CN1687005A - Method for preparing acrylic ester and separation 1,2-dichloropropane by using DD mixing agent - Google Patents
Method for preparing acrylic ester and separation 1,2-dichloropropane by using DD mixing agent Download PDFInfo
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Abstract
The present invention relates to a method capable of utilizing DD mixture to prepare acrylate and separating 1,2-dichloropropane from it. Said invention utilizes the action of 1,3-dichloropropene in the DD mixture and acrylic acid or methylacrylic acid, alkali, catalyst and and polymerization inhibitor to synthesize 3-chloro-2-propenyl acrylate or 3-chloro-2-propenyl 2-methacrylate, and utilizes the distillation to make it be separated from 1,2-dichloropropane. Said method includes the steps of raw material pretreatment, catalytic esterification reaction, product separation and product refinement.
Description
The technical field is as follows:
the invention relates to a comprehensive utilization method of a chemical by-product DD mixing agent, in particular to a method for separating and preparing 1, 2-dichloropropane and acrylic ester by using the DD mixing agent as a main raw material.
Background art:
the DD mixing agent is a high-boiling point byproduct generated in the production of 3-chloropropene by a propylene thermal chlorination method, the main components of the DD mixing agent are 1, 2-dichloropropane and 1, 3-dichloropropene (including cis-isomer and trans-isomer), and the 3-chloropropene is mainly used for producing epichlorohydrin. At present, the production capacity of epichlorohydrin in China is 4.5 ten thousand tons per year, about 230 kilograms of DD mixed agent is generated when one ton of epichlorohydrin is produced, and nearly ten thousand tons of DD mixed agent are generated every year. And the production device of the epichlorohydrin is increased, and the generation amount of the DD mixing agent is correspondingly increased, so that the problem of treatment and utilization of the DD mixing agent is to be solved.
In 1943, Kate (Carter) first discovered the nematicidal effect of DD mixture, and had been widely used in various countries. The DD mixed agent has been used as nematicide in the last seventies of China, and the insecticidal effect and the yield increasing effect are obvious. The effective component for killing the nematodes in the DD mixed agent is 1, 3-dichloropropene, and a large amount of ineffective 1, 2-dichloropropane is dispersed in soil and air, which causes serious pollution to the environment, so that the DD mixed agentis limited to be used as the nematicide at home and abroad in recent years.
The DD mixed agent can also be used as paint thinner or equipment cleaning agent after simple distillation. Even the DD blend introduced into the propylene chlorination plant of Japan by Qilu petrochemical has been disposed of by incineration in the past. From the viewpoint of environmental protection, the treatment modes are the transfer of three wastes, which wastes resources and pollutes the environment. The purity of 1, 3-dichloropropene fraction can be improved to more than 90% by adopting a rectification method in Japan, and the product is used for synthesizing pesticides or other fine chemical intermediates, and the sale price of the product is higher than that of epichlorohydrin. In China, a rectification method is tried to separate 1, 3-dichloropropene and 1, 2-dichloropropane in a DD mixed agent and carry out small-scale production, but because the boiling points of all components are close (the boiling points of the 1, 2-dichloropropane are 97 ℃, the boiling points of the cis-1, 3-dichloropropene are 102 ℃ and the boiling points of the trans-1, 3-dichloropropene are 110 ℃), all components are difficult to be completely rectified and separated, and HCl can be decomposed after the DD mixed agent is heated, so that high requirements are provided for the tower efficiency and the corrosion resistance of a rectification device. In conclusion, the treatment methods of the DD mixture are not complete at present. The development of a more effective comprehensive utilization way of the DD mixed agent has important practical significance for reducing environmental pollution and improving the utilization rate of resources.
The invention content is as follows:
aiming at the current situation of treatment and utilization of the DD mixed agent, the invention provides a method for comprehensively utilizing the DD mixed agent.
The invention uses DD mixed agent as main raw material, and uses acrylate or methacrylate to produce selective esterification reaction with 1, 3-dichloropropene in the DD mixed agent to synthesize acrylic acid-3-chloro-2-propenyl ester or 2-methacrylic acid-3-chloro-2-propenyl ester. The boiling points of the acrylic acid-3-chlorine-2-propylene ester and the 2-methacrylic acid-3-chlorine-2-propylene ester are far higher than that of the 1, 2-dichloropropane, so that the separation of the 1, 2-dichloropropane and the acrylic acid-3-chlorine-2-propylene ester or the 2-methacrylic acid-3-chlorine-2-propylene ester can be realized through distillation, and useful chemical products, namely the 1, 2-dichloropropane and the acrylic acid-3-chlorine-2-propylene ester or the 2-methacrylic acid-3-chlorine-2-propylene ester, can be obtained, so that the aim of fully utilizing the DD mixed agent is fulfilled.
The acrylic acid-3-chlorine-2-propylene ester comprises cis-isomer and trans-isomer, and the structural formulas are respectively
And
the 2-methacrylic acid-3-chlorine-2-propylene ester also comprises cis-isomer and trans-isomer, and the structural formulas are respectively
And
the method of the invention uses a chemical by-product-DD mixing agent as a main raw material, and the main component of the DD mixing agent is 1, 2-dichloropropane (CH)3CHClCH2Cl) and 1, 3-dichloropropene (ClCH ═ CHCH)2Cl), contains four forms of chloride ion, but there are significant differences in their chemical activities, with allyl chloride being the most reactive for chemical reactions. The mixed agent of acrylic acid or methacrylic acid, alkali, polymerization inhibitor and catalyst and DD is used to react 1, 3-dichloropropene (A), (B), (C), (ClCH＝CHCH2Cl) will take part in the esterification reaction to generate acrylic acid-3-chlorine-2-propylene ester (CH)2＝CHCOOCH2CH ═ CHCl) or 2-methacrylic acid 3-chloro-2-propenyl ester (CH)2＝CCH3COOCH2CH ═ CHCl), the basic reaction formula is as follows:
or
Or
The boiling points of 3-chloro-2-propenyl acrylate and 3-chloro-2-propenyl 2-methacrylate are far higher than that of 1, 2-dichloropropane, so that the separation of products can be realized by distillation, and useful chemical products, namely 1, 2-dichloropropane and 3-chloro-2-propenyl acrylate or 3-chloro-2-propenyl 2-methacrylate can be obtained.
The invention comprises four process steps: raw material pretreatment, catalytic esterification reaction, product separation and product refining.
1. Feedstock and pretreatment of feedstock
The DD mixed agent is an industrial byproduct dark brown oily liquid, the contents of main components 1, 2-dichloropropane and 1, 3-dichloropropene (including cis-isomer and trans-isomer) are more than 95%, and a small amount of 3-chloropropene, carbonized impurities, water and the like are also contained. Therefore, the DD mixed agent needs to be dehydrated and simply distilled to remove impurities, and 97-100 ℃ fractions are received. Because the content of the 1, 3-dichloropropene in each DD mixed agent is different, the content of each DD mixed agent needs to be analyzed by gas chromatography, and the DD mixed agent is used as the basis for the proportion of the reaction raw materials, and generally comprises 37-75% of 1, 2-dichloropropane and 63-23% of 1, 3-dichloropropene (including cis-isomer and trans-isomer).
According to the measured content of 1, 3-dichloropropene in the DD mixed agent, a certain amount of acrylic acid or methacrylic acid is adopted as another main raw material, and industrial products of the acrylic acid or the methacrylic acid are refined by reduced pressure distillation before use to remove polymers and impurities possibly contained, and a proper amount of polymerization inhibitor is added to prevent further polymerization.
The polymerization inhibitor for acrylic acid or methacrylic acid in the present invention includes various polymerization inhibitors for radical polymerization such as hydroquinone, p-hydroxyanisole or phenothiazine, and preferably a nitrogen radical type polymerization inhibitor such as DPPH. The polymerization inhibitor needs to be added into acrylic acid or methacrylic acid before distillation, and the dosage of the polymerization inhibitor is 0.001-0.1% of the mass of the acrylic acid or the methacrylic acid.
The alkali used in the process of the invention can be sodium hydroxide, potassium hydroxide or other alkaline compounds, and can also be aqueous solution of the corresponding alkali. The molar ratio of the acrylic acid or the methacrylic acid to the alkali is 1: 1-1.5.
The catalyst adopted in the catalytic esterification reaction is triethylamine, cuprous chloride or a phase transfer catalyst, such as polyethylene glycol and various quaternary ammonium salts, and the dosage of the catalyst is 1-10% of the mass of acrylic acid or methacrylic acid.
2. Catalytic esterification reaction
The catalytic esterification process of the present invention may be a two-step process or a one-step process.
The two-step method is that alkali and acrylic acid or methacrylic acid are neutralized to prepare corresponding acrylate or methacrylate, then the generated salt is taken as a raw material of esterification reaction, the raw material is mixed with DD mixing agent, catalyst and polymerization inhibitor in an esterification reactor, and the mixture is stirred and heated to the reaction temperature to carry out catalytic esterification reaction. The reaction temperature can be 60-100 ℃, the reaction time can be 3-8 hours, and the reaction is carried out under normal pressure.
The one-step method is that DD mixed agent, acrylic acid or methacrylic acid, polymerization inhibitor, alkali and catalyst are added into an esterification reactor in sequence according to a certain proportion, stirred and heated to the reaction temperature, and catalytic esterification reaction is carried out. The reaction temperature can be 60-100 ℃, the reaction time can be 3-8 hours, and the reaction is carried out under normal pressure.
The catalytic esterification reaction is also characterized in that the DD mixed agent and water are subjected to azeotropy, the water contained in the system is removed at the reflux temperature, namely the reaction temperature, and the DD mixed agent returns to the system for reaction after standing and layering so as to utilize the full esterification reaction.
The catalytic esterification reaction is also characterized in that the temperature rising mode can adopt conventional heating technologies such as water bath heating, oil bath heating, electric heating, steam heating and the like, and can also adopt a microwave heating technology.
3. Product separation
After the catalytic esterification reaction is finished, the system is cooled to room temperature and stands, inorganic salt generated by the reaction is precipitated and can be directly filtered and separated out; or adding a proper amount of water into the system to dissolve the generated inorganic salt, standing for layering, and removing the water phase. If the organic phase contains a small amount of water, a proper amount of drying agent such as anhydrous magnesium sulfate can be added for drying.
The organic phase after the desalting mainly contains 1, 2-dichloropropane and acrylic acid-3-chlorine-2-propylene ester or 2-methacrylic acid-3-chlorine-2-propylene ester, distillation is carried out at normal pressure, and a fraction at 95-100 ℃ is collected to obtain the 1, 2-dichloropropane, wherein the separation rate is 80-100%, and the purity is 95-100%.
4. Product refinement
The organic phase after the 1, 2-dichloropropane is separated is mainly acrylic acid-3-chlorine-2-propylene ester or 2-methacrylic acid-3-chlorine-2-propylene ester, and also contains impurities such as polymers and the like, the purity is not high, the distillation and the refining can be carried out under the vacuum degree of 0.5-3 KPa, the main fraction is collected, namely acrylic acid-3-chlorine-2-propylene ester or 2-methacrylic acid-3-chlorine-2-propylene ester, the yield is more than 70%, and the purity is more than 95%.
The component content of the DD mixture and the purity of the 1, 2-dichloropropane and acrylic acid-3-chloro-2-propenyl ester or 2-methacrylic acid-3-chloro-2-propenyl ester can be analyzed and determined by a gas chromatograph.
The method can realize the effective separation of 1, 2-dichloropropane and the preparation of acrylic acid-3-chloro-2-propenyl ester or 2-methacrylic acid-3-chloro-2-propenyl ester in the industrial byproduct DD mixed agent, and is an effective way for realizing the comprehensive utilization of the DD mixed agent. The product acrylic acid-3-chlorine-2-propylene ester or 2-methacrylic acid-3-chlorine-2-propylene ester is a novel acrylate monomer, and can be used for producing a high polymer resin material by utilizing the self-polymerization or the copolymerization reaction with other monomers; the separated 1, 2-dichloropropane is more important organic synthesis intermediate and solvent, and can be converted into useful chemical products by chemical reactions of chlorination, ammoniation, hydrolysis, elimination and the like.
The specific implementation mode is as follows:
example 1 (two-step method)
The DD mixture was dehydrated and briefly distilled to remove impurities, and the contents of its components were analyzed by gas chromatography. Acrylic acid is refined by reduced pressure distillation, polymers and impurities which may be contained are removed, and a proper amount of polymerization inhibitor is added to prevent the polymerization.
After a stirring device, a water separator and a condenser are arranged on a three-mouth bottle, 36g (0.5mol) of acrylic acid and 0.04g of polymerization inhibitor DPPH0 are added, stirred and cooled, and then 20g (0.5mol) of sodium hydroxide is added for neutralization. Then, the product was azeotropically dehydrated with benzene and dried in vacuo to obtain about 47g of sodium acrylate.
A stirring device, a condenser and a thermometer are arranged on a 500ml three-mouth bottle, and 241.3g (containing 23 percent of 1, 3-dichloropropene and 0.5mol) of DD mixed agent, 47g (0.5mol) of sodium acrylate, 0.04g of DPPH0 and 3ml of triethylamine are added in turn under stirring. Heating the mixture to 85-90 ℃ in an oil bath, and reacting for 5 hours at constant temperature. After the esterification reaction is finished, cooling to room temperature, and filtering to remove the generated inorganic salt precipitate. (or adding water to dissolve inorganic salt, standing for layering, and removing a water phase.) adding a proper amount of anhydrous magnesium sulfate into an organic phase to remove residual water, adding 0.1g of hydroquinone, distilling at normal pressure, collecting a fraction at 95-100 ℃ to obtain 1, 2-dichloropropane, analyzing and determining the purity of the 1, 2-dichloropropane by using a gas chromatograph to be 95.2%, and calculating the yield to be 84.5%. The remainder was distilled and refined under a vacuum of 1.3KPa, the main fraction was collected, i.e., 3-chloro-2-propenylacrylate, the purity was 97.0% by gas chromatograph analysis, and the calculated yield was 75.6%.
Example 2 (two-step method)
The procedure was carried out as in example 1. The conditions for the esterification reaction were changed as follows: the reaction temperature is 75-80 ℃, the reaction time is 4 hours, and the dosage of triethylamine is 2.5ml, so that the yield of the acrylic acid-3-chloro-2-propenyl ester is 6.8%.
Example 3 (two-step method)
The procedure was carried out as in example 1. The conditions for the esterification reaction were changed as follows: the reaction temperature is 75-80 ℃, the reaction time is 5 hours, and the dosage of triethylamine is 3.0ml, so that the yield of the acrylic acid-3-chloro-2-propenyl ester is 22.7%.
Example 4 (two-step method)
The procedure was carried out as in example 1. The conditions for the esterification reaction were changed as follows: the reaction temperature is 75-80 ℃, the reaction time is 6 hours, and the dosage of triethylamine is 3.5ml, so that the yield of the acrylic acid-3-chloro-2-propenyl ester is 35.3%.
Example 5 (two-step method)
The procedure was carried out as in example 1. The conditions for the esterification reaction were changed as follows: the reaction temperature is 85-90 ℃, the reaction time is 5 hours, and the dosage of triethylamine is 2.5ml, so that the yield of the acrylic acid-3-chloro-2-propenyl ester is 70.8%.
Example 6 (two-step method)
The procedure was carried out as in example 1. The conditions for the esterification reaction were changed as follows: the reaction temperature is 85-90 ℃, the reaction time is 6 hours, and the dosage of triethylamine is 3.0ml, so that the yield of the acrylic acid-3-chloro-2-propenyl ester is 63.3%.
Example 7 (two-step method)
The procedure was carried out as in example 1. The conditions for the esterification reaction were changed as follows: the reaction temperature is 85-90 ℃, the reaction time is 4 hours, and the dosage of triethylamine is 3.5ml, so that the yield of the acrylic acid-3-chloro-2-propenyl ester is 55.2%.
Example 8 (two-step method)
The procedure was carried out as in example 1. The conditions for the esterification reaction were changed as follows: the reaction temperature is 95-100 ℃, the reaction time is 6 hours, and the dosage of triethylamine is 2.5ml, so that the yield of the acrylic acid-3-chloro-2-propenyl ester is 66.6%.
Example 9 (two-step method)
The procedure was carried out as in example 1. The conditions for the esterification reaction were changed as follows: the reaction temperature is 95-100 ℃, the reaction time is 4 hours, and the dosage of triethylamine is 3.0ml, so that the yield of the acrylic acid-3-chloro-2-propenyl ester is 59.7%.
Example 10 (two-step method)
The procedure was carried out as in example 1. The conditions for the esterification reaction were changed as follows: the reaction temperature is 95-100 ℃, the reaction time is 5 hours, and the dosage of triethylamine is 3.5ml, so that the yield of the acrylic acid-3-chloro-2-propenyl ester is 57.3%.
Example 11 (two-step method)
The feedstock pretreatment was the same as in example 1.
43g (0.5mol) of methacrylic acid reacts with 20g (0.5mol) of sodium hydroxide to prepare 54g (0.5mol) of sodium methacrylate, and 102.8g (containing 54 percent of 1, 3-dichloropropene and 0.5mol) of DD mixture, 54g (0.5mol) of sodium methacrylate, 0.05g of DPPH0 and 3.0ml of triethylamine are added in turn under stirring after a stirring device, a water separator and a condenser are arranged on a 500ml three-necked bottle. Heating the mixture to 95-100 ℃ in an oil bath, and reacting the mixture for 6 hours at constant temperature, wherein the rest steps are the same as those of the example 1. The purity of the 1, 2-dichloropropane is 96.0 percent through gas chromatograph analysis and determination, and the calculated yield is 84.5 percent; the purity of the 2-methacrylic acid-3-chloro-2-propenyl ester was 97.0% by gas chromatograph analysis, calculated as a yield of 64.8%.
Example 12 (one-step method)
The raw material pretreatment process is the same as above.
After a stirring device, a water separator and a condenser are arranged on a 500ml three-necked bottle, 241.3g (containing 23 percent of 1, 3-dichloropropene and 0.5mol) of DD mixed agent, 36g (0.5mol) of acrylic acid, 0.04g of DPPH0 and 20g (0.5mol) of sodium hydroxide are added in turn under stirring, and the rest is the same as the example 9, so that the yield of the 1, 2-dichloropropane is 81.2 percent and the yield of the 3-chloro-2-propenyl acrylate is 23.5 percent.
Example 13 (one-step Process)
The raw material pretreatment process is the same as above.
After a stirring device, a water separator and a condenser are arranged on a 500ml three-necked bottle, 100.9g (containing 55 percent of 1, 3-dichloropropene and 0.5mol) of DD mixed agent, 43g (0.5mol) of methacrylic acid, 0.06g of DPPH0, 20g (0.5mol) of sodium hydroxide and 3.0ml of triethylamine are added in turn under stirring, the mixture is heated to 95-100 ℃ in an oil bath and reacted for 6 hours at constant temperature, and the other steps are the same as the step in the example 9. The purity of the 1, 2-dichloropropane is 96.0 percent through gas chromatograph analysis and determination, and the calculated yield is 84.5 percent; the purity of 2-methacrylic acid-3-chloro-2-propenyl ester was 97.0% by gas chromatograph analysis, calculated as a yield of 66.8%.
Claims (9)
1. A method for preparing acrylic ester and separating 1, 2-dichloropropane by using DD mixed agent is characterized by that it utilizes the action of 1, 3-dichloropropene, acrylic acid or methacrylic acid, alkali, catalyst and polymerization inhibitor in DD mixed agent to synthesize acrylic acid-3-chloro-2-propenyl ester or 2-methacrylic acid-3-chloro-2-propenyl ester, and makes it be separated from 1, 2-dichloropropane by means of distillation, and its technological process includes the following steps: raw material pretreatment, catalytic esterification reaction, product separation and product refining.
2. The method for preparing acrylic ester and separating 1, 2-dichloropropane by using the DD mixture as claimed in claim 1, wherein the raw material pretreatment process comprises the steps of simply distilling the DD mixture to remove impurities, receiving a fraction at 99-110 ℃, wherein the fraction comprises 75-37% of 1, 2-dichloropropane and 63-23% of 1, 3-dichloropropene; the industrial products of acrylic acid or methacrylic acid are refined by reduced pressure distillation before use, and a proper amount of polymerization inhibitor is added to prevent polymerization.
3. The method for preparing acrylic ester and separating 1, 2-dichloropropane by using DD mixed agent according to claim 1, characterized in that the catalytic esterification reaction can adopt two-step method or one-step method, the two-step method is that firstly acrylic acid or methacrylic acid and alkali are neutralized to prepare corresponding acrylate or methacrylate, then the acrylate or methacrylate is mixed with DD mixed agent, catalyst and polymerization inhibitor in a reactor, and the mixture is stirred and heated to carry out catalytic esterification reaction; the one-step method is that DD mixing agent, acrylic acid or methacrylic acid, polymerization inhibitor, alkali and catalyst are added into a reactor in sequence according to a certain proportion, the mixture is stirred and heated to carry out catalytic esterification reaction, the reaction temperature of the two-step method or the one-step method can be 60-100 ℃, the reaction time can be 3-8 hours, and the reaction is carried out under normal pressure.
4. The method for preparing acrylic ester and separating 1, 2-dichloropropane by using the DD mixing agent as claimed in claim 3, which is characterized by that in the described catalytic esterification reaction process the DD mixing agent and water are azeotropic, and at the reflux temperature, i.e. reaction temperature, the water content in the system can be removed, and after standing still and layering, the DD mixing agent can be returned into the system to make reaction so as to benefit the completion of esterification reaction.
5. The method for preparing two acrylic esters and separating 1, 2-dichloropropane as claimed in claim 3, which comprises using DD mixture, and the temperature rising mode of the catalytic esterification reaction is conventional heating or microwave heating.
6. The method for preparing acrylic ester and separating 1, 2-dichloropropane by using the DD mixture as claimed in claim 1, wherein the product separation is that after the catalytic esterification reaction is completed, the system is cooled to room temperature, inorganic salt generated by the reaction is precipitated, the inorganic salt is directly filtered to be separated or is dissolved by adding water, the mixture is kept stand and layered, then the water phase is removed, the organic phase after the salt removal is distilled under normal pressure, and the fraction at 95-100 ℃ is collected, namely the 1, 2-dichloropropane.
7. The method for preparing acrylic ester and separating 1, 2-dichloropropane as claimed in claim 1, which comprises distilling the organic phase after separating 1, 2-dichloropropane under reduced pressure, collecting the main fraction to obtain 3-chloro-2-propenyl acrylate or 2-chloro-2-propenyl methacrylate.
8. The 3-chloro-2-propenyl acrylate prepared by the method for preparing acrylic ester and separating 1, 2-dichloropropane by using the DD mixture as claimed in claim 1, which comprises cis-isomer and trans-isomer, and has the structural formula of
And
9. the 2-methacrylic acid-3-chloro-2-propenyl ester prepared by the method for preparing acrylic ester and separating 1, 2-dichloropropane by using the DD mixed agent as claimed in claim 1, which comprises cis-isomer and trans-isomer, and has the structural formulas of cis-isomer and trans-isomer
And
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107879891A (en) * | 2017-11-20 | 2018-04-06 | 天津辰力工程设计有限公司 | A kind of method that dichloropropane and dichloropropylene are purified using DD mixtures |
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2005
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107879891A (en) * | 2017-11-20 | 2018-04-06 | 天津辰力工程设计有限公司 | A kind of method that dichloropropane and dichloropropylene are purified using DD mixtures |
| CN107879891B (en) * | 2017-11-20 | 2020-09-29 | 天津辰力工程设计有限公司 | Method for purifying dichloropropane and dichloropropene by using DD (DD) mixing agent |
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