CN109721570A - A method of producing epoxychloropropane - Google Patents
A method of producing epoxychloropropane Download PDFInfo
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- CN109721570A CN109721570A CN201711034532.7A CN201711034532A CN109721570A CN 109721570 A CN109721570 A CN 109721570A CN 201711034532 A CN201711034532 A CN 201711034532A CN 109721570 A CN109721570 A CN 109721570A
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- dichlorohydrin
- alkaline chamber
- bipolar membrane
- membrane electrodialysis
- epoxychloropropane
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Abstract
The invention discloses a kind of methods for producing epoxychloropropane, it include: to contact chloropropene with water and chlorine, the obtained chlorohydrin action mixture containing dichlorohydrin is subjected to gas-liquid separation, obtain gaseous stream and liquid phase stream, liquid phase stream is contacted with extractant, the extract liquor rich in dichlorohydrin is obtained, dichlorohydrin is isolated from extract liquor;Dichlorohydrin, the additive selected from water-soluble alkali metal salts and water soluble salt of ammonia and water are sent into the alkaline chamber of bipolar membrane electrodialysis device and carry out bipolar membrane electrodialysis, obtains the alkaline chamber efflux containing epoxychloropropane.In accordance with the present production process, it does not generate or does not generate waste water and waste residue substantially, it is environmentally protective;Catalyst is not used, production cost is reduced;According to the method for the present invention, separation costs are low and operating method is succinct.Epoxychloropropane is prepared using method of the invention, higher feed stock conversion can be obtained, while higher production efficiency can also be obtained.
Description
Technical field
The present invention relates to a kind of methods for producing epoxychloropropane.
Background technique
Epoxychloropropane is a kind of important basic organic chemical industry raw material and intermediate, is widely used in synthesizing epoxy tree
The multiple products such as rouge, glycerol, chlorohydrin rubber, drug, pesticide, surfactant and plasticizer.
Currently, China industrially frequently with technique be propylene high-temperature chloridising, including propylene high-temperature chlorination prepares chlorine third
Alkene, chloropropene hypochlorination generate dichlorohydrin, dichlorohydrin occurs saponification and prepares epoxychloropropane, subsequent to pass through rectifying
Etc. processes obtain product epoxychloropropane.The advantages of this method is that production process is flexible, technical maturity, stable operation, the disadvantage is that
Equipment seriously corroded caused by raw material chlorine, requires the material of purified propylene and reactor that high, energy consumption is high, chlorine consumption is high, secondary
Product is more, product yield is low.Meanwhile the chloride containing calcium of saponification process generation and the sewage quantity of organic chloride are big, seriously endanger
Environment, the investment for administering waste water usually account for the 15%-20% of gross investment.
In addition, epoxychloropropane can also be synthesized using acetate propylene ester process, including propylene synthesizes allyl acetate, acetic acid
Propylene ester hydrolysis allyl alcohol, allyl alcohol addition refining dichlorohydrin and dichlorohydrin saponification generate epoxychloropropane.This method
Reaction condition is mild, easily controllable, noncoking, stable operation, while reduce the dosage of propylene, calcium hydroxide and chlorine with
And the discharge amount of byproduct of reaction and chloride containing calcium waste water, it can be easier to obtain the high-purity alkene that current technology can't obtain
Propyl alcohol.It is however a drawback of the method that process flow is longer, catalyst life is short, needs the anti-acetic acid corrosion of stainless steel material, prevents
Only allyl alcohol unit gaseous mixture explodes, and investment cost is relatively high.
In short supply with Global Oil resource, especially to the increasingly strict of environmental requirement, applicable industry production method is solid
Some defects are increasingly apparent, and people has been promoted to reinforce the exploitation of new process.
CN101157670A discloses a kind of synthetic method of epoxychloropropane, comprising the following steps:
1) using the by-product glycerin during production of biodiesel as raw material, have solvent or it is solvent-free when, catalyst is deposited
1,3- dichlorohydrin is generated in lower react with chlorination reagent, the molar ratio of catalyst and glycerol is 0.1-0.5:1, can in chlorinating agent
The molar ratio of the chlorine and glycerol that participate in reaction is 2-6:1;End of reaction alkali neutralization filters to obtain 1,3- dichlorohydrin, does not need
Purifying is directly used in annulation;
2) in water, under base catalysis, 1,3- dichlorohydrin dehydrochlorination is at epoxychloropropane, 1,3- dichlorohydrin and water
Or the molar ratio of organic solvent is 1:8-15, the molar ratio of 1,3- dichlorohydrin and base catalyst is 1:1-1.5;In reaction process
Product, stratification are steamed at any time with water vapour, and organic layer rectifying obtains the epoxychloropropane of high-purity.
But this method needs to steam product at any time with water vapour during the reaction in epoxidation reaction step, this
On the one hand the complexity for improving operation, on the other hand also improves operating cost.
CN101172970A discloses a kind of method for preparing epoxychloropropane with chloropropene Direct Epoxidation, this method with
The mixture of chloropropene, hydrogen peroxide and solvent is raw material, and solvent is acetonitrile, methanol, acetone or the tert-butyl alcohol, chloropropene and hydrogen peroxide
Molar ratio be 1-7:1, the weight ratio of solvent and chloropropene is 1-6:1, wherein in temperature is 35-85 DEG C and chloropropene air speed
It is 0.1-6 hours-1Under conditions of, raw material carries out chloropropene oxidation catalysis in the fixed bed reactors existing for insulation and catalyst
Epoxychloropropane, the forming mixture that catalyst is made of Titanium Sieve Molecular Sieve and inertia silica, titanium silicon point is made in reaction
Son sieve is the molecular sieve containing titanium for having topological structure for MFI or MWW, and Titanium Sieve Molecular Sieve and the weight ratio of inertia silica are 7:
3。
But due to the catalyst and H of technique use2O2It is at high cost, and reaction process needs to increase using solvent
Separating energy consumption.
In summary, it is necessary to the epoxychloropropane production technology developed greenization, adapt to sustainable development.
Summary of the invention
It is an object of the invention to overcome the shortcomings of existing epichlorohydrin production process, provide a kind of environmentally protective, suitable
Answer the epoxychloropropane production technology of sustainable development.
The present invention provides a kind of methods for producing epoxychloropropane, this method comprises:
(1) under the conditions of chlorohydrin action, chloropropene is contacted with water and chlorine, obtains the chlorohydrination containing dichlorohydrin
Reaction mixture
(2) the chlorohydrin action mixture is subjected to gas-liquid separation, gaseous stream and liquid phase stream is obtained, by the liquid
Phase logistics is contacted with extractant, is obtained the extract liquor rich in dichlorohydrin, is separated from the extract liquor rich in dichlorohydrin
Dichlorohydrin out;
(3) dichlorohydrin is sent into the alkaline chamber of bipolar membrane electrodialysis device, is carried out in the presence of at least one additive
Bipolar membrane electrodialysis, obtains the alkaline chamber efflux containing epoxychloropropane, the additive be selected from water-soluble alkali metal salts and
One or more of water soluble salt of ammonia.
In accordance with the present production process, dichlorohydrin is subjected in the alkaline chamber of bipolar membrane electrodialysis device epoxidation, made
Standby epoxychloropropane has the advantage that according to the method for the present invention compared with existing epoxy chloropropane production method
(1) it compared with traditional propylene high-temperature chloridising and acetate propylene ester process, does not produce in accordance with the present production process
Life does not generate waste water and waste residue substantially;
(2) compared with chloropropene Direct Epoxidation method, catalyst is not used in accordance with the present production process, reduces life
Produce cost;Also, epoxychloropropane is contained as solvent rather than using organic solvent using water according to the method for the present invention
Reaction solution can be divided into organic phase and poor epoxy chlorine rich in epoxy epoxychloropropane using sedimentation method for separating such as standing, centrifugations
The water phase of propane, reduces separation costs;
(3) according to the method for the present invention, during the reaction, product is steamed without the methods of steam distillation,
Operating method is succinct.
Epoxychloropropane is prepared in accordance with the present production process, and dichloro third is carried out in the presence of at least one additive
The epoxidation reaction of alcohol can obtain the feed stock conversion significantly improved and production efficiency, while can also improve for epoxy chloropropionate
The selectivity of alkane.
Detailed description of the invention
The film unit for the bipolar membrane electrodialysis device that Fig. 1 is used to illustrate that epoxy chloropropane production method according to the present invention uses
A kind of embodiment.
The film unit for the bipolar membrane electrodialysis device that Fig. 2 is used to illustrate that epoxy chloropropane production method according to the present invention uses
A kind of preferred embodiment.
Fig. 3 is used to illustrate a kind of embodiment of epoxy chloropropane production method according to the present invention.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of methods for producing epoxychloropropane, this method comprises:
(1) under the conditions of chlorohydrin action, chloropropene is contacted with water and chlorine, obtains the chlorohydrination containing dichlorohydrin
Reaction mixture
(2) the chlorohydrin action mixture is subjected to gas-liquid separation, gaseous stream and liquid phase stream is obtained, by the liquid
Phase logistics is contacted with extractant, is obtained the extract liquor rich in dichlorohydrin, is separated from the extract liquor rich in dichlorohydrin
Dichlorohydrin out;
(3) dichlorohydrin is sent into the alkaline chamber of bipolar membrane electrodialysis device, is carried out in the presence of at least one additive
Bipolar membrane electrodialysis, obtains the alkaline chamber efflux containing epoxychloropropane, the additive be selected from water-soluble alkali metal salts and
One or more of water soluble salt of ammonia.
In accordance with the present production process, step (1), can be known to those skilled in the art for providing dichlorohydrin
Under conditions of by chloropropene chlorohydrination.Preferably, chloropropene relative to chlorine be more than stoichiometric ratio, it is to ensure that chlorine is complete
Portion's conversion, unreacted chloropropene can then be recycled, such as: the molar ratio of chloropropene and chlorine can be 1:0.8-
0.98, preferably 1:0.9-0.95.On the one hand water is used as chlorine conversion to become hypochlorous raw material, be on the other hand situated between as reaction
Matter, dosage, which is subject to, is able to achieve above-mentioned function.Chloropropene and water and chlorine can 50-90 DEG C at a temperature of contact, preferably
60-80 DEG C at a temperature of contact.Chloropropene can be contacted with water and chlorine under normal pressure (that is, 1 standard atmospheric pressure).
Chlorohydrin action mixture is in addition to containing dichlorohydrin, it is also possible to contain unreacted chloropropene and/or chlorine, step
Suddenly in (2), chlorohydrin action mixture is subjected to gas-liquid separation, on the one hand can reduce the content of gaseous matter in liquid phase, thus
Improve the safety of subsequent reactions;On the other hand unreacted chloropropene and/or chlorine circulation can also be used for chlorohydrin action,
To further increase the raw material availability of the method for the present invention.Chlorohydrin action mixture can be flashed, thus by chlorine
Alcoholization reaction mixture is separated into gaseous stream and liquid phase stream.
The liquid phase stream is contacted with extractant carries out extraction and separation, to isolate dichlorohydrin.The extractant can
Think the common substance that dichlorohydrin can be extracted.Preferably, the extractant is chloropropene.Using chloropropene conduct
Extractant can not only be separated dichlorohydrin with higher extraction efficiency from the liquid phase stream, and will not be additional
Introduce impurity.
It is separated by extraction, dichlorohydrin is enriched in extract liquor, can be using conventional method from the extract liquor
Dichlorohydrin is isolated, while obtaining recycling extractant.Recycling extractant can be recycled as extractant.Specifically, it can incite somebody to action
The extract liquor is distilled, and recycling chloropropene and dichlorohydrin are obtained, and regard at least partly chloropropene circulation as extractant.
The raffinate phase being separated by extraction can export.Contacting chloropropene with chlorine and water, progress chlorohydrination is anti-
At once, raffinate phase is to contain aqueous hydrochloric acid solution, which can directly export, and is sent into downstream process and produces hydrochloric acid.
In accordance with the present production process, in step (3), Bipolar Membrane electric osmose is carried out in the presence of at least one additive
Analysis, can effectively improve the operational efficiency of bipolar membrane electrodialysis device.
The additive is selected from one or more of water-soluble alkali metal salts and water soluble salt of ammonia.In the present invention
, term " water-soluble alkali metal salts " and " water soluble salt of ammonia " refer to alkali metal salt and ammonium salt in 100g water in 25 DEG C and 1 mark
Solubility under quasi- atmospheric pressure is 1g or more.
The additive can be the chloride of alkali metal, the sulfate of alkali metal, the nitrate of alkali metal, alkali metal
Carboxylate, the phosphate of alkali metal, ammonium chloride, ammonium sulfate, ammonium nitrate, carboxylic acid ammonium, ammonium phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate
One or more of.The specific example of the additive can include but is not limited to: sodium chloride, potassium chloride, lithium chloride,
Sodium sulphate, potassium sulfate, sodium nitrate, potassium nitrate, lithium nitrate, sodium formate, sodium acetate, potassium acetate, sodium phosphate, potassium phosphate, phosphoric acid hydrogen
Sodium, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium phosphate, ammonium hydrogen phosphate, di(2-ethylhexyl)phosphate
One or more of hydrogen ammonium and ammonium acetate.
Under the premise of improving the operational efficiency of bipolar membrane electrodialysis device, from the angle further reduced the cost, institute
It states additive and is preferably selected from sodium chloride, potassium chloride and ammonium chloride.
The content of the additive can be selected according to expected current density.Although in bipolar membrane electrodialysis device
A small amount of additive is introduced in alkaline chamber, such as: on the basis of by additive, dichlorohydrin and entering the total amount of water of alkaline chamber, addition
The content of agent is that the operational efficiency for improving bipolar membrane electrodialysis device can be realized in 0.01 weight %, but the present inventor exists
It is found in research process, if further increasing the content of the additive, can be further improved the choosing for epoxychloropropane
Selecting property.
Therefore, according to the method for the present invention, by additive, dichlorohydrin and on the basis of entering the total amount of water of alkaline chamber,
The weight percentage when content of the additive can be saturated for 0.01 weight % to the additive in water, such as 0.02-
40 weight %, preferably 0.05-35 weight %.Weight percentage when additive is saturated in water refers to the temperature at 25 DEG C
Under, additive forms weight percentage when saturated solution in water.
According to the method for the present invention, in one embodiment, with the water of additive, dichlorohydrin and entrance alkaline chamber
On the basis of total amount, the content of the additive is 0.01 weight % to 5 weight %, preferably 0.02-4.6 weight % are lower than, more
Preferably 0.05-4.2 weight %, further preferably 0.1-3.8 weight %.According to the embodiment, can significantly improve bipolar
The operational efficiency of membrane electrodialysis device.
According to the method for the present invention, in a kind of more preferably embodiment, with additive, dichlorohydrin and entrance
On the basis of the total amount of the water of alkaline chamber, the content of the additive is 5 weight % or more, such as 5.5-30 weight %.Preferably, with
On the basis of the total amount of the water of additive, dichlorohydrin and entrance alkaline chamber, the content of the additive is 6 weight % or more, such as
8-26 weight %, further preferably 10-20 weight %.According to the more preferably embodiment, higher epoxy can be obtained
Chloropropane selectivity.
Method according to the invention it is possible to which the alkaline chamber charging that the additive is added to bipolar membrane electrodialysis device (is existed
When salt room, fed for salt room, hereinafter abbreviated as " alkaline chamber charging/salt room charging ") in.Generally, by dichlorohydrin and can add
(there are when salt room, be in salt room) after adding agent to be configured to aqueous solution, is sent into the alkaline chamber of bipolar membrane electrodialysis device, to realize
Bipolar membrane electrodialysis is carried out in the presence of additive.Method according to the invention it is possible to bipolar membrane electrodialysis device it is initial into
It introduces the additive in material, can not supplement the additive during circular response, but those skilled in the art can be with
Understand, during circular response when the content deficiency of additive, the additive can be supplemented.
According to the method for the present invention, by additive, dichlorohydrin and on the basis of entering the total amount of water of alkaline chamber, dichloro
The content of propyl alcohol can be 1-80 weight %, preferably 3-60 weight %, more preferably 5-50 weight %, further preferably 7-
40 weight % are still more preferably 8-30 weight %, particularly preferably 10-20 weight %.According to the method for the present invention, described
Dichlorohydrin can be the chloro- 2- propyl alcohol of 1,3- bis- and/or bis- trimethylewne chlorohydrin 3- of 2,3-.
According to the method for the present invention, dichlorohydrin is sent into the alkaline chamber of bipolar membrane electrodialysis device, with bipolar membrane electrodialysis
Hydroxide ion (the OH of generation-) immediate reaction in situ, obtain epoxychloropropane.Film unit in the bipolar membrane electrodialysis device
Setting form, which is subject to, is able to achieve above-mentioned function.
In one embodiment, the bipolar membrane electrodialysis device is two Room bipolar membrane electrodialysis devices, i.e., the described Bipolar Membrane
The film unit of electric dialyzator contains acid compartment and alkaline chamber.As a preferred embodiment of two Room bipolar membrane electrodialysis devices, such as Fig. 1 institute
Show, the bipolar membrane electrodialysis device includes anode, at least one of cathode and setting between the anode and the cathode
Film unit, the film unit contain a Bipolar Membrane and an anion-exchange membrane, and anion-exchange membrane replaces row with Bipolar Membrane
Column, space between anion-exchange membrane and the anion exchange layer of adjacent bipolar film are alkaline chamber, anion-exchange membrane with it is adjacent
Space between the cation exchange layer of another Bipolar Membrane is acid compartment.
According to the embodiment, when carrying out bipolar membrane electrodialysis, water enters acid compartment, containing dichlorohydrin and additive
Aqueous solution enters alkaline chamber, and under the action of DC electric field, water decomposition is hydrogen ion (H by Bipolar Membrane+) and hydroxide ion (OH-),
OH-Enter alkaline chamber by the anion exchange layer of Bipolar Membrane, with dichlorohydrin haptoreaction, forms epoxychloropropane, thus
The alkaline chamber efflux containing epoxychloropropane is obtained by the alkaline chamber;H+Acid is then entered by the cation exchange layer of Bipolar Membrane
Room, with the Cl for entering acid compartment by anion-exchange membrane-In conjunction with formation HCl, to obtain the acid containing hydrochloric acid by the acid compartment
Room efflux.
In a kind of more preferably embodiment, the bipolar membrane electrodialysis device is three Room bipolar membrane electrodialysis devices, i.e.,
The film unit of the bipolar membrane electrodialysis device includes acid compartment, alkaline chamber and salt room.It is that three Room are bipolar in the bipolar membrane electrodialysis device
When membrane electrodialysis device, the output port of the salt room is connected to the input port of the alkaline chamber, thus using salt room efflux as
Alkaline chamber charging.
Bipolar Membrane, cation-exchange membrane and anion-exchange membrane can be combined arrangement, to obtain that there are three Room
Bipolar membrane electrodialysis device.In an example, the film unit of the bipolar membrane electrodialysis device includes Bipolar Membrane, anion exchange
Film, the first cation-exchange membrane and the second cation-exchange membrane, the anion of the first cation-exchange membrane and adjacent Bipolar Membrane
Space between switching layer is alkaline chamber, and the space between the cation exchange layer of Bipolar Membrane and adjacent anion-exchange membrane is acid
Room, space between anion-exchange membrane and the second adjacent cation-exchange membrane are salt room, the output port of the salt room with
The input port of the alkaline chamber is connected to.In another example, the film unit of the bipolar membrane electrodialysis device includes Bipolar Membrane, sun
Amberplex, the first anion-exchange membrane and the second anion-exchange membrane, the first anion-exchange membrane and adjacent Bipolar Membrane
Cation exchange layer between space be acid compartment, between the anion exchange layer of Bipolar Membrane and adjacent cation-exchange membrane
Space is alkaline chamber, the space between cation-exchange membrane and the second adjacent anion-exchange membrane be salt room, the salt room it is defeated
Exit port is connected to the input port of the alkaline chamber.
In a preferred embodiment, as shown in Fig. 2, the bipolar membrane electrodialysis device includes that anode, cathode and setting exist
At least one film unit between the anode and the cathode, the film unit contain the first Bipolar Membrane, the second Bipolar Membrane, yin
Amberplex and cation-exchange membrane, the anion-exchange membrane and the cation-exchange membrane arranged adjacent are simultaneously arranged the
Between one Bipolar Membrane and the second Bipolar Membrane, the first Bipolar Membrane and the second Bipolar Membrane are separated, cation-exchange membrane and adjacent the
Space between the anion exchange layer of one Bipolar Membrane is alkaline chamber, the cation of anion-exchange membrane and the second adjacent Bipolar Membrane
Space between switching layer is acid compartment, and the space between the anion-exchange membrane and cation-exchange membrane of arranged adjacent is salt room,
The output port of the salt room is connected to the input port of the alkaline chamber.In the preferred example, the setting of salt room in acid compartment and
Between alkaline chamber, the charging of salt room enters alkaline chamber, and dichlorohydrin carries out reaction in alkaline chamber and generates epoxychloropropane, and epoxychloropropane exists
Concentration in salt room is very low, can further decrease the concentration of epoxychloropropane in acid compartment in this way, to further increase product receipts
Rate.
According to the more preferably embodiment, when carrying out bipolar membrane electrodialysis, water enters acid compartment, contains dichlorohydrin
Enter salt room with the aqueous solution of additive and alkaline chamber is entered by salt room, under the action of DC electric field, water decomposition is by Bipolar Membrane
Hydrogen ion (H+) and hydroxide ion (OH-), OH-Enter alkaline chamber by the anion exchange layer of Bipolar Membrane, is connect with dichlorohydrin
Touching reaction, forms epoxychloropropane, to obtain the alkaline chamber efflux containing epoxychloropropane by the alkaline chamber;H+Then by double
The cation exchange layer of pole film and enter acid compartment, and pass through the anion-exchange membrane of salt room side and eventually enter into the Cl of acid compartment-
In conjunction with formation HCl, to obtain the acid compartment efflux containing hydrochloric acid by the acid compartment.
Although the bipolar membrane electrodialysis device shown in Fig. 1 and 2 only has a film unit, those skilled in the art are known
, the quantity of the film unit is not limited to one group, and the bipolar membrane electrodialysis device can have multiple film units.Specifically
Ground, the bipolar membrane electrodialysis device can have 1-1000 film unit, preferably have 5-500 film unit, more preferably have
8-300 film unit further preferably has 10-100 film unit.
According to the method for the present invention, the pole liquid that the pole room of bipolar membrane electrodialysis device uses is the aqueous solution containing electrolyte.
The electrolyte can be inorganic electrolyte and/or organic bath, and specific example can include but is not limited to ammonium sulfate, sulphur
Sour sodium, sodium nitrate, sodium phosphate, dibastic sodium phosphate, sodium dihydrogen phosphate, potassium nitrate, potassium phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, hydrogen-oxygen
Change one or more of sodium, potassium hydroxide, formic acid, acetic acid, sodium formate, potassium formate and quaternary ammonium type electrolyte.Preferably,
The electrolyte is inorganic electrolyte.It is highly preferred that the electrolyte is sodium sulphate and/or ammonium sulfate.Generally, the pole liquid
The content of middle electrolyte can be 1-15 weight %, preferably 3-10 weight %.According to the method for the present invention, into Bipolar Membrane electricity
The type and content of electrolyte can be identical in the cathode chamber of dialyzer and the pole liquid of anode chamber, or different.From behaviour
The angle for making simplicity is set out, into bipolar membrane electrodialysis device cathode chamber and anode chamber pole liquid in electrolyte type and contain
Amount is identical.
According to the method for the present invention, operation is preferably adjusted during bipolar membrane electrodialysis, the adjustment operation makes
The pH value for obtaining alkaline chamber efflux is 5.5-10, can significantly improve the selectivity and/or dichlorohydrin for epoxychloropropane in this way
Conversion ratio.Such as: it is described adjustment operation so that alkaline chamber efflux pH value be 5.5,5.6,5.7,5.8,5.9,6,6.1,
6.2、6.3、6.4、6.5、6.6、6.7、6.8、6.9、7、7.1、7.2、7.3、7.4、7.5、7.6、7.7、7.8、7.9、8、8.1、
8.2,8.3,8.4,8.5,8.6,8.7,8.8,8.9,9,9.1,9.2,9.3,9.4,9.5,9.6,9.7,9.8,9.9 or 10.
It should be noted that the pH value of the alkaline chamber efflux refers to by alkaline chamber outflow and the operation of the pH value without that can change efflux
And the pH value measured.It, can be using the pH value measured at alkaline chamber output port end as the pH value of alkaline chamber efflux in practical operation.
In one embodiment, the adjustment operation is so that the pH value of alkaline chamber efflux is 8-10.According to the embodiment party
Formula can obtain higher dichlorohydrin conversion ratio under conditions of can obtain higher epoxychloropropane selectivity.
In a kind of more embodiment, the adjustment operation is so that the pH value of alkaline chamber efflux is 6 to being lower than 8, such as
6.5-7.9, preferably 7-7.8, more preferably 7.2-7.6.According to the more preferably embodiment, higher two can obtained
Under conditions of chloropropyl alcohol conversion ratio, higher epoxychloropropane selectivity can be obtained.
The adjustment operation can be the operation that the pH value of alkaline chamber efflux can be adjusted.Preferably, the adjustment
Operation includes adjusting the amount for the dichlorohydrin for entering alkaline chamber.When the pH value of alkaline chamber efflux is higher than above range, dichloro is improved
The amount of propyl alcohol, to being adjusted to the pH value of alkaline chamber efflux within above range;It is lower than in the pH value of alkaline chamber efflux
When above range, the amount of dichlorohydrin is reduced, to being adjusted to the pH value of alkaline chamber efflux within above range.
According to the method for the present invention, during bipolar membrane electrodialysis, the voltage applied to each film unit can be 0.5-
2.5V, preferably 0.6-2.3V, more preferably 0.8-2.2V, further preferably 1-2.1V.The bipolar membrane electrodialysis can be with
5-45 DEG C at a temperature of carry out, preferably 10-42 DEG C at a temperature of carry out, more preferably 25-40 DEG C at a temperature of carry out.
According to the method for the present invention, the decentralized medium using water as dichlorohydrin, the alkaline chamber efflux is also with water
Alkaline chamber efflux may make to be separated into rich in epoxychloropropane as the efflux of decentralized medium, therefore by sedimentation separation
Organic phase and the water phase for being enriched unreacted dichlorohydrin.The sedimentation separation can be settle and separate, or from
Heart separation can also be the combination of settle and separate and centrifuge separation, such as: first alkaline chamber efflux can be centrifuged,
Then it is stood, so that alkaline chamber efflux is divided into the organic phase rich in epoxychloropropane and is enriched unreacted two
The water phase of chloropropyl alcohol.
Method according to the invention it is possible to which alkaline chamber efflux is separated, is obtained after bipolar membrane electrodialysis completion
Organic phase rich in epoxychloropropane.
From the angle for the selectivity for further increasing epoxychloropropane, preferably during bipolar membrane electrodialysis, from
The organic phase rich in epoxychloropropane is isolated in alkaline chamber efflux, by isolated the organic phase remaining liquid phase and can
The fresh dichlorohydrin circulation of choosing is sent into the alkaline chamber of bipolar membrane electrodialysis device.Alkaline chamber charging/salt room charging can be described surplus
Extraction raffinate phase, or the mixture of the residue liquid phase and fresh dichlorohydrin.Such as: it is being carried out in a batch mode Bipolar Membrane
When electrodialysis, alkaline chamber charging/salt room charging can be the remaining liquid phase;In bipolar membrane electrodialysis in a continuous manner,
Alkaline chamber charging/salt room charging can be the mixture of the remaining liquid phase and fresh dichlorohydrin.The intermittent mode refers to
At the beginning of each bipolar membrane electrodialysis, a certain amount of aqueous solution containing dichlorohydrin and additive is added, carries out the predetermined time
After bipolar membrane electrodialysis, whole alkaline chamber effluxes are discharged.The continuation mode refers at the beginning of bipolar membrane electrodialysis, is added
A certain amount of aqueous solution containing dichlorohydrin and additive will at least partly epoxy chloropropionate in the process of bipolar membrane electrodialysis
Alkane discharge, while supplementing fresh dichlorohydrin.
According to the method for the present invention, alkaline chamber efflux carries out sedimentation separation, be divided into organic phase rich in epoxychloropropane and
Water phase, in general, the water phase is upper phase, the organic phase is lower layer's liquid phase.But the additive is fed in alkaline chamber
And/or the content in the charging of salt room, when being 25 weight % or more, alkaline chamber efflux carries out obtained from sedimentation separation in two-phase, on
Layer liquid phase is the organic phase rich in epoxychloropropane, and lower layer's liquid phase is water phase.
The organic phase rich in epoxychloropropane isolated from the alkaline chamber efflux can export.It is according to the present invention
Method obtains epoxychloropropane product it is also preferable to include the organic phase rich in epoxychloropropane is refined.The present invention
The method of the purification is not particularly limited, common epoxychloropropane crude product refining methd can be used, such as: it can
Rectifying is carried out will be enriched in the organic phase of epoxychloropropane, to obtain epoxychloropropane product.
It is excellent in subtractive process when the organic phase rich in epoxychloropropane also contains unreacted dichlorohydrin
Choosing further includes recycling unreacted dichlorohydrin, and at least partly dichlorohydrin preferred cycle of recycling enters bipolar membrane electrodialysis device
Alkaline chamber in, to further increase the utilization rate of dichlorohydrin, and further decrease the method for the present invention generation waste liquid amount.It is described
Organic phase rich in epoxychloropropane is also possible to be preferably also included in essence according to the method for the present invention containing by-products such as glycerine
During system, the by-product is recycled.The by-product of recycling can export.
Epoxy chloropropane production method according to the present invention can be implemented in following production system, the production system packet
Include chlorohydrin action unit, chlorohydrin action mixture separative unit and epoxidation reaction unit.The chlorohydrin action list
The output port of dichlorohydrin of member is connected to the material input port to be separated of chlorohydrin action mixture separative unit, described
The dichlorohydrin output port of chlorohydrin action mixture separative unit and the dichlorohydrin input port of epoxidation reaction unit
Connection.
The chlorohydrin action unit is used to chloropropene progress chlorohydrin action obtaining the chlorohydrination containing dichlorohydrin
Reaction mixture.The chlorohydrin action unit can obtain dichloro third using conventional reaction unit by chloropropene chlorohydrination
Alcohol.
The chlorohydrin action mixture separative unit is for isolating dichloro third from the chlorohydrin action mixture
Alcohol, including gas-liquid separation device, extraction equipment and dichlorohydrin recyclable device.
The gas-liquid separation device receives the chlorohydrin action mixture of chlorohydrin action unit output, and by the chloropharin
Change reaction mixture separation gaseous stream and liquid phase stream.The gas-liquid separation device can use common gas-liquid separating function
Device, such as: flash column.
The extraction equipment contacts the liquid phase stream with extractant, and dichloro third is isolated from the liquid phase stream
Alcohol.The extraction equipment can be common extraction tower.Extractant can be sent into from the top of extraction tower, by the liquid phase object
Stream is sent into from the middle part of the extraction tower or lower part, so that extractant and the liquid phase stream carry out counter current contacting, obtains richness
The extract liquor of dichlorohydrin is collected.
The dichlorohydrin recyclable device is for recycling dichlorohydrin from the extract liquor.The dichlorohydrin recycling dress
The device for being enough that dichlorohydrin is recycled from the extract liquor can be used by setting, such as: flash column.
The gaseous stream that gas-liquid separation device is isolated can be recycled for chlorohydrin action unit, the chlorohydrin action
Mixture separative unit is preferably provided with gaseous stream output port and chlorohydrin action of the corresponding pipeline by gas-liquid separation device
The raw material input port of unit is connected to, so that the gaseous stream circulation that gas-liquid separation device is isolated is sent into chlorohydrin action list
In member.
The epoxidation reaction unit includes bipolar membrane electrodialysis device, for by dichlorohydrin in bipolar membrane electrodialysis device
Bipolar membrane electrodialysis is carried out in alkaline chamber, obtains the alkaline chamber efflux containing epoxychloropropane.
The film unit of the bipolar membrane electrodialysis device contains alkaline chamber and acid compartment.
The film unit of the bipolar membrane electrodialysis device can only contain alkaline chamber and acid compartment, i.e., the described bipolar membrane electrodialysis device can
Think that two Room bipolar membrane electrodialysis devices, the two Room bipolar membrane electrodialysis device preferably have film unit shown in fig. 1.Preferably,
The bipolar membrane electrodialysis device is three Room bipolar membrane electrodialysis devices, and the film unit of the three Room bipolar membrane electrodialysis device contains alkali
Room, salt room and acid compartment, and the salt room efflux output port of the salt room is connected to the input port of the alkaline chamber, contains dichloro
The aqueous solution of propyl alcohol and additive enters the alkaline chamber by the salt room, and the hydrogen-oxygen generated in alkaline chamber with bipolar membrane electrodialysis
Radical ion combines, and reacts, and forms epoxychloropropane, and then obtain the outflow of the alkaline chamber containing epoxychloropropane by the alkaline chamber
Liquid;The acid compartment efflux containing HCl is obtained in acid compartment simultaneously.The three Room bipolar membrane electrodialysis device preferably have Fig. 2 shows
Film unit.
The epoxidation reaction unit further includes alkaline chamber efflux settling tank, the alkaline chamber efflux settling tank and described double
The alkaline chamber of pole membrane electrodialysis device is connected to, for receiving the alkaline chamber efflux of bipolar membrane electrodialysis device, and will at least partly alkaline chamber stream
Liquid and optional fresh dichlorohydrin are fed in bipolar membrane electrodialysis device as alkaline chamber charging/salt room out.
In a preferred embodiment, the alkaline chamber efflux settling tank include alkaline chamber efflux input port, it is new
Fresh dichlorohydrin input port, alkaline chamber charging output port and organic phase output port, the alkaline chamber efflux input port
It is connected to the alkaline chamber efflux output port of the bipolar membrane electrodialysis device, the alkaline chamber charging output port and Bipolar Membrane electric osmose
Alkaline chamber feed input mouth (there are when salt room, be salt room feed input mouth) connection of parser, the alkaline chamber efflux sedimentation
Partition is arranged in the inside of tank, and the inner space of the alkaline chamber efflux settling tank is divided into the first liquid phase region and second liquid phase
The lower part in area, first liquid phase region and the second liquid phase area passes through separator adjacent, first liquid phase region and described second
The top of liquid phase region is connected to, and the alkaline chamber efflux input port, which is arranged, (is preferably provided at the first liquid phase region in the first liquid phase region
Top), the fresh dichlorohydrin input port, which is arranged, (is preferably provided at the upper of second liquid phase area in the second liquid phase area
Portion), alkaline chamber charging output port setting is described organic in second liquid phase area (lower part for being preferably provided at second liquid phase area)
Phase output terminal mouth is arranged in first liquid phase region (lower part and/or top that are preferably provided at the first liquid phase region).The partition
Height not only can ensure that the inventory in second liquid phase area meets the feed needs of bipolar membrane electrodialysis device, but also can retain enough
Alkaline chamber efflux separated subject to.
According to the preferred embodiment, in system operation, the alkaline chamber outflow of the alkaline chamber output of bipolar membrane electrodialysis device
Liquid enters first liquid phase region by the alkaline chamber efflux input port, and the height of materials into the first liquid phase region is more than partition
When, partial material enters second liquid phase area by overflow at the top of the partition, and the alkaline chamber efflux for being retained in the first liquid phase region carries out
Sedimentation separation, obtains the organic phase rich in epoxychloropropane, and the organic phase rich in epoxychloropropane passes through the organic phase
Output port output.According to the embodiment, it can isolate and be rich in from alkaline chamber efflux during bipolar membrane electrodialysis
The organic phase of epoxychloropropane, to further increase epoxychloropropane selectivity.
In the preferred embodiment, the organic phase output port is preferably provided at the lower part of first liquid phase region
The top and/or.In a preferred embodiment, organic phase output is respectively provided in the lower part of first liquid phase region and top
Port can select to open according to the relative position for the organic phase and remaining liquid phase that alkaline chamber efflux sedimentation separation goes out in this way
Portion's organic phase output port, or lower part organic phase output port is opened, the organic phase is exported.
In the startup stage of the production system, it can be filled in alkaline chamber efflux settling tank and contain dichlorohydrin and extremely
The aqueous solution of few a kind of additive, as alkaline chamber charging/salt room charging;Water is filled in acid compartment outflow liquid storage tank, as acid compartment
Raw material.When the alkaline chamber efflux settling tank includes previously described first liquid phase region and second liquid phase area, two will be contained
The aqueous solution of chloropropyl alcohol and additive is filled into second liquid phase area.
Organic phase rich in epoxychloropropane can export, and can also be refined with further progress, obtain epoxychloropropane production
Product.Preferably, the production system further includes refined unit, and the refined unit is settled for receiving from the alkaline chamber efflux
The organic phase rich in epoxychloropropane of tank output, and the organic phase is refined, obtain epoxychloropropane product.
The refined unit can recycle epoxychloropropane using various from the organic phase rich in epoxychloropropane
Device.In one embodiment, the refined unit includes rectifying column, and the organic phase rich in epoxychloropropane enters institute
It states rectifying column and carries out rectifying, obtain epoxychloropropane product, while recycling unreacted dichlorohydrin that may be present and third
The by-products such as triol, the unreacted dichlorohydrin circulation of recycling, which is sent into the alkaline chamber of bipolar membrane electrodialysis device, carries out Bipolar Membrane electricity
Dialysis, the epoxychloropropane product and by-product of recycling then export respectively.
It is also preferable to include the storage tanks for storing dichlorohydrin for the production system, for mentioning to alkaline chamber efflux settling tank
For initial feed, and fresh dichlorohydrin is supplemented when needed.
The production system is preferably adjusted operation during carrying out bipolar membrane electrodialysis.Specifically, Ke Yi
Flow valve is set on the connecting line between the storage tank of dichlorohydrin and alkaline chamber efflux settling tank for storing, to enter alkaline chamber
The amount of the dichlorohydrin of efflux settling tank is adjusted.
The production system at runtime, can take intermittent mode, can also take continuation mode, not limit especially
It is fixed.
Fig. 3 shows a kind of embodiment of epoxy chloropropane production method according to the present invention, below in conjunction with Fig. 3 to this
Embodiment is described in detail.
As shown in figure 3, including: chlorohydrin action unit, chloropharin according to the epoxychloropropane production system of the embodiment
Change reaction mixture separative unit, epoxidation reaction unit and refined unit.The epoxidation reaction unit includes Bipolar Membrane
Electric dialyzator, alkaline chamber efflux settling tank, acid compartment outflow liquid storage tank and refined unit.The bipolar membrane electrodialysis device is that two Room are double
Pole membrane electrodialysis device, film unit contain alkaline chamber and acid compartment.Partition is arranged in the inside of the alkaline chamber efflux settling tank, will be described
The inner space of alkaline chamber efflux settling tank is divided into the first liquid phase region and second liquid phase area.The refined unit includes rectifying
Tower.
When system is run, in chlorohydrin action unit, chlorine gas and water and chloropropene enter in chlorohydrination reactor contact it is anti-
It answers, obtains chlorohydrin action mixture.Chlorohydrin action mixture subsequently enters in the extraction tower of extraction cells to be connect with extractant
Touching, obtains the extract liquor for being enriched dichlorohydrin, which subsequently enters flash column (being not shown in Fig. 3), isolates dichloro
Propyl alcohol and recycling extractant.At least partly recycling extractant, which is sent into extraction tower, is recycled.The dichlorohydrin isolated with
Water and additive enter second liquid phase area, to obtain the aqueous solution containing dichlorohydrin and additive.It is stored up to acid compartment efflux
Tank fills water.The acid compartment for opening alkaline chamber charging output port and acid compartment outflow liquid storage tank feeds output port, and accordingly opens
Aqueous solution containing dichlorohydrin and additive and water are pumped into the alkali of bipolar membrane electrodialysis device by the pump on pipeline respectively
In room and acid compartment, after establishing stable logistics circulation, starting bipolar membrane electrodialysis device carries out bipolar membrane electrodialysis, the alkaline chamber of generation
Efflux enters the first liquid phase region, and when the height of the material in the first liquid phase region is more than divider height, overflow enters second liquid phase
Area.The liquid phase for being retained in the first liquid phase region carries out sedimentation separation in the first liquid phase region, obtains organic rich in epoxychloropropane
Phase, the organic phase are exported by organic phase output port.During bipolar membrane electrodialysis, according to mode of operation, such as adopt
When with continuation mode, fresh dichlorohydrin can be supplemented to second liquid phase area by fresh dichlorohydrin input port.Bipolar Membrane
The acid compartment efflux containing HCl that electrodialysis generates recycles between acid compartment and acid compartment outflow liquid storage tank.In continuation mode, it is
It, can be according to system loss in system operational process, it is determined whether supplement additive when system loss is lower, can not supplement and add
Add agent, when system loss is higher, additive can be supplemented.
Entered by the organic phase rich in epoxychloropropane that the first liquid phase region exports and carries out essence in the rectifying column of refined unit
It evaporating, obtains the byproducts such as product propylene and glycerine, the unreacted dichlorohydrin isolated is sent into second liquid phase area,
It recycles.
According to the embodiment shown in Fig. 3, at runtime, it is preferably adjusted operation.
In embodiment shown in Fig. 3, bipolar membrane electrodialysis device is two Room bipolar membrane electrodialysis devices, those skilled in the art
It is understood that the two Room bipolar membrane electrodialysis device can be replaced as three Room bipolar membrane electrodialysis devices, such as institute above
The three Room bipolar membrane electrodialysis devices stated.
The range for being described in detail, but being not intended to limit the present invention with reference to embodiments.
In following embodiment and comparative example, the Bipolar Membrane used is the homogeneous Bipolar Membrane (model purchased from Hebei Guang Ya company
For BP-1), anion-exchange membrane is the anion-exchange membrane (model AHA) purchased from Japanese sub- stone company, cation exchange
Film is the cation-exchange membrane (model CMX) purchased from Japanese sub- stone company.
In following embodiment and comparative example, using the composition for the alkaline chamber efflux that gas chromatography analysis obtains, in this base
Dichlorohydrin conversion ratio and epoxychloropropane selectivity are calculated by following formula on plinth:
Dichlorohydrin conversion ratio (%)=[(mole of the unreacted dichlorohydrin of the mole-of the dichlorohydrin of addition
Amount)/be added dichlorohydrin mole] × 100%;
Epoxychloropropane selectivity (%)=[mole for the epoxychloropropane that reaction generates/(dichlorohydrin of addition
The mole of the unreacted dichlorohydrin of mole -)] × 100%.
In following embodiment, the defeated of liquid storage tank is flowed out with alkaline chamber in the output port of the alkaline chamber of connection bipolar membrane electrodialysis device
Online pH meter is set on the pipeline of inbound port, the pH value of alkaline chamber efflux is detected.
Embodiment 1-26 is for illustrating the present invention.
Embodiment 1
(1) chlorohydrin action step
Chloropropene and chlorine is anti-according to progress chlorohydrination is contacted in molar ratio 1:0.9 feeding chlorohydrination reactor with water
It answers, wherein reaction temperature is 80 DEG C, and the pressure in reactor is normal pressure (that is, 1 standard atmospheric pressure).Obtained reaction is mixed
Object carries out gas-liquid separation, and obtained liquid phase carries out extraction and separation as extractant using chloropropene, dichlorohydrin is enriched in extraction
It takes in liquid, extract liquor is flashed, obtain dichlorohydrin.
Obtained dichlorohydrin and sodium chloride are dispersed in water, obtain making containing the aqueous solution of dichlorohydrin and additive
For the raw material of epoxidation reaction step, in the aqueous solution, the concentration of dichlorohydrin is 20 weight %, and the content of sodium chloride is 10 weights
Measure %.
(2) epoxidation reaction step
The present embodiment is using production system (but the not set rectifying column, and in alkaline chamber efflux settling tank shown in Fig. 3
It is not provided with partition) it is carried out in a batch mode bipolar membrane electrodialysis, the bipolar membrane electrodialysis device used is two Room bipolar membrane electrodialysis
Device, film unit is as shown in Figure 1, the bipolar membrane electrodialysis device has 10 film units.
It is sent into alkaline chamber efflux settling tank using 2000g as raw material containing the aqueous solution of dichlorohydrin and additive,
2000g deionized water is sent into acid compartment outflow liquid storage tank, wherein the alkaline chamber efflux input port of alkaline chamber efflux settling tank
Be connected to the alkaline chamber efflux output port of bipolar membrane electrodialysis device, the alkaline chamber of alkaline chamber efflux settling tank charging output port with
The alkaline chamber feed input mouth of bipolar membrane electrodialysis device is connected to;Acid compartment flow out liquid storage tank acid compartment efflux input port with it is bipolar
The acid compartment efflux output port of membrane electrodialysis device is connected to, and acid compartment flows out the acid compartment charging output port and Bipolar Membrane electricity of liquid storage tank
The acid compartment feed input mouth of dialyzer is connected to.It will be as the aqueous sodium persulfate solution of pole liquid (content of sodium sulphate is 5 weight %)
It is sent into the flow container of pole.
The acid compartment of the alkaline chamber charging output port, acid compartment outflow liquid storage tank of opening alkaline chamber efflux settling tank feeds output end
The output port of mouth and pole flow container contains alkaline chamber from dichlorohydrin to bipolar membrane electrodialysis device, acid compartment and pole room feeding respectively
With the aqueous solution, water and pole liquid of additive, stable material input and output circulation is established.Open the electricity of bipolar membrane electrodialysis device
Source applies voltage to the film unit of bipolar membrane electrodialysis device, the voltage applied to each film unit is adjusted to 1.5V and is kept
Constant voltage operation, while being 35 DEG C by the control of the temperature of acid compartment and alkaline chamber.During bipolar membrane electrodialysis, the pH of alkaline chamber efflux
Value gradually rises, and when the pH value of alkaline chamber efflux reaches 8.5, stops bipolar membrane electrodialysis.
After the completion of bipolar membrane electrodialysis, water phase and organic phase to alkaline chamber efflux carry out gas chromatographic analysis, determine, two
The conversion ratio of chloropropyl alcohol is 99%, and the selectivity of epoxychloropropane is 82%.
Embodiment 2
Method same as Example 1 is used to carry out bipolar membrane electrodialysis to prepare epoxychloropropane, the difference is that, as
In the aqueous solution containing dichlorohydrin and additive of raw material, the content of sodium chloride is 20 weight %.Bipolar membrane electrodialysis is completed
Afterwards, the water phase to alkaline chamber efflux and organic phase carry out gas chromatographic analysis, are computed determination, the conversion ratio of dichlorohydrin is
99%, the selectivity of epoxychloropropane is 85%.
Embodiment 3
Method same as Example 1 is used to carry out bipolar membrane electrodialysis to prepare epoxychloropropane, the difference is that: as
In the aqueous solution containing dichlorohydrin and additive of raw material, the concentration of sodium chloride is 25 weight %.Bipolar membrane electrodialysis is completed
Afterwards, the water phase to alkaline chamber efflux and organic phase carry out gas chromatographic analysis, are computed determination, the conversion ratio of dichlorohydrin is
99%, the selectivity of epoxychloropropane is 87%.
Embodiment 4
Method same as Example 1 is used to carry out bipolar membrane electrodialysis to prepare epoxychloropropane, the difference is that, as
In the aqueous solution containing dichlorohydrin and additive of raw material, the concentration of sodium chloride is 5 weight %.Bipolar membrane electrodialysis is completed
Afterwards, the water phase to alkaline chamber efflux and organic phase carry out gas chromatographic analysis, are computed determination, the conversion ratio of dichlorohydrin is
99%, the selectivity of epoxychloropropane is 77%.
Embodiment 5
Method same as Example 1 is used to carry out bipolar membrane electrodialysis to prepare epoxychloropropane, the difference is that, as
In the aqueous solution containing dichlorohydrin and additive of raw material, the concentration of sodium chloride is 3 weight %.Bipolar membrane electrodialysis is completed
Afterwards, the water phase to alkaline chamber efflux and organic phase carry out gas chromatographic analysis, are computed determination, the conversion ratio of dichlorohydrin is
99%, the selectivity of epoxychloropropane is 69%.
Embodiment 6
Method same as Example 1 is used to carry out bipolar membrane electrodialysis to prepare epoxychloropropane, the difference is that, as
In the aqueous solution containing dichlorohydrin and additive of raw material, the concentration of sodium chloride is 0.5 weight %.Bipolar membrane electrodialysis is completed
Afterwards, the water phase to alkaline chamber efflux and organic phase carry out gas chromatographic analysis, are computed determination, the conversion ratio of dichlorohydrin is
99%, the selectivity of epoxychloropropane is 64%.
Embodiment 7
(1) chlorohydrin action step
Chloropropene and chlorine is anti-according to progress chlorohydrination is contacted in molar ratio 1:0.95 feeding chlorohydrination reactor with water
It answers, wherein reaction temperature is 60 DEG C, and the pressure in reactor is normal pressure (that is, 1 standard atmospheric pressure).Obtained reaction is mixed
Object carries out gas-liquid separation, and obtained liquid phase carries out extraction and separation as extractant using chloropropene, dichlorohydrin is enriched in extraction
It takes in liquid, extract liquor is flashed, obtain dichlorohydrin.
Obtained dichlorohydrin and ammonium chloride are dispersed in water, obtain making containing the aqueous solution of dichlorohydrin and additive
For the raw material of epoxidation reaction step, in the aqueous solution, the concentration of dichlorohydrin is 10 weight %, and the content of ammonium chloride is 18 weights
Measure %.
(2) epoxidation reaction step
The present embodiment uses production system same as Example 1 and bipolar membrane electrodialysis device, but uses continuation mode
Bipolar membrane electrodialysis is carried out, and partition is set in alkaline chamber efflux settling tank, alkaline chamber efflux settling tank is divided into first
Liquid phase region and second liquid phase area.
(2-1) is sent into the sedimentation of alkaline chamber efflux containing the aqueous solution of dichlorohydrin and additive using 2000g as raw material
In tank, 2000g deionized water is sent into acid compartment outflow liquid storage tank, wherein the alkaline chamber efflux of alkaline chamber efflux settling tank is defeated
Inbound port is connected to the alkaline chamber efflux output port of bipolar membrane electrodialysis device, and the alkaline chamber of alkaline chamber efflux settling tank feeds output
Port is connected to the alkaline chamber feed input mouth of bipolar membrane electrodialysis device;The acid compartment efflux input port of acid compartment outflow liquid storage tank
It is connected to the acid compartment efflux output port of bipolar membrane electrodialysis device, acid compartment flows out the acid compartment charging output port of liquid storage tank and double
The acid compartment feed input mouth of pole membrane electrodialysis device is connected to.By as the aqueous sodium persulfate solution of pole liquid, (content of sodium sulphate is 8 weights
Measure %) it is sent into the flow container of pole.
The acid compartment of the alkaline chamber charging output port, acid compartment outflow liquid storage tank of opening alkaline chamber efflux settling tank feeds output end
The output port of mouth and pole flow container contains alkaline chamber from dichlorohydrin to bipolar membrane electrodialysis device, acid compartment and pole room feeding respectively
With the aqueous solution, water and pole liquid of additive, stable material input and output circulation is established.Open the electricity of bipolar membrane electrodialysis device
Source applies voltage to the film unit of bipolar membrane electrodialysis device, the voltage applied to each film unit is adjusted to 1.5V and is kept
Constant voltage operation, while being 30 DEG C by the control of the temperature of acid compartment and alkaline chamber.
The alkaline chamber efflux of (2-2) bipolar membrane electrodialysis device output enters the first liquid phase region, the material in the first liquid phase region
Height be more than divider height when, overflow enters second liquid phase area, and the material in second liquid phase area is together with fresh dichlorohydrin
It is recycled into the alkaline chamber of bipolar membrane electrodialysis device and carries out bipolar membrane electrodialysis.The liquid phase of the first liquid phase region is retained in the first liquid
Carry out sedimentation separation in phase region, obtain the organic phase rich in epoxychloropropane, organic phase in alkaline chamber efflux settling tank first
After organic phase accumulation is a certain amount of, organic phase is released from the first liquid phase region of alkaline chamber efflux settling tank for the lower layer of liquid phase region.
24 hours bipolar membrane electrodialysis are carried out altogether, during bipolar membrane electrodialysis, by adjusting fresh dichlorohydrin
Additional amount, control alkaline chamber efflux pH value be 8.5.Gas chromatographic analysis is carried out to alkaline chamber efflux, is determined, dichlorohydrin
Conversion ratio be 97%, the selectivity of epoxychloropropane is 83%.
Embodiment 8
Method same as Example 7 is used to carry out bipolar membrane electrodialysis to prepare epoxychloropropane, the difference is that, double
During the membrane electrodialysis of pole, by adjusting the additional amount of fresh dichlorohydrin, the pH value of control alkaline chamber efflux is 10.0.It is double
After the completion of the membrane electrodialysis of pole, gas chromatographic analysis is carried out to alkaline chamber efflux, is determined, the conversion ratio of dichlorohydrin is 99%, ring
The selectivity of oxygen chloropropane is 73%.
Embodiment 9
Method same as Example 7 is used to carry out bipolar membrane electrodialysis to prepare epoxychloropropane, the difference is that, double
During the membrane electrodialysis of pole, by adjusting the additional amount of fresh dichlorohydrin, the pH value of control alkaline chamber efflux is 5.7.It is double
After the completion of the membrane electrodialysis of pole, gas chromatographic analysis is carried out to alkaline chamber efflux, is determined, the conversion ratio of dichlorohydrin is 80%, ring
The selectivity of oxygen chloropropane is 96%.
Embodiment 10
Method same as Example 7 is used to carry out bipolar membrane electrodialysis to prepare epoxychloropropane, the difference is that, double
During the membrane electrodialysis of pole, by adjusting the additional amount of fresh dichlorohydrin, the pH value of control alkaline chamber efflux is 7.2.It is double
After the completion of the membrane electrodialysis of pole, gas chromatographic analysis is carried out to alkaline chamber efflux, is determined, the conversion ratio of dichlorohydrin is 93%, ring
The selectivity of oxygen chloropropane is 89%.
Embodiment 11
Method same as in Example 10 is used to carry out bipolar membrane electrodialysis to prepare epoxychloropropane, the difference is that, make
For in the aqueous solution containing dichlorohydrin and additive of raw material, the content of ammonium chloride is 11 weight %.Bipolar membrane electrodialysis is complete
Cheng Hou carries out gas chromatographic analysis to alkaline chamber efflux, determines, the conversion ratio of dichlorohydrin is 91%, the choosing of epoxychloropropane
Selecting property is 87%.
Embodiment 12
Method same as in Example 10 is used to carry out bipolar membrane electrodialysis to prepare epoxychloropropane, the difference is that, make
For in the aqueous solution containing dichlorohydrin and additive of raw material, the content of ammonium chloride is 3.5 weight %.Bipolar membrane electrodialysis is complete
Cheng Hou carries out gas chromatographic analysis to alkaline chamber efflux, determines, the conversion ratio of dichlorohydrin is 88%, the choosing of epoxychloropropane
Selecting property is 73%.
Comparative example 1
Method same as in Example 10 is used to carry out bipolar membrane electrodialysis to prepare epoxychloropropane, the difference is that, make
For the not containing ammonium chloride of the aqueous solution containing dichlorohydrin and additive of raw material.After the completion of bipolar membrane electrodialysis, alkaline chamber is flowed out
Liquid carries out gas chromatographic analysis, determines, the conversion ratio of dichlorohydrin is 8.9%, and the selectivity of epoxychloropropane is 65%.
Embodiment 13
(1) chlorohydrin action step
Dichlorohydrin is prepared using method same as Example 7, unlike, as epoxidation reaction step raw material
In aqueous solution containing dichlorohydrin and additive, the content of dichlorohydrin is 10 weight %, and the content of ammonium chloride is 12 weights
Measure %.
(2) epoxidation reaction step
The present embodiment using shown in Fig. 3 production system (but and not set rectifying column, and alkaline chamber efflux settling tank
In be not provided with partition) be carried out in a batch mode bipolar membrane electrodialysis, the bipolar membrane electrodialysis device used is three Room Bipolar Membrane electric osmose
Parser, film unit is as shown in Fig. 2, the bipolar membrane electrodialysis device has 10 film units.
Be sent into 2000g as solution of the raw material containing dichlorohydrin in alkaline chamber efflux settling tank, by 2000g go from
Sub- water is sent into acid compartment outflow liquid storage tank, wherein, alkaline chamber efflux input port and the Bipolar Membrane electricity of alkaline chamber efflux settling tank
The alkaline chamber efflux output port of dialyzer is connected to, the alkaline chamber charging output port and Bipolar Membrane electric osmose of alkaline chamber efflux settling tank
The salt room feed input mouth of parser is connected to, and salt room efflux output port is connected to alkaline chamber feed input mouth;Acid compartment outflow
The acid compartment efflux input port of liquid storage tank is connected to the acid compartment efflux output port of bipolar membrane electrodialysis device, acid compartment efflux
The acid compartment charging output port of storage tank is connected to the acid compartment feed input mouth of bipolar membrane electrodialysis device.By the sulfuric acid as pole liquid
Sodium water solution (content of sodium sulphate is 5 weight %) is sent into the flow container of pole.
The acid compartment of the alkaline chamber charging output port, acid compartment outflow liquid storage tank of opening alkaline chamber efflux settling tank feeds output end
The output port of mouth and pole flow container contains dichlorohydrin to the salt room of bipolar membrane electrodialysis device, acid compartment and pole room feeding respectively
With the aqueous solution, water and pole liquid (wherein, salt room efflux is fed as alkaline chamber) of additive, it is defeated to establish stable material input
It recycles out.The power supply for opening bipolar membrane electrodialysis device applies voltage to the film unit of bipolar membrane electrodialysis device, will give each film list
The voltage that member applies is adjusted to 1.5V and keeps constant voltage operation, while being 40 DEG C by the temperature control in film unit.In Bipolar Membrane
In electrodialytic process, the pH value of alkaline chamber efflux is gradually risen, and when the pH value of alkaline chamber efflux reaches 8.5, stops Bipolar Membrane
Electrodialysis.
After the completion of bipolar membrane electrodialysis, water phase and organic phase to alkaline chamber efflux carry out gas chromatographic analysis, are computed
It determines, the conversion ratio of dichlorohydrin is 99%, and the selectivity of epoxychloropropane is 84%.
Embodiment 14
Method identical with embodiment 13 is used to carry out bipolar membrane electrodialysis to prepare epoxychloropropane, the difference is that, make
For in the aqueous solution containing dichlorohydrin and additive of raw material, the concentration of ammonium chloride is 18 weight %.Bipolar membrane electrodialysis is complete
Cheng Hou, water phase and organic phase to alkaline chamber efflux carry out gas chromatographic analysis, determine, the conversion ratio of dichlorohydrin is 99%,
The selectivity of epoxychloropropane is 87%.
Embodiment 15
Method identical with embodiment 13 is used to carry out bipolar membrane electrodialysis to prepare epoxychloropropane, the difference is that, make
For in the aqueous solution containing dichlorohydrin and additive of raw material, the concentration of ammonium chloride is 24 weight %.Bipolar membrane electrodialysis is complete
Cheng Hou, water phase and organic phase to alkaline chamber efflux carry out gas chromatographic analysis, are computed determination, the conversion ratio of dichlorohydrin is
99%, the selectivity of epoxychloropropane is 90%.
Embodiment 16
Method identical with embodiment 13 is used to carry out bipolar membrane electrodialysis to prepare epoxychloropropane, the difference is that, make
For in the aqueous solution containing dichlorohydrin and additive of raw material, the concentration of ammonium chloride is 6 weight %.Bipolar membrane electrodialysis is completed
Afterwards, the water phase to alkaline chamber efflux and organic phase carry out gas chromatographic analysis, are computed determination, the conversion ratio of dichlorohydrin is
99%, the selectivity of epoxychloropropane is 80%.
Embodiment 17
Method identical with embodiment 13 is used to carry out bipolar membrane electrodialysis to prepare epoxychloropropane, the difference is that, make
For in the aqueous solution containing dichlorohydrin and additive of raw material, the concentration of ammonium chloride is 2.5 weight %.Bipolar membrane electrodialysis is complete
Cheng Hou, water phase and organic phase to alkaline chamber efflux carry out gas chromatographic analysis, are computed determination, the conversion ratio of dichlorohydrin is
99%, the selectivity of epoxychloropropane is 70%.
Embodiment 18
Method identical with embodiment 13 is used to carry out bipolar membrane electrodialysis to prepare epoxychloropropane, the difference is that, make
For in the aqueous solution containing dichlorohydrin and additive of raw material, the concentration of ammonium chloride is 0.1 weight %.Bipolar membrane electrodialysis is complete
Cheng Hou, water phase and organic phase to alkaline chamber efflux carry out gas chromatographic analysis, are computed determination, the conversion ratio of dichlorohydrin is
99%, the selectivity of epoxychloropropane is 68%.
Embodiment 19
(1) chlorohydrin action step
Dichlorohydrin is prepared using method same as Example 7, unlike, as epoxidation reaction step raw material
Aqueous solution containing dichlorohydrin is the aqueous solution containing dichlorohydrin and potassium chloride, wherein the content of dichlorohydrin is 15 weights
% is measured, the content of potassium chloride is 10 weight %.
(2) epoxidation reaction step
The present embodiment uses production system identical with embodiment 13 and bipolar membrane electrodialysis device, but uses continuation mode
Bipolar membrane electrodialysis is carried out, and partition is set in alkaline chamber efflux settling tank, alkaline chamber efflux settling tank is divided into first
Liquid phase region and second liquid phase area.
(2-1) is sent into the sedimentation of alkaline chamber efflux containing the aqueous solution of dichlorohydrin and additive using 2000g as raw material
In tank, 2000g deionized water is sent into acid compartment outflow liquid storage tank, wherein the alkaline chamber efflux of alkaline chamber efflux settling tank is defeated
Inbound port is connected to the alkaline chamber efflux output port of bipolar membrane electrodialysis device, and the alkaline chamber of alkaline chamber efflux settling tank feeds output
Port is connected to the salt room feed input mouth of bipolar membrane electrodialysis device, salt room efflux output port and alkaline chamber feed input
Mouth connection;Acid compartment flows out the acid compartment efflux input port of liquid storage tank and the acid compartment efflux output port of bipolar membrane electrodialysis device
The acid compartment charging output port of connection, acid compartment outflow liquid storage tank is connected to the acid compartment feed input mouth of bipolar membrane electrodialysis device.
It will be sent into the flow container of pole as the aqueous sodium persulfate solution of pole liquid (content of sodium sulphate is 7 weight %).
The acid compartment of the alkaline chamber charging output port, acid compartment outflow liquid storage tank of opening alkaline chamber efflux settling tank feeds output end
The output port of mouth and pole flow container contains dichlorohydrin to the salt room of bipolar membrane electrodialysis device, acid compartment and pole room feeding respectively
With the aqueous solution, water and pole liquid (wherein, salt room efflux is fed as alkaline chamber) of additive, it is defeated to establish stable material input
It recycles out.The power supply for opening bipolar membrane electrodialysis device applies voltage to the film unit of bipolar membrane electrodialysis device, will give each film list
The voltage that member applies is adjusted to 1.4V and keeps constant voltage operation, while being 35 DEG C by the temperature control in film unit.
The alkaline chamber efflux of (2-2) bipolar membrane electrodialysis device output enters the first liquid phase region, the material in the first liquid phase region
Height be more than divider height when, overflow enters second liquid phase area, and the material in second liquid phase area is together with fresh dichlorohydrin
It is recycled into the alkaline chamber of bipolar membrane electrodialysis device and carries out bipolar membrane electrodialysis.The liquid phase of the first liquid phase region is retained in the first liquid
Carry out sedimentation separation in phase region, obtain the organic phase rich in epoxychloropropane, organic phase in alkaline chamber efflux settling tank first
After organic phase accumulation is a certain amount of, organic phase is released from the first liquid phase region of alkaline chamber efflux settling tank for the lower layer of liquid phase region.
36 hours bipolar membrane electrodialysis are carried out altogether, during bipolar membrane electrodialysis, by adjusting fresh dichlorohydrin
Additional amount, control alkaline chamber efflux pH value be 8.0.Gas chromatographic analysis is carried out to alkaline chamber efflux, is determined, dichlorohydrin
Conversion ratio be 87%, the selectivity of epoxychloropropane is 85%.
Embodiment 20
Method identical with embodiment 19 is used to carry out bipolar membrane electrodialysis to prepare epoxychloropropane, the difference is that, it is double
During the membrane electrodialysis of pole, by adjusting the additional amount of fresh dichlorohydrin, the pH value of control alkaline chamber efflux is 7.4.It is right
Alkaline chamber efflux carries out gas chromatographic analysis, is computed determination, and the conversion ratio of dichlorohydrin is 84%, the selection of epoxychloropropane
Property is 90%.
Embodiment 21
Method identical with embodiment 19 is used to carry out bipolar membrane electrodialysis to prepare epoxychloropropane, the difference is that, it is double
During the membrane electrodialysis of pole, by adjusting the additional amount of fresh dichlorohydrin, the pH value of control alkaline chamber efflux is 5.7.It is right
Alkaline chamber efflux carries out gas chromatographic analysis, is computed determination, and the conversion ratio of dichlorohydrin is 75%, the selection of epoxychloropropane
Property is 95%.
Embodiment 22
Method identical with embodiment 20 is used to carry out bipolar membrane electrodialysis to prepare epoxychloropropane, the difference is that, make
For in the aqueous solution containing dichlorohydrin and additive of raw material, the content of potassium chloride is 16 weight %.To alkaline chamber efflux into
Promoting the circulation of qi analysis of hplc is computed determination, and the conversion ratio of dichlorohydrin is 86%, and the selectivity of epoxychloropropane is 91%.
Embodiment 23
Method identical with embodiment 20 is used to carry out bipolar membrane electrodialysis to prepare epoxychloropropane, the difference is that, make
For in the aqueous solution containing dichlorohydrin and additive of raw material, the content of potassium chloride is 22 weight %.To alkaline chamber efflux into
Promoting the circulation of qi analysis of hplc is computed determination, and the conversion ratio of dichlorohydrin is 89%, and the selectivity of epoxychloropropane is 93%.
Embodiment 24
Method identical with embodiment 20 is used to carry out bipolar membrane electrodialysis to prepare epoxychloropropane, the difference is that, make
For in the aqueous solution containing dichlorohydrin and additive of raw material, the content of potassium chloride is 6 weight %.Alkaline chamber efflux is carried out
Gas chromatographic analysis is computed determination, and the conversion ratio of dichlorohydrin is 82%, and the selectivity of epoxychloropropane is 84%.
Embodiment 25
Method identical with embodiment 20 is used to carry out bipolar membrane electrodialysis to prepare epoxychloropropane, the difference is that, make
For in the aqueous solution containing dichlorohydrin and additive of raw material, the content of potassium chloride is 3 weight %.Alkaline chamber efflux is carried out
Gas chromatographic analysis is computed determination, and the conversion ratio of dichlorohydrin is 80%, and the selectivity of epoxychloropropane is 74%.
Embodiment 26
Method identical with embodiment 20 is used to carry out bipolar membrane electrodialysis to prepare epoxychloropropane, the difference is that, make
For in the aqueous solution containing dichlorohydrin and additive of raw material, the content of potassium chloride is 0.05 weight %.To alkaline chamber efflux
Gas chromatographic analysis is carried out, determination is computed, the conversion ratio of dichlorohydrin is 78%, and the selectivity of epoxychloropropane is 72%.
Comparative example 2
Method identical with embodiment 20 is used to carry out bipolar membrane electrodialysis to prepare epoxychloropropane, the difference is that, make
Potassium chloride is free of for the aqueous solution containing dichlorohydrin and additive of raw material.Gas chromatographic analysis is carried out to alkaline chamber efflux,
It is computed determination, the conversion ratio of dichlorohydrin is 9.1%, and the selectivity of epoxychloropropane is 69%.
Embodiment 1-26's as a result, it was confirmed that using method of the invention, send dichlorohydrin into bipolar membrane electrodialysis device
Bipolar membrane electrodialysis is carried out in alkaline chamber, dichlorohydrin can not only be transformed into epoxychloropropane, and can obtain higher original
Expect conversion ratio and selectivity of product.Meanwhile according to the method for the present invention, solid slag is not generated, do not generate or is not generated substantially
Waste liquid, it is environmentally protective.In addition, method of the invention steams product without in epoxidization reaction process, operation is succinct.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (14)
1. a kind of method for producing epoxychloropropane, this method comprises:
(1) under the conditions of chlorohydrin action, chloropropene is contacted with water and chlorine, obtains the chlorohydrin action containing dichlorohydrin
Mixture
(2) the chlorohydrin action mixture is subjected to gas-liquid separation, gaseous stream and liquid phase stream is obtained, by the liquid phase object
Stream is contacted with extractant, is obtained the extract liquor rich in dichlorohydrin, is isolated two from the extract liquor rich in dichlorohydrin
Chloropropyl alcohol;
(3) dichlorohydrin is sent into the alkaline chamber of bipolar membrane electrodialysis device, is carried out in the presence of at least one additive bipolar
Membrane electrodialysis, obtains the alkaline chamber efflux containing epoxychloropropane, and the additive is selected from water-soluble alkali metal salts and water-soluble
One or more of property ammonium salt.
2. production method according to claim 1, wherein isolate dichloro from the extract liquor rich in dichlorohydrin
The method of propyl alcohol includes: to distill the extract liquor, obtains recycling chloropropene and dichlorohydrin, will at least partly recycle chlorine
Propylene circulation is used as extractant.
3. production method according to claim 1 or 2, wherein the extractant is chloropropene.
4. production method according to claim 1, wherein at least partly gaseous stream circulation is used for chlorohydrin action.
5. production method according to claim 1, wherein with the total of the water of additive, dichlorohydrin and entrance alkaline chamber
On the basis of amount, the content of the additive is weight percentage when 0.01 weight % is saturated in water to the additive;
Preferably, by additive, dichlorohydrin and on the basis of entering the total amount of water of alkaline chamber, the content of the additive is
0.02-40 weight %, preferably 0.05-35 weight %, more preferably 5.5-30 weight %, further preferably 8-26 weight
Measure %.
6. according to claim 1, production method described in any one of 4 and 5, wherein the additive is selected from alkali metal
Chloride, the sulfate of alkali metal, the nitrate of alkali metal, the carboxylate of alkali metal, the phosphate of alkali metal, ammonium chloride,
One or more of ammonium sulfate, ammonium nitrate, carboxylic acid ammonium, ammonium phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate;
Preferably, the additive is selected from one or more of sodium chloride, ammonium chloride and potassium chloride.
7. according to claim 1 with the production method described in any one of 4-6, wherein this method further includes in Bipolar Membrane electricity
The adjustment operation carried out during dialysis, the adjustment operation is so that the pH value of alkaline chamber efflux is 6-10;
Preferably, the adjustment operation includes adjusting the content for the dichlorohydrin for entering alkaline chamber;
It is highly preferred that the adjustment operation is so that the pH value of alkaline chamber efflux is 8-10;
It is highly preferred that the adjustment operation is so that the pH value of alkaline chamber efflux is 6 to 8, preferably 6.5-7.9 is lower than, more preferably
For 7-7.8.
8. according to claim 1 with the production method described in any one of 4-7, wherein during bipolar membrane electrodialysis, to every
The voltage that a film unit applies is 0.5-2.5V.
9. according to claim 1 with the production method described in any one of 4-8, wherein the bipolar membrane electrodialysis is in 5-45
It is carried out at a temperature of DEG C.
10. according to claim 1 with the production method described in any one of 4-9, wherein the bipolar membrane electrodialysis device includes
Anode, at least one film unit of cathode and setting between the anode and the cathode, the film unit contain alkaline chamber
And acid compartment;Or
The bipolar membrane electrodialysis device includes anode, at least one of cathode and setting between the anode and the cathode
Film unit, the film unit contain acid compartment, alkaline chamber and salt room, and the output port of the salt room and the input port of the alkaline chamber connect
Logical, the aqueous solution containing dichlorohydrin and additive enters alkaline chamber by salt room.
11. production method described in any one of -10 according to claim 1, wherein described to contain dichlorohydrin and additive
Aqueous solution in, the content of dichlorohydrin is 1-80 weight %, preferably 5-50 weight %.
12. production method described in any one of -11 according to claim 1, wherein the dichlorohydrin is that 1,3- bis- is chloro-
Bis- trimethylewne chlorohydrin 3- of 2- propyl alcohol and/or 2,3-.
13. production method described in any one of -12 according to claim 1, wherein this method further includes from the alkaline chamber stream
It isolates the organic phase rich in epoxychloropropane in liquid out, and the remaining liquid phase of the organic phase and optional will have been isolated
Fresh dichlorohydrin is sent into the alkaline chamber of bipolar membrane electrodialysis device;
Preferably, the organic phase is isolated from the alkaline chamber efflux by sedimentation separation;
It is highly preferred that the sedimentation separation is the combination of one or both of settle and separate, centrifuge separation.
14. production method described in any one of -13 according to claim 1, wherein this method further includes by described rich in ring
The organic phase of oxygen chloropropane is refined, and epoxychloropropane product is obtained.
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