CN109721570A - A method of producing epoxychloropropane - Google Patents

A method of producing epoxychloropropane Download PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
dichlorohydrin
alkaline chamber
bipolar membrane
membrane electrodialysis
epoxychloropropane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201711034532.7A
Other languages
Chinese (zh)
Other versions
CN109721570B (en
Inventor
刘中清
罗一斌
周丽娜
舒兴田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Original Assignee
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to CN201711034532.7A priority Critical patent/CN109721570B/en
Publication of CN109721570A publication Critical patent/CN109721570A/en
Application granted granted Critical
Publication of CN109721570B publication Critical patent/CN109721570B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Epoxy Compounds (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

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

A method of producing epoxychloropropane
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.
CN201711034532.7A 2017-10-30 2017-10-30 Method for producing epoxy chloropropane Active CN109721570B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711034532.7A CN109721570B (en) 2017-10-30 2017-10-30 Method for producing epoxy chloropropane

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711034532.7A CN109721570B (en) 2017-10-30 2017-10-30 Method for producing epoxy chloropropane

Publications (2)

Publication Number Publication Date
CN109721570A true CN109721570A (en) 2019-05-07
CN109721570B CN109721570B (en) 2022-07-15

Family

ID=66291326

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711034532.7A Active CN109721570B (en) 2017-10-30 2017-10-30 Method for producing epoxy chloropropane

Country Status (1)

Country Link
CN (1) CN109721570B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112957770A (en) * 2021-03-11 2021-06-15 江苏扬农化工集团有限公司 Continuous extraction device and continuous extraction method for epichlorohydrin
CN113230980A (en) * 2021-04-07 2021-08-10 江苏瑞恒新材料科技有限公司 Continuous production device and production method of epichlorohydrin

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102971450A (en) * 2010-06-18 2013-03-13 花王株式会社 Method for producing alkylglycidyl ether
CN106518624A (en) * 2016-03-14 2017-03-22 江西苏克尔新材料有限公司 Method for preparing halogenohydrin and epoxide
CN106883199A (en) * 2017-04-20 2017-06-23 汇智工程科技股份有限公司 A kind of cleaning procedure of the preparing epoxy chloropropane by using glycerol method of zero-emission

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102971450A (en) * 2010-06-18 2013-03-13 花王株式会社 Method for producing alkylglycidyl ether
CN106518624A (en) * 2016-03-14 2017-03-22 江西苏克尔新材料有限公司 Method for preparing halogenohydrin and epoxide
CN106883199A (en) * 2017-04-20 2017-06-23 汇智工程科技股份有限公司 A kind of cleaning procedure of the preparing epoxy chloropropane by using glycerol method of zero-emission

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
董恒 等: "双极膜电渗析技术的研究进展", 《化工进展》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112957770A (en) * 2021-03-11 2021-06-15 江苏扬农化工集团有限公司 Continuous extraction device and continuous extraction method for epichlorohydrin
CN112957770B (en) * 2021-03-11 2023-02-21 江苏扬农化工集团有限公司 Continuous extraction device and continuous extraction method for epichlorohydrin
CN113230980A (en) * 2021-04-07 2021-08-10 江苏瑞恒新材料科技有限公司 Continuous production device and production method of epichlorohydrin

Also Published As

Publication number Publication date
CN109721570B (en) 2022-07-15

Similar Documents

Publication Publication Date Title
CN109721573A (en) A kind of epoxychloropropane synthetic method
CN104650008B (en) A kind of technique and system being prepared expoxy propane by oxygen, hydrogen direct oxidation propylene
CN106957283B (en) A kind of mono-acid method alcoholizing propenyl chloride Synthesis of Propylene Oxide
CN109721570A (en) A method of producing epoxychloropropane
CN103012386A (en) Preparation method of five-membered cyclic sulphate
CN109721572A (en) A kind of epoxychloropropane preparation method
CN101979365B (en) Method for continuously preparing dichlorohydrin
CN101357880B (en) Technique and system for preparing dichloropropanol by autocatalysis reaction of glycerine and hydrogen chloride
CN109721571A (en) Epoxy chloropropane production method and epoxychloropropane production system
CN103025692A (en) Method for preparing chlorohydrins composition and method for preparing epichlorohydrin using chlorohydrins composition prepared thereby
CN109721569A (en) A kind of preparation method of epoxychloropropane
CN109721574A (en) Epoxy chloropropane production method and epoxychloropropane production system
EP2589586B1 (en) Method for preparing chlorohydrins composition and method for preparing epichlorohydrin using chlorohydrins composition prepared thereby
US10807927B2 (en) Methods and systems to form propylene chlorohydrin from dichloropropane using lewis acid
CN110304995B (en) Extraction process of isopropyl ether generated in process of preparing isopropanol by acetone method
CN101676261A (en) Adiponitrile production technology
CN100503588C (en) Ring-opening reaction new method of process for reclaiming epoxy cyclohexane from light oil
CN101455908A (en) High pure hexafluoropropylene oxide preparation method using extraction rectification
JP6004962B2 (en) Method for producing epoxy compound
CN101182283B (en) Method for preparing dichloropropanol by glycerol
US10100026B2 (en) Process for treating homoserine-based compound
EP4193004B1 (en) Method for preparing 3-hydroxy-3-methylbutyric acid (hmb) or salts thereof
CN210595865U (en) Epichlorohydrin's separator
CN201272752Y (en) Apparatus for producing dichlorohydrin by glycerol hydrochlorination
EP3938313A1 (en) Processes useful in the manufacture of cyclododecasulfur

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant