containing epoxychloropropane, methanol, chlorallylene and water, obtain the liquid phase rich in epoxychloropropane and the liquid phase rich in methanol, distill the obtained liquid phase rich in epoxychloropropane, obtain epoxychloropropane；It is characterized in that, described extractant includes water and organic solvent containing carbonyl and not halogen atom-containing immiscible with water, the ability of organic solvent extraction methanol is higher than water lower than the ability of water and extraction epoxychloropropane, and organic solvent is different from the boiling point of epoxychloropropane, the density ratio water of organic solvent is big, described organic solvent 10-2000 kilograms per cubic meter bigger than the density of water, organic solvent boiling point at 1 atmosphere pressure is higher than the boiling point of epoxychloropropane 20-300 DEG C, wherein, described organic solvent is hyacinthin, benzenpropanal, 2-tolyl aldehyde, 4-tolyl aldehyde, P-methoxybenzal-dehyde, 1-naphthaldehyde, propiophenone, 2, 4-dimethyl acetophenone, 3-methoxyacetophenone, to one or more in methoxybenzene acetone and 2 methyl benzophenone.
2. method according to claim 1, wherein, the liquid phase rich in epoxychloropropane and the density contrast at 20 DEG C of the liquid phase rich in methanol that described separation obtains are 60-2000 kilograms per cubic meter.
3. method according to claim 1, wherein, relative to the solution containing epoxychloropropane, methanol, chlorallylene and water described in 100 mass parts, the consumption of described water is 10-1000 mass parts, and the consumption of described organic solvent is 10-1000 mass parts.
4. method according to claim 1, wherein, the described temperature mixed with extractant by the solution containing epoxychloropropane, methanol, chlorallylene and water is 1-80 DEG C.
5. method according to claim 1, wherein, the content of the described solution in ethylene chloropropane containing epoxychloropropane, methanol, chlorallylene and water be 5-25 mass %, methanol content be 35-65 mass %, chlorallylene the content that content is 4-35 mass % and water be 5-25 mass %.
6. method according to claim 5, wherein, the described solution containing epoxychloropropane, methanol, chlorallylene and water is: titanium-silicon molecular sieve catalyst exist under, with methanol for solvent, chlorallylene contact with hydrogen peroxide or aqueous hydrogen peroxide solution after product.
7. method according to claim 6, wherein, the method also includes: distill the obtained liquid phase rich in methanol obtain containing or methanol stream without chlorallylene and water logistics, using described containing or methanol stream without chlorallylene partly or entirely return the solvent replacing methanol to contact with hydrogen peroxide or aqueous hydrogen peroxide solution as described chlorallylene, be used for extracting by the return of described water stream portions.
8. method according to claim 6, wherein, the method is additionally included in while the obtained liquid phase rich in epoxychloropropane of distillation obtains epoxychloropropane and obtains chlorallylene logistics and organic solvent logistics, using described chlorallylene stream portions or all return as raw material contact with hydrogen peroxide or aqueous hydrogen peroxide solution, by described organic solvent stream portions or all return be used for extracting.
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| US6350888B1 (en) * | 1997-09-18 | 2002-02-26 | Solvay (Societe Anonyme) | Method for making an oxirane |
| 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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| US6350888B1 (en) * | 1997-09-18 | 2002-02-26 | Solvay (Societe Anonyme) | Method for making an oxirane |
| 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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