WO2021017362A1 - Dechlorination method of chloro-substituted aromatic compound (r 1-x m) using copper as catalyst - Google Patents

Dechlorination method of chloro-substituted aromatic compound (r 1-x m) using copper as catalyst Download PDF

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WO2021017362A1
WO2021017362A1 PCT/CN2019/124169 CN2019124169W WO2021017362A1 WO 2021017362 A1 WO2021017362 A1 WO 2021017362A1 CN 2019124169 W CN2019124169 W CN 2019124169W WO 2021017362 A1 WO2021017362 A1 WO 2021017362A1
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present
catalyst
copper
dechlorination
mixture
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郑南峰
荆文彤
吴康宁
刘圣杰
陈洁
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厦门大学
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation

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  • the present invention relates to a method for dechlorination of chlorinated aromatic compounds (R 1 -X m ) using copper as a catalyst.
  • Polychlorinated benzene compounds and their derivatives have stable chemical properties and are easy to accumulate in organisms. Once it enters the environment, it will pose a long-term threat to humans and the ecological environment, and it has been listed as one of the pollutants that are prioritized by the global environment. But the current industrial production will inevitably generate polychlorinated benzene by-products, including trichlorobenzene and tetrachlorobenzene. The annual output of polychlorinated benzene by-products is above 10,000 tons, which not only pollutes the environment but also occupies space, coupled with high processing costs, has become a great burden in industrial production.
  • Low-chlorine aromatic hydrocarbons are widely used chemical raw materials, organic synthesis intermediates and organic solvents in the chemical, pharmaceutical, leather, and electronics industries. Therefore, if the polychlorinated benzene waste produced in the industry can be processed, not only high value-added low-chlorine aromatic products can be obtained, but also the environmental pollution problem can be solved.
  • the industrial methods for degrading polychlorobenzene compounds mainly include: storage method, high temperature treatment method, chemical removal method, biodegradation method, catalytic hydrodechlorination method, etc.
  • catalytic hydrodechlorination is achieved by dissociating hydrogen on precious metal catalysts such as palladium, platinum, rhodium, etc., to replace chlorine atoms on polychlorinated benzene with the generated hydrogen atoms to achieve the purpose of degradation.
  • the conventional hydrodechlorination process includes dissolving the polychlorinated substrate in an organic solvent, adding a sufficient amount of catalyst, and introducing high-purity hydrogen for the reaction. Since there are many flammable and explosive materials in the factory, if hydrogen can be avoided as a hydrogen source, on the one hand, the processing cost can be reduced, and on the other hand, the safety index of the factory can be improved to a certain extent.
  • One aspect of the present invention provides a method for dechlorination of chlorinated aromatic compounds (R 1 -X m ) using copper as a catalyst.
  • the method is characterized in that the method comprises the following steps: R 1 -X m is used as a substrate and R 2 ( OH) n , a basic substance with a pH value greater than 7 and a copper catalyst to form a mixture, wherein R 1 is a substituted or unsubstituted aromatic group, X is a chloride ion, and m is a positive integer; R 2 is a methyl group, And n is 1; stirring the mixture; and heating the mixture to perform a hydrogenation reaction to obtain R 1 -X m' , wherein m'is less than m, and m'is an integer.
  • R 1 is a substituted or unsubstituted phenyl group.
  • R 1 is an unsubstituted phenyl group.
  • m is a positive integer not less than 1.
  • m is a positive integer selected from 1 to 6.
  • the R 1 -X m is
  • the size of the copper catalyst is not greater than 200 nm.
  • the copper catalyst is a nano copper catalyst.
  • the heating step is to raise the temperature to not less than 100°C.
  • the molar ratio of the copper catalyst and the R 1 -X m is 1:1-5.
  • kits for dechlorination of chlorinated aromatic compounds (R 1 -X m ), characterized in that, in the R 1 -X m , R 1 is a substituted or unsubstituted aromatic group, X is a chloride ion, and m is a positive integer, and the kit includes: a copper catalyst, and the molar ratio of the copper catalyst to the chlorinated aromatic compound (R 1 -X m ) is 1:1-5; R 2 (OH) n , where R 2 is a methyl group and n is 1; and an alkaline substance with a pH value greater than 7 to provide an alkaline environment; wherein, in the alkaline environment, the copper catalyst Under the action of, using the R 2 (OH) n as a hydrogen donor, the chlorinated aromatic compound (R 1 -X m ) is subjected to the dechlorination reaction.
  • the dechlorination method of the present invention uses alcohols to replace conventional hydrogen sources, such as hydrogen as a hydrogen donor, and uses non-precious metal copper as a catalyst.
  • the chlorinated aromatic compounds R 1 -X m
  • Figure 1 shows a gas chromatogram of the product after dechlorination reaction with 1,2,3-trichlorobenzene as a substrate and the dechlorination kit provided by the present invention.
  • peaks a, b, c, d, and e from left to right represent benzene, chlorobenzene, m-dichlorobenzene, o-dichlorobenzene, and 1,2,3-trichlorobenzene.
  • Figure 2 shows the conversion rate of the dechlorination kit provided by the present invention for repeated application of the catalyst.
  • the present invention provides a method for dechlorination of chlorinated aromatic compounds (R 1 -X m ) using copper as a catalyst.
  • the method includes the following steps: using R 1 -X m as a substrate, adding R 2 (OH) n , A basic substance with a pH value greater than 7 and a copper catalyst to form a mixture, wherein R 1 is a substituted or unsubstituted aromatic group, X is a chloride ion, and m is a positive integer; R 2 is a methyl group, and n is 1. ; Stir the mixture; and heat the mixture for hydrogenation reaction to obtain R 1 -X m' , wherein m'is less than m, and m'is an integer.
  • R 1 in the R 1 -X m , R 1 may be a substituted or unsubstituted phenyl group. According to a preferred embodiment of the present invention, in the R 1 -X m , R 1 may be an unsubstituted phenyl group.
  • m in the R 1 -X m , m may be a positive integer not less than 1. According to an embodiment of the present invention, in the R 1 -X m , m may be a positive integer selected from 1 to 6.
  • the R 1 -X m may be Wherein n can be 1 to 6; preferably, the R 1 -X m can be E.g, More preferably, the R 1 -X m may be
  • the size of the copper catalyst may be less than 200 nm; preferably, the copper catalyst may be a nano copper catalyst.
  • the copper is used as a metal catalyst to catalyze the dechlorination reaction of chlorinated aromatic compounds (R 1 -X m ).
  • the heating step is to raise the temperature to not less than 100°C.
  • the reaction temperature range can be heated to 100-180°C. More preferably, the reaction temperature can be 120-130°C.
  • the molar ratio of the copper catalyst to the R 1 -X m may be 1:1-5. According to a preferred embodiment of the present invention, the molar ratio of the copper catalyst to the R 1 -X m may be 1:1.1 to 1.5.
  • the alkaline substance with a pH value greater than 7 can be a compound such as sodium hydroxide, potassium hydroxide, or a solution of sodium hydroxide, potassium hydroxide, or the like.
  • the amount ratio of the substrate to the alkaline substance is 1:2-6; preferably, the amount concentration ratio of the substrate to the sodium hydroxide substance is preferably 1:3 to 5 .
  • the catalytic time of the reaction can be 1 to 4 hours; preferably, it can be 1 to 2 hours.
  • kits for dechlorination of chlorinated aromatic compounds comprising: a copper catalyst; R 2 (OH) n , wherein R 2 is a methyl group, and n Is 1; and an alkaline substance with a pH greater than 7 to provide an alkaline environment; wherein, in the alkaline environment, under the action of the copper catalyst, the R 2 (OH) n is used as a supply Hydrogen body, the R 1 -X m is subjected to the dechlorination reaction.
  • R 1 may be a substituted or unsubstituted aromatic group
  • X is a chloride ion
  • m is a positive integer
  • R 1 in the R 1 -X m , R 1 may be a substituted or unsubstituted phenyl group. According to a preferred embodiment of the present invention, in the R 1 -X m , R 1 may be an unsubstituted phenyl group.
  • X may be chlorine.
  • m in the R 1 -X m , m may be a positive integer not less than 1. According to an embodiment of the present invention, in the R 1 -X m , m may be a positive integer selected from 1 to 6.
  • the R 1 -X m may be Wherein n can be 1 to 6; preferably, the R 1 -X m can be E.g, More preferably, preferably, the R 1 -X m may be
  • the size of the copper catalyst is on the nanometer level; preferably, the copper catalyst may be less than 200 nm.
  • the copper is used as a metal catalyst to catalyze the dechlorination reaction of chlorinated aromatic compounds (R 1 -X m ).
  • the heating step is to raise the temperature to not less than 100°C.
  • the reaction temperature range can be heated to 100-180°C. More preferably, the reaction temperature can be 120-130°C.
  • the molar ratio of the copper catalyst to the R 1 -X m may be 1:1-5. According to a preferred embodiment of the present invention, the molar ratio of the copper catalyst to the R 1 -X m may be 1:1.1 to 1.5.
  • the alkaline substance with a pH value greater than 7 can be a compound such as sodium hydroxide, potassium hydroxide, or a solution of sodium hydroxide, potassium hydroxide, or the like.
  • the amount concentration ratio of the substrate and the alkaline substance is 1:2-6; preferably, the amount concentration ratio of the substrate and the sodium hydroxide substance is preferably 1:3-5.
  • the solution with a pH value greater than 7 is used to provide an alkaline reaction environment for the dechlorination reaction.
  • the solution with a pH value greater than 7 may be an aqueous solution of alkaline compounds such as NaOH and KOH.
  • the R 2 (OH) n is used as a hydrogen donor, and the chlorinated aromatic compound (R 1 -X m ) is The dechlorination reaction.
  • reaction time of the method and the kit of the present invention can be adjusted as needed. If the reaction time is shortened, less halogen in the polyhaloaromatic hydrocarbon can be removed, for example, a chlorine can be removed from trichlorobenzene Dichlorobenzene is obtained; conversely, if the reaction time is prolonged, more halogens in the polyhaloaromatics can be removed, such as removing two chlorines from trichlorobenzene to obtain chlorobenzene, or even further benzene.
  • the dechlorination kit and method provided by the present invention add 10 mL methanol, 0.9073 g 1,2,3-trichlorobenzene as the substrate, 292 mg Cu catalyst, 0.8 g NaOH into 100 mL polytetrafluoroethylene lining. mixture. The mixture was stirred uniformly, placed in an autoclave, and subjected to a hydrogenation reaction at 130°C, and the reaction time was 80 minutes. After the reaction, the reaction product was analyzed by gas chromatography, as shown in Figure 1.
  • the peaks a, b, c, d, and e from left to right represent benzene, chlorobenzene, m-dichlorobenzene, and o-dichlorobenzene, respectively.
  • 1,2,3-Trichlorobenzene The conversion rate of 1,2,3-trichlorobenzene is 90%, and the selectivity of dichlorobenzene is 88%.
  • the reaction result shows that the dechlorination kit provided by the present invention has high selectivity.
  • the dechlorination kit in a 100-mL polytetrafluoroethylene lining, add 10mL methanol, 0.9073g 1,2,3-trichlorobenzene as a substrate, 292mg Cu catalyst, 0.8g NaOH to obtain mixture.
  • the mixture was stirred uniformly, placed in an autoclave, and subjected to hydrogenation reaction at 130°C, and the reaction time was 80 minutes.
  • the reaction product was analyzed by gas chromatography, and then the copper catalyst was washed with water and put into fresh substrate and solvent for reaction, which was repeated 5 times. The results showed that after 5 cycles, the conversion rate of the substrate was maintained at 90%, and the selectivity of dichlorobenzene was also maintained at 88%.
  • the dechlorination method proposed by the present invention uses inexpensive metal copper as a catalyst, and dechlorinates chlorinated aromatic compounds (R 1 -X m ) with high selectivity through a catalytic hydrogenation process in an alcohol solvent to generate a large amount of dichlorobenzene and improve the product Value:
  • the present invention uses alcohols as a hydrogen source. During the hydrogenation process, there is no need to provide a gaseous hydrogen source.
  • the catalyst of the kit of the present invention can be reused to reduce costs.
  • the dechlorination method and kit provided by the present invention avoid the problems of deep hydrogenation of traditional Pd, Pt and other precious metal catalysts and poor selectivity.
  • the non-precious metal Cu catalyst is not only low in price, high in catalytic efficiency, but also recyclable.

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Abstract

Provided is a dechlorination method of a chloro-substituted aromatic compound (R 1-X m) using copper as a catalyst, comprising using R 1-X m as a substrate, adding R 2(OH) n, an alkaline substance with a pH value greater than 7, and a copper catalyst to form a mixture, in which R 1 is a substituted or unsubstituted aromatic group, X is a chloride ion, m is a positive integer, R 2 is methyl, and n is 1; stirring the mixture; and heating the mixture to perform a hydrogenation reaction to obtain R 1-X m', in which m' is less than m, and m' is an integer.

Description

一种以铜为催化剂的氯代芳香化合物(R 1-X m)的脱氯方法 A chlorinated aromatic compound (R 1-X m) Dechlorination method 技术领域Technical field
本发明涉及一种以铜为催化剂的氯代芳香化合物(R 1-X m)的脱氯方法。 The present invention relates to a method for dechlorination of chlorinated aromatic compounds (R 1 -X m ) using copper as a catalyst.
背景技术Background technique
多氯苯化合物及其衍生物的化学性质稳定，容易积累在生物体内。一旦进入环境将对人类及生态环境造成长期威胁，目前已被列为全球环境优先控制的污染物之一。但目前的工业生产中不可避免地会生成多氯苯副产物，包括三氯苯、四氯苯等。每年的多氯苯副产物的产出都在万吨级以上，不但污染环境而且占用场地，加上高昂的处理费用，成为工业生产中很大的负担。Polychlorinated benzene compounds and their derivatives have stable chemical properties and are easy to accumulate in organisms. Once it enters the environment, it will pose a long-term threat to humans and the ecological environment, and it has been listed as one of the pollutants that are prioritized by the global environment. But the current industrial production will inevitably generate polychlorinated benzene by-products, including trichlorobenzene and tetrachlorobenzene. The annual output of polychlorinated benzene by-products is above 10,000 tons, which not only pollutes the environment but also occupies space, coupled with high processing costs, has become a great burden in industrial production.
低氯芳烃是化工、医药、制革、电子等行业广泛应用的化工原料及有机合成中间体和有机溶剂。因此，如果能对工业上产生的多氯苯废料加以处理，不仅可以得到高附加值的低氯芳烃产物，而且可以解决污染环境问题。Low-chlorine aromatic hydrocarbons are widely used chemical raw materials, organic synthesis intermediates and organic solvents in the chemical, pharmaceutical, leather, and electronics industries. Therefore, if the polychlorinated benzene waste produced in the industry can be processed, not only high value-added low-chlorine aromatic products can be obtained, but also the environmental pollution problem can be solved.
目前工业上降解多氯苯化合物的方法主要包括：封存法，高温处理法，化学脱除法，生物降解法、催化加氢脱氯法等。At present, the industrial methods for degrading polychlorobenzene compounds mainly include: storage method, high temperature treatment method, chemical removal method, biodegradation method, catalytic hydrodechlorination method, etc.
其中，催化加氢脱氯是通过在钯、铂、铑等贵金属催化剂上对氢气进行解离，以产生的氢原子来取代多氯苯上的氯原子，以此达到降解目的。常规的加氢脱氯工艺包括将多氯底物溶解在有机溶剂中，加入足量催化剂后，通入高纯氢气进行反应。由于工厂中易燃易爆物较多，若能避免氢气作为氢源，一方面可以降低处理成本，另一方面也可在一定程度上提高工厂的安全指数。Among them, catalytic hydrodechlorination is achieved by dissociating hydrogen on precious metal catalysts such as palladium, platinum, rhodium, etc., to replace chlorine atoms on polychlorinated benzene with the generated hydrogen atoms to achieve the purpose of degradation. The conventional hydrodechlorination process includes dissolving the polychlorinated substrate in an organic solvent, adding a sufficient amount of catalyst, and introducing high-purity hydrogen for the reaction. Since there are many flammable and explosive materials in the factory, if hydrogen can be avoided as a hydrogen source, on the one hand, the processing cost can be reduced, and on the other hand, the safety index of the factory can be improved to a certain extent.
Hydrogen-transfer hydrodehalogenation of aromatic halides with alcohols in tiae presence of noble metal catalysts(Y.Ukisu,T.Miyadera.1997.Journal of Molecular Catalysis A:Chemical 125:135-142)中指出在Rh/C或Pd/C存在的情况下，1,2,4-三氯苯在碱性化合物(如氢氧化钠或氢氧化钾)的异丙醇溶液中，在温度低于65℃的情况下，1,2,4-三氯苯脱氯生成苯是有效的。但其所需要的贵金属催化剂很多，成本极高。Hydrogen-transfer hydrodehalogenation of aromatic halfes with alcohols in tiae presence of noble metal catalysts (Y. Ukisu, T. Miyadera. 1997. Journal of Molecular Catalysis A: Chemical 125: 135-142) pointed out in Rh/C or Pd/C In the presence of 1,2,4-trichlorobenzene in isopropanol solution of alkaline compounds (such as sodium hydroxide or potassium hydroxide), when the temperature is lower than 65℃, 1,2,4 -Dechlorination of trichlorobenzene to benzene is effective. However, many precious metal catalysts are required, and the cost is extremely high.
另一方面，由于贵金属催化剂氢解能力极强，大多数情况下使含氯有机物深度加氢，完全降解。不产生氯代中间产物，或生成的氯代中间产物极少量，使产物的附加值大大降低。同时贵金属作催化剂的使用也加大了处理成本。On the other hand, due to the extremely strong hydrogenolysis ability of precious metal catalysts, in most cases, the chlorine-containing organic matter is deeply hydrogenated and completely degraded. No chlorinated intermediate products are produced, or the generated chlorinated intermediate products are very small, which greatly reduces the added value of the product. At the same time, the use of precious metals as catalysts also increases processing costs.
因此，业界亟需一种能够防止含氯有机物深度加氢，高效、高选择性且经济的氢化脱氯生成低氯芳香化合物的制备方法。Therefore, the industry urgently needs a method for preparing low-chlorine aromatic compounds that can prevent the deep hydrogenation of chlorine-containing organic substances, and is efficient, highly selective and economical.
发明内容Summary of the invention
本发明一方面提供以铜为催化剂的氯代芳香化合物(R 1-X m)的脱氯方法，其特征在于，该方法包括以下步骤：以R 1-X m为底物，加入R 2(OH) n、pH值大于7的碱性物质以及铜催化剂以形成混合物，其中R 1为经取代或未经取代的芳香基，X为氯离子，且m为正整数；R 2为甲基，且n为1；搅拌所述混合物；以及加热所述混合物进行加氢反应，制得R 1-X m’，其中m’小于m，且m’为整数。 One aspect of the present invention provides a method for dechlorination of chlorinated aromatic compounds (R 1 -X m ) using copper as a catalyst. The method is characterized in that the method comprises the following steps: R 1 -X m is used as a substrate and R 2 ( OH) n , a basic substance with a pH value greater than 7 and a copper catalyst to form a mixture, wherein R 1 is a substituted or unsubstituted aromatic group, X is a chloride ion, and m is a positive integer; R 2 is a methyl group, And n is 1; stirring the mixture; and heating the mixture to perform a hydrogenation reaction to obtain R 1 -X m' , wherein m'is less than m, and m'is an integer.
根据本发明的实施例，所述R 1-X m中，R 1为经取代或未经取代的苯基。 According to an embodiment of the present invention, in the R 1 -X m , R 1 is a substituted or unsubstituted phenyl group.
根据本发明的实施例，所述R 1-X m中，R 1为未经取代的苯基。 According to an embodiment of the present invention, in the R 1 -X m , R 1 is an unsubstituted phenyl group.
根据本发明的实施例，所述R 1-X m中，m为不小于1的正整数。 According to an embodiment of the present invention, in the R 1 -X m , m is a positive integer not less than 1.
根据本发明的实施例，所述R 1-X m中，m为选自1至6中的正整数。 According to an embodiment of the present invention, in the R 1 -X m , m is a positive integer selected from 1 to 6.
根据本发明的实施例，所述R 1-X m为
Figure PCTCN2019124169-appb-000001
According to an embodiment of the present invention, the R 1 -X m is
Figure PCTCN2019124169-appb-000001
根据本发明的实施例，所述铜催化剂的尺寸不大于200nm。According to an embodiment of the present invention, the size of the copper catalyst is not greater than 200 nm.
根据本发明的实施例，所述铜催化剂为纳米铜催化剂。According to an embodiment of the present invention, the copper catalyst is a nano copper catalyst.
根据本发明的实施例，所述加热步骤是升温至不小于100℃。According to an embodiment of the present invention, the heating step is to raise the temperature to not less than 100°C.
根据本发明的实施例，所述铜催化剂和所述R 1-X m的摩尔比为1：1～5。 According to an embodiment of the present invention, the molar ratio of the copper catalyst and the R 1 -X m is 1:1-5.
本发明一方面提供一种氯代芳香化合物(R 1-X m)脱氯的套组，其特征在于，所述R 1-X m中，R 1为经取代或未经取代的芳香基，X为氯离子，且m为正整数，以及该套组包括：铜催化剂，所述铜催化剂和所述氯代芳香化合物(R 1-X m)的摩尔比为1：1～5；R 2(OH) n，其中，R 2为甲基，且n为1；以及pH值大于7的碱性物质，以提供一碱性环境；其中，在所述碱性环境中，在所述铜催化剂的作用下，以所述R 2(OH) n作为供氢体，将所述氯代芳香化合物(R 1-X m)进行所述脱氯反应。 One aspect of the present invention provides a kit for dechlorination of chlorinated aromatic compounds (R 1 -X m ), characterized in that, in the R 1 -X m , R 1 is a substituted or unsubstituted aromatic group, X is a chloride ion, and m is a positive integer, and the kit includes: a copper catalyst, and the molar ratio of the copper catalyst to the chlorinated aromatic compound (R 1 -X m ) is 1:1-5; R 2 (OH) n , where R 2 is a methyl group and n is 1; and an alkaline substance with a pH value greater than 7 to provide an alkaline environment; wherein, in the alkaline environment, the copper catalyst Under the action of, using the R 2 (OH) n as a hydrogen donor, the chlorinated aromatic compound (R 1 -X m ) is subjected to the dechlorination reaction.
相较于先前技术，本发明的脱氯方法是使用醇类取代常规氢源，如氢气等作为供氢体，以非贵金属铜作催化剂，在碱性环境中，对氯代芳香化合物(R 1-X m)进行催化加氢脱氯的方法，生成附加值较高的低氯芳烃化合物。与传统脱氯工艺相比，不需要氢气参与反应，因此是安全且催化效率高的低氯芳烃生产工艺。 Compared with the prior art, the dechlorination method of the present invention uses alcohols to replace conventional hydrogen sources, such as hydrogen as a hydrogen donor, and uses non-precious metal copper as a catalyst. In an alkaline environment, the chlorinated aromatic compounds (R 1 -X m ) A method for catalytic hydrodechlorination to generate low-chlorine aromatic compounds with higher added value. Compared with the traditional dechlorination process, it does not require hydrogen to participate in the reaction, so it is a safe and highly efficient low-chlorine aromatic production process.
附图说明Description of the drawings
图1显示以1,2,3-三氯苯为底物，通过本发明提供的脱氯套组行脱氯反应后的产物气相色谱图。图中由左至右出峰a、b、c、d、e分别代表苯、氯苯、间二氯苯、邻二氯苯、1，2，3-三氯苯。Figure 1 shows a gas chromatogram of the product after dechlorination reaction with 1,2,3-trichlorobenzene as a substrate and the dechlorination kit provided by the present invention. In the figure, peaks a, b, c, d, and e from left to right represent benzene, chlorobenzene, m-dichlorobenzene, o-dichlorobenzene, and 1,2,3-trichlorobenzene.
图2显示本发明提供的脱氯套组的催化剂重复套用的转化率。Figure 2 shows the conversion rate of the dechlorination kit provided by the present invention for repeated application of the catalyst.
具体实施方式Detailed ways
以下藉由特定的具体实施例说明本发明的实施方式，熟悉此技艺的人士可由本说明书所揭示的内容轻易地了解本发明的其他优点及功效。The following specific examples are used to illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification.
须知，本说明书所附图式所绘示的结构、比例、大小等，均仅用以配合说明书所揭示的内容，以供熟悉此技艺的人士的了解与阅读，并非用以限定本发明可实施的限定条件，故不具技术上的实质意义，任何结构的修饰、比例关系的改变或大小的调整，在不影响本发明所能产生的功效及所能达成的目的下，均应落在本发明所揭示的技术内容得能涵盖的范围内。同时，本说明书中所引用的如「上」、「内」、「外」、「底」、「一」、「中」等用语，也仅为便于叙述的明了，而非用以限定本发明可实施的范围，其相对关系的改变或调整，在无实质变更技术内容下，当也视为本发明可实施的范畴，合先叙明。It should be noted that the structure, ratio, size, etc. shown in the drawings in this specification are only used to match the content disclosed in the specification for the understanding and reading of those familiar with the art, and are not intended to limit the implementation of the present invention Therefore, it does not have any technical significance. Any structural modification, proportional relationship change or size adjustment shall fall under the present invention without affecting the effects and objectives that can be achieved by the present invention. The disclosed technical content must be within the scope of coverage. At the same time, the terms such as "upper", "inner", "outer", "bottom", "one", "in" and other terms quoted in this manual are only for ease of description, not to limit the present invention The scope of implementation, the change or adjustment of the relative relationship, shall be regarded as the scope of the implementation of the present invention without substantial changes to the technical content, and shall be described first.
本发明提供一种以铜为催化剂的氯代芳香化合物(R 1-X m)的脱氯方法，该方法包括以下步骤：以R 1-X m为底物，加入R 2(OH) n、pH值大于7的碱性物质以及铜催化剂以形成混合物，其中R 1为经取代或未经取代的芳香基，X为氯离子，且m为正整数；R 2为甲基，且n为1；搅拌所述混合物；以及加热所述混合物进行加氢反应，制得R 1-X m’，其中m’小于m，且m’为整数。 The present invention provides a method for dechlorination of chlorinated aromatic compounds (R 1 -X m ) using copper as a catalyst. The method includes the following steps: using R 1 -X m as a substrate, adding R 2 (OH) n , A basic substance with a pH value greater than 7 and a copper catalyst to form a mixture, wherein R 1 is a substituted or unsubstituted aromatic group, X is a chloride ion, and m is a positive integer; R 2 is a methyl group, and n is 1. ; Stir the mixture; and heat the mixture for hydrogenation reaction to obtain R 1 -X m' , wherein m'is less than m, and m'is an integer.
根据本发明的一实施例，所述R 1-X m中，R 1可为经取代或未经取代的苯基。根据本发明的较佳实施例，所述R 1-X m中，R 1可为未经取代的苯基。 According to an embodiment of the present invention, in the R 1 -X m , R 1 may be a substituted or unsubstituted phenyl group. According to a preferred embodiment of the present invention, in the R 1 -X m , R 1 may be an unsubstituted phenyl group.
根据本发明的实施例，所述R 1-X m中，m可为不小于1的正整数。根据本发明的实施例，所述R 1-X m中，m可为选自1至6中的正整数。 According to an embodiment of the present invention, in the R 1 -X m , m may be a positive integer not less than 1. According to an embodiment of the present invention, in the R 1 -X m , m may be a positive integer selected from 1 to 6.
根据本发明的一实施例，所述R 1-X m可为
Figure PCTCN2019124169-appb-000002
其中n可为1～6；较佳，所述R 1-X m 可为
Figure PCTCN2019124169-appb-000003
例如，
Figure PCTCN2019124169-appb-000004
更佳，所述R 1-X m可为
Figure PCTCN2019124169-appb-000005
According to an embodiment of the present invention, the R 1 -X m may be
Figure PCTCN2019124169-appb-000002
Wherein n can be 1 to 6; preferably, the R 1 -X m can be
Figure PCTCN2019124169-appb-000003
E.g,
Figure PCTCN2019124169-appb-000004
More preferably, the R 1 -X m may be
Figure PCTCN2019124169-appb-000005
根据本发明的一实施例，所述铜催化剂的尺寸可在200nm以下；较佳，所述铜催化剂可为纳米铜催化剂。于本发明中，所述铜是作为一种金属催化剂，用于催化氯代芳香化合物(R 1-X m)的脱氯反应。 According to an embodiment of the present invention, the size of the copper catalyst may be less than 200 nm; preferably, the copper catalyst may be a nano copper catalyst. In the present invention, the copper is used as a metal catalyst to catalyze the dechlorination reaction of chlorinated aromatic compounds (R 1 -X m ).
根据本发明的一实施例，所述加热步骤是升温至不小于100℃。根据本发明的一实施例，反应温度范围可加热至100～180℃。更佳，该反应温度可为120～130℃。According to an embodiment of the present invention, the heating step is to raise the temperature to not less than 100°C. According to an embodiment of the present invention, the reaction temperature range can be heated to 100-180°C. More preferably, the reaction temperature can be 120-130°C.
根据本发明的一实施例，所述铜催化剂和所述R 1-X m的摩尔比可为1：1～5。根据本发明较佳实施例，铜催化剂与所述R 1-X m的的摩尔比可为1：1.1～1.5。 According to an embodiment of the present invention, the molar ratio of the copper catalyst to the R 1 -X m may be 1:1-5. According to a preferred embodiment of the present invention, the molar ratio of the copper catalyst to the R 1 -X m may be 1:1.1 to 1.5.
根据本发明所提供的脱氯方法，所述pH值大于7的碱性物质，可为氢氧化钠、氢氧化钾等化合物，或是氢氧化钠、氢氧化钾等的溶液。根据本发明的实施例，所述底物与碱性物质的物质的量比为1：2～6；较佳，所述底物与氢氧化钠的物质的量浓度比优选1：3～5。According to the dechlorination method provided by the present invention, the alkaline substance with a pH value greater than 7 can be a compound such as sodium hydroxide, potassium hydroxide, or a solution of sodium hydroxide, potassium hydroxide, or the like. According to an embodiment of the present invention, the amount ratio of the substrate to the alkaline substance is 1:2-6; preferably, the amount concentration ratio of the substrate to the sodium hydroxide substance is preferably 1:3 to 5 .
根据本发明所提供的脱氯方法，所述反应的催化时间可为1～4小时；较佳，可为1～2小时。According to the dechlorination method provided by the present invention, the catalytic time of the reaction can be 1 to 4 hours; preferably, it can be 1 to 2 hours.
本发明另方面还提供一种氯代芳香化合物(R 1-X m)脱氯的套组，该套组包括：铜催化剂；R 2(OH) n，其中，R 2为甲基，且n为1；以及pH值大于7的碱性物质，以提供一碱性环境；其中，在所述碱性环境中，在所述铜催化剂的作用下，以所述R 2(OH) n作为供氢体，将所述R 1-X m进行所述脱氯反应。 Another aspect of the present invention also provides a kit for dechlorination of chlorinated aromatic compounds (R 1 -X m ), the kit comprising: a copper catalyst; R 2 (OH) n , wherein R 2 is a methyl group, and n Is 1; and an alkaline substance with a pH greater than 7 to provide an alkaline environment; wherein, in the alkaline environment, under the action of the copper catalyst, the R 2 (OH) n is used as a supply Hydrogen body, the R 1 -X m is subjected to the dechlorination reaction.
根据本发明，所述R 1-X m中，R 1可为经取代或未经取代的芳香基，X为氯离子，且m为正整数。 According to the present invention, in the R 1 -X m , R 1 may be a substituted or unsubstituted aromatic group, X is a chloride ion, and m is a positive integer.
根据本发明的一实施例，所述R 1-X m中，R 1可为经取代或未经取代的苯基。根据本发明的较佳实施例，所述R 1-X m中，R 1可为未经取代的苯基。 According to an embodiment of the present invention, in the R 1 -X m , R 1 may be a substituted or unsubstituted phenyl group. According to a preferred embodiment of the present invention, in the R 1 -X m , R 1 may be an unsubstituted phenyl group.
根据本发明的较佳实施例，所述R 1-X m中，X可为氯。 According to a preferred embodiment of the present invention, in the R 1 -X m , X may be chlorine.
根据本发明的实施例，所述R 1-X m中，m可为不小于1的正整数。根据本发明的实施例，所述R 1-X m中，m可为选自1至6中的正整数。 According to an embodiment of the present invention, in the R 1 -X m , m may be a positive integer not less than 1. According to an embodiment of the present invention, in the R 1 -X m , m may be a positive integer selected from 1 to 6.
根据本发明的一实施例，所述R 1-X m可为
Figure PCTCN2019124169-appb-000006
其中n可为1～6；较佳，所述R 1-X m可为
Figure PCTCN2019124169-appb-000007
例如，
Figure PCTCN2019124169-appb-000008
更佳，较佳，所述R 1-X m可为
Figure PCTCN2019124169-appb-000009
According to an embodiment of the present invention, the R 1 -X m may be
Figure PCTCN2019124169-appb-000006
Wherein n can be 1 to 6; preferably, the R 1 -X m can be
Figure PCTCN2019124169-appb-000007
E.g,
Figure PCTCN2019124169-appb-000008
More preferably, preferably, the R 1 -X m may be
Figure PCTCN2019124169-appb-000009
根据本发明的一实施例，所述铜催化剂的尺寸在纳米级别；较佳，所述铜催化剂可为200nm以下。于本发明中，所述铜是作为一种金属催化剂，用于催化氯代芳香化合物(R 1-X m)的脱氯反应。 According to an embodiment of the present invention, the size of the copper catalyst is on the nanometer level; preferably, the copper catalyst may be less than 200 nm. In the present invention, the copper is used as a metal catalyst to catalyze the dechlorination reaction of chlorinated aromatic compounds (R 1 -X m ).
根据本发明的一实施例，所述加热步骤是升温至不小于100℃。根据本发明的一实施例，反应温度范围可加热至100～180℃。更佳，该反应温度可为120～130℃。According to an embodiment of the present invention, the heating step is to raise the temperature to not less than 100°C. According to an embodiment of the present invention, the reaction temperature range can be heated to 100-180°C. More preferably, the reaction temperature can be 120-130°C.
根据本发明的一实施例，所述铜催化剂和所述R 1-X m的摩尔比可为1：1～5。根据本发明较佳实施例，铜催化剂与所述R 1-X m的摩尔比可为1：1.1～1.5。 According to an embodiment of the present invention, the molar ratio of the copper catalyst to the R 1 -X m may be 1:1-5. According to a preferred embodiment of the present invention, the molar ratio of the copper catalyst to the R 1 -X m may be 1:1.1 to 1.5.
根据本发明所提供的脱氯方法，所述pH值大于7的碱性物质，可为氢氧化钠、氢氧化钾等化合物，或是氢氧化钠、氢氧化钾等的溶液。根据本发明的实施例，所述底物与碱性物质的量浓度比为1：2～6；较佳，所述底物与氢氧化钠的物质的量浓度比优选1：3～5。According to the dechlorination method provided by the present invention, the alkaline substance with a pH value greater than 7 can be a compound such as sodium hydroxide, potassium hydroxide, or a solution of sodium hydroxide, potassium hydroxide, or the like. According to an embodiment of the present invention, the amount concentration ratio of the substrate and the alkaline substance is 1:2-6; preferably, the amount concentration ratio of the substrate and the sodium hydroxide substance is preferably 1:3-5.
根据本发明的脱氯套组，所述pH值大于7的溶液，是用以提供所述脱氯反应一个碱性的反应环境。根据本领域技术人员可知，该pH值大于7的溶液可以是NaOH、KOH等碱性化合物的水溶液。其中，在所述碱性环境中，在所述铜做为催化剂作用下，以所述R 2(OH) n作为供氢体，将所述氯代芳香化合物(R 1-X m)进行所述脱氯反应。 According to the dechlorination kit of the present invention, the solution with a pH value greater than 7 is used to provide an alkaline reaction environment for the dechlorination reaction. According to those skilled in the art, the solution with a pH value greater than 7 may be an aqueous solution of alkaline compounds such as NaOH and KOH. Wherein, in the alkaline environment, under the action of the copper as a catalyst, the R 2 (OH) n is used as a hydrogen donor, and the chlorinated aromatic compound (R 1 -X m ) is The dechlorination reaction.
本领域技术人员应理解，本发明方法以及套组的反应时间可视所需调整，若缩短反应时间，则可脱去多卤芳烃中的较少的卤素，例如从三氯苯脱去一个氯制得二氯苯；反之，若反应时间延长，则可脱去多卤芳烃中的较多的卤素，例如自三氯苯脱去二个氯以制得氯苯，甚至是进一步制得苯。Those skilled in the art should understand that the reaction time of the method and the kit of the present invention can be adjusted as needed. If the reaction time is shortened, less halogen in the polyhaloaromatic hydrocarbon can be removed, for example, a chlorine can be removed from trichlorobenzene Dichlorobenzene is obtained; conversely, if the reaction time is prolonged, more halogens in the polyhaloaromatics can be removed, such as removing two chlorines from trichlorobenzene to obtain chlorobenzene, or even further benzene.
实施例1Example 1
根据本发明所提供的脱氯套组及方法，在100mL聚四氟乙烯内衬中，加入10mL甲醇，0.9073g 1,2,3-三氯苯作为底物，292mg Cu催化剂，0.8g NaOH得混合物。将该混合物搅拌均匀，置于高压反应釜中，在130℃行氢化反应，反应时间为80分钟。反应结束后，反应产物采用气相色谱分析，如图1所示，图中由左至右出峰a、b、c、d、e分别代表苯、氯苯、间二氯苯、邻二氯苯、1，2，3-三氯苯。1,2,3-三氯苯的转化率为90％，二氯苯选择性为88％，反应结果表明本发明所提供的脱氯套组具有高选择性。According to the dechlorination kit and method provided by the present invention, add 10 mL methanol, 0.9073 g 1,2,3-trichlorobenzene as the substrate, 292 mg Cu catalyst, 0.8 g NaOH into 100 mL polytetrafluoroethylene lining. mixture. The mixture was stirred uniformly, placed in an autoclave, and subjected to a hydrogenation reaction at 130°C, and the reaction time was 80 minutes. After the reaction, the reaction product was analyzed by gas chromatography, as shown in Figure 1. The peaks a, b, c, d, and e from left to right represent benzene, chlorobenzene, m-dichlorobenzene, and o-dichlorobenzene, respectively. , 1,2,3-Trichlorobenzene. The conversion rate of 1,2,3-trichlorobenzene is 90%, and the selectivity of dichlorobenzene is 88%. The reaction result shows that the dechlorination kit provided by the present invention has high selectivity.
实施例2Example 2
根据本发明所提供的脱氯套组及方法，在100-mL聚四氟乙烯内衬中，加入10mL甲醇，0.9073g 1,2,3-三氯苯作为底物，292mg Cu催化剂，0.8g NaOH得混合物。将该混合物搅拌均匀，置于高压反应釜中，在180℃进行氢化反应，反应时间为30分钟。反应结束后，反应产物采用气相色谱分析，采用气相色谱分析，结果1,2,3-三氯苯的转化率为100％，二氯苯选择性为79％。According to the dechlorination kit and method provided by the present invention, 10mL methanol, 0.9073 g 1,2,3-trichlorobenzene as a substrate, 292mg Cu catalyst, 0.8g are added to a 100-mL polytetrafluoroethylene lining NaOH is a mixture. The mixture was stirred uniformly, placed in an autoclave, and hydrogenated at 180°C for a reaction time of 30 minutes. After the reaction, the reaction product was analyzed by gas chromatography, and it was found that the conversion rate of 1,2,3-trichlorobenzene was 100%, and the selectivity of dichlorobenzene was 79%.
实施例3Example 3
根据本发明所提供的脱氯套组及方法，在100-mL聚四氟乙烯内衬中，加入10mL甲醇，0.9073g 1,2,3-三氯苯作为底物，292mg Cu催化剂，1.12g KOH得混合物。将该混合物搅拌均匀，置于高压反应釜中，在130℃进行氢化反应，反应时间为60分钟。反应结束后，反应产物采用气相色谱分析，采用气相色谱分析，结果1,2,3-三氯苯的转化率为93％，二氯苯选择性为89％。According to the dechlorination kit and method provided by the present invention, 10mL methanol, 0.9073 g 1,2,3-trichlorobenzene as a substrate, 292mg Cu catalyst, 1.12g are added to a 100-mL polytetrafluoroethylene lining KOH gets a mixture. The mixture was stirred uniformly, placed in an autoclave, and hydrogenated at 130°C, and the reaction time was 60 minutes. After the reaction, the reaction product was analyzed by gas chromatography, and the result was that the conversion rate of 1,2,3-trichlorobenzene was 93%, and the selectivity of dichlorobenzene was 89%.
实施例4Example 4
根据本发明所提供的脱氯套组及方法，在100-mL聚四氟乙烯内衬中，加入10mL甲醇，0.9073g 1,2,3-三氯苯作为底物，292mg Cu催化剂，1.12g KOH得混合物。将该混合物搅 拌均匀，置于高压反应釜中，在100℃进行氢化反应，反应时间为120分钟。反应结束后，反应产物采用气相色谱分析，采用气相色谱分析，结果1,2,3-三氯苯的转化率为90％，二氯苯选择性为88％。According to the dechlorination kit and method provided by the present invention, 10mL methanol, 0.9073 g 1,2,3-trichlorobenzene as a substrate, 292mg Cu catalyst, 1.12g are added to a 100-mL polytetrafluoroethylene lining KOH gets a mixture. The mixture was stirred uniformly, placed in an autoclave, and hydrogenated at 100°C. The reaction time was 120 minutes. After the reaction, the reaction product was analyzed by gas chromatography, and the result was that the conversion rate of 1,2,3-trichlorobenzene was 90%, and the selectivity of dichlorobenzene was 88%.
实施例5–本发明脱氯套组的重复套用Example 5-Repeated application of the dechlorination kit of the present invention
根据本发明所提供的脱氯套组，在100-mL聚四氟乙烯内衬中，加入10mL甲醇，0.9073g 1,2,3-三氯苯作为底物，292mg Cu催化剂，0.8g NaOH得混合物。将该混合物搅拌均匀，置于高压反应釜中，在130℃行氢化反应，反应时间为80分钟。反应结束后，反应产物采用气相色谱分析，随后将铜催化剂水洗重新投入新鲜底物和溶剂进行反应，以此重复5次。结果显示，套用5圈，底物的转化率维持在90％，同时二氯苯的选择性也维持88％。According to the dechlorination kit provided by the present invention, in a 100-mL polytetrafluoroethylene lining, add 10mL methanol, 0.9073 g 1,2,3-trichlorobenzene as a substrate, 292mg Cu catalyst, 0.8g NaOH to obtain mixture. The mixture was stirred uniformly, placed in an autoclave, and subjected to hydrogenation reaction at 130°C, and the reaction time was 80 minutes. After the reaction, the reaction product was analyzed by gas chromatography, and then the copper catalyst was washed with water and put into fresh substrate and solvent for reaction, which was repeated 5 times. The results showed that after 5 cycles, the conversion rate of the substrate was maintained at 90%, and the selectivity of dichlorobenzene was also maintained at 88%.
本发明提出的脱氯方法是使用廉价金属铜作为催化剂，在醇溶剂中通过催化加氢工艺将氯代芳香化合物(R 1-X m)高选择性脱氯，生成大量二氯苯，提升产品价值；本发明又以醇类作为氢源，加氢过程中，无需提供气态氢源，此外，本发明套组的催化剂可重复使用，降低成本。本发明提供的脱氯方法及套组避免了传统Pd、Pt等贵金属催化剂深度加氢，选择性差等问题。非贵金属Cu催化剂不仅价格低廉，催化效率高，还可以循环使用。 The dechlorination method proposed by the present invention uses inexpensive metal copper as a catalyst, and dechlorinates chlorinated aromatic compounds (R 1 -X m ) with high selectivity through a catalytic hydrogenation process in an alcohol solvent to generate a large amount of dichlorobenzene and improve the product Value: The present invention uses alcohols as a hydrogen source. During the hydrogenation process, there is no need to provide a gaseous hydrogen source. In addition, the catalyst of the kit of the present invention can be reused to reduce costs. The dechlorination method and kit provided by the present invention avoid the problems of deep hydrogenation of traditional Pd, Pt and other precious metal catalysts and poor selectivity. The non-precious metal Cu catalyst is not only low in price, high in catalytic efficiency, but also recyclable.
上述实施例仅用以例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟习此项技艺的人士均可在不违背本发明的精神及范畴下，对上述实施例进行修改。因此本发明的权利保护范围，应如权利要求书所列。The above-mentioned embodiments are only used to exemplify the principles and effects of the present invention, but not to limit the present invention. Anyone familiar with this technique can modify the above-mentioned embodiments without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention should be as listed in the claims.

Claims (7)

  1. 一种以铜为催化剂的氯代芳香化合物(R 1-X m)的脱氯方法，其特征在于，该方法包括以下步骤： A method for dechlorination of chlorinated aromatic compounds (R 1 -X m ) using copper as a catalyst, characterized in that the method includes the following steps:
    以R 1-X m为底物，加入R 2(OH) n、pH值大于7的碱性物质以及铜催化剂以形成混合物，其中R 1为经取代或未经取代的芳香基，X为氯离子，且m为正整数；R 2为甲基，且n为1； Using R 1 -X m as the substrate, adding R 2 (OH) n , a basic substance with a pH value greater than 7 and a copper catalyst to form a mixture, wherein R 1 is a substituted or unsubstituted aromatic group, and X is chlorine Ion, and m is a positive integer; R 2 is a methyl group, and n is 1;
    搅拌所述混合物；以及Stirring the mixture; and
    加热所述混合物进行加氢反应，制得R 1-X m’，其中m’小于m，且m’为整数。 Heating the mixture to perform hydrogenation reaction to obtain R 1 -X m' , where m'is less than m, and m'is an integer.
  2. 如权利要求1所述的方法，其特征在于，所述R 1-X m中，R 1为经取代或未经取代的苯基。 The method of claim 1, wherein in the R 1 -X m , R 1 is a substituted or unsubstituted phenyl group.
  3. 如权利要求1所述的方法，其特征在于，所述R 1-X m中，m为选自1至6中的正整数。 The method according to claim 1, wherein in the R 1 -X m , m is a positive integer selected from 1 to 6.
  4. 如权利要求2或3所述的方法，其特征在于，所述R 1-X m为
    Figure PCTCN2019124169-appb-100001
    The method of claim 2 or 3, wherein the R 1 -X m is
    Figure PCTCN2019124169-appb-100001
  5. 如权利要求1所述的方法，其特征在于，所述铜催化剂的尺寸不大于200nm。The method of claim 1, wherein the size of the copper catalyst is not greater than 200 nm.
  6. 如权利要求1所述的方法，其特征在于，所述加热步骤是升温至不小于100℃。The method of claim 1, wherein the heating step is to raise the temperature to not less than 100°C.
  7. 如权利要求1所述的方法，其特征在于，所述铜催化剂和所述R 1-X m的摩尔比为1：1～5。 The method of claim 1, wherein the molar ratio of the copper catalyst and the R 1 -X m is 1:1-5.
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