Preparation method and application of graphene oxide supported quadri (4-carboxyphenyl) manganese porphyrin catalysis material

A porphyrin catalytic material, carboxyphenyl technology, applied in the direction of oxidation reaction preparation, organic compound preparation, hydrocarbon oxidation preparation of oxygen-containing compounds, etc., can solve the problem of low reuse rate, low catalytic efficiency of metal porphyrin, and oxidation conversion rate low cost, low cost, easy recycling and reuse, and low consumption

Inactive Publication Date: 2016-12-07
GUANGXI UNIV
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  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] In order to overcome the current problems of low conversion rate of toluene catalytic oxidation, low catalytic efficiency of metal porphyrin, and low reuse rate, the invention provides a method for preparing graphene oxide-immobilized tetrakis (4-carboxyphenyl) manganese porphyrin catalytic material And its applica

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  • Preparation method and application of graphene oxide supported quadri (4-carboxyphenyl) manganese porphyrin catalysis material
  • Preparation method and application of graphene oxide supported quadri (4-carboxyphenyl) manganese porphyrin catalysis material
  • Preparation method and application of graphene oxide supported quadri (4-carboxyphenyl) manganese porphyrin catalysis material

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Embodiment 1

[0028] A graphene oxide immobilized four (4-carboxyphenyl) manganese porphyrin catalytic material, comprising the following raw materials in parts by weight: 550.8 parts of concentrated sulfuric acid, 12 parts of graphite powder, 6 parts of sodium nitrate, 42 parts of potassium permanganate , 2190 parts of distilled water, 180 parts of 5% hydrogen peroxide, 1500 parts of 5% hydrochloric acid, 0.030 parts of tetrakis (4-carboxyphenyl) manganese porphyrin, 4.8 parts of N.N-dimethylformamide, and 103.8 parts of toluene.

[0029] The preparation method of described graphene oxide immobilized tetrakis (4-carboxyphenyl) manganese porphyrin catalytic material comprises the following steps:

[0030] (1) Preparation of graphite oxide: Weigh 550.8 parts of concentrated sulfuric acid in a round bottom flask, add 12 parts of graphite powder and 6 parts of sodium nitrate after ice-water bath for 5 minutes, continue stirring in ice-water bath for 30 minutes, then slowly add 42 parts of perma...

Embodiment 2

[0036] Application of graphene oxide immobilized four (4-carboxyphenyl) manganese porphyrin catalytic material: Weigh 0.5 g of graphene oxide immobilized tetrakis (4-carboxyphenyl) manganese porphyrin immobilized catalytic material in Example 1, Put it into a 250mL autoclave, add 200mL toluene, control the stirring speed to 200r / min, and feed oxygen to react when the temperature rises to 150°C, the oxygen pressure is 0.8MPa, and the oxygen flow rate is 0.02m 3 / h, reaction 4.0h. The conversion rate of cyclohexane is 4.2%, the selectivity of ketone alcohol is 47.5%, and the catalyst conversion number is 7.6×104 , the ketol yield was 2.0%.

Embodiment 3

[0038] Application of graphene oxide-immobilized tetrakis(4-carboxyphenyl)manganese porphyrin catalytic material: Weigh 0.5g of graphene oxide-immobilized tetrakis(4-carboxyphenyl)manganese porphyrin catalytic material in Example 1 , put it into a 250mL autoclave, add 200mL toluene, stir at a speed of 200r / min, feed oxygen when the temperature rises to 160°C, the oxygen pressure is 0.8MPa, and the oxygen flow rate is 0.02m 3 / h, reaction 4.0h. The conversion rate of cyclohexane is 8.5%, the selectivity of ketone alcohol is 42.3%, and the catalyst conversion number is 1.5×10 5 , the ketol yield was 3.6%.

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Abstract

The invention relates to a preparation method and application of a graphene oxide supported quadri (4-carboxyphenyl) manganese porphyrin catalysis material. The preparation method comprises the following steps of: firstly preparing graphene oxide by an improved Hummers method, enabling graphite oxide to be ultrasonically dispersed in water to obtain the graphene oxide, then adding the graphene oxide to quadri (4-carboxyphenyl) manganese porphyrin dissolved by N. N-dimethyl formamide, performing ultrasonic treatment at the temperature of 50 DEG C for 5 hours, and performing pressure reduction and suction filtration so as to obtain filter cakes; and drying the obtained filter cakes at 70 DEG C for 36h so as to obtain the required catalysis material. The preparation method of the catalysis material is raid and simple, low in cost, and low in energy consumption; the catalysis material is used for catalyzing oxygen for oxidizing toluene so as to generate benzaldehyde and benzyl alcohol, the highest conversion ratio reaches 16.3%, and the yield of alcohol ketone is 5.8%; and in addition, the catalyst is convenient to recover, after cyclic catalysis for 7 times, the catalysis efficiency is not reduced obviously, and the catalysis material has practical application values, and is an ideal biomimic catalyst.

Description

technical field [0001] The invention relates to the technical field of catalytic materials, in particular to a preparation method and application of a graphene oxide immobilized tetrakis(4-carboxyphenyl)manganese porphyrin catalytic material. Background technique [0002] Catalytic oxidation of toluene mainly produces benzaldehyde and benzyl alcohol, both of which are important raw materials in today's chemical production. As a very important fine chemical product and intermediate, benzaldehyde is widely used in industries such as food, medicine, dyes and spices. Benzyl alcohol is widely used in industries such as coatings, inks and dyeing, and its strong polarity and low water solubility make it also have many other uses. At present, the process of catalytic oxidation of toluene at home and abroad is becoming more and more mature and efficient, from the traditional chlorination hydrolysis method to gas phase oxidation method and liquid phase oxidation method. Among them, ...

Claims

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Application Information

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IPC IPC(8): B01J31/22C07C45/36C07C47/54C07C29/50C07C33/22C07C27/12
CPCB01J31/1616B01J31/183B01J2231/70B01J2531/0213B01J2531/025B01J2531/72C07C29/50C07C45/36C07C47/54C07C33/22Y02P20/50
Inventor 黄冠原汝迅陈祥凤晏超郭勇安危素娟
Owner GUANGXI UNIV
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