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A New Method for Selective Oxidation of Alcohols Catalyzed by Nano-nickel Oxide

A nickel oxide catalyzed alcohol and nano-nickel oxide technology, which is applied in the direction of oxidative preparation of carbonyl compounds, chemical instruments and methods, and preparation of organic compounds, can solve problems such as increased content, serious dehalogenation side reactions, and influence on selectivity. The preparation process is simple, the price is cheap, and the yield is suitable

Inactive Publication Date: 2016-03-30
YANGZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the industry-leading catalyst Raney-Ni has a large amount of impurities and micropores after caustic alkali treatment in the preparation process, which affects its selectivity, which increases the content of by-product azobenzene oxide and azobenzene, and the catalyst The heat resistance is also poor, and it is easy to form local overheating, which limits the production capacity and catalyst life
In addition, in the industry, hydrogen is generally used as a reducing gas to directly reduce halogenated aromatic nitro compounds, which not only requires strict equipment and safety, but also has serious dehalogenation side reactions.
Chinese patent CN1219598C uses aromatic nitro compounds as raw materials, ammonia synthesis gas or hydrogen as hydrogen source, nickel powder, aluminum powder, and silicon compound melted alloy post-treatment product as catalyst, and a synthesis process for preparing aromatic amines through catalytic hydrogenation , although a good yield is obtained, but because the reaction is carried out in an autoclave, and ammonia synthesis gas or hydrogen is directly used as the hydrogen source, the reaction is in a high-pressure (greater than 1MPa) environment, and the equipment and safety requirements are strict

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0014] p-Nitrochlorophenoxy isopropanol

[0015] 1.1g potassium hydroxide, 0.16g nickel oxide nanopowder and 20mL isopropanol are added in the 100ml three-necked flask successively, and then 3.2g p-chloronitrobenzene is added thereto, wherein the amount of catalyst is the reactant p-chloronitrobenzene quality 3%, reacted at 83°C for 4h. The reaction product was dissolved in 1,2-dichloroethane, filtered, and detected and analyzed by gas chromatography. The yield of product acetone is 50%, and the yield of p-chloroaniline is 65%.

Embodiment 2

[0017] O-Nitrochlorophenoxy Isopropanol

[0018] Add 1.1g of potassium hydroxide, 0.1g of nickel oxide nanopowder and 20mL of isopropanol into a 100ml three-necked flask successively, and then add 3.2g of o-chloronitrobenzene, wherein the amount of catalyst is 1% of the mass of the reactant o-chloronitrobenzene 3%, reacted at 83°C for 4h. The reaction product was dissolved in 1,2-dichloroethane, filtered, and detected and analyzed by gas chromatography. The yield of product acetone is 56%, and the yield of o-chloroaniline is 77%.

Embodiment 3

[0020] Nitrophenoxy isopropanol

[0021] 1.1g potassium hydroxide, 0.16g nickel oxide nanopowder and 20mL isopropanol were added successively in a 100ml three-necked flask, and then 2.1g nitrobenzene was added thereto, wherein the catalyst consumption was 5% of the reactant nitrobenzene quality, Reaction at 97°C for 4h. The reaction product 1,2-dichloroethane was dissolved and filtered, and then detected and analyzed by gas chromatography. Product acetone yield is 56%, aniline yield is 68%

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PUM

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Abstract

The invention relates to a novel method for catalyzing selective oxidization of an alcohol substance by using nanometer nickel oxide. The method disclosed by the invention comprises the steps of: with nanometer nickel oxide as a catalyst, a nitro-compound as an oxidizing agent and KOH as a synergist, catalyzing and oxidizing an alcohol compound so as to prepare aldehyde or ketone at a gage pressure of 0-1 MPa and at a reaction temperature of 50-150 DEG C, and a corresponding nitro-compound is reduced into amine. According to the method disclosed by the invention, the defects that a catalyst is expensive, unsafe and not environment-friendly, and has high requirements on equipment, etc are overcome. The method disclosed by the invention can be used for simultaneously catalyzing selective oxidization of the alcohol compound and selective reduction of the nitro-compound; a preparation process of the needed catalyst is simple; the catalyst is cheap; the novel method can be operated at low temperature and normal pressure when being applied to the reaction and are mild in condition, high in selectivity and moderate in yield.

Description

technical field [0001] The invention relates to a new application of nano-nickel oxide, in particular to a new method for catalyzing the selective oxidation of alcohols by nano-nickel oxide. Background technique [0002] Aldehydes and ketones are an important class of organic compounds, and their synthesis occupies a very important position in organic synthesis. The production of aldehydes or ketones is not only extracted from natural products, but also the selective oxidation of alcohols to produce aldehydes or ketones in industry. Alcohol selective oxidation is widely used in large-scale chemical industrial production, and it is also an important content of fine chemical research. However, the catalytic oxidation reaction of alcohols is prone to deep oxidation. For example, the catalytic oxidation of primary alcohols can easily generate the corresponding acid, CO 2 The product of the deep oxidation, which makes the selectivity of the target product lower. For this reaso...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C45/29C07C49/08C07C47/02C07C211/52C07C211/46C07C209/36B01J23/755
Inventor 菅盘铭陈玲尤亮刘建禹王菲孔黎明
Owner YANGZHOU UNIV
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