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Synthesis method of halogenated aniline

A synthesis method, the technology of halogenated nitrobenzene, applied in the field of catalysis, can solve the problems of high price and cost of precious metal catalysts, lower product yield and quality, and great environmental hazards, so as to suppress dehalogenation side reactions, increase yield and The effect of high quality and low risk

Inactive Publication Date: 2020-07-31
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Pt and Pd noble metal catalysts have the advantages of high catalytic activity and mild reaction conditions, but the price and cost of noble metal catalysts are too high, and the loss of noble metals is harmful to the environment, so their application in industrial production is limited.
Non-precious metal catalysts, such as nickel, also have a series of problems in actual production and application, for example, they are prone to agglomeration during the preparation process, easy to be eluted during the catalytic hydrogenation process, poor stability, and greater safety hazards, etc.
In addition, whether it is a noble metal catalyst or a non-noble metal catalyst, the problem of dehalogenation of halonitrobenzene is common in the process of catalytic hydrogenation of p-halogenated nitrobenzene, which reduces the yield and quality of the product, and the dehalogenation reaction produces Hydrohalic acid will corrode equipment, so the key technology for preparing haloaniline by catalytic hydrogenation reduction method when suppressing dehalogenation side reactions

Method used

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  • Synthesis method of halogenated aniline
  • Synthesis method of halogenated aniline
  • Synthesis method of halogenated aniline

Examples

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preparation example Construction

[0055] The invention provides a kind of synthetic method of haloaniline, comprising:

[0056] The carbon-coated nickel nanocomposite material containing alkali metal is used as the catalyst to catalyze the hydrogenation reduction reaction of halonitrobenzene under hydrogen atmosphere; the chemical reaction equation is exemplified as follows, where R represents one or more substitutions on the benzene ring group, at least one of said substituents is halogen:

[0057]

[0058] Wherein, the nanocomposite material has a core-shell structure with a shell and a core, the shell is a graphitized carbon layer containing alkali metal, nitrogen and oxygen, and the core is nickel nanoparticles.

[0059] In some embodiments, the benzene ring of the halogenated nitrobenzene also contains a substituent, and the substituent is selected from C 1-20 One or more of the alkyl, cycloalkyl and aryl groups. The halogenated nitrobenzene includes but not limited to p-chloronitrobenzene, o-chloron...

preparation example 1

[0099] (1) Weigh 10g of nickel acetate, 10g of citric acid and 20g of hexamethylenetetramine into a beaker filled with 30mL of deionized water, stir at 70°C to obtain a homogeneous solution, and continue to heat and evaporate to dryness to obtain a solid precursor body. Tests have proved that the solid precursor obtained in this step is soluble in water.

[0100] (2) Place the solid precursor obtained in step (1) in a porcelain boat, then place the porcelain boat in the constant temperature zone of the tube furnace, feed nitrogen gas with a flow rate of 100mL / min, and set the temperature at a rate of 5°C / min. Raise the temperature to 650°C, stop the heating after keeping the temperature for 2 hours, and cool to room temperature under a nitrogen atmosphere to obtain a carbon-coated nickel material.

[0101] (3) Weigh 2g of the carbon-coated nickel material obtained in step (2), add 15mL of 1M KOH aqueous solution, stir at room temperature for 24h, filter, and then dry the prod...

preparation example 2

[0108] (1) Weigh 10g of nickel acetate, 20g of citric acid, and 20g of hexamethylenetetramine into a beaker containing 100mL of deionized water, stir at 80°C to obtain a homogeneous solution, and continue to heat and evaporate to dryness to obtain a solid precursor .

[0109] (2) Put the precursor obtained in step (1) in the porcelain boat, then place the porcelain boat in the constant temperature zone of the tube furnace, feed nitrogen gas with a flow rate of 150mL / min, and raise the temperature at a rate of 5°C / min to 600°C, keep the temperature for 2 hours, stop heating, and cool to room temperature under a nitrogen atmosphere to obtain a carbon-coated nickel material.

[0110] (3) Weigh 2g of the carbon-coated nickel material obtained in step (2), add 4mL aqueous sodium carbonate solution containing 0.3290g, stir at room temperature for 24h, filter, and finally dry the product at 120°C.

[0111] (4) The dried material obtained in step (3) is placed in a porcelain boat, an...

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Abstract

The invention provides a synthesis method of halogenated aniline. The synthesis method comprises the following steps: taking a carbon-coated nickel nano composite material containing alkali metals asa catalyst, and catalyzing a hydrogenation reduction reaction of halogenated nitrobenzene in a hydrogen atmosphere; wherein the nano composite material contains a core-shell structure with a shell layer and an inner core, the shell layer is a graphitized carbon layer containing alkali metals, nitrogen and oxygen, and the inner core is nickel nano particles. According to the method, the nano composite material is used as a catalyst; a carbon material and the nickel nano particles generate a synergistic effect and a good catalytic effect, the alkali metals of the shell layer further synergistically improve the catalytic performance of the nano composite material, and the catalyst is used for hydrogenation reduction of halogenated nitrobenzene to synthesize halogenated aniline, has excellentactivity, selectivity and safety, and can effectively solve the dehalogenation problem in the reaction process.

Description

technical field [0001] The invention belongs to the field of catalysis, and in particular relates to a synthesis method of halogenated aniline. Background technique [0002] Halogenated aniline is an important organic chemical intermediate, which is widely used in the synthesis of fine chemicals such as medicine, pesticide, fuel, etc. It is usually prepared by reduction synthesis of halogenated aromatic compounds. The reduction methods of halogenated aromatic compounds include chemical reduction methods such as alkali sulfide reduction method, iron powder reduction method, hydrazine hydrate reduction method, electrolytic reduction method, and catalytic hydrogenation reduction method. Although the chemical reduction method has a simple process route and is relatively mature in technology, this method generally has defects such as large environmental pollution, low product yield, poor product quality and high energy consumption, and it is showing a tendency to be eliminated. ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C209/36C07C211/52B01J27/24
CPCC07C209/365B01J27/24B01J35/33B01J35/615B01J35/633B01J35/647C07C211/52
Inventor 宗明生谢婧新荣峻峰吴耿煌于鹏林伟国纪洪波
Owner CHINA PETROLEUM & CHEM CORP