CN102746119A - Method for preparing dichlorohydrin from glycerol - Google Patents
Method for preparing dichlorohydrin from glycerol Download PDFInfo
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- CN102746119A CN102746119A CN2011101001440A CN201110100144A CN102746119A CN 102746119 A CN102746119 A CN 102746119A CN 2011101001440 A CN2011101001440 A CN 2011101001440A CN 201110100144 A CN201110100144 A CN 201110100144A CN 102746119 A CN102746119 A CN 102746119A
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- glycerine
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Abstract
The invention relates to a method for preparing dichlorohydrin from glycerol, and mainly solves the problems of great catalyst consumption, high production cost, and low dichlorohydrin yield in the prior art. The method of the invention consists of: adopting glycerol and a chlorinating agent as raw materials, and under the conditions of a normal pressure, a reaction temperature of 80-180DEG C, a chlorinating agent dosage of 1-40% of that of the glycerol, and a catalyst dosage of 0.5-20% of that of the glycerol, contacting the raw materials with a catalyst for reaction for 10-50 hours, thus obtaining dichlorohydrin. Specifically, the catalyst comprises the following components by weight: a) 1-95 parts of carboxylic acid with a boiling point higher than or equal to 100DEG C under normal pressure; and b) 5-95 parts of a chloride. The technical scheme adopted in the invention well solves the problem, and can be used in the industrial production of dichlorohydrin from glycerol.
Description
Technical field
The present invention relates to the method that a kind of glycerine prepares dichlorohydrine.
Background technology
Dichlorohydrine DCH is the raw material of multiple Chemicals such as synthetic Dichloro acetone, acetate fiber, water conditioner, also is the midbody of materials such as synthesizing epoxy chloropropane, epoxy resin, ion exchange resin.DCH mainly is as midbody in large-scale industrial application, utilizes alkali lye such as liming that it is carried out saponification, sloughs an one's share of expenses for a joint undertaking HCl, and cyclisation generates epoxy chloropropane (being called for short ECH).ECH is a kind of important Organic Chemicals and fine chemical product, and purposes very extensively.It is strong to be with it that epoxy resin that raw material makes has cohesiveness; Characteristics such as resistant to chemical media burn into shrinking percentage is low, chemicalstability good, excellent in cushion effect and dielectric properties excellence have widely in industries such as coating, sizing agent, strongthener, cast material and electronic shell stampings and to use.In addition, ECH can also be used for multiple products such as synthetic glycerine, nitroglycerine explosive, glass reinforced plastic, electrical isolation article, tensio-active agent, medicine, coating, sizing material, ion exchange resin, softening agent, glycidyl derivatives, chlorohydrin rubber, be used to produce chemical stabilizer, chemical dyestuff and water conditioner etc.The market requirement of DCH is inseparable with ECH.In the consumption of ECH increased, major part was to be applied to synthetic epoxy resin.After getting into 21 century, along with the further increase of industries such as electronics, sizing agent, coating, building to the epoxy resin demand, the epoxy resin demand increases fast, has greatly promoted the development of global ECH.The market requirement of ECH is very vigorous, and tangible ever-increasing trend is arranged, and conventional production methods receives certain limitation again, so the synthetic ECH of exploitation novel process becomes very urgent problem.
The method of dichlorohydrine production at present mainly contains propylene high-temperature chlorination, acetate propylene method and glycerine method.Because facility investment is big when propylene high-temperature chlorination, acetate propylene method suitability for industrialized production; Complex process; Wastewater discharge is big, affects to environment, and especially the propylene high-temperature chlorination obtains trichloropropane and chlorination aliphatic ether and polymkeric substance; Make industrial production cause cost rising and sub product to increase, brought certain limitation to industrial production.
At present many pieces of patent reports are arranged glycerine in the presence of catalyzer such as carboxylic acid, acid anhydrides, sour chlorine, carboxylate salt, generate the method for dichlorohydrine through the hydrogenchloride addition reaction, like document WO2006/020234 and WO2005/054167.The catalyzer that existing bibliographical information is adopted all adopts the bigger organic acid of carboxylic acid, carboxylic acid derivative or volatility, because these catalyzer boiling points are low, catalyst levels is big in the reaction process, and production cost is high; In addition, these catalyzer are water-soluble strong, and are acid strong, and the final product that generates tar has easily perhaps finally become the higher carboxylic acid product of boiling point and has been difficult to evaporation, has reduced the yield of dichlorohydrine.
Summary of the invention
Technical problem to be solved by this invention is that prior art exists catalyst levels big, and production cost is high, and the problem that the dichlorohydrine yield is low provides a kind of new glycerine to prepare the method for dichlorohydrine.This method has that catalyst levels is little, and production cost is low, the characteristics that the dichlorohydrine yield is high.
In order to solve the problems of the technologies described above; The technical scheme that the present invention adopts is following: a kind of glycerine prepares the method for dichlorohydrine, is raw material with glycerine and chlorizating agent, under normal pressure; Temperature of reaction is 80~180 ℃; The chlorizating agent consumption is 1~40% of a glycerine consumption, and catalyst levels is under 0.5~20% condition of glycerine consumption, and raw material and catalyzer contact reacts obtained dichlorohydrine in 10~50 hours; Wherein, said catalyzer comprises following component in parts by weight: a) boiling point is greater than or equal to 100 ℃ carboxylic acid under 1~95 part the normal pressure; B) 5~95 parts muriate.
In the technique scheme, said chlorizating agent is an anhydrous hydrogen chloride gas.Said carboxylic acid preferred version is to be selected from least a in sad, propanedioic acid, Succinic Acid or the hexanodioic acid; Said muriate preferred version is to be selected from least a in zinc chloride, aluminum chloride or the cupric chloride.In parts by weight, the consumption preferable range of carboxylic acid is 30~75 parts, and muriatic consumption preferable range is 25~70 parts.The temperature of reaction preferable range is 90~140 ℃, and chlorizating agent consumption preferable range is 1.5~35% of a glycerine consumption, and the catalyst levels preferable range is 1~12% of a glycerine consumption, and the reaction times preferable range is 15~30 hours.Preferred version is for constantly shifting out the water that reaction generates in the reaction process, makes that the content of water is less than or equal to 15 weight % in the reaction mixture.
Glycerine and hydrogen chloride gas react under the composite catalyst effect, and after its chlorination reaction finished, filtering catalyst was reused, the more refining dichlorohydrine that steams from the reaction gains.
The inventive method is Primary Catalysts through using composite catalyst with the carboxylic acid, is promotor with the muriate; Prepare the reaction mechanism of dichlorohydrine from glycerine, glycerine and carboxylic acid at first carry out esterification, generate short and long-chain acyl triglyceride molecules; Cl ions combines with short and long-chain acyl triglyceride molecules then; Generate glycerine monochlorohydrin, discharge carboxylic acid simultaneously, need a large amount of cl ionss in the reaction process.So the muriatic adding of promotor will promote the substitution reaction of cl ions, the carrying out of accelerated reaction improved the yield of dichlorohydrine, and yield can reach 92%; Simultaneously, can reduce catalyst consumption, reduce production cost, obtain better technical effect.
Through embodiment the present invention is done further elaboration below.
Embodiment
[embodiment 1]
In the four-hole boiling flask that 500 milliliters of bands stir, add 126 gram glycerine and 50 gram catalyzer, under the normal pressure, temperature of reaction is 110 ℃, anhydrous hydrogen chloride gas is fed continuously in the homogeneous mixture solotion of glycerine and catalyzer, carries out blistering reaction.For guaranteeing that gas-liquid two-phase fully contacts, glycerine can transform as much as possible fully, hydrogenchloride ventilation speed is 300 ml/min, under the condition that refluxes, reacts 15 hours, and the HCl gas that reaction is overflowed reclaims with alkali lye.Hexanodioic acid and zinc chloride are composite as catalyzer, and wherein in parts by weight, hexanodioic acid is 70 parts, and zinc chloride is 30 parts.
Reaction result: the yield of dichlorohydrine is 92%.
[embodiment 2]
In the four-hole boiling flask that 500 milliliters of bands stir, add 126 gram glycerine and 25 gram catalyzer, under the normal pressure, temperature of reaction is 90 ℃, anhydrous hydrogen chloride gas is fed continuously in the homogeneous mixture solotion of glycerine and catalyzer, carries out blistering reaction.For guaranteeing that gas-liquid two-phase fully contacts, glycerine can transform as much as possible fully, hydrogenchloride ventilation speed is 300 ml/min, under the condition that refluxes, reacts 15 hours, and the HCl gas that reaction is overflowed reclaims with alkali lye.Hexanodioic acid and aluminum chloride are composite as catalyzer, and wherein in parts by weight, hexanodioic acid is 50 parts, and aluminum chloride is 50 parts.
Reaction result: the yield of dichlorohydrine is 87%.
[comparative example 1]
With [embodiment 1], just catalyst system therefor is merely hexanodioic acid.Reaction result: the yield of dichlorohydrine is 80%.
[embodiment 3]
In the four-hole boiling flask that 500 milliliters of bands stir, add 126 gram glycerine and 75 gram catalyzer, under the normal pressure, temperature of reaction is 140 ℃, anhydrous hydrogen chloride gas is fed continuously in the homogeneous mixture solotion of glycerine and catalyzer, carries out blistering reaction.For guaranteeing that gas-liquid two-phase fully contacts, glycerine can transform as much as possible fully, hydrogenchloride ventilation speed is 300 ml/min, under the condition that refluxes, reacts 30 hours, and the HCl gas that reaction is overflowed reclaims with alkali lye.Propanedioic acid and zinc chloride composite as catalyzer, wherein in parts by weight, propanedioic acid is 30 parts, zinc chloride is 70 parts.
Reaction result: the yield of dichlorohydrine is 86%.
[embodiment 4]
In the four-hole boiling flask that 500 milliliters of bands stir, add 126 gram glycerine and 10 gram catalyzer, under the normal pressure, temperature of reaction is 120 ℃, anhydrous hydrogen chloride gas is fed continuously in the homogeneous mixture solotion of glycerine and catalyzer, carries out blistering reaction.For guaranteeing that gas-liquid two-phase fully contacts, glycerine can transform as much as possible fully, hydrogenchloride ventilation speed is about 300 ml/min, under the condition that refluxes, reacts 20 hours, and the HCl gas that reaction is overflowed reclaims with alkali lye.Propanedioic acid and cupric chloride are composite as catalyzer, and wherein in parts by weight, propanedioic acid is 65 parts, and cupric chloride is 35 parts.
Reaction result: the yield of dichlorohydrine is 82%.
[comparative example 2]
With [embodiment 3], just catalyst system therefor is merely propanedioic acid.Reaction result: the yield of dichlorohydrine is 78%.
[embodiment 5]
In the four-hole boiling flask that 500 milliliters of bands stir, add 1000 gram glycerine and 75 gram catalyzer, under the normal pressure, temperature of reaction is 120 ℃, anhydrous hydrogen chloride gas is fed continuously in the homogeneous mixture solotion of glycerine and catalyzer, carries out blistering reaction.For guaranteeing that gas-liquid two-phase fully contacts, glycerine can transform as much as possible fully, hydrogenchloride ventilation speed is 300 ml/min, under the condition that refluxes, reacts 25 hours, and the HCl gas that reaction is overflowed reclaims with alkali lye.Succinic Acid and zinc chloride are composite as catalyzer, and wherein in parts by weight, Succinic Acid is 55 parts, and zinc chloride is 45 parts.
Reaction result: the yield of dichlorohydrine is 85%.
[embodiment 6]
In the four-hole boiling flask that 500 milliliters of bands stir, add 1000 gram glycerine and 20 gram catalyzer, under the normal pressure, temperature of reaction is 140 ℃, anhydrous hydrogen chloride gas is fed continuously in the homogeneous mixture solotion of glycerine and catalyzer, carries out blistering reaction.For guaranteeing that gas-liquid two-phase fully contacts, glycerine can transform as much as possible fully, hydrogenchloride ventilation speed is 300 ml/min, under the condition that refluxes, reacts 20 hours, and the HCl gas that reaction is overflowed reclaims with alkali lye.Succinic Acid and aluminum chloride are composite as catalyzer, and wherein in parts by weight, Succinic Acid is 45 parts, and aluminum chloride is 65 parts.
Reaction result: the yield of dichlorohydrine is 83%.
[comparative example 3]
With [embodiment 5], just catalyst system therefor is merely Succinic Acid.Reaction result: the yield of dichlorohydrine is 80%.
Claims (6)
1. a glycerine prepares the method for dichlorohydrine; With glycerine and chlorizating agent is raw material; Under normal pressure, temperature of reaction is 80~180 ℃, and the chlorizating agent consumption is 1~40% of a glycerine consumption; Catalyst levels is under 0.5~20% condition of glycerine consumption, and raw material and catalyzer contact reacts obtained dichlorohydrine in 10~50 hours; Wherein, said catalyzer comprises following component in parts by weight: a) boiling point is greater than or equal to 100 ℃ carboxylic acid under 1~95 part the normal pressure; B) 5~95 parts muriate.
2. the method for preparing dichlorohydrine according to the said glycerine of claim 1 is characterized in that said carboxylic acid is selected from least a in sad, propanedioic acid, Succinic Acid or the hexanodioic acid; Said muriate is selected from least a in zinc chloride, aluminum chloride or the cupric chloride.
3. prepare the method for dichlorohydrine according to the said glycerine of claim 1, it is characterized in that said catalyzer in parts by weight, the consumption of carboxylic acid is 30~75 parts, and muriatic consumption is 25~70 parts.
4. the method for preparing dichlorohydrine according to the said glycerine of claim 1 is characterized in that temperature of reaction is 90~140 ℃, and the chlorizating agent consumption is 1.5~35% of a glycerine consumption, and catalyst levels is 1~12% of a glycerine consumption, and the reaction times is 15~30 hours.
5. the method for preparing dichlorohydrine according to the said glycerine of claim 1 is characterized in that said chlorizating agent is an anhydrous hydrogen chloride gas.
6. the method for preparing dichlorohydrine according to the said glycerine of claim 1 is characterized in that constantly shifting out in the reaction process water that reaction generates, and makes that the content of water is less than or equal to 15 weight % in the reaction mixture.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109516901A (en) * | 2018-12-28 | 2019-03-26 | 山东泰和水处理科技股份有限公司 | A kind of synthetic method of 2,2 '-dichloroether |
CN114181040A (en) * | 2021-12-14 | 2022-03-15 | 山东鲁泰控股集团有限公司石墨烯高分子复合材料研发中心 | Preparation method of dichloropropanol |
Citations (4)
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CN1976886A (en) * | 2004-07-21 | 2007-06-06 | 陶氏环球技术公司 | Conversion of a multihydroxylated-aliphatic hydrocarbon or ester thereof to a chlorohydrin |
CN101184715A (en) * | 2005-04-18 | 2008-05-21 | 阿塞尔有限责任公司 | Process for the production of alpha, gamma-dichlorohydrin from glycerin and hydrochloric acid |
CN101773851A (en) * | 2009-01-13 | 2010-07-14 | 德纳(南京)化工有限公司 | Dichloropropanol catalyst prepared by glycerol method |
CN101921175A (en) * | 2003-11-20 | 2010-12-22 | 索尔维公司 | Be used to produce the method for organic compound |
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2011
- 2011-04-20 CN CN2011101001440A patent/CN102746119A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101921175A (en) * | 2003-11-20 | 2010-12-22 | 索尔维公司 | Be used to produce the method for organic compound |
CN1976886A (en) * | 2004-07-21 | 2007-06-06 | 陶氏环球技术公司 | Conversion of a multihydroxylated-aliphatic hydrocarbon or ester thereof to a chlorohydrin |
CN101184715A (en) * | 2005-04-18 | 2008-05-21 | 阿塞尔有限责任公司 | Process for the production of alpha, gamma-dichlorohydrin from glycerin and hydrochloric acid |
CN101773851A (en) * | 2009-01-13 | 2010-07-14 | 德纳(南京)化工有限公司 | Dichloropropanol catalyst prepared by glycerol method |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109516901A (en) * | 2018-12-28 | 2019-03-26 | 山东泰和水处理科技股份有限公司 | A kind of synthetic method of 2,2 '-dichloroether |
CN114181040A (en) * | 2021-12-14 | 2022-03-15 | 山东鲁泰控股集团有限公司石墨烯高分子复合材料研发中心 | Preparation method of dichloropropanol |
CN114181040B (en) * | 2021-12-14 | 2023-12-12 | 山东鲁泰控股集团有限公司石墨烯高分子复合材料研发中心 | Preparation method of dichloropropanol |
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