CN101792424B - Environment-friendly preparation process for producing epoxy chloropropane by complexation and extraction - Google Patents
Environment-friendly preparation process for producing epoxy chloropropane by complexation and extraction Download PDFInfo
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- CN101792424B CN101792424B CN2010101388618A CN201010138861A CN101792424B CN 101792424 B CN101792424 B CN 101792424B CN 2010101388618 A CN2010101388618 A CN 2010101388618A CN 201010138861 A CN201010138861 A CN 201010138861A CN 101792424 B CN101792424 B CN 101792424B
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Abstract
The invention discloses an environment-friendly preparation process for producing epoxy chloropropane by complexation and extraction. The process comprises the following steps: adding complexation extractant into dichloropropanol solution so as to extract HCL and dichloropropanol from the solution in one time; returning the extracted reacting liquid to a chlorohydrination system, and adding lime milk or liquid caustic soda and sodium carbonate into the complexation extraction liquid containing the HCL and the dichloropropanol for saponification so as to produce the epoxy chloropropane, wherein the content of the calcium chloride in raffinate in the bottom of a saponificationcolumn is about 30-40% (such as producing sodium chloride by utilizing the liquid caustic soda by saponification); and carrying out multiple-effect evaporation and concentration on the treated mother liquor to producing the calcium chloride, wherein the concentrated water is used for preparing the lime milk. The invention has the advantages that no process waster water is exhausted during the whole production, the process is simple, continuous operations can be easily realized and improvements can be made on the original production device.
Description
Technical field
The present invention relates to a kind of preparation method of oxygen chloropropane, belong to field of fine chemical.
Background technology
Epoxy chloropropane is a kind of important Organic Chemicals and fine chemical product.Can produce multiple products such as epoxy resin, chlorohydrin rubber, nitroglycerine explosive, glass reinforced plastic, electrical isolation article, tensio-active agent, medicine, agricultural chemicals, sizing material, ion exchange resin, softening agent.The solvent that can also be used for cellulose ester, resin, ether of cellulose.Be used for chemical stabilizer, chemical dyestuff and water conditioner etc.
At present, the production technique of epoxy chloropropane mainly contains following several kinds:
1. propylene high-temperature chlorination:
CH
2＝CHCH
3+Cl
2→CH
2＝CHCH
2Cl
H
2O+Cl
2→HOCl+HCl
2. allyl acetate method:
3. glycerine method:
4. propenyl chloride direct oxidation method:
At present, epichlorohydrin production process mainly contains two in the world: propylene high-temperature chlorination and allyl acetate method.
The propylene high-temperature chlorination has reached production equipment maximization, production technique serialization, operation automation, this technical maturity, and stable operation, the epoxy chloropropane more than 90% adopts this method production in the world.
Allyl acetate method reaction conditions is gentle, is easy to control, has avoided high-temperature chlorination, noncoking, and stable operation, chlorine and slaked lime consumption reduce half the than the propylene high-temperature chlorination.Shortcoming is that technical process is long, and catalyst life is short, and the facility investment expense is higher relatively, only has a few producer to adopt this method to produce.
Though having, other working methods such as glycerine method, propenyl chloride hydrogen peroxide catalytic oxidation method produce or report.Because of resource or technical reason, not by wide-scale adoption aborning.
The propylene high-temperature chlorination is bigger because of wastewater flow rate, more and more receives the restriction of environment.The producer that has adopts reverse osmosis membrane filtration, and saponification waste-water is concentrated half, concentrates waste water through multiple-effect evaporation again, and the water jacket that steams is used in the system and gone.This method film loss is bigger, and steam consumption is higher.
Number of patent application: 200810159078.2 Chinese patent discloses a kind of preparation method of epoxy chloropropane; This invention has overcome big this shortcoming of traditional propylene high-temperature chlorination Process wastewater flow rate; Adopt the way of extraction, extract dichlorohydrine in the chlorohydrination liquid, extract the HCL in the reaction solution in way through complexometric extraction; Reaction solution overlaps after treatment to use in the reactive system and goes, and whole process does not have spent process water and effluxes.This technology shortcoming is to use the low-carbon ester class, should consume certain low-carbon ester in the production process, and again because of reclaim increasing energy consumption, and low-carbon ester is because of the inflammable and explosive potential safety hazard that exists, and production cost increases.
Summary of the invention
Not enough to existing technology; The environment-friendly preparation process that the purpose of this invention is to provide a kind of producing epoxy chloropropane by complexation and extraction; The efficient complexing extractant of this kind process using is disposable to extract HCL and dichlorohydrine, and the chlorohydrination liquid after the extraction turns back to chlorohydrination workshop section, and complexometric extraction liquid is directly produced epoxy chloropropane with the milk of lime saponification; Technology is simple, and the more former propylene high-temperature chlorination of cost reduces.
The technical scheme that the present invention takes is:
A kind of environment-friendly preparation process of producing epoxy chloropropane by complexation and extraction comprises the steps:
(1) in dichlorohydrine solution, adds the complexing extractant multi-stage solvent extraction, with HCL with dichlorohydrine is disposable extracts;
(2) complexometric extraction goes out behind HCL and the dichlorohydrine rest solution and after activated carbon treatment, turns back to the propylene chlorohydrin system and apply mechanically;
(3) the complexometric extraction liquid that contains HCL and dichlorohydrine is with milk of lime or alkali lye, soda ash saponification; Generate the epoxy chloropropane bullion and get epoxy chloropropane through rectifying; Tell organic phase the liquid effluent at the bottom of the saponification column; Organic phase turns back to the complexometric extraction system, and water is handled after multiple-effect evaporation is produced calcium chloride, and the water that steams turns back to the milk of lime configuration-system.
The volume ratio of described complexing extractant and dichlorohydrine solution is 1: 5～1: 1.
The solvent that described complexing extractant uses is in 200# solvent oil, trichloropropane, tetrachloroethane, decane, dodecyl, n-Octanol, isooctyl alcohol, kerosene, trimethylbenzene, the ditane one or more; The complexing agent that described complexing extractant uses is domiphen, dodecyl dibenzyl amine, tribenzylamine, trioctylamine, N
235In a kind of.The volume ratio of its solvent and complexing agent is 10: 0.5～5.Described saponification directly 60～110 ℃ with 10～30% (wt%) milk of limes or alkali lye saponification, the residual alkali content of mother liquor＜0.5% (wt%) that discharges at the bottom of the tower.
Advantage of the present invention:
Compare with traditional producing epoxy chloropropane by propylene high temperature chlorination technology that no spent process water effluxes in the production process; With 200810159078.2 patents ratio, the present invention has reduced with the step of SX dichlorohydrine and solvent recuperation, has also reduced complexometric extraction liquid back extraction regeneration complexing extractant; Not only simplified technology; Reduce investment, and because of without the esters solvent extraction, the consumption of minimizing esters solvent and recovery and the cost that increases.Production cost of the present invention decreases than traditional technology, and technology is simple, is prone to operate continuously, can realize industrial automation control.
Embodiment
Embodiment 1:
A kind of environment-friendly preparation process of producing epoxy chloropropane by complexation and extraction comprises the steps:
(1) the dichlorohydrine solution that is obtained by traditional technology is with complexing extractant (n-dodecane: N
235: n-Octanol volume ratio 6: 3: 1) extract, its volume ratio is a dichlorohydrine solution: complexing extractant=5: 3, and three grades of extractions, the dichlorohydrine percentage extraction is 96%, and the percentage extraction of HCL is 98%, and HCL content is 0.094% in the solution of extraction back;
(2) extracted residual chlorohydrination mother liquor turns back to the propylene chlorohydrin reactive system, and chlorohydrin action is unaffected;
(3) contain milk of lime 82～96 ℃ between the saponification of the complexometric extraction liquid of HCL and dichlorohydrine with 20% (wt%), generate the epoxy chloropropane bullion, rectifying obtains the epoxy chloropropane of purity more than 99%;
(4) tell organic phase and water after saponification liquor filters, organic phase is returned the complexometric extraction system, and complexometric extraction is unaffected, and the water multiple-effect evaporation is produced calcium chloride, and the water that steams is used for preparing lime milk.
Embodiment 2:
With the N among the embodiment 1
235Change the dodecyl dibenzyl amine into, its operation steps is with embodiment 1, and the result is with embodiment 1 basically identical.
Embodiment 3:
Change the n-dodecane among the embodiment 1 into n-decane, other operation stepss are with embodiment 1, and the result is with embodiment 3 basically identicals.
Claims (5)
1. the environment-friendly preparation process of a producing epoxy chloropropane by complexation and extraction is characterized in that, comprises the steps:
(1) in dichlorohydrine solution, add the complexing extractant multi-stage solvent extraction, with HCL with dichlorohydrine is disposable extracts, the complexing agent that described complexing extractant uses is domiphen, dodecyl dibenzyl amine, tribenzylamine, trioctylamine, N
235In a kind of;
(2) complexometric extraction goes out behind HCL and the dichlorohydrine rest solution and turns back to the propylene chlorohydrin system and apply mechanically;
(3) the complexometric extraction liquid that contains HCL and dichlorohydrine is used the milk of lime saponification; Generate the epoxy chloropropane bullion and get epoxy chloropropane through rectifying; Tell organic phase the liquid effluent at the bottom of the saponification column; Organic phase turns back to the complexometric extraction system, and water is handled after multiple-effect evaporation is produced calcium chloride, and the water that steams turns back to the milk of lime configuration-system.
2. according to the environment-friendly preparation process of the described producing epoxy chloropropane by complexation and extraction of claim 1, it is characterized in that the volume ratio of described complexing extractant and dichlorohydrine solution is 1: 5～1: 1.
3. according to the environment-friendly preparation process of the described producing epoxy chloropropane by complexation and extraction of claim 1; It is characterized in that the solvent that described complexing extractant uses is in 200# solvent oil, trichloropropane, tetrachloroethane, decane, dodecyl, n-Octanol, isooctyl alcohol, kerosene, trimethylbenzene, the ditane one or more.
4. according to the environment-friendly preparation process of the described producing epoxy chloropropane by complexation and extraction of claim 3, it is characterized in that the volume ratio of described solvent and complexing agent is 10: 0.5～5.
5. according to the environment-friendly preparation process of the described producing epoxy chloropropane by complexation and extraction of claim 1, it is characterized in that described saponification is that complexometric extraction liquid directly carries out in 10～30% milk of limes down at 60～110 ℃, the residual alkali content of mother liquor＜0.5% of discharging at the bottom of the tower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101388618A CN101792424B (en) | 2010-04-06 | 2010-04-06 | Environment-friendly preparation process for producing epoxy chloropropane by complexation and extraction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101388618A CN101792424B (en) | 2010-04-06 | 2010-04-06 | Environment-friendly preparation process for producing epoxy chloropropane by complexation and extraction |
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| Publication Number | Publication Date |
|---|---|
| CN101792424A CN101792424A (en) | 2010-08-04 |
| CN101792424B true CN101792424B (en) | 2012-02-29 |
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|---|---|---|---|
| CN2010101388618A Expired - Fee Related CN101792424B (en) | 2010-04-06 | 2010-04-06 | Environment-friendly preparation process for producing epoxy chloropropane by complexation and extraction |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005116004A1 (en) * | 2004-05-21 | 2005-12-08 | Dow Global Technologies Inc. | Process for preparing epichlorohydrin from ethane |
| CN100513401C (en) * | 2007-01-25 | 2009-07-15 | 中国林业科学研究院林产化学工业研究所 | Method for preparing epoxy chloropropane by using glycerol method |
| JP2009215246A (en) * | 2008-03-11 | 2009-09-24 | Daiso Co Ltd | Catalyst for producing chlorohydrin |
| WO2009104961A3 (en) * | 2008-02-21 | 2009-10-15 | Bouwe De Jong | Process for the preparation of a dichloropropanol product |
| FR2935699A1 (en) * | 2008-09-10 | 2010-03-12 | Solvay | PROCESS FOR PRODUCING A CHEMICAL |
-
2010
- 2010-04-06 CN CN2010101388618A patent/CN101792424B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005116004A1 (en) * | 2004-05-21 | 2005-12-08 | Dow Global Technologies Inc. | Process for preparing epichlorohydrin from ethane |
| CN100513401C (en) * | 2007-01-25 | 2009-07-15 | 中国林业科学研究院林产化学工业研究所 | Method for preparing epoxy chloropropane by using glycerol method |
| WO2009104961A3 (en) * | 2008-02-21 | 2009-10-15 | Bouwe De Jong | Process for the preparation of a dichloropropanol product |
| JP2009215246A (en) * | 2008-03-11 | 2009-09-24 | Daiso Co Ltd | Catalyst for producing chlorohydrin |
| FR2935699A1 (en) * | 2008-09-10 | 2010-03-12 | Solvay | PROCESS FOR PRODUCING A CHEMICAL |
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| CN101792424A (en) | 2010-08-04 |
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Granted publication date: 20120229 Termination date: 20180406 |