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A kind of method for preparing 1,4-cyclohexanediol by catalytic hydrogenation of p-benzoquinone

A technology for catalytic hydrogenation of cyclohexanediol, which is applied in hydrogenation preparation, chemical instruments and methods, preparation of hydroxyl compounds, etc., can solve problems such as high price of samarium iodide, difficulty in industrialization, non-green solvent and other problems, and achieve Conducive to competition, reduced post-processing steps, and low cost effects

Active Publication Date: 2019-02-05
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

For example, CN101811937A discloses a catalytic hydrogenation reaction of hydroquinone with a supported transition metal ruthenium as a catalyst and supercritical carbon dioxide as a reaction medium. The yield is only about 60% and the method is difficult to realize industrialization; Foreign reports use Raney nickel as a catalyst, and use ethanol solution of sodium hydroxide as a reaction solvent to catalyze the synthesis of 1,4-cyclohexanediol, but the solvent is not environmentally friendly, and the reaction time is also very long, and hydroquinone is produced from hydroquinone. Prepared by hydrogenation of quinone;
[0005] 2) Reduction of hydroquinone with samarium iodide, Y.Komachi used samarium iodide as a reducing agent to reduce hydroquinone in potassium hydroxide solution to prepare 1,4-cyclohexanediol, but the price of samarium iodide was too high Expensive, economically unsuitable for industrialization

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment example 1

[0026] Weigh 0.5g of titanium dioxide and dissolve it in 10ml of aqueous solution in a round-bottomed flask, add 0.054g of palladium nitrate dihydrate solid under continuous stirring, continue stirring for 12 hours, turn off the stirring, and remove excess aqueous solution by rotary evaporation after standing still for 12 hours. It was dried overnight, calcined at 450°C for 8 hours, and finally reduced at 300°C for 6 hours under hydrogen atmosphere to obtain a catalyst of noble metal palladium supported on titania. Take the catalyst 0.1g of titanium dioxide supported noble metal palladium prepared above, 25ml of water, and 0.5g of p-benzoquinone and add them to the reaction kettle, replace the air in the reaction kettle with hydrogen for 5 times, at a temperature of 80°C, a pressure of 0.5MPa, and a stirring speed of 900rpm, After reacting for 1 h, after cooling to room temperature, the reaction solution was taken out and analyzed by gas chromatography: the conversion rate was ...

Embodiment example 2

[0028] Weigh 0.5g of titanium dioxide and dissolve it in 10ml of aqueous solution in a round-bottomed flask, add 0.054g of palladium nitrate dihydrate solid under continuous stirring, continue stirring for 6 hours, turn off the stirring, and remove the excess aqueous solution by rotary evaporation after 12 hours of standing still , dried overnight, calcined at 550°C for 4 hours, and finally reduced at 200°C for 8 hours under a hydrogen atmosphere to obtain a catalyst of noble metal palladium supported on titania. Take 0.1g of catalyst, 25ml of water, and 0.5g of p-benzoquinone into the reaction kettle, replace the air in the reaction kettle with hydrogen for 5 times, react at a temperature of 120°C, a pressure of 0.5MPa, a stirring speed of 900rpm, and react for 2 hours. After cooling to room temperature, take out The reaction solution was analyzed by gas chromatography: the conversion rate was 95.97%, and the selectivity was 98.34%.

Embodiment example 3

[0030] Weigh 0.5g of titanium dioxide and dissolve it in 10ml of aqueous solution in a round-bottomed flask, add 0.054g of palladium nitrate dihydrate as a solid under continuous stirring, continue stirring for 12 hours, turn off the stirring, and remove the excess aqueous solution by rotary evaporation after standing still for 4 hours , dried overnight, calcined at 450°C for 8 hours, and finally reduced at 300°C for 6 hours under a hydrogen atmosphere to obtain a catalyst of noble metal palladium supported on titania. Take 0.1g of catalyst, 25ml of water, and 0.5g of p-benzoquinone into the reaction kettle, replace the air in the reaction kettle with hydrogen 5 times, react at a temperature of 100°C, a pressure of 1.5MPa, and a stirring speed of 900rpm, and react for 3h. After cooling to room temperature, take out The reaction solution was analyzed by gas chromatography: the conversion rate was 94.21%, and the selectivity was 70.22%.

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Abstract

The invention relates to a method for preparing 1,4-cyclohexanediol from p-benzoquinone through catalytic hydrogenation. According to the method, palladium supported titanium dioxide is taken as a catalyst, p-benzoquinone is taken as a reaction raw material in an aqueous solution, and 1,4-cyclohexanediol is directly synthesized through direct catalytic hydrogenation. Water is taken as a solvent in both steps of reactions in the method, any other organic or inorganic solvents are not required to be added, a post-processing step for catalyst preparation is reduced, an operation process is simplified, green catalysis is realized, prevention of environmental pollution is realized, and the requirement for environmental protection is met; the reaction conditions are mild, post-processing is convenient, all that is required is to remove filter residues through filtering to obtain a product, the catalytic activity, the conversion rate and the selectivity are high, the yield can reach 98% or higher, the conversion degree can reach 100%, the industrial cost is low, the profit is large, and competition is facilitated.

Description

technical field [0001] The invention belongs to the technical field of catalytic hydrogenation, and in particular relates to a method for preparing 1,4-cyclohexanediol by catalytic hydrogenation of p-benzoquinone. Background technique [0002] 1,4-Cyclohexanediol is of great significance in medicine and new materials. For example, it is an important intermediate of anticancer drugs, drug blockers, inositol phosphate inhibitors, and benzotriazoles; spectrally pure 1,4-cyclohexanediol is a liquid crystal material, organic electrical material, biological One of the key raw materials such as controller markers. [0003] At present, the synthesis of 1,4-cyclohexanediol is mainly divided into two categories: [0004] 1) Synthesis of 1,4-cyclohexanediol by catalytic hydrogenation of hydroquinone as raw material. Based on the characteristics of the molecular structure of 1,4-cyclohexanediol, 1,4-cyclohexanediol is generally synthesized from hydroquinone. For example, CN101811937...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C29/17C07C35/14B01J23/44
CPCB01J23/44C07C29/175C07C35/14
Inventor 王建国韩冰冰周虎胡晖
Owner ZHEJIANG UNIV OF TECH