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Synthetic method for halogenated aniline

一种合成方法、卤代苯胺的技术,应用在催化领域,能够解决易发生团聚、降低产品收率与品质、易被洗脱等问题,达到高活性及高选择性、提高收率与品质、适合保存与运输的效果

Active Publication Date: 2019-02-05
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

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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  • Synthetic method for halogenated aniline
  • Synthetic method for halogenated aniline
  • Synthetic method for halogenated aniline

Examples

Experimental program
Comparison scheme
Effect test

preparation example Construction

[0072] The invention provides a kind of synthetic method of haloaniline, comprising:

[0073] The carbon-coated nickel nanocomposite is used as a catalyst to catalyze the hydrogenation reduction reaction of halonitrobenzene under a hydrogen atmosphere; the chemical reaction equation is illustrated as follows, wherein R represents one or more substituents on the benzene ring, and the At least one of the substituents is halogen:

[0074]

[0075] Wherein, the nanocomposite material contains a core-shell structure with a shell and an inner core, the shell layer is a graphitized carbon layer doped with nitrogen and oxygen, the inner core is nickel nanoparticles, and the nanocomposite material has at least A mesoporous material with a mesoporous distribution peak. That is to say, the nanocomposite material has at least one mesopore distribution peak on the pore distribution curve obtained by calculating the desorption curve according to the Barrett-Joyner-Halenda (BJH) method. ...

preparation example 1

[0108] (1) Weigh 10g of nickel acetate, 10g of citric acid, and 20g of hexamethylenetetramine, add them to a beaker containing 30mL of deionized water, stir at 70°C to obtain a homogeneous solution, and continue heating and evaporating to dryness Obtain a solid precursor. Tests have proved that the solid precursor obtained in this step is soluble in water.

[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 100mL / min, and raise the temperature at a rate of 5°C / min to 650°C, keep the temperature for 2 hours, stop heating, and cool to room temperature under nitrogen atmosphere to obtain a carbon-coated nickel nanocomposite material. The mass percentages of the elements contained in the nanocomposite are listed in Table 1 as measured by an elemental analyzer and an X-ray fluorescence spectrometer (XRF).

[0110] Characterization of the...

preparation example 2

[0115] (1) Weigh 10g of nickel acetate, 20g of citric acid, and 20g of hexamethylenetetramine, add them into a beaker containing 100mL of deionized water, stir at 80°C to obtain a homogeneous solution, and continue heating and evaporating to dryness to obtain solid precursor.

[0116] (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 carbon-coated nanomaterials. After being measured by an elemental analyzer and an X-ray fluorescence spectrometer (XRF), the mass percentages of the elements contained in the nanocomposite are listed in Table 1.

[0117] Material characterization: The nanocomposite material contains a core-shell structure with nano-metallic nicke...

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Abstract

The invention provides a synthetic method for halogenated aniline. The method comprises the following steps that a carbon-coated nickel nanocomposite serves as a catalyst, and halogenated nitrobenzeneis catalyzed to be subjected to hydrogenation reduction reaction in a hydrogen atmosphere, wherein the nanocomposite contains a core-shell structure with a shell layer and a core, the shell layer isa graphitized carbon layer doped with nitrogen and oxygen, the core is nickel nano-particles, and the nanocomposite is a mesoporous material with at least one mesopore distribution peak. According tothe method, the carbon-coated nickel nanocomposite is adopted as the catalyst, the rich mesoporous structure facilitates the mass transfer of the catalytic reaction, the nanocomposite is tightly coated with the metal nano-particles, so that the effect can be conveniently achieved under a more severe condition, the method is used for synthesizing the halogenated aniline through the hydrogenation reduction of the halogenated nitrobenzene, excellent activity, selectivity and safety are achieved, and the dehalogenation problem in the reaction process can be effectively ameliorated.

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): C07C211/52C07C209/36B01J23/755B01J35/10B01J35/00B22F1/054B22F1/145B22F1/16
CPCB01D53/8687H01M4/366H01M4/38H01M4/525H01M4/583H01M4/625H01M10/0525B82Y30/00B82Y40/00C01B32/05C01B32/914C07C5/03C07C5/05C07C5/10C07C29/141C07C29/145C07C29/20C07C209/36C07C209/365C07C213/02B01J23/75B01J23/755B01J27/22B01J27/24B01J31/0205B01J37/084B22F9/20B22F9/22B22F9/30C01P2002/72C01P2002/85C01P2004/04C01P2004/64C01P2006/17C07C2601/02C07C2601/14C07C2527/24C07C2531/04C07C2523/755C07C2523/75B01D2257/708B01J2231/641B01J2231/645B22F1/07B22F1/054B22F1/16B22F1/145B22F1/056B01J35/393B01J35/33B01J35/396B01J35/397B01J35/398B01J35/40B01J35/633B01J35/635B01J35/638B01J35/647B01J35/69B01J35/615B01J35/505B01J35/45B01J2235/30B01J35/80B01J2235/15B01J2235/00B01J35/70C07C13/18C07C31/12C07C13/28C07C31/10C07C217/84C07C215/76C07C15/073C07C211/52C07C35/08C07C211/46C07C35/21C07C211/47B01J31/02Y02C20/20Y02E60/10B22F3/1143B01J37/0072B01J23/745B01J23/72B01J23/06C07C29/172C07C2523/06C07C2523/72C07C2523/745C07D307/60Y02E60/13B01J35/66B22F9/24B01D53/44B01J37/086B01D53/8668B01D2255/20746B01D2255/20753B01D2255/702B01D2255/9205B01J21/18B01J37/04B01J37/088C07B43/04B01J35/23
Inventor 宗明生荣峻峰谢婧新吴耿煌于鹏林伟国纪洪波
Owner CHINA PETROLEUM & CHEM CORP