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A kind of esterification-saponification reaction catalyst and its preparation method and application

A saponification reaction and catalyst technology, applied in the field of esterification-saponification reaction catalyst and preparation thereof, can solve the problems of easy explosion, environmental pollution, and high equipment requirements, and achieve the effects of prolonging catalyst life, reducing production costs, and reducing equipment requirements.

Active Publication Date: 2021-07-16
KUNMING UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Boron anhydride and metaboric acid catalysts are the most commonly used in industry, and the production process is mature, but the exothermic heat is violent during the reaction process, it is not easy to control, the yield of borneol is not ideal, and isoborneol accounts for a relatively large proportion of the total amount of borneol. High, produces a large amount of isoborneol
The performance of metatitanic acid catalysts is relatively stable, but the consumption of oxalic acid is relatively large, and the requirements for equipment are high
According to current reports, the solid superacid S prepared by the precipitation method 2 o 8 2- / ZrO 2 -NiO catalyst, with anhydrous oxalic acid as esterification agent, synthesize borneol by esterification-saponification two-step method, the yield of borneol is as high as 55.8%, and the content of orthoborneol can reach 77.01%, although this method has obtained high High-quality orthoborneol, stable reaction, easy separation of catalyst, but using S 2 o 8 2- As the active component, there are potential safety hazards, and it is prone to explosion, which is not conducive to the realization of industrialization; the use of solid super acid SO 4 2- / TiO 2 As a catalyst, using chloroacetic acid as an esterification agent, the yield of borneol is as high as 45%, and the content of orthoborneol is more than 97%. However, the use of chloroacetic acid as an esterification agent pollutes the environment and does not meet the requirements of environmental protection Requirements, not conducive to the realization of industrialization

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019] Embodiment 1: the preparation method and application of this esterification-saponification reaction catalyst are as follows:

[0020] (1) Weigh 1-ethyl-3-methylimidazolium bromide, orthophosphoric acid, Aluminum isopropoxide, hydrofluoric acid and zinc acetate; the ionic liquid [Emim]Br was put into a four-necked flask, and the four-necked flask was heated and stirred in an oil bath at 100°C, then orthophosphoric acid was added and stirred for 10 minutes, isopropyl Aluminum alkoxide stirring for 20 minutes, zinc acetate stirring for 10 minutes and hydrofluoric acid, fully stirring;

[0021] (2) After stirring evenly, transfer the mixture to a microwave reactor, and conduct crystallization under microwave at 150°C, and the crystallization time is 20 minutes;

[0022] (3) After the crystallization is completed, filter, wash the crystals with acetone and deionized water in turn, and after drying, raise the temperature to 350°C at a heating rate of 5°C / min and keep it for ...

Embodiment 2

[0024] Embodiment 2: the preparation method and application of this esterification-saponification reaction catalyst are as follows:

[0025] (1) Weigh 1-ethyl-3-methylimidazolium bromide, orthophosphoric acid, Aluminum isopropoxide, hydrofluoric acid and zinc acetate; the ionic liquid [Emim]Br was put into a four-necked flask, and the four-necked flask was heated and stirred in an oil bath at 110°C, followed by adding orthophosphoric acid and stirring for 12 minutes, isopropyl Aluminum alkoxide stirring for 15 minutes, zinc acetate stirring for 15 minutes and hydrofluoric acid, fully stirring;

[0026] (2) After stirring evenly, transfer the mixture to a microwave reactor, and conduct crystallization under microwave at 130°C, and the crystallization time is 50 minutes;

[0027] (3) After the crystallization is completed, filter, wash the crystals with acetone and deionized water in sequence, and after drying, raise the temperature to 350°C at a heating rate of 2°C / min and kee...

Embodiment 3

[0029] Embodiment 3: the preparation method and application of this esterification-saponification reaction catalyst are as follows:

[0030] (1) Weigh 1-ethyl-3-methylimidazolium bromide, orthophosphoric acid, Aluminum isopropoxide, hydrofluoric acid and zinc acetate; the ionic liquid [Emim]Br was put into a four-necked flask, and the four-necked flask was heated and stirred in an oil bath at 105°C, followed by adding orthophosphoric acid and stirring for 12 minutes, isopropyl Aluminum alkoxide stirring for 15 minutes, zinc acetate stirring for 15 minutes and hydrofluoric acid, fully stirring;

[0031] (2) After stirring evenly, transfer the mixture to a microwave reactor, and conduct crystallization under microwave at 140°C, and the crystallization time is 40 minutes;

[0032] (3) After the crystallization is completed, filter, wash the crystals with acetone and deionized water in sequence, and after drying, raise the temperature to 350°C at a heating rate of 3°C / min and kee...

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PUM

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Abstract

The invention discloses an esterification-saponification reaction catalyst and a preparation method thereof. The method uses 1-ethyl-3-methylimidazolium bromide salt ionic liquid as a solvent and a structure-directing agent, adopts a microwave radiation enhancement method, and uses Zn Part of the Al in the aluminum phosphate molecular sieve is replaced by crystal to prepare the modified aluminum phosphorus molecular sieve, and the prepared molecular sieve is repeatedly washed with acetone and deionized water, and the esterification-saponification reaction catalyst is obtained after roasting and cooling; the esterification-saponification reaction catalyst is applied in In the turpentine esterification-saponification reaction, high-selectivity orthoborneol is obtained; this method avoids the disadvantages that the hydrothermal method cannot be operated under normal pressure and the organic amine is a structure-directing agent, and is green, environmentally friendly, and has a short crystallization time , mild crystallization temperature and so on.

Description

technical field [0001] The invention relates to an esterification-saponification reaction catalyst, a preparation method and application thereof, and belongs to the field of chemical industry. Background technique [0002] China is a major producer of turpentine, most of which is masson pine turpentine, and a small part is slash pine turpentine and Simao pine turpentine. Turpentine is widely distributed in my country, and it is produced in all southern provinces, but the main producing areas are concentrated in Guangxi, Guangdong, Yunnan, Jiangxi and Fujian. Turpentine is a renewable essential oil that contains a variety of terpenes, the main components of which are α-pinene and β-pinene, of which the content of α-pinene is more than 90%. Turpentine can be directly used in medicine and as a solvent, but more importantly, it is used in fine chemistry, such as synthesizing daily chemical spices, pharmacological active substances, agricultural and household biological active s...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J29/84C07C27/02C07C35/30
CPCB01J29/84B01J37/0018B01J2229/183C07C29/095C07C67/08C07C2602/20C07C35/30C07C69/36Y02P20/54
Inventor 蒋丽红来倩李恒王亚明郑燕娥贾庆明陕绍云黄照熊
Owner KUNMING UNIV OF SCI & TECH