Tridentate copper chelate catalyst and method for synthesizing dimethyl carbonate thereby

A technology of dimethyl carbonate and copper chelate, applied in organic compound/hydride/coordination complex catalyst, physical/chemical process catalyst, carbonate/haloformate preparation, etc., can solve the difficult product. Separation, poor solubility, low methanol conversion rate, etc., to achieve the effect of good selectivity and stability, improved conversion rate, and low corrosiveness

Inactive Publication Date: 2010-06-16
HUBEI XINGFA CHEM GRP CO LTD +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, due to the poor solubility of CuCl in the reaction system, a high concentration of CuCl must be used in the Enichem process to obtain a sufficient reaction rate; at the same time, CuCl is highly corrosive to the reaction equipment, and anti-corrosion such as glass or enamel lining must be added to the inner wall of the reactor. materials; in addition, the process has problems such as catalysts, reactants, and products that are difficult to separate
Chinese patent CN 1197792A (1998) uses CuCl as the main catalyst, MgCl and CaCl as cocatalysts, and prepares a composite catalyst modified by alkaline earth metal salts, which improves the solubility of cuprous chloride in the reaction solution to a certain extent, improves the Catalytic activity, but it does not solve the problem of corrosion of equipment, nor does it solve the problem of difficult separation of catalysts, reactants and products
Chinese patent CN 0610104944.9 (2006) adopts ionic liquid as the solvent for the reaction, and uses metal copper salt as the catalyst to realize the simple and effective separation of the catalyst, the product and the reactant, but the conversion rate of methanol is low and the ionic liquid is not suitable for industrialization

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0018] Add 100ml of methanol and 2% terpyridine copper catalyst into the autoclave, replace the air in the reactor with CO three times, heat the temperature at 120-130°C until the pressure in the autoclave no longer rises, and then press CO / O 2 = 9:1 ratio into CO and O successively 2 , until the total pressure reaches 2.5MPa, and react for 3 hours. After cooling, it was analyzed by gas chromatography. The selectivity of dimethyl carbonate is greater than 99.0%, the space-time conversion rate of methanol is higher than 0.85gDMC / gcat.h, and the corrosion rate of Q345 steel is lower than 0.035mm.a -1 .

Embodiment 2

[0020] According to the method of Example 1, 2% triimidazole-containing copper catalyst was added, the total pressure was 2.0 MPa, the reaction temperature was 110° C., and the reaction time was 2.5 h. The selectivity of dimethyl carbonate is greater than 99%, the space-time conversion rate of methanol is higher than 0.78gDMC / gcat.h, and the corrosion rate of Q345 steel is lower than 0.038mm.a -1 .

Embodiment 3

[0022] Add 200mL methanol in the autoclave, according to the method of embodiment 1, add 5.0g polyethylene terpyridine polymer catalyst, pass into CO and O 2 The total pressure is 3.0MPa, the reaction temperature is 150°C, the reaction time is 3h, and analyzed after cooling. The selectivity of dimethyl carbonate is 99.5%, the space-time conversion rate of methanol is 0.72gDMC / gcat.h, and the corrosion rate of Q345 steel is 0.030mm.a -1 .

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Abstract

The invention discloses a tridentate copper chelate catalyst and a method for synthesizing dimethyl carbonate thereby. The catalyst belongs to the chelate of cuprous chloride, tridentate heterocyclic compound and macromolecule derivant thereof. Methyl alcohol, carbon monoxide and oxygen serve as raw materials; and at the temperature of 25-300 DEG C, the raw materials react for 0.5-20 hours under the total reaction pressure of 0.2-10 MPa and catalyst concentration of 0.1-1.0 mol/ L to synthesize dimethyl carbonate. The average time-space conversion rate of methyl alcohol is more than or equal to 0.7 g DMC/ gcat.h, and the average selectivity of dimethyl carbonate is more than or equal to 99%. The catalyst of the invention has simple preparation technology, high catalyst activity and favorable selectivity and stability; no accessory ingredient needs to be added, a reaction system nearly has no corrosivity on a reactor, and catalyst, reactant and reaction products are easy to be separated; thus, the invention can improve the conversion rate of methyl alcohol and dimethyl carbonate selectivity, has quite small corrosivity on a high pressure reactor and has favorable industrial application prospect.

Description

technical field [0001] The invention belongs to the technical field of chemical industry, in particular to the catalyst of the tridentate ligand-cuprous chloride chelate and polymer complex thereof synthesized from methanol liquid-phase oxidative carbonylation of dimethyl carbonate (DMC). A method for synthesizing dimethyl carbonate using this catalyst. Background technique [0002] Dimethyl carbonate is a high value-added organic chemical raw material, widely used in medicine, pesticides, synthetic materials, dyes, solvents, lubricating oil additives, food flavor enhancers, electronic chemicals and other fields. The preparation methods of dimethyl carbonate mainly include phosgene method, transesterification method, electrochemical method, urea hydrolysis method, methanol liquid phase oxidative carbonylation method, etc. Among them, the methanol liquid-phase oxidative carbonylation method has the advantages of cheap and easy-to-obtain raw materials, low corrosion, high deg...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/22C07C69/96C07C68/00
Inventor 胡泉源袁兵娄兆文陈晓清安港袁木平周保英
Owner HUBEI XINGFA CHEM GRP CO LTD
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