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Method for synthesizing formic ester and specific catalyzer thereof

A technology of catalyst and formate, which is applied in the direction of physical/chemical process catalyst, carbon monoxide or formate reaction preparation, metal/metal oxide/metal hydroxide catalyst, etc., can solve the problem of improving process cost, space-time yield and Low selectivity, high synthesis cost of esterification method, etc., to achieve huge economic and social benefits, high conversion efficiency and selectivity, and wide industrial application prospects

Inactive Publication Date: 2008-03-05
PEKING UNIV
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  • Summary
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  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, these methods have some disadvantages, for example, the esterification method has high synthesis cost and serious equipment corrosion; the formaldehyde dimerization method has poor effect and high cost; the methanol oxidative dehydrogenation method has low air rate and poor selectivity; the synthesis gas is directly synthesized. The space-time yield and selectivity of methyl formate are low, and it is difficult to realize industrialization
Methanol carbonylation is currently the most advanced production method of methyl formate. Sodium formate is used as the catalyst. At a reaction temperature of 80°C and a pressure of 4-6 MPa, the conversion rates of CO and methanol are 95% and 30%, respectively. Methyl formate The selectivity is nearly 100%; but there are also the following disadvantages: need to use higher price anhydrous methanol; must use expensive CO with a concentration higher than 80%
In addition, water and CO in the reaction system 2 The existence of will cause operational problems, greatly increasing the cost of the process
At the same time, the strong alkalinity of the catalyst is easy to corrode the reaction equipment, which violates the purpose of green chemistry

Method used

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  • Method for synthesizing formic ester and specific catalyzer thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0018] Embodiment 1, synthetic methyl formate

[0019] Place 0.5mmol of copper nitrate and 50.0mmol of polyvinylpyrrolidone (PVP) in the reaction flask successively, add 20.0mL of methanol, stir, and dropwise add 10.0mL of 0.5mol / L NaBH 4 Methanol solution was reacted at room temperature for 30 minutes to obtain a copper nanoparticle catalyst.

[0020] The catalyst was placed in a 100mL reactor, filled with 3.0MPaCO, and reacted at 150°C for 12 hours.

[0021] The conversion rate of CO was 45%, and the selectivity of the target product methyl formate detected by GC / MS was 100%.

[0022] The photo of the copper nanoparticles observed by the electron microscope is shown in Figure 1a, and the particle size distribution is shown in Figure 1b. It can be seen from the figure that the particle size distribution of the nanoparticles is relatively narrow, about 3.3±0.5nm. Utilizing the catalyst to synthesize methyl formate can obtain a high CO conversion rate of 45%, and the selecti...

Embodiment 2

[0023] Embodiment 2, synthetic methyl formate

[0024] Put the metal salt copper chloride and PVP in the reaction flask at a molar ratio of 1:50, add 30mL of methanol, stir, and dropwise add 10mL of 0.1mol / L NaBH 4 Methanol solution, react at room temperature for 0.5 hour to obtain nanometer particle catalyst, the particle diameter of which is 2-4nm.

[0025] The catalyst was placed in a 100mL reactor, filled with 0.3MPaCO, and reacted at 170°C for 16 hours.

[0026] The conversion rate of CO was 25%, and the selectivity of the target product methyl formate detected by GC / MS was 100%.

Embodiment 3

[0027] Embodiment 3, synthetic methyl formate

[0028] Put the metal salt copper acetylacetonate and PVP in a molar ratio of 1:100 successively in the reaction flask, add 30mL of methanol, stir, add dropwise 10mL of 0.1mol / L NaBH 4 The methanol solution is reacted at room temperature for 1 hour to obtain a nanoparticle catalyst with a particle size of 2-4nm.

[0029] The catalyst was placed in a 100mL reactor, filled with 2.0MPaCO, and reacted at 130°C for 8 hours.

[0030] The conversion rate of CO was 38%, and the selectivity of the target product methyl formate detected by GC / MS was 100%.

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Abstract

The present invention discloses nanometer metal catalyst catalyzed formic acid ester synthesizing process, in which alcohol is catalyzed for caronylation reaction in the presence of nanometer metal catalyst and CO. The nanometer metal catalyst with particle size of 1-10 nm is prepared through mixing metal salt and macromolecular stabilizer, dispersing in liquid medium and reducing with reductant. The nanometer metal catalyst has the following advantages: capacity of realizing 3D free rotation, excellent low temperature activity capable of catalyzing formic acid ester synthesis at 60-200 deg.c, high conversion efficiency and high selectivity of formic acid ester, stable performance, environment friendship, etc. The nanometer metal catalyst catalyzed formic acid ester synthesizing process of the present invention has broad application foreground.

Description

technical field [0001] The invention relates to a method for synthesizing formate, in particular to a method for catalyzing the synthesis of formate by using a metal nanoparticle catalyst. Background technique [0002] Formic esters are a large class of carboxylate compounds that are widely used. They are not only important chemical products but also important intermediates in organic synthesis. For example, methyl formate is a versatile low-boiling solvent that can be directly used as an insecticide, fungicide, and fumigant for treating grain, fruit, dried fruit, and tobacco. It is often used as an intermediate in medicine, pesticide and organic synthesis, and a solvent for cellulose acetate. At present, it is mainly used as an intermediate product in the production of dimethylformamide and formic acid in industry. Ethyl formate is an important organic solvent, used in organic synthesis, and can also be used as spices for wine making, fungicides for cigarettes, food indus...

Claims

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Application Information

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IPC IPC(8): B01J23/72B01J23/89B01J23/38C07C67/36C07C69/04
Inventor 寇元何玲肖超贤
Owner PEKING UNIV
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