Method for preparing sulfonic acid group-modified mesoporous material-loaded heteropolyacid catalyst and application thereof during esterification reaction

A technology for loading heteropolyacids and mesoporous materials, which is applied in catalytic reactions, preparation of organic compounds, preparation of carboxylate esters, etc., can solve the problems of easy dissolution and desorption of active components, and achieves simple preparation process, strong acidity, and large pores. the effect of

Active Publication Date: 2016-08-17
XIANGTAN UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0007] The purpose of the present invention is to improve the acid content of the immobilized heteropolyacid, overcome the problem that the active component of the immobilized heteropolyacid is easy to dissolve and detach, and provide a mesoporous material modified with sulfonic acid groups to catalyze the heteropolyacid. The preparation method of the new material, and it is used to catalyze the esterification reaction of cyclohexene and formic acid

Method used

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  • Method for preparing sulfonic acid group-modified mesoporous material-loaded heteropolyacid catalyst and application thereof during esterification reaction
  • Method for preparing sulfonic acid group-modified mesoporous material-loaded heteropolyacid catalyst and application thereof during esterification reaction

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Embodiment 1

[0026] Dissolve 4g of P123 in 120g of 2mol / L hydrochloric acid solution, stir at 35°C for 3 hours to completely dissolve the templating agent; raise the temperature to 40°C, and add 8.42g of tetraethyl orthosilicate (TEOS) dropwise to the above solution, Continue to stir for 60 minutes; add 3-mercaptopropyltrimethoxysilane (MPTMS), phosphotungstic acid (HPW) and hydrogen peroxide solution (30wt%) to the above solution in sequence, molar composition α=n(MPTMS) / n(MPTMS +TEOS)=0.1, β=n(H 2 o 2) / n(MPTMS)=9, mass component γ=m(HPW / m(TEOS)=0.1, under nitrogen protection, continue to stir for 20h, then crystallize at 100°C for 24h, filter, wash with ethanol and aqueous solution respectively , vacuum-dried at 80°C for 12h, ethanol Soxhlet extraction for 24h, vacuum-dried at 80°C for 12h, and the obtained sample was designated as HPW-SBA-15-SO 3 H (α=0.1, β=9, γ=0.1).

Embodiment 2

[0028] The application of a heteropolyacid catalyst supported by a sulfonic acid group-modified mesoporous material in esterification reaction. Weigh 1.23g of heteropoly acid catalyst HPW-SBA-15-SO 3 H (α=0.1, β=9, γ=0.1), then weighed 8.21g cyclohexene and 13.81g formic acid into a 50ml three-necked flask, stirred at 80°C for 6h, cooled to room temperature, and used gas chromatography Analysis of the components of the reaction solution showed that the conversion rate of cyclohexene was 82%, and the selectivity of cyclohexyl formate was 99%.

Embodiment 3

[0030] Loading heteropolyacid catalyst HPW-SBA-15-SO on recycled sulfonic acid group-modified mesoporous materials 3 H (α=0.1, β=9, γ=0.1) was vacuum-dried at 100°C for 12 hours, cooled to room temperature, weighed 1.23g, then weighed 8.21g cyclohexene and 13.81g formic acid and added them to a 50ml three-necked flask in turn, Stirring at 80° C. for 6 h, cooling to room temperature, and analyzing the components of the reaction solution by gas chromatography showed that the conversion rate of cyclohexene was 83%, and the selectivity of cyclohexyl formate was 99%.

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Abstract

The present invention discloses a method for preparing a sulfonic acid group-modified mesoporous material-loaded heteropolyacid catalyst and the application thereof during the esterification reaction. 3-mercapto propyl trimethoxy silane is adopted as an organic silicon source, and tetraethoxysilane is adopted as an inorganic silicon source. A tri-block copolymer is adopted as a template agent, and H2O2 solution is adopted as an oxidant. Phosphotungstic acid is added as an active ingredient and the sulfonic acid group-modified mesoporous material-loaded heteropolyacid catalyst is obtained through the one-step hydro-thermal synthesis process based on the copolycondensation method in the acidic condition. According to the technical scheme of the invention, the catalyst has the advantage of strong acidity, and the specific surface area thereof is 300-600 m2 / g. The pore volume of the catalyst is 0.4-1.4 cm3 / g, and the pore diameter of the catalyst is 3-7 nm. When the catalyst is used for catalyzing the esterification reaction of cyclohexene and formic acid, the catalyst exhibits good catalytic activity. The conversion rate of cyclohexene can reach 87% and the selectivity of cyclohexyl formate is up to 99%. Moreover, even after the catalyst is recycled, the catalyst is still good in activity. Therefore, the catalyst can be recycled and used repeatedly, and has a considerable industrial application prospect.

Description

technical field [0001] The invention relates to the technical field of catalytic material preparation and catalytic application, in particular to a preparation method and application of a heteropolyacid catalyst supported by a sulfonic acid group-modified mesoporous material. Background technique [0002] Cyclohexanol is an important chemical intermediate, widely used in organic chemical industry, paint and textile industry, etc., such as raw material for the production of adipic acid, caprolactam, polyamide (nylon-66) and various vinyl paints , It can also be used as a solvent for many polymers. The methods for producing cyclohexanol at home and abroad mainly include: cyclohexane oxidation method, phenol hydrogenation method and cyclohexene hydration method. At present, the industrial production of cyclohexanol mainly adopts cyclohexane oxidation method, but the oxidant used in this process is air, which is easy to form an explosive mixture with raw materials, which has po...

Claims

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Application Information

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IPC IPC(8): B01J31/18C07C69/06C07C67/04
CPCB01J31/0225B01J31/34B01J2231/49C07C67/04C07C69/06Y02P20/50Y02P20/584
Inventor 袁霞吴照伟吴剑陆标
Owner XIANGTAN UNIV
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