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Method for preparing formic acid by catalyzing and oxidizing biomass using oxygen

A technology of oxygen oxidation and biomass, applied in the preparation of organic compounds, chemical instruments and methods, carboxylate preparation, etc., can solve the problems of cellulose ineffectiveness, achieve low cost, improve catalytic performance, and simple synthesis Effect

Inactive Publication Date: 2017-07-25
BEIJING UNIV OF CHEM TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Wasserscheid et al. ( Taccardi N, and WasserscheidP.Selective catalytic conversion of biobased carbohydrates toformic acid using molecular oxygen.Green Chem.,2011,13:2759-2763) showed that: at 80°C and an initial oxygen pressure of 3MPa, H 5 PV 2 Mo 10 o 40 Catalytic oxidation of glucose for 7 hours, the yield of formic acid can reach 49% (carbon yield, the same below), but under this condition, the catalytic system has little effect on cellulose

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] This embodiment is a comparative example, that is, only with NaVO 3 / H 2 SO 4 For catalyst system, without FeCl 3 (or Fe 2 (SO 4 ) 3 ), to produce formic acid by oxidation of cellulose. The specific operation is as follows:

[0023] The cellulose catalytic oxidation reaction was carried out in a 25mL high temperature and high pressure reactor. Mix 0.1g of cellulose with particle size less than or equal to 90μm and 6mL of NaVO 3 The mass fraction is 0.35%, H 2 SO 4 Add the aqueous solution with a mass fraction of 2.0% into the reactor, add the magnet and seal it; after checking the airtightness of the device, use O 2 The air in the reactor was replaced twice (the purpose was to exhaust the air in the reactor), and then filled with 3MPa of O 2 ; Put the reactor into the heating and stirring controller whose temperature has been set in advance, the stirring speed is 1000 rpm, and start timing when the temperature of the reactor reaches 160°C. After 50 minutes of...

Embodiment 2

[0027] The cellulose catalytic oxidation reaction was carried out in a 25mL high temperature and high pressure reactor. Mix 0.1g of cellulose with particle size less than or equal to 90μm and 6mL of FeCl 3 The mass fraction is 0.05%, NaVO 3 The mass fraction is 0.35%, H 2 SO 4 Add the aqueous solution with a mass fraction of 2.0% into the reactor, add the magnet and seal it; after checking the airtightness of the device, use O 2 The air in the reactor was replaced twice (the purpose was to exhaust the air in the reactor), and then filled with 3MPa of O 2 ; Put the reactor into the heating and stirring controller whose temperature has been set in advance, the stirring speed is 1000 rpm, and start timing when the temperature of the reactor reaches 160°C. After 50 minutes of reaction, immediately take out the reactor for heating and stirring control instrument, and immediately placed in cold water to cool to terminate the reaction; when the temperature of the reactor dropped ...

Embodiment 3

[0030] The cellulose catalytic oxidation reaction was carried out in a 25mL high temperature and high pressure reactor. Mix 0.1g of cellulose with particle size less than or equal to 90μm and 6mL of FeCl 3 The mass fraction is 0.02%, NaVO 3 The mass fraction is 0.35%, H 2 SO 4 Add the aqueous solution with a mass fraction of 2.0% into the reactor, add the magnet and seal it; after checking the airtightness of the device, use O 2 The air in the reactor was replaced twice (the purpose was to exhaust the air in the reactor), and then filled with 3MPa of O 2 ; Put the reactor into the heating and stirring controller whose temperature has been set in advance, the stirring speed is 1000 rpm, and start timing when the temperature of the reactor reaches 160°C. After 50 minutes of reaction, immediately take out the reactor for heating and stirring control instrument, and immediately placed in cold water to cool to terminate the reaction; when the temperature of the reactor dropped ...

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Abstract

The invention relates to a method for preparing formic acid by catalyzing and oxidizing biomass using oxygen in the presence of FeCl3 (or Fe2(SO4)3)-NaVO3-H2SO4 as a catalyst system in an aqueous solution. The method uses FeCl3 (or Fe2(SO4)3)-NaVO3-H2SO4 as the catalyst system, and oxygen as an oxidant to selectively oxidize biomass in the aqueous solution to prepare high-yield formic acid. Compared with the method for preparing formic acid by catalyzing and oxidizing biomass in an NaVO3 / H2SO4 system, the method provided by the invention has the advantages that in the FeCl3 (or Fe2(SO4)3)-NaVO3-H2SO4 system, the catalytic performance of the NaVO3-H2SO4 system can be improved by adding a ferric salt, and the synergistic catalysis between the ferric salt and sodium metavanadate occurs to improve the yield of the formic acid.

Description

technical field [0001] The present invention relates to a kind of NaVO 3 -FeCl 3 (or Fe 2 (SO 4 ) 3 )-H 2 SO 4 In order to cooperate with the catalyst system, the method for preparing formic acid by catalyzing oxygen oxidation of biomass is provided. [0002] technical background [0003] Fossil fuels are the main form of energy in our country and also the main source of organic chemicals. However, the non-renewability of fossil fuels and the environmental pollution caused during use force people to look for alternatives to fossil fuels. Biomass is the clean and renewable energy with the most abundant output in nature. The rational utilization of biomass energy is of great significance to alleviate various social problems caused by fossil energy. Formic acid is a basic chemical widely used in the fields of rubber, printing and dyeing, pesticides, etc. In recent years, research has found that: (1) Formic acid can be catalytically decomposed to generate hydrogen under mi...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C51/21C07C53/02
CPCC07C51/21C07C53/02
Inventor 吴卫泽蔺增琪牛牧歌鲁婷
Owner BEIJING UNIV OF CHEM TECH
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