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A kind of solid acid porous material and preparation method thereof

A porous material and solid acid technology, which is applied in the field of solid strong acid materials and their preparation, can solve the problems of limiting the application range of resin catalysts, unsatisfactory catalytic activity, easy loss of active sites, etc., to achieve energy saving, simple and easy regeneration, The effect of simple and convenient operation

Active Publication Date: 2017-02-08
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Cationic exchange resin catalyst, as an industrialized macroporous solid acid catalyst, has been widely used in organic catalytic reactions such as etherification, alkylation, and polymerization. However, the operating temperature of resin catalysts is generally below 120°C. When the reaction temperature reaches At 140-150°C, it is easy to lose the sulfonic acid group and deactivate, which limits the application range of the resin catalyst
Another type of solid acid catalyst that is widely industrialized is microporous molecular sieve, which is widely used in high temperature reactions such as petroleum catalytic cracking because of its high heat resistance temperature, but its catalytic activity is not ideal for medium and low temperature reactions (room temperature-200°C).
In order to improve the catalytic activity of microporous molecular sieves at medium and low temperatures, it is generally used as a carrier, and then loaded with heteropolyacid (CN1289641A) or Al 2 o 3 (CN101298053A), etc., but these supported catalysts also have problems such as easy loss of active sites

Method used

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Examples

Experimental program
Comparison scheme
Effect test

preparation example Construction

[0013] The present invention further provides a method for preparing the above-mentioned solid acid porous material, which is characterized in that it comprises the following steps:

[0014] a) Dissolve 1-hydroxyethylidene-1,1-diphosphonic acid in water, add zirconium isopropoxide at a constant temperature within the temperature range of 20 to 80°C, and mix evenly to obtain a component mass ratio of zirconium isopropoxide : 1-hydroxyethylidene-1,1-diphosphonic acid: the mixture of water=(0.5~1.5):(0.3~2):(15~100);

[0015] b) Transfer the mixture into a reaction kettle and crystallize at 40-120°C for 10-100 hours;

[0016] c) After the crystallized product is filtered, washed and dried, it is contacted with a mixed solution of anhydrous pyridine and chlorosulfonic acid with a volume ratio of 1:0.5-2 for at least 1 hour, and then filtered, washed and dried to obtain a porous material.

[0017] In the method of the present invention, the temperature range in step a) is 40-60°C....

Embodiment 1

[0024] Add 1.0 g of 1-hydroxyethylidene-1,1-diphosphonic acid to 20 ml of water, stir at 45°C for 1 hour, then slowly add zirconium isopropoxide (purity: 99.9%, Bailingwei Technology Co., Ltd.) 1.0 g, continue to stir at a slow speed for 24 hours, put into a reaction kettle and crystallize at 110°C for 24 hours. After the solid product was filtered, washed with water, and dried at 80°C, it was added to 10 ml of anhydrous pyridine (AR, Tianjin Concord Technology Co., Ltd.) and chlorosulfonic acid (AR, Gracia (Chengdu) Chemical Co., Ltd. Technology Co., Ltd.) mixed solution, stirred slowly for 5 hours, then filtered, washed with water, and dried to obtain a synthetic material.

[0025] The resulting material has a BET specific surface area of ​​700 m 2 / g, the pore volume is 0.85cm 3 / g, the pore size distribution is mainly in the range of 1.7-5.5nm, and the hydrogen ion exchange capacity is 6.6mmol / g.

Embodiment 2

[0027] The preparation process of Example 1 was adopted, except that 1.5 g of zirconium isopropoxide was added and crystallized at 60° C. for 48 hours.

[0028] The BET specific surface area of ​​the resulting material is 480 m 2 / g, the pore volume is 0.75cm 3 / g, the pore size distribution is mainly in the range of 1.6-5.0nm; the hydrogen ion exchange capacity is 5.8mmol / g.

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Abstract

The invention discloses a solid acid porous material which is characterized from sulfoacid functionalized zirconium phosphonate porous solid acid obtained by hydrothermal synthesis; the specific surface area is 450-750m<2> / g, the pore volume is 0.7-1.1cm<3> / g, and the aperture distribution is mainly 1.6-5.5nm; the hydrogen ion exchange capacity is 5.8-6.6mmol / g. The material is obtained by performing hydrothermal synthesis and sulfoacid functionalization on zirconium isopropoxide, 1-hydroxy ethylidene-1,1-diphosphonate and chlorosulfonic acid which serve as raw materials by adopting a simple self-assembly strategy. The material is high in acidity, can be used as a solid strong-acid catalyst and is higher in actual industrial production value.

Description

technical field [0001] The invention relates to a solid strong acid material and a preparation method thereof, in particular to a solid strong acid porous material of zirconium sulfonated phosphonate and a preparation method thereof. Background technique [0002] In recent years, with the continuous enhancement of people's awareness of environmental protection and the stricter requirements of environmental protection legislation, the pollution problems in the chemical industry have been paid more and more attention. Acid catalysts have been widely used in the field of catalysis, traditional liquid acid catalysts such as H 2 SO 4 , HCl, H 3 PO 4 The wide application of the catalyst produces a large amount of waste liquid, and there are shortcomings such as serious corrosion of equipment, difficulty in separating catalysts and reactants, and difficulty in achieving continuous production in chemical processes. Solid acid catalyst, due to its advantages of high selectivity, ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J31/02B01J35/10
Inventor 袁忠勇林秀珍李永祥慕旭宏
Owner CHINA PETROLEUM & CHEM CORP