WO2023102821A1 - Method for preparing 1,2-dichloroethane - Google Patents

Method for preparing 1,2-dichloroethane Download PDF

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Publication number
WO2023102821A1
WO2023102821A1 PCT/CN2021/136758 CN2021136758W WO2023102821A1 WO 2023102821 A1 WO2023102821 A1 WO 2023102821A1 CN 2021136758 W CN2021136758 W CN 2021136758W WO 2023102821 A1 WO2023102821 A1 WO 2023102821A1
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Prior art keywords
ethylene glycol
monomethyl ether
glycol monomethyl
hydrochloride
hydrogen chloride
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PCT/CN2021/136758
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French (fr)
Chinese (zh)
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袁丹华
徐云鹏
刘中民
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中国科学院大连化学物理研究所
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Priority to PCT/CN2021/136758 priority Critical patent/WO2023102821A1/en
Publication of WO2023102821A1 publication Critical patent/WO2023102821A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/16—Preparation of halogenated hydrocarbons by replacement by halogens of hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/01—Acyclic saturated compounds containing halogen atoms containing chlorine
    • C07C19/043—Chloroethanes
    • C07C19/045—Dichloroethanes

Definitions

  • the application relates to a preparation method of dichloroethane, which belongs to the field of preparation and synthesis of dichloroethane.
  • Ethylene dichloride is an important raw material for the preparation of vinyl chloride monomer, which is mainly used in the production of polyvinyl chloride, and ethylene dichloride is also often used as a solvent in chemical processes.
  • the preparation of ethylene dichloride is mainly obtained by chlorination of ethylene (using petroleum as raw material), but my country lacks oil, so the production of ethylene dichloride in my country fails to meet the market demand.
  • methyl methoxyacetate has attracted widespread attention as an important organic intermediate, which can be prepared by gas-phase carbonylation of methylal.
  • Methyl methoxyacetate can produce ethylene glycol monomethyl ether through hydrogenation, and about the downstream product of ethylene glycol monomethyl ether, only a small amount of patents (Chinese patent CN106554250A) have introduced its hydrolysis reaction to produce ethylene glycol monomethyl ether. Alcohol-related processes. But the technology that ethylene glycol monomethyl ether is converted into dichloroethane or other products has not been reported yet.
  • the purpose of the invention is to provide a kind of method that ethylene glycol monomethyl ether produces ethylene dichloride for the deficiencies existing in the current technology.
  • the method uses ethylene glycol monomethyl ether and hydrogen chloride as reaction raw materials, and the ethylene glycol monomethyl ether can be efficiently converted to obtain a higher yield of dichloroethane.
  • a method for preparing ethylene dichloride comprising the steps of:
  • the raw materials also include a solvent.
  • the solvent includes at least one of water, acetic acid, benzene, toluene, xylene and dioxane.
  • the catalyst includes at least one of zinc chloride, chromium chloride, tin chloride, copper chloride, pyridine hydrochloride, triethylamine hydrochloride, and imidazole hydrochloride.
  • the catalyst used in this application can efficiently catalyze the conversion of ethylene glycol monomethyl ether and/or the yield of dichloroethane.
  • the imidazole hydrochloride includes imidazole hydrochloride, 1-methylimidazole hydrochloride, 1-ethyl-3-methylimidazole hydrochloride, 1-butyl-3-methylimidazole at least one of hydrochloride;
  • the pyridine hydrochloride includes pyridine hydrochloride, 2-chloromethylpyridine hydrochloride, 1-butylpyridine hydrochloride, at least one of 1-butyl-4-methylpyridine chloride hydrochloride A sort of.
  • ethylene glycol monomethyl ether hydrogen chloride is selected from 1:0.1, 1:0.2, 1:0.5, 1:0.8, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:1: Any value in 18, 1:19, 1:20 or any range between the two.
  • ethylene glycol monomethyl ether:hydrogen chloride 1:0.1 ⁇ 15.
  • ethylene glycol monomethyl ether: catalyst is selected from 1:0.01, 1:0.05, 1:0.1, 1:0.2, 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3.0, 1:3.5, 1:4.0, 1:4.5, 1:5.0, 1:5.5, 1:6.0, 1:6.5, 1:7.0, 1:7.5, 1:8.0, 1:8.5, 1:8.0 Any value among 9.0, 1:9.5 and 1:10.0 or any range value in between.
  • ethylene glycol monomethyl ether:catalyst 1:0.01 ⁇ 8.
  • ethylene glycol monomethyl ether:catalyst 1:0.4 ⁇ 9.
  • ethylene glycol monomethyl ether: solvent is selected from 1:0, 1:0.01, 1:0.05, 1:0.1, 1:0.2, 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3.0, 1:3.5, 1:4.0, 1:4.5, 1:5.0, 1:5.5, 1:6.0, 1:6.5, 1:7.0, 1:7.5, 1:8.0, 1: 8.5, 1:9.0, 1:9.5, 1:10.0, 1:12.0, 1:13.0, 1:14.0, 1:15.0, 1:16.0, 1:17.0, 1:19.0, 1:19.0, 1:20.0 Any value of or any range value in between.
  • ethylene glycol monomethyl ether:solvent 1:0.5 ⁇ 1.5.
  • the conditions of the reaction include:
  • the pressure is 0.1 ⁇ 10Mpa.
  • the pressure is any value selected from 0.1Mpa, 0.2Mpa, 0.5Mpa, 1.0Mpa, 2.0Mpa, 3.0Mpa, 4.0Mpa, 5.0Mpa, 6.0Mpa, 7.0Mpa, 8.0Mpa, 9.0Mpa, 10.0Mpa or any range value in between.
  • the pressure is 0.1-1Mpa.
  • the pressure is 0.5-8Mpa.
  • the pressure is 1.5-6Mpa.
  • the conditions of the reaction include: the temperature is 50-220°C.
  • the reaction temperature is selected from 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 110°C, 120°C, 130°C, 140°C, Any value among 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C and 220°C or any range between them.
  • the temperature is 130-160°C.
  • the conditions of the reaction include:
  • the time is 0.1 to 10 hours.
  • the time is selected from 0.1h, 0.2h, 0.5h, 1.0h, 1.2h, 1.5h, 2.0h, 2.5h, 3.0h, 3.5h, 4.0h, 4.5h, 5.0h, 5.5h, Any value in 6.0h, 6.5h, 7.0h, 7.5h, 8.0h, 8.5h, 9.0h, 9.5h, 10.0h or any value in the range between the two.
  • the time ranges from 0.1 to 9 hours.
  • the method for preparing dichloroethane comprises the following steps:
  • reaction raw materials ethylene glycol monomethyl ether and hydrogen chloride, specific solvents and catalysts are added to a corrosion-resistant high-pressure reactor in a certain proportion, and then reacted at a certain pressure and temperature for a certain period of time to obtain the reaction product 1,2-dichloro ethane.
  • the specific solvent includes at least one of water, acetic acid, benzene, toluene, xylene, and dioxane;
  • the solvent is preferably at least one of water, benzene, toluene and dioxane.
  • the catalyst includes at least one of zinc chloride, chromium chloride, tin chloride, copper chloride, pyridine hydrochloride, triethylamine hydrochloride, and imidazole hydrochloride.
  • imidazole hydrochloride is selected from imidazole hydrochloride, 1-methylimidazole hydrochloride, 1-ethyl-3-methylimidazole hydrochloride, 1-butyl-3-methylimidazole one of the salts.
  • the pyridine hydrochloride is selected from pyridine hydrochloride, 2-chloromethylpyridine hydrochloride, 1-butylpyridine hydrochloride, 1-butyl-4-methylpyridine chloride hydrochloride One of.
  • the corrosion-resistant high-pressure reactor includes a corrosion-resistant tank reactor and a corrosion-resistant tubular reactor, and its material is selected from one of glass-lined, enamel, tetrafluoroethylene-lined, Hastelloy and titanium. kind.
  • the mass ratio of said ethylene glycol monomethyl ether and hydrogen chloride is:
  • the mass ratio of ethylene glycol monomethyl ether and hydrogen chloride is selected from 1:0.1, 1:0.2, 1:0.5, 1:0.8, 1:1, 1:2, 1:3, 1:4, 1 :5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17 , any value among 1:18, 1:19 and 1:20 or any range value between them.
  • the mass ratio of the ethylene glycol monomethyl ether and the catalyst is:
  • the mass ratio of ethylene glycol monomethyl ether to the catalyst is selected from 1:0.01, 1:0.05, 1:0.1, 1:0.2, 1:0.5, 1:1, 1:1.5, 1:2, 1 :2.5, 1:3.0, 1:3.5, 1:4.0, 1:4.5, 1:5.0, 1:5.5, 1:6.0, 1:6.5, 1:7.0, 1:7.5, 1:8.0, 1:8.5 , any value among 1:9.0, 1:9.5 and 1:10.0 or any range value between them.
  • the mass ratio of ethylene glycol monomethyl ether and solvent is:
  • the mass ratio of ethylene glycol monomethyl ether to the solvent is selected from 1:0, 1:0.01, 1:0.05, 1:0.1, 1:0.2, 1:0.5, 1:1, 1:1.5, 1 :2, 1:2.5, 1:3.0, 1:3.5, 1:4.0, 1:4.5, 1:5.0, 1:5.5, 1:6.0, 1:6.5, 1:7.0, 1:7.5, 1:8.0 , any value among 1:8.5, 1:9.0, 1:9.5 and 1:10.0 or any range value between them.
  • the reaction conditions are as follows: the pressure is 0.1-10 MPa, the reaction temperature is 50-220° C., and the reaction time is 0.1-10 hours.
  • the reaction pressure is selected from any value in 0.1Mpa, 0.2Mpa, 0.5Mpa, 1.0Mpa, 2.0Mpa, 3.0Mpa, 4.0Mpa, 5.0Mpa, 6.0Mpa, 7.0Mpa, 8.0Mpa, 9.0Mpa and 10.0Mpa or any range value in between.
  • the reaction temperature is selected from 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 110°C, 120°C, 130°C, Any value among 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C and 220°C or any range between them.
  • the reaction time is selected from 0.1h, 0.2h, 0.5h, 1.0h, 1.2h, 1.5h, 2.0h, 2.5h, 3.0h, 3.5h, 4.0h, 4.5h, 5.0h, 5.5h, Any value in 6.0h, 6.5h, 7.0h, 7.5h, 8.0h, 8.5h, 9.0h, 9.5h, 10.0h or any value in the range between the two.
  • the application discloses a method for preparing dichloroethane, which uses ethylene glycol monomethyl ether and hydrogen chloride as reaction raw materials, in the presence of a certain amount of solvent, under the action of a catalyst, under high pressure
  • the reaction is carried out under a certain pressure and a certain temperature to generate 1,2-dichloroethane.
  • the reaction pressure is 0.1-10 MPa
  • the reaction temperature is 50-220°C
  • the reaction time is 0.1-10 hours.
  • the solvent can be one of water, acetic acid, benzene, toluene, xylene and dioxane.
  • the catalyst can be one of zinc chloride, chromium chloride, tin chloride, pyridine hydrochloride, triethylamine hydrochloride and imidazole hydrochloride.
  • the method is characterized in that ethylene glycol monomethyl ether is used as a reaction raw material, which can effectively avoid excessive dehydration and carbonization reactions in the reaction system, and significantly reduce by-products. It is a new method for producing dichloroethane.
  • the application provides a method for preparing ethylene dichloride from ethylene glycol monomethyl ether.
  • Ethylene glycol monomethyl ether can be converted efficiently, and the yield of ethylene dichloride is very high.
  • the conversion ratio of ethylene glycol monomethyl ether is calculated in the following way:
  • the gas chromatographic peak area is obtained by configuring the content of ethylene glycol monomethyl ether in the standard solution, and the peak area is used as the abscissa, and the concentration of ethylene glycol monomethyl ether is used as the ordinate to obtain the standard curve; further, the reaction after reaction can be calculated.
  • the concentration of ethylene glycol monomethyl ether in the liquid is used to calculate the conversion rate of ethylene glycol monomethyl ether.
  • the yield of ethylene dichloride is calculated in the following way:
  • the gas chromatographic peak area is obtained by configuring the dichloroethane content in the standard solution, and the peak area is used as the abscissa, and the concentration of dichloroethane is used as the ordinate to obtain the standard curve; further, the dichloroethane in the reaction solution after the reaction can be calculated.
  • the concentration of ethane is used to calculate the yield of dichloroethane.
  • solvent is that 60g dimethylbenzene and catalyzer are that 30g1-butylpyridine hydrochloride joins in the corrosion-resistant high-pressure reactor, then reacted 0.5 hour under 1Mpa pressure and 170 degree of temperature.
  • Gas chromatographic analysis and calculation showed that the conversion rate of ethylene glycol monomethyl ether was 95%, and the yield of dichloroethane was 94%.

Abstract

Disclosed is a method for preparing 1,2-dichloroethane. The method comprises the following steps: reacting raw materials containing ethylene glycol monomethyl ether, hydrogen chloride and a catalyst, obtaining the 1,2-dichloroethane. According to the method, ethylene glycol monomethyl ether and hydrogen chloride are used as the raw materials for reaction, and the ethylene glycol monomethyl ether can be efficiently converted, obtaining a relatively high 1,2-dichloroethane yield.

Description

一种制备二氯乙烷的方法A kind of method for preparing dichloroethane 技术领域technical field
本申请涉及一种二氯乙烷的制备方法，属于二氯乙烷的制备合成领域。The application relates to a preparation method of dichloroethane, which belongs to the field of preparation and synthesis of dichloroethane.
背景技术Background technique
二氯乙烷是制备氯乙烯单体的重要原料，氯乙烯单体主要用于生产聚氯乙烯，另外二氯乙烷在化工过程中也常作溶剂使用。目前二氯乙烷的制备主要是通过乙烯(以石油为原料)氯化法得到，而我国缺少石油，导致我国二氯乙烷的生产未能满足市场需求。Ethylene dichloride is an important raw material for the preparation of vinyl chloride monomer, which is mainly used in the production of polyvinyl chloride, and ethylene dichloride is also often used as a solvent in chemical processes. At present, the preparation of ethylene dichloride is mainly obtained by chlorination of ethylene (using petroleum as raw material), but my country lacks oil, so the production of ethylene dichloride in my country fails to meet the market demand.
近年来甲氧基乙酸甲酯作为一个重要的有机中间体引起了人们的广泛关注，它可以通过甲缩醛气相羰基化法制备。甲氧基乙酸甲酯通过加氢可以制取乙二醇一甲醚，而关于乙二醇一甲醚的下游产品，仅有少量专利(中国专利CN106554250A)介绍了其经水解反应制取乙二醇的相关过程。但乙二醇一甲醚转化为二氯乙烷或者其它产物的技术还未见报道。In recent years, methyl methoxyacetate has attracted widespread attention as an important organic intermediate, which can be prepared by gas-phase carbonylation of methylal. Methyl methoxyacetate can produce ethylene glycol monomethyl ether through hydrogenation, and about the downstream product of ethylene glycol monomethyl ether, only a small amount of patents (Chinese patent CN106554250A) have introduced its hydrolysis reaction to produce ethylene glycol monomethyl ether. Alcohol-related processes. But the technology that ethylene glycol monomethyl ether is converted into dichloroethane or other products has not been reported yet.
发明内容Contents of the invention
本发明的目的是针对当前技术中存在的不足，提供一种乙二醇一甲醚生产二氯乙烷的方法。该方法以乙二醇一甲醚和氯化氢为反应原料，乙二醇一甲醚的可高效转化，获得较高的二氯乙烷收率。The purpose of the invention is to provide a kind of method that ethylene glycol monomethyl ether produces ethylene dichloride for the deficiencies existing in the current technology. The method uses ethylene glycol monomethyl ether and hydrogen chloride as reaction raw materials, and the ethylene glycol monomethyl ether can be efficiently converted to obtain a higher yield of dichloroethane.
一种制备二氯乙烷的方法，包括以下步骤：A method for preparing ethylene dichloride, comprising the steps of:
将含有乙二醇一甲醚、氯化氢、催化剂的原料反应，得到所述二氯乙烷。The raw materials containing ethylene glycol monomethyl ether, hydrogen chloride and catalyst are reacted to obtain the dichloroethane.
可选地，所述原料中还包括溶剂。Optionally, the raw materials also include a solvent.
所述溶剂包括水、乙酸、苯、甲苯、二甲苯、二氧六环中的至少一种。The solvent includes at least one of water, acetic acid, benzene, toluene, xylene and dioxane.
可选地，所述催化剂包括氯化锌、氯化铬、氯化锡、氯化铜、吡啶类盐酸盐、三乙胺盐酸盐、咪唑类盐酸盐中的至少一种。Optionally, the catalyst includes at least one of zinc chloride, chromium chloride, tin chloride, copper chloride, pyridine hydrochloride, triethylamine hydrochloride, and imidazole hydrochloride.
本申请所采用的催化剂，可以高效催化乙二醇一甲醚转化和/二氯乙烷的收率。The catalyst used in this application can efficiently catalyze the conversion of ethylene glycol monomethyl ether and/or the yield of dichloroethane.
可选地，所述咪唑类盐酸盐包括咪唑盐酸盐，1-甲基咪唑盐酸盐，1-乙基-3-甲基咪唑盐酸盐，1-丁基-3-甲基咪唑盐酸盐中的至少一种；Optionally, the imidazole hydrochloride includes imidazole hydrochloride, 1-methylimidazole hydrochloride, 1-ethyl-3-methylimidazole hydrochloride, 1-butyl-3-methylimidazole at least one of hydrochloride;
所述吡啶类盐酸盐包括吡啶盐酸盐，2-氯甲基吡啶盐酸盐，1-丁基吡啶盐酸盐，1-丁基-4-甲基氯化吡啶盐酸盐中的至少一种。The pyridine hydrochloride includes pyridine hydrochloride, 2-chloromethylpyridine hydrochloride, 1-butylpyridine hydrochloride, at least one of 1-butyl-4-methylpyridine chloride hydrochloride A sort of.
可选地，所述乙二醇一甲醚和氯化氢的质量比为：乙二醇一甲醚:氯化氢＝1:0.1～20。Optionally, the mass ratio of ethylene glycol monomethyl ether to hydrogen chloride is: ethylene glycol monomethyl ether:hydrogen chloride=1:0.1-20.
可选地，乙二醇一甲醚:氯化氢选自1：0.1、1：0.2、1：0.5、1：0.8、1：1、1：2、1：3、1：4、1：5、1：6、1：7、1：8、1：9、1：10、1：11、1：12、1：13、1：14、1：15、1：16、1：17、1：18、1：19、1：20中的任意值或任意两者之间的范围值。Optionally, ethylene glycol monomethyl ether: hydrogen chloride is selected from 1:0.1, 1:0.2, 1:0.5, 1:0.8, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:1: Any value in 18, 1:19, 1:20 or any range between the two.
可选地，乙二醇一甲醚:氯化氢＝1:0.1～15。Optionally, ethylene glycol monomethyl ether:hydrogen chloride=1:0.1～15.
可选地，乙二醇一甲醚:氯化氢＝1:4～12。Optionally, ethylene glycol monomethyl ether:hydrogen chloride=1:4～12.
可选地，所述乙二醇一甲醚和催化剂的质量比为：乙二醇一甲醚:催化剂＝1:0.01～10。Optionally, the mass ratio of the ethylene glycol monomethyl ether to the catalyst is: ethylene glycol monomethyl ether:catalyst=1:0.01˜10.
可选地，乙二醇一甲醚:催化剂选自1：0.01、1：0.05、1：0.1、1：0.2、1：0.5、1：1、1：1.5、1：2、1：2.5、1：3.0、1：3.5、1：4.0、1：4.5、1：5.0、1：5.5、1：6.0、1：6.5、1：7.0、1：7.5、1：8.0、1：8.5、1：9.0、1：9.5和1：10.0中的任意值或任意两者之间的范围值。Optionally, ethylene glycol monomethyl ether: catalyst is selected from 1:0.01, 1:0.05, 1:0.1, 1:0.2, 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3.0, 1:3.5, 1:4.0, 1:4.5, 1:5.0, 1:5.5, 1:6.0, 1:6.5, 1:7.0, 1:7.5, 1:8.0, 1:8.5, 1:8.0 Any value among 9.0, 1:9.5 and 1:10.0 or any range value in between.
可选地，乙二醇一甲醚:催化剂＝1:0.01～8。Optionally, ethylene glycol monomethyl ether:catalyst=1:0.01～8.
可选地，乙二醇一甲醚:催化剂＝1:0.4～9。Optionally, ethylene glycol monomethyl ether:catalyst=1:0.4～9.
可选地，所述乙二醇一甲醚和溶剂的质量比为：乙二醇一甲醚:溶剂＝1:0～20。Optionally, the mass ratio of the ethylene glycol monomethyl ether to the solvent is: ethylene glycol monomethyl ether:solvent=1:0-20.
可选地，乙二醇一甲醚:溶剂选自1：0、1：0.01、1：0.05、1：0.1、1：0.2、1：0.5、1：1、1：1.5、1：2、1：2.5、1：3.0、1：3.5、1：4.0、1：4.5、1：5.0、1：5.5、1：6.0、1：6.5、1：7.0、1：7.5、1：8.0、1：8.5、1：9.0、1：9.5、1：10.0、1：12.0、1：13.0、1：14.0、1：15.0、1：16.0、1：17.0、1：19.0、1：19.0、1：20.0中的任意值 或任意两者之间的范围值。Optionally, ethylene glycol monomethyl ether: solvent is selected from 1:0, 1:0.01, 1:0.05, 1:0.1, 1:0.2, 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3.0, 1:3.5, 1:4.0, 1:4.5, 1:5.0, 1:5.5, 1:6.0, 1:6.5, 1:7.0, 1:7.5, 1:8.0, 1: 8.5, 1:9.0, 1:9.5, 1:10.0, 1:12.0, 1:13.0, 1:14.0, 1:15.0, 1:16.0, 1:17.0, 1:19.0, 1:19.0, 1:20.0 Any value of or any range value in between.
可选地，乙二醇一甲醚:溶剂＝1:0.5～1.5。Optionally, ethylene glycol monomethyl ether:solvent=1:0.5～1.5.
可选地，所述反应的条件包括：Optionally, the conditions of the reaction include:
压力为0.1～10Mpa。The pressure is 0.1 ~ 10Mpa.
可选地，压力为选自0.1Mpa、0.2Mpa、0.5Mpa、1.0Mpa、2.0Mpa、3.0Mpa、4.0Mpa、5.0Mpa、6.0Mpa、7.0Mpa、8.0Mpa、9.0Mpa、10.0Mpa中的任意值或任意两者之间的范围值。Optionally, the pressure is any value selected from 0.1Mpa, 0.2Mpa, 0.5Mpa, 1.0Mpa, 2.0Mpa, 3.0Mpa, 4.0Mpa, 5.0Mpa, 6.0Mpa, 7.0Mpa, 8.0Mpa, 9.0Mpa, 10.0Mpa or any range value in between.
可选地，压力为0.1～1Mpa。Optionally, the pressure is 0.1-1Mpa.
可选地，压力为0.5～8Mpa。Optionally, the pressure is 0.5-8Mpa.
可选地，压力为1.5～6Mpa。Optionally, the pressure is 1.5-6Mpa.
可选地，所述反应的条件包括：温度为50～220℃。Optionally, the conditions of the reaction include: the temperature is 50-220°C.
反应温度为选自50℃、55℃、60℃、65℃、70℃、75℃、80℃、85℃、90℃、95℃、100℃、110℃、120℃、130℃、140℃、150℃、160℃、170℃、180℃、190℃、200℃、210℃和220℃中的任意值或任意两者之间的范围值。The reaction temperature is selected from 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 110°C, 120°C, 130°C, 140°C, Any value among 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C and 220°C or any range between them.
可选地，温度为130～160℃。Optionally, the temperature is 130-160°C.
可选地，所述反应的条件包括：Optionally, the conditions of the reaction include:
时间为0.1～10小时。The time is 0.1 to 10 hours.
可选地，时间为选自0.1h、0.2h、0.5h、1.0h、1.2h、1.5h、2.0h、2.5h、3.0h、3.5h、4.0h、4.5h、5.0h、5.5h、6.0h、6.5h、7.0h、7.5h、8.0h、8.5h、9.0h、9.5h、10.0h中的任意值或任意两者之间的范围值。Optionally, the time is selected from 0.1h, 0.2h, 0.5h, 1.0h, 1.2h, 1.5h, 2.0h, 2.5h, 3.0h, 3.5h, 4.0h, 4.5h, 5.0h, 5.5h, Any value in 6.0h, 6.5h, 7.0h, 7.5h, 8.0h, 8.5h, 9.0h, 9.5h, 10.0h or any value in the range between the two.
可选地，时间为0.1～9小时。Optionally, the time ranges from 0.1 to 9 hours.
作为一种实施方案，所述制备二氯乙烷的方法，包括以下步骤：As an embodiment, the method for preparing dichloroethane comprises the following steps:
将反应原料乙二醇一甲醚和氯化氢，特定的溶剂和催化剂按照一定比例加入到耐腐蚀高压反应器中，然后在一定压力和一定温度下反应一定时间，得到反应产物1,2-二氯乙烷。The reaction raw materials ethylene glycol monomethyl ether and hydrogen chloride, specific solvents and catalysts are added to a corrosion-resistant high-pressure reactor in a certain proportion, and then reacted at a certain pressure and temperature for a certain period of time to obtain the reaction product 1,2-dichloro ethane.
可选地，所述特定的溶剂包括水、乙酸、苯、甲苯、二甲苯、二氧六环中的至少一种；Optionally, the specific solvent includes at least one of water, acetic acid, benzene, toluene, xylene, and dioxane;
可选地，所述溶剂优选水、苯、甲苯和二氧六环中的至少一种。Optionally, the solvent is preferably at least one of water, benzene, toluene and dioxane.
可选地，所述催化剂包括氯化锌、氯化铬、氯化锡、氯化铜、吡啶类盐酸盐、三乙胺盐酸盐、咪唑类盐酸盐中的至少一种。Optionally, the catalyst includes at least one of zinc chloride, chromium chloride, tin chloride, copper chloride, pyridine hydrochloride, triethylamine hydrochloride, and imidazole hydrochloride.
可选地，咪唑类盐酸盐选自咪唑盐酸盐，1-甲基咪唑盐酸盐，1-乙基-3-甲基咪唑盐酸盐，1-丁基-3-甲基咪唑盐酸盐中的一种。Optionally, imidazole hydrochloride is selected from imidazole hydrochloride, 1-methylimidazole hydrochloride, 1-ethyl-3-methylimidazole hydrochloride, 1-butyl-3-methylimidazole one of the salts.
可选地，吡啶类盐酸盐选自吡啶盐酸盐，2-氯甲基吡啶盐酸盐，1-丁基吡啶盐酸盐，1-丁基-4-甲基氯化吡啶盐酸盐中的一种。Optionally, the pyridine hydrochloride is selected from pyridine hydrochloride, 2-chloromethylpyridine hydrochloride, 1-butylpyridine hydrochloride, 1-butyl-4-methylpyridine chloride hydrochloride One of.
可选地，所述耐腐蚀高压反应器包括耐腐蚀釜式反应器和耐腐蚀管式反应器，其材质选自搪玻璃、搪瓷、衬四氟乙烯、哈氏合金材质和钛材质中的一种。Optionally, the corrosion-resistant high-pressure reactor includes a corrosion-resistant tank reactor and a corrosion-resistant tubular reactor, and its material is selected from one of glass-lined, enamel, tetrafluoroethylene-lined, Hastelloy and titanium. kind.
可选地，所述乙二醇一甲醚和氯化氢的质量比为：Optionally, the mass ratio of said ethylene glycol monomethyl ether and hydrogen chloride is:
乙二醇一甲醚：氯化氢＝1:0.1～20。Ethylene glycol monomethyl ether: hydrogen chloride = 1:0.1～20.
可选地，乙二醇一甲醚和氯化氢的质量比选自1：0.1、1：0.2、1：0.5、1：0.8、1：1、1：2、1：3、1：4、1：5、1：6、1：7、1：8、1：9、1：10、1：11、1：12、1：13、1：14、1：15、1：16、1：17、1：18、1：19和1：20中的任意值或任意两者之间的范围值。Optionally, the mass ratio of ethylene glycol monomethyl ether and hydrogen chloride is selected from 1:0.1, 1:0.2, 1:0.5, 1:0.8, 1:1, 1:2, 1:3, 1:4, 1 :5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17 , any value among 1:18, 1:19 and 1:20 or any range value between them.
可选地，所述乙二醇一甲醚和催化剂的质量比为：Optionally, the mass ratio of the ethylene glycol monomethyl ether and the catalyst is:
乙二醇一甲醚：催化剂＝1:0.01～10。Ethylene glycol monomethyl ether: catalyst=1:0.01～10.
可选地，乙二醇一甲醚和催化剂的质量比选自1：0.01、1：0.05、1：0.1、1：0.2、1：0.5、1：1、1：1.5、1：2、1：2.5、1：3.0、1：3.5、1：4.0、1：4.5、1：5.0、1：5.5、1：6.0、1：6.5、1：7.0、1：7.5、1：8.0、1：8.5、1：9.0、1：9.5和1：10.0中的任意值或任意两者之间的范围值。Optionally, the mass ratio of ethylene glycol monomethyl ether to the catalyst is selected from 1:0.01, 1:0.05, 1:0.1, 1:0.2, 1:0.5, 1:1, 1:1.5, 1:2, 1 :2.5, 1:3.0, 1:3.5, 1:4.0, 1:4.5, 1:5.0, 1:5.5, 1:6.0, 1:6.5, 1:7.0, 1:7.5, 1:8.0, 1:8.5 , any value among 1:9.0, 1:9.5 and 1:10.0 or any range value between them.
可选地，乙二醇一甲醚和溶剂的质量比为：Optionally, the mass ratio of ethylene glycol monomethyl ether and solvent is:
乙二醇一甲醚：溶剂＝1:0～20。Ethylene glycol monomethyl ether: solvent = 1:0~20.
可选地，乙二醇一甲醚和溶剂的质量比选自1：0、1：0.01、1：0.05、1：0.1、1：0.2、1：0.5、1：1、1：1.5、1：2、1：2.5、1：3.0、1：3.5、1：4.0、1：4.5、1：5.0、1：5.5、1：6.0、1：6.5、1：7.0、1：7.5、1：8.0、1：8.5、1：9.0、1：9.5和1：10.0中的任意值或任意两者之间的范围值。Optionally, the mass ratio of ethylene glycol monomethyl ether to the solvent is selected from 1:0, 1:0.01, 1:0.05, 1:0.1, 1:0.2, 1:0.5, 1:1, 1:1.5, 1 :2, 1:2.5, 1:3.0, 1:3.5, 1:4.0, 1:4.5, 1:5.0, 1:5.5, 1:6.0, 1:6.5, 1:7.0, 1:7.5, 1:8.0 , any value among 1:8.5, 1:9.0, 1:9.5 and 1:10.0 or any range value between them.
可选地，反应的条件为：压力为0.1～10Mpa，反应温度为50～220℃， 反应时间为0.1～10小时。Optionally, the reaction conditions are as follows: the pressure is 0.1-10 MPa, the reaction temperature is 50-220° C., and the reaction time is 0.1-10 hours.
可选地，反应压力选自0.1Mpa、0.2Mpa、0.5Mpa、1.0Mpa、2.0Mpa、3.0Mpa、4.0Mpa、5.0Mpa、6.0Mpa、7.0Mpa、8.0Mpa、9.0Mpa和10.0Mpa中的任意值或任意两者之间的范围值。Optionally, the reaction pressure is selected from any value in 0.1Mpa, 0.2Mpa, 0.5Mpa, 1.0Mpa, 2.0Mpa, 3.0Mpa, 4.0Mpa, 5.0Mpa, 6.0Mpa, 7.0Mpa, 8.0Mpa, 9.0Mpa and 10.0Mpa or any range value in between.
可选地，反应温度选自50℃、55℃、60℃、65℃、70℃、75℃、80℃、85℃、90℃、95℃、100℃、110℃、120℃、130℃、140℃、150℃、160℃、170℃、180℃、190℃、200℃、210℃和220℃中的任意值或任意两者之间的范围值。Optionally, the reaction temperature is selected from 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 110°C, 120°C, 130°C, Any value among 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C and 220°C or any range between them.
可选地，反应时间选自0.1h、0.2h、0.5h、1.0h、1.2h、1.5h、2.0h、2.5h、3.0h、3.5h、4.0h、4.5h、5.0h、5.5h、6.0h、6.5h、7.0h、7.5h、8.0h、8.5h、9.0h、9.5h、10.0h中的任意值或任意两者之间的范围值。Optionally, the reaction time is selected from 0.1h, 0.2h, 0.5h, 1.0h, 1.2h, 1.5h, 2.0h, 2.5h, 3.0h, 3.5h, 4.0h, 4.5h, 5.0h, 5.5h, Any value in 6.0h, 6.5h, 7.0h, 7.5h, 8.0h, 8.5h, 9.0h, 9.5h, 10.0h or any value in the range between the two.
作为一种实施方案，本申请公开了一种制备二氯乙烷的方法，该方法以乙二醇一甲醚和氯化氢为反应原料，在一定量溶剂存在下，在催化剂的作用下，在高压反应器中，在一定压力和一定温度下进行反应生成1,2-二氯乙烷。反应压力为0.1～10MPa，反应温度为50～220℃，反应时间为0.1～10小时。溶剂可以为水、乙酸、苯、甲苯、二甲苯、二氧六环中的一种。催化剂可以为氯化锌、氯化铬、氯化锡、吡啶类盐酸盐、三乙胺盐酸盐、咪唑类盐酸盐中的一种。该方法的特点是采用乙二醇一甲醚作为反应原料，能够有效避免反应体系发生过度脱水碳化反应，副产物显著降低，是一种生产二氯乙烷的新方法。As an embodiment, the application discloses a method for preparing dichloroethane, which uses ethylene glycol monomethyl ether and hydrogen chloride as reaction raw materials, in the presence of a certain amount of solvent, under the action of a catalyst, under high pressure In the reactor, the reaction is carried out under a certain pressure and a certain temperature to generate 1,2-dichloroethane. The reaction pressure is 0.1-10 MPa, the reaction temperature is 50-220°C, and the reaction time is 0.1-10 hours. The solvent can be one of water, acetic acid, benzene, toluene, xylene and dioxane. The catalyst can be one of zinc chloride, chromium chloride, tin chloride, pyridine hydrochloride, triethylamine hydrochloride and imidazole hydrochloride. The method is characterized in that ethylene glycol monomethyl ether is used as a reaction raw material, which can effectively avoid excessive dehydration and carbonization reactions in the reaction system, and significantly reduce by-products. It is a new method for producing dichloroethane.
本申请能产生的有益效果包括：The beneficial effect that this application can produce comprises:
1)本申请提供了一种乙二醇一甲醚制备二氯乙烷的方法，乙二醇一甲醚可以高效转化，而且二氯乙烷的收率很高。1) The application provides a method for preparing ethylene dichloride from ethylene glycol monomethyl ether. Ethylene glycol monomethyl ether can be converted efficiently, and the yield of ethylene dichloride is very high.
2)本申请中提供的制备二氯乙烷的方法具有较大的经济利益，不但开拓了乙二醇一甲醚的下游产品，而且与氯乙烯工业紧密连接。2) The method for preparing ethylene dichloride provided in this application has great economic benefits, not only develops downstream products of ethylene glycol monomethyl ether, but also is closely connected with the vinyl chloride industry.
具体实施方式Detailed ways
下面结合实施例详述本申请，但本申请并不局限于这些实施例。The present application is described in detail below in conjunction with the examples, but the present application is not limited to these examples.
如无特别说明，本申请的实施例中的原料均通过商业途径购买。Unless otherwise specified, the raw materials in the examples of the present application were purchased through commercial channels.
本申请的实施例中分析方法如下：Analytic method is as follows in the embodiment of the application:
本申请的实施例中，乙二醇一甲醚的转化率通过以下方式进行计算：In the embodiment of the application, the conversion ratio of ethylene glycol monomethyl ether is calculated in the following way:
通过配置标准溶液中的乙二醇一甲醚含量得到气相色谱峰面积，将峰面积作为横坐标，乙二醇一甲醚的浓度作为纵坐标，得到标准曲线；进一步即可计算出反应后反应液中乙二醇一甲醚的浓度，通过浓度算出乙二醇一甲醚的转化率。The gas chromatographic peak area is obtained by configuring the content of ethylene glycol monomethyl ether in the standard solution, and the peak area is used as the abscissa, and the concentration of ethylene glycol monomethyl ether is used as the ordinate to obtain the standard curve; further, the reaction after reaction can be calculated. The concentration of ethylene glycol monomethyl ether in the liquid is used to calculate the conversion rate of ethylene glycol monomethyl ether.
本申请的实施例中，二氯乙烷的收率通过以下方式进行计算：In the embodiments of the application, the yield of ethylene dichloride is calculated in the following way:
通过配置标准溶液中的二氯乙烷含量得到气相色谱峰面积，将峰面积作为横坐标，二氯乙烷的浓度作为纵坐标，得到标准曲线；进一步即可计算出反应后反应液中二氯乙烷的浓度，通过浓度算出二氯乙烷的收率。The gas chromatographic peak area is obtained by configuring the dichloroethane content in the standard solution, and the peak area is used as the abscissa, and the concentration of dichloroethane is used as the ordinate to obtain the standard curve; further, the dichloroethane in the reaction solution after the reaction can be calculated. The concentration of ethane is used to calculate the yield of dichloroethane.
实施例1Example 1
将5g乙二醇一甲醚和10g氯化氢，溶剂为50g水和催化剂为0.05g氯化锌加入到耐腐蚀高压反应器中，然后在0.5Mpa压力和120度温度下反应4小时。气相色谱分析计算得到：乙二醇一甲醚转化率97％，二氯乙烷收率91％。Add 5g of ethylene glycol monomethyl ether and 10g of hydrogen chloride, 50g of water as a solvent and 0.05g of zinc chloride as a catalyst into a corrosion-resistant high-pressure reactor, and then react for 4 hours at a pressure of 0.5Mpa and a temperature of 120 degrees. Gas chromatographic analysis and calculation showed that the conversion rate of ethylene glycol monomethyl ether was 97%, and the yield of dichloroethane was 91%.
本实施例中，乙二醇一甲醚:氯化氢＝1:2；In the present embodiment, ethylene glycol monomethyl ether: hydrogen chloride=1:2;
乙二醇一甲醚:催化剂＝1:0.01；Ethylene glycol monomethyl ether: catalyst=1:0.01;
乙二醇一甲醚:溶剂＝1:10。Ethylene glycol monomethyl ether: solvent=1:10.
实施例2Example 2
将5g乙二醇一甲醚和100g氯化氢，溶剂为100g醋酸和催化剂为50g1-丁基-3-甲基咪唑盐酸盐加入到耐腐蚀高压反应器中，然后在10Mpa压力和50度温度下反应10小时。气相色谱分析计算得到：乙二醇一甲醚转化率93％，二氯乙烷收率92％。5g ethylene glycol monomethyl ether and 100g hydrogen chloride, the solvent is 100g acetic acid and the catalyst is 50g 1-butyl-3-methylimidazole hydrochloride to join in the corrosion-resistant high-pressure reactor, then under 10Mpa pressure and 50 degrees of temperature React for 10 hours. Gas chromatographic analysis and calculation showed that the conversion rate of ethylene glycol monomethyl ether was 93%, and the yield of dichloroethane was 92%.
本实施例中，乙二醇一甲醚:氯化氢＝1:20；In the present embodiment, ethylene glycol monomethyl ether: hydrogen chloride=1:20;
乙二醇一甲醚:催化剂＝1:10；Ethylene glycol monomethyl ether: catalyst=1:10;
乙二醇一甲醚:溶剂＝1:20。Ethylene glycol monomethyl ether: solvent=1:20.
实施例3Example 3
将5g乙二醇一甲醚和50g氯化氢，溶剂为50g苯和催化剂为6g氯化锡加入到耐腐蚀高压反应器中，然后在6Mpa压力和90度温度下反应6小时。气相色谱分析计算得到：乙二醇一甲醚转化率95％，二氯乙烷收率95％。Add 5g of ethylene glycol monomethyl ether and 50g of hydrogen chloride, 50g of benzene as a solvent and 6g of tin chloride as a catalyst into a corrosion-resistant high-pressure reactor, and then react for 6 hours at a pressure of 6Mpa and a temperature of 90 degrees. Gas chromatographic analysis and calculation obtained: the conversion rate of ethylene glycol monomethyl ether is 95%, and the yield of dichloroethane is 95%.
本实施例中，乙二醇一甲醚:氯化氢＝1:10；In the present embodiment, ethylene glycol monomethyl ether: hydrogen chloride=1:10;
乙二醇一甲醚:催化剂＝1:1.2；Ethylene glycol monomethyl ether: catalyst=1:1.2;
乙二醇一甲醚:溶剂＝1:10。Ethylene glycol monomethyl ether: solvent=1:10.
实施例4Example 4
将5g乙二醇一甲醚和30g氯化氢，溶剂为30g二氧六环和催化剂为15g1-甲基咪唑盐酸盐加入到耐腐蚀高压反应器中，然后在3Mpa压力和150度温度下反应2小时。气相色谱分析计算得到：乙二醇一甲醚转化率97％，二氯乙烷收率97％。5g of ethylene glycol monomethyl ether and 30g of hydrogen chloride, the solvent is 30g of dioxane and the catalyst is 15g of 1-methylimidazole hydrochloride into a corrosion-resistant high-pressure reactor, and then react at a pressure of 3Mpa and a temperature of 150 degrees for 2 Hour. Gas chromatographic analysis and calculation showed that the conversion rate of ethylene glycol monomethyl ether was 97%, and the yield of dichloroethane was 97%.
本实施例中，乙二醇一甲醚:氯化氢＝1:6；In the present embodiment, ethylene glycol monomethyl ether: hydrogen chloride=1:6;
乙二醇一甲醚:催化剂＝1:3；Ethylene glycol monomethyl ether: catalyst=1:3;
乙二醇一甲醚:溶剂＝1:6。Ethylene glycol monomethyl ether: solvent=1:6.
实施例5Example 5
将5g乙二醇一甲醚和0.5g氯化氢，催化剂为20g吡啶盐酸盐加入到耐腐蚀高压反应器中，然后在0.1Mpa压力和200度温度下反应8小时。气相色谱分析计算得到：乙二醇一甲醚转化率94％，二氯乙烷收率94％。Add 5g of ethylene glycol monomethyl ether and 0.5g of hydrogen chloride, and the catalyst is 20g of pyridine hydrochloride into a corrosion-resistant high-pressure reactor, and then react for 8 hours at a pressure of 0.1Mpa and a temperature of 200 degrees. Gas chromatographic analysis and calculation showed that the conversion rate of ethylene glycol monomethyl ether was 94%, and the yield of dichloroethane was 94%.
本实施例中，乙二醇一甲醚:氯化氢＝1:0.1；In the present embodiment, ethylene glycol monomethyl ether: hydrogen chloride=1:0.1;
乙二醇一甲醚:催化剂＝1:4；Ethylene glycol monomethyl ether: catalyst=1:4;
乙二醇一甲醚:溶剂＝1:0。Ethylene glycol monomethyl ether: solvent=1:0.
实施例6Example 6
将5g乙二醇一甲醚和70g氯化氢，溶剂为60g二甲苯和催化剂 为30g1-丁基吡啶盐酸盐加入到耐腐蚀高压反应器中，然后在1Mpa压力和170度温度下反应0.5小时。气相色谱分析计算得到：乙二醇一甲醚转化率95％，二氯乙烷收率94％。With 5g ethylene glycol monomethyl ether and 70g hydrogen chloride, solvent is that 60g dimethylbenzene and catalyzer are that 30g1-butylpyridine hydrochloride joins in the corrosion-resistant high-pressure reactor, then reacted 0.5 hour under 1Mpa pressure and 170 degree of temperature. Gas chromatographic analysis and calculation showed that the conversion rate of ethylene glycol monomethyl ether was 95%, and the yield of dichloroethane was 94%.
本实施例中，乙二醇一甲醚:氯化氢＝1:14；In the present embodiment, ethylene glycol monomethyl ether: hydrogen chloride=1:14;
乙二醇一甲醚:催化剂＝1:6；Ethylene glycol monomethyl ether: catalyst=1:6;
乙二醇一甲醚:溶剂＝1:12。Ethylene glycol monomethyl ether: solvent=1:12.
实施例7Example 7
将5g乙二醇一甲醚和15g氯化氢，溶剂为10g甲苯和催化剂为2g氯化铬加入到耐腐蚀高压反应器中，然后在2Mpa压力和220度温度下反应0.1小时。气相色谱分析计算得到：乙二醇一甲醚转化率96％，二氯乙烷收率94％。Add 5g of ethylene glycol monomethyl ether and 15g of hydrogen chloride, 10g of toluene as a solvent and 2g of chromium chloride as a catalyst into a corrosion-resistant high-pressure reactor, and then react for 0.1 hour at a pressure of 2Mpa and a temperature of 220 degrees. Gas chromatographic analysis and calculation showed that the conversion rate of ethylene glycol monomethyl ether was 96%, and the yield of dichloroethane was 94%.
本实施例中，乙二醇一甲醚:氯化氢＝1:3；In the present embodiment, ethylene glycol monomethyl ether: hydrogen chloride=1:3;
乙二醇一甲醚:催化剂＝1:0.4；Ethylene glycol monomethyl ether: catalyst=1:0.4;
乙二醇一甲醚:溶剂＝1:2。Ethylene glycol monomethyl ether: solvent=1:2.
实施例8Example 8
将5g乙二醇一甲醚和20g氯化氢，溶剂为5g水和催化剂为40g2-氯甲基吡啶盐酸盐加入到耐腐蚀高压反应器中，然后在1.5Mpa压力和140度温度下反应4小时。气相色谱分析计算得到：乙二醇一甲醚转化率100％，二氯乙烷收率99％。Add 5g of ethylene glycol monomethyl ether and 20g of hydrogen chloride, 5g of water as a solvent and 40g of 2-chloromethylpyridine hydrochloride as a catalyst into a corrosion-resistant high-pressure reactor, and then react for 4 hours at a pressure of 1.5Mpa and a temperature of 140 degrees . Gas chromatographic analysis and calculation showed that the conversion rate of ethylene glycol monomethyl ether was 100%, and the yield of dichloroethane was 99%.
本实施例中，乙二醇一甲醚:氯化氢＝1:4；In the present embodiment, ethylene glycol monomethyl ether: hydrogen chloride=1:4;
乙二醇一甲醚:催化剂＝1:8；Ethylene glycol monomethyl ether: catalyst=1:8;
乙二醇一甲醚:溶剂＝1:1。Ethylene glycol monomethyl ether: solvent=1:1.
以上所述，仅是本申请的几个实施例，并非对本申请做任何形式的限制，虽然本申请以较佳实施例揭示如上，然而并非用以限制本申请，任何熟悉本专业的技术人员，在不脱离本申请技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。The above are only a few embodiments of the application, and do not limit the application in any form. Although the application is disclosed as above with preferred embodiments, it is not intended to limit the application. Any skilled person familiar with this field, Without departing from the scope of the technical solution of the present application, any changes or modifications made using the technical content disclosed above are equivalent to equivalent implementation cases, and all belong to the scope of the technical solution.

Claims (20)

  1. 一种制备二氯乙烷的方法，其特征在于，包括以下步骤：A kind of method for preparing ethylene dichloride, is characterized in that, comprises the following steps:
    将含有乙二醇一甲醚、氯化氢、催化剂的原料反应，得到所述二氯乙烷。The raw materials containing ethylene glycol monomethyl ether, hydrogen chloride and catalyst are reacted to obtain the dichloroethane.
  2. 根据权利要求1所述的方法，其特征在于，所述原料中还包括溶剂；The method according to claim 1, wherein the raw material also includes a solvent;
    所述溶剂包括水、乙酸、苯、甲苯、二甲苯、二氧六环中的至少一种。The solvent includes at least one of water, acetic acid, benzene, toluene, xylene and dioxane.
  3. 根据权利要求1所述的方法，其特征在于，所述催化剂包括氯化锌、氯化铬、氯化锡、氯化铜、吡啶类盐酸盐、三乙胺盐酸盐、咪唑类盐酸盐中的至少一种。The method according to claim 1, wherein the catalyst comprises zinc chloride, chromium chloride, tin chloride, copper chloride, pyridine hydrochloride, triethylamine hydrochloride, imidazole hydrochloride at least one of the salts.
  4. 根据权利要求3所述的方法，其特征在于，所述咪唑类盐酸盐包括咪唑盐酸盐，1-甲基咪唑盐酸盐，1-乙基-3-甲基咪唑盐酸盐，1-丁基-3-甲基咪唑盐酸盐中的至少一种；The method according to claim 3, wherein the imidazole hydrochloride comprises imidazole hydrochloride, 1-methylimidazole hydrochloride, 1-ethyl-3-methylimidazole hydrochloride, 1 - at least one of butyl-3-methylimidazole hydrochloride;
    所述吡啶类盐酸盐包括吡啶盐酸盐，2-氯甲基吡啶盐酸盐，1-丁基吡啶盐酸盐，1-丁基-4-甲基氯化吡啶盐酸盐中的至少一种。The pyridine hydrochloride includes pyridine hydrochloride, 2-chloromethylpyridine hydrochloride, 1-butylpyridine hydrochloride, at least one of 1-butyl-4-methylpyridine chloride hydrochloride A sort of.
  5. 根据权利要求1所述的方法，其特征在于，所述乙二醇一甲醚和氯化氢的质量比为：method according to claim 1, is characterized in that, the mass ratio of described ethylene glycol monomethyl ether and hydrogen chloride is:
    乙二醇一甲醚:氯化氢＝1:0.1～20。Ethylene glycol monomethyl ether: hydrogen chloride=1:0.1～20.
  6. 根据权利要求1所述的方法，其特征在于，所述乙二醇一甲醚和氯化氢的质量比为：method according to claim 1, is characterized in that, the mass ratio of described ethylene glycol monomethyl ether and hydrogen chloride is:
    乙二醇一甲醚:氯化氢＝1:0.1～15。Ethylene glycol monomethyl ether: hydrogen chloride=1:0.1～15.
  7. 根据权利要求1所述的方法，其特征在于，所述乙二醇一甲 醚和氯化氢的质量比为：method according to claim 1, is characterized in that, the mass ratio of described ethylene glycol monomethyl ether and hydrogen chloride is:
    乙二醇一甲醚:氯化氢＝1:4～12。Ethylene glycol monomethyl ether:hydrogen chloride=1:4～12.
  8. 根据权利要求1所述的方法，其特征在于，所述乙二醇一甲醚和催化剂的质量比为：method according to claim 1, is characterized in that, the mass ratio of described ethylene glycol monomethyl ether and catalyzer is:
    乙二醇一甲醚:催化剂＝1:0.01～10。Ethylene glycol monomethyl ether: catalyst=1:0.01～10.
  9. 根据权利要求1所述的方法，其特征在于，所述乙二醇一甲醚和催化剂的质量比为：method according to claim 1, is characterized in that, the mass ratio of described ethylene glycol monomethyl ether and catalyzer is:
    乙二醇一甲醚:催化剂＝1:0.01～8。Ethylene glycol monomethyl ether: catalyst=1:0.01～8.
  10. 根据权利要求1所述的方法，其特征在于，所述乙二醇一甲醚和催化剂的质量比为：method according to claim 1, is characterized in that, the mass ratio of described ethylene glycol monomethyl ether and catalyzer is:
    乙二醇一甲醚:催化剂＝1:0.4～9。Ethylene glycol monomethyl ether: catalyst=1:0.4～9.
  11. 根据权利要求1所述的方法，其特征在于，所述乙二醇一甲醚和溶剂的质量比为：method according to claim 1, is characterized in that, the mass ratio of described ethylene glycol monomethyl ether and solvent is:
    乙二醇一甲醚:溶剂＝1:0～20。Ethylene glycol monomethyl ether: solvent=1:0～20.
  12. 根据权利要求1所述的方法，其特征在于，所述乙二醇一甲醚和溶剂的质量比为：method according to claim 1, is characterized in that, the mass ratio of described ethylene glycol monomethyl ether and solvent is:
    乙二醇一甲醚:溶剂＝1:0.5～1.5。Ethylene glycol monomethyl ether: solvent=1:0.5～1.5.
  13. 根据权利要求1所述的方法，其特征在于，所述反应的条件包括：method according to claim 1, is characterized in that, the condition of described reaction comprises:
    压力为0.1～10Mpa。The pressure is 0.1 ~ 10Mpa.
  14. 根据权利要求1所述的方法，其特征在于，所述反应的条件包括：method according to claim 1, is characterized in that, the condition of described reaction comprises:
    压力为0.1～1Mpa。The pressure is 0.1 ~ 1Mpa.
  15. 根据权利要求1所述的方法，其特征在于，所述反应的条件包括：method according to claim 1, is characterized in that, the condition of described reaction comprises:
    压力为0.5～8Mpa。The pressure is 0.5 ~ 8Mpa.
  16. 根据权利要求1所述的方法，其特征在于，所述反应的条件包括：method according to claim 1, is characterized in that, the condition of described reaction comprises:
    压力为1.5～6Mpa。The pressure is 1.5 ~ 6Mpa.
  17. 根据权利要求1所述的方法，其特征在于，所述反应的条件包括：method according to claim 1, is characterized in that, the condition of described reaction comprises:
    温度为50～220℃。The temperature is 50-220°C.
  18. 根据权利要求1所述的方法，其特征在于，所述反应的条件包括：method according to claim 1, is characterized in that, the condition of described reaction comprises:
    温度为130～160℃。The temperature is 130-160°C.
  19. 根据权利要求1所述的方法，其特征在于，所述反应的条件包括：method according to claim 1, is characterized in that, the condition of described reaction comprises:
    时间为0.1～10小时。The time is 0.1 to 10 hours.
  20. 根据权利要求1所述的方法，其特征在于，所述反应的条件包括：method according to claim 1, is characterized in that, the condition of described reaction comprises:
    时间为0.1～9小时。The time is 0.1 to 9 hours.
PCT/CN2021/136758 2021-12-09 2021-12-09 Method for preparing 1,2-dichloroethane WO2023102821A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0106356A1 (en) * 1982-10-18 1984-04-25 The Dow Chemical Company Catalytic process for producing saturated dihalohydrocarbons
US20060129008A1 (en) * 2004-12-02 2006-06-15 Sud-Chemie Catalysts Italia S.R.L. Catalysts for oxychlorination of ethylene to 1,2-dichlorethane
US20080146854A1 (en) * 2004-12-22 2008-06-19 Harald Hafenscher Method for Producing 1,2-Dichloroethane by Means of Direct Chlorination
CN104209128A (en) * 2013-05-29 2014-12-17 上海氯碱化工股份有限公司 Composite catalyst for direct chlorination reaction to prepare dichloroethane
CN107698423A (en) * 2017-09-12 2018-02-16 沈阳化工大学 A kind of method for preparing ethylene glycol and by-product halogenated alkane

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0106356A1 (en) * 1982-10-18 1984-04-25 The Dow Chemical Company Catalytic process for producing saturated dihalohydrocarbons
US20060129008A1 (en) * 2004-12-02 2006-06-15 Sud-Chemie Catalysts Italia S.R.L. Catalysts for oxychlorination of ethylene to 1,2-dichlorethane
US20080146854A1 (en) * 2004-12-22 2008-06-19 Harald Hafenscher Method for Producing 1,2-Dichloroethane by Means of Direct Chlorination
CN104209128A (en) * 2013-05-29 2014-12-17 上海氯碱化工股份有限公司 Composite catalyst for direct chlorination reaction to prepare dichloroethane
CN107698423A (en) * 2017-09-12 2018-02-16 沈阳化工大学 A kind of method for preparing ethylene glycol and by-product halogenated alkane

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