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Preparation method of organic acid

A technology of organic acid and acetic acid, which is applied in the preparation of organic compounds, carboxylate salts, organic chemistry, etc., can solve the problems of long reaction route, low product yield, high reaction temperature, etc., and achieve high added value, wide range of sources, The effect of low oxidant cost

Inactive Publication Date: 2019-04-09
陶富名
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The existing research results have shortcomings such as long reaction route (two-step reaction), high reaction temperature, low product yield, and the need to add additives.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021] The process conditions described in this example are: 0.5 g of cellulose, 15 ml of water, an initial oxygen pressure of 4 MPa, a reaction temperature of 240° C., and a reaction time of 30 min.

[0022] Add 0.5005g of cellulose, 15ml of water and a stirring bar into a 25ml high-temperature and high-pressure reaction kettle and seal it, fill it with oxygen to 0.5MPa and discharge it, repeat three times to replace the air in the kettle, and finally fill it with oxygen to 4.03MPa, Turn on the stirring, and raise the temperature to 240°C for 30 minutes. After the reaction was over, the reaction kettle was placed in ice water for rapid cooling to terminate the reaction. The reaction material is filtered to obtain a filter residue and a filtrate. The filter residue was dried in an oven, weighed, and the conversion rate of cellulose was calculated. The filtrate was analyzed by high performance liquid chromatography (Waters 2695 HPLC; shodex SH1011 chromatographic column; PDA ...

Embodiment 2

[0024] The process conditions described in this example are: 0.5g cellulose, 15ml water, initial pressure of oxygen 4MPa, catalyst 0.1gMn7Ce3Oz, reaction temperature 240°C, reaction time 30min.

[0025] Preparation of Mn7Ce3Oz catalyst:

[0026] 3.821g of 50% Mn(NO3)2 solution and 2.000g of Ce(NO3)3·6H2Og (purity>99wt%) solid were dissolved in a beaker containing an appropriate amount of water. Slowly add NaOH solution to the above-mentioned beaker under stirring condition, and continue stirring for 2 h after the dropwise addition is completed. Use a Buchner funnel to filter and wash the filter residue to neutrality, then vacuum-dry the filter residue at 110°C for 12 hours, and finally roast it at 350°C for 4 hours to obtain the Mn7Ce3Oz catalyst (the value of z is uncertain because the elements Mn and Ce may exist in multiple valence states).

[0027] Cellulose conversion reaction:

[0028] Add 0.5007g of cellulose, 0.1008g of Mn7Ce3Oz catalyst, 15ml of water and a stirrer...

Embodiment 3

[0030] The process conditions described in this example are: 0.5g of cellulose, 15ml of water, 4MPa of oxygen initial pressure, 0.1g of activated carbon as a catalyst, a reaction temperature of 240° C., and a reaction time of 30 minutes.

[0031] Activated carbon catalyst preparation:

[0032] Take 20g of 40-60 mesh activated carbon into a 250ml single-necked flask, add 100ml of 10% (volume) nitric acid solution, put it into a stirrer, and stir in an oil bath at 60°C for 6h. Then the activated carbon was filtered, washed with deionized water until neutral, and dried under vacuum at 110°C for 3h.

[0033] Cellulose conversion reaction:

[0034] Add 0.5010g of cellulose, 0.1004g of activated carbon prepared by the above method, 15ml of water and a stirrer into a 25ml high-temperature and high-pressure reaction kettle and seal it up. Fill it with oxygen to 0.5MPa and then discharge it. Repeat three times to replace the Air, and finally oxygen up to 4.01MPa, start stirring, and ...

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PUM

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Abstract

The invention provides a preparation method of organic acid. According to the preparation method, cellulose is used as a reaction raw material, water is used as a reaction medium and a catalyst is notadded or one of MnxCeyOz, V2O5 and activated carbon is used as the catalyst; and oxygen gas or air is used as an oxidant and then the materials are stirred in a closed high-temperature and high-pressure kettle to react. The initial partial pressure is 1 to 6MPa when the temperature of the oxygen gas in the reaction kettle is room temperature, the reaction temperature is 180 to 290 DEG C and the reaction time is 15min to 5h. After reaction is finished, the materials are cooled; then the materials are taken out to separate a liquid phase and a solid phase. The preparation method provided by theinvention has the specific advantages in the following aspects: 1, an organic solvent with relatively high cost does not need to be used as a reaction medium and only water is used as the reaction medium; in a reaction process, any acid or alkali is not added and the problems of environment pollution and equipment corrosion are avoided; and 2, a renewable biomass resource cellulose with the greatest quantity in the nature is used as a reaction raw material and has the advantages of abundant reserves, wide source and low cost.

Description

technical field [0001] The invention relates to the field of biomass energy application technology and the field of chemical product production, and more specifically relates to a method for preparing small molecule carboxylic acids such as formic acid and acetic acid by oxidizing cellulose in subcritical water. Background technique [0002] Formic acid is one of the basic organic chemical raw materials and one of the important export chemical products in my country. Acetic acid is a bulk chemical product and one of the most important organic acids. Both formic acid and acetic acid can be used in industries such as pesticides, pharmaceuticals, dyes and rubber, and the consumption is increasing year by year. In addition, calcium-magnesium salts of formic acid and acetic acid are a new type of environmentally friendly deicing agent, but due to the high cost of preparation of formic acid and acetic acid, this method is difficult to be widely applied. [0003] At present, the ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C53/02C07C53/08C07C51/21B01J23/34B01J21/18
CPCC07C51/21B01J21/18B01J23/002B01J23/34C07C53/02
Inventor 陶富名
Owner 陶富名