CN106944134B - Resin catalyst for synthesis and preparation of ethylene glycol tert-butyl ether and modification method thereof - Google Patents
Resin catalyst for synthesis and preparation of ethylene glycol tert-butyl ether and modification method thereof Download PDFInfo
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- CN106944134B CN106944134B CN201710245084.9A CN201710245084A CN106944134B CN 106944134 B CN106944134 B CN 106944134B CN 201710245084 A CN201710245084 A CN 201710245084A CN 106944134 B CN106944134 B CN 106944134B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/22—Halogenating
- B01J37/24—Chlorinating
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Abstract
The application provides a resin catalyst for synthesizing and preparing ethylene glycol tert-butyl ether and a modification method thereof, wherein the resin catalyst for synthesizing and preparing the ethylene glycol tert-butyl ether is obtained by modifying and purifying a polystyrene hydrogen type cationic resin catalyst, the dried polystyrene hydrogen type cationic resin catalyst is put into one or a mixed solution of acetone and butanone, the mixture is stirred and reacts for 8-10 hours in a hydrogen chloride gas environment at the temperature of 70-80 ℃, and the mixture is filtered and purified to obtain the ethylene glycol tert-butyl ether. The technical scheme is used as a catalyst for preparing the ethylene glycol tert-butyl ether by etherification, and has higher catalytic activity and selectivity.
Description
Technical Field
The present application relates to a resin catalyst and a modification method thereof, and more particularly to a resin catalyst used in an etherification organic catalytic reaction and a modification method thereof.
Background
A strong-acidic cation exchange resin in polystyrene series is a solid high-molecular acid, which is prepared from styrene and divinylbenzene through copolymerizing to obtain beads, sulfonating, and features high catalytic activity, and high catalytic activity. However, the attention and technical research on the modification of the resin catalyst are lacked at present, and the research on the modification technology of the resin catalyst prepared by the synthesis of the ethylene glycol tert-butyl ether is not self-referenced. The existing hydrogen type resin catalyst generally has the technical problems of low exchange equivalent and poor catalytic activity, and also has the practical technical problems of low catalyst strength, easy shedding of sulfonic groups and short service life.
Disclosure of Invention
The invention of the present patent application aims to provide a resin catalyst for synthesis and preparation of ethylene glycol tert-butyl ether which has high strength, suitable specific surface area and specific pore volume, especially high catalytic activity and stability, and is especially suitable for being used as a catalyst for synthesis reaction of ethylene glycol tert-butyl ether, and a modification method thereof.
The application provides a resin catalyst for synthesizing and preparing ethylene glycol tert-butyl ether, and the main technical content of the technical scheme is as follows: a resin catalyst for synthesizing and preparing ethylene glycol tert-butyl ether is obtained by modifying and purifying a polystyrene hydrogen type cation resin catalyst:
①, modification treatment, namely putting a dry polystyrene hydrogen type cationic resin catalyst into a stainless steel stirring kettle, adding one or a mixture of acetone and butanone into the kettle, heating to 40-50 ℃, filling hydrogen chloride gas into the kettle, stirring and reacting for 8-10 hours at the temperature of 70-80 ℃ under the pressure of 0.2-0.5 MPa, and filtering liquid;
②, purification treatment:
the resin catalyst modified in the step ① is put into deionized water at the temperature of 80-95 ℃, and is boiled under reduced pressure for 3-6 hours under the pressure of-0.090-0.095 MPa, and then is washed by the deionized water and is dried at room temperature.
The water content of the dry styrene hydrogen type cation resin catalyst is not more than 10 percent.
The application also provides a modification method of the resin catalyst for synthesizing and preparing the ethylene glycol tert-butyl ether.
The technical scheme of the resin catalyst for synthesizing and preparing the ethylene glycol tert-butyl ether and the modification method thereof is actually used as a catalyst for preparing the ethylene glycol tert-butyl ether by etherification, so that the catalytic activity and the selectivity of the resin catalyst are obviously improved, and the technical effect can be fully proved by the following embodiments and detection data thereof. The modified resin catalyst obtained by the modification method of the technical scheme is applied to the etherification synthesis preparation of the ethylene glycol tert-butyl ether, and the high conversion rate and selectivity of the modified resin catalyst prove that the modified resin catalyst has excellent catalytic performance, the strength of the modified resin catalyst is improved, and the service life of the catalyst is effectively prolonged.
Detailed Description
The technical solution of the present invention will be illustrated in detail by the following examples, but the scope of the present invention is not limited by the following specific examples.
Example 1:
modified catalyst C-1:
①, modification treatment, namely adding 200ml of acetone into a stainless steel stirring kettle with a reflux condensing device, adding 50g of dry polystyrene hydrogen type cationic resin catalyst into the kettle, heating to 40 ℃, introducing hydrogen chloride gas into the kettle to ensure that the pressure in the kettle is 0.2MPa, heating to 80 ℃, stirring and reacting for 10 hours, and then filtering out liquid;
②, purification treatment:
placing the resin catalyst subjected to modification treatment in the step ① in deionized water at the temperature of 80 ℃, boiling the resin catalyst for 6 hours under the pressure of-0.090 MPa, washing the resin catalyst for 2 times by using the deionized water, and airing the resin catalyst at room temperature to obtain 50ml of the fresh modified resin catalyst, which is filled in a fixed bed reactor with the inner diameter of 10mm and the length of 1000mm and is applied to the synthesis reaction of the ethylene glycol tert-butyl ether, wherein the reaction pressure value is 1.2MPa, the molar ratio of the ethylene glycol to the isobutene is 2:1, and the space velocity is 0.5h-1The reaction temperature was 70 ℃ and the conversion of isobutene was found to be 90.13% with a selectivity of 92.46%.
Example 2:
modified catalyst C-2:
①, modification treatment:
in a stainless steel stirred tank equipped with a reflux condenser, 200ml of acetone was added, and 50g of a dry polystyrene hydrogen type cationic resin catalyst was charged into the tank. After the temperature is raised to 50 ℃, introducing hydrogen chloride gas into the kettle to ensure that the pressure in the kettle is 0.2MPa, raising the temperature to 80 ℃, stirring and reacting for 8 hours, and then filtering out liquid; the dry polystyrene hydrogen type cationic resin catalyst is obtained by drying for 4 hours in an oven at the temperature of 100 ℃ and then naturally cooling;
②, purification treatment:
and (3) placing the resin catalyst subjected to the modification treatment in the step ① in deionized water at the temperature of 85 ℃, boiling for 6 hours under reduced pressure at the pressure of-0.095 MPa, washing for 2 times by using the deionized water, and airing at room temperature to obtain the catalyst.
50ml of the fresh modified resin catalyst is loaded into a fixed bed reactor with the inner diameter of 10mm and the length of 1000mm for the synthesis reaction of the ethylene glycol tert-butyl ether, the reaction pressure value is 1.2MPa, the molar ratio of the ethylene glycol to the isobutene is 4:1, and the space velocity is 2h-1The reaction temperature was 80 ℃ and the conversion of isobutene was found to be 89.58% with a selectivity of 90.38%.
Example 3:
modified catalyst C-3:
①, modification treatment, namely adding 200ml of acetone into a stainless steel stirring kettle with a reflux condensing device, adding 70g of dry polystyrene hydrogen type cationic resin catalyst into the kettle, heating to 50 ℃, introducing hydrogen chloride gas into the kettle to ensure that the pressure in the kettle is 0.5MPa, heating to 75 ℃, stirring and reacting for 8 hours, and then filtering out liquid;
②, purification treatment:
and (3) placing the resin catalyst subjected to the modification treatment in the step ① in deionized water at the temperature of 80 ℃, boiling for 3 hours under reduced pressure at the pressure of-0.090 MPa, washing for 2 times by using the deionized water, and airing at room temperature to obtain the catalyst.
50ml of the fresh modified resin catalyst is loaded into a fixed bed reactor with the inner diameter of 10mm and the length of 1000mm for the synthesis reaction of the ethylene glycol tert-butyl ether, the reaction pressure value is 1.2MPa, the molar ratio of the ethylene glycol to the isobutene is 4:1, and the space velocity is 1h-1The reaction temperature was 80 ℃ and the conversion of isobutene was found to be 91.58% with a selectivity of 90.71%.
Example 4:
modified catalyst C-4:
①, modification treatment, namely adding 300ml of butanone into a stainless steel stirring kettle with a reflux condensing device, adding 100g of dry polystyrene hydrogen type cationic resin catalyst into the kettle, heating to 50 ℃, introducing hydrogen chloride gas into the kettle to ensure that the pressure in the kettle is 0.4MPa, heating to 80 ℃, stirring and reacting for 8 hours, and then filtering out liquid;
②, purification treatment:
and (3) placing the resin catalyst subjected to the modification treatment in the step ① in deionized water at the temperature of 80 ℃, boiling for 4 hours under reduced pressure at the pressure of-0.095 MPa, washing for 2 times by using the deionized water, and airing at room temperature to obtain the catalyst.
50ml of the fresh modified resin catalyst is loaded into a fixed bed reactor with the inner diameter of 10mm and the length of 1000mm for the synthesis reaction of the ethylene glycol tert-butyl ether, the reaction pressure value is 1.2MPa, the molar ratio of the ethylene glycol to the isobutene is 4:1, and the space velocity is 2h-1The reaction temperature was 80 ℃ and it was found that the conversion of isobutylene was 91.55% and the selectivity was 91.86%.
Example 5:
modified catalyst C-5:
①, modification treatment, namely adding 400ml of acetone into a stainless steel stirring kettle with a reflux condensing device, adding 150g of dry polystyrene hydrogen type cationic resin catalyst into the kettle, heating to 50 ℃, introducing hydrogen chloride gas into the kettle to ensure that the pressure in the kettle is 0.4MPa, heating to 70 ℃, stirring and reacting for 8 hours, and then filtering out liquid;
②, purification treatment:
and (3) placing the resin catalyst subjected to the modification treatment in the step ① in deionized water at the temperature of 75 ℃, boiling the resin catalyst for 5 hours under reduced pressure at the pressure of-0.090 MPa, washing the resin catalyst for 2 times by using the deionized water, and airing the resin catalyst at room temperature to obtain the catalyst.
50ml of the fresh modified resin catalyst is loaded into a fixed bed reactor with the inner diameter of 10mm and the length of 1000mm and applied to ethylene glycol tert-butylEther synthesis reaction, wherein the reaction pressure value is 1.2MPa, the molar ratio of ethylene glycol to isobutene is 3:1, and the space velocity is 3h-1The reaction temperature was 75 ℃ and the conversion of isobutene was found to be 90.97% with a selectivity of 91.88%.
Example 6:
modified catalyst C-6:
①, modification treatment:
300ml of acetone was added to a stainless steel stirred tank equipped with a reflux condenser, and 100g of a dry polystyrene hydrogen type cationic resin catalyst was charged into the tank. After the temperature is raised to 45 ℃, introducing hydrogen chloride gas into the kettle, raising the pressure in the kettle to 0.5MPa, raising the temperature to 75 ℃, stirring and reacting for 9 hours, and then filtering out liquid; the dry polystyrene hydrogen type cationic resin catalyst is obtained by drying for 4 hours at the temperature of 120 ℃ in an oven and then naturally cooling;
②, purification treatment:
and (3) placing the resin catalyst subjected to the modification treatment in the step ① in deionized water at the temperature of 75 ℃, boiling for 4 hours under reduced pressure at the pressure of-0.090 MPa, washing for 2 times by using the deionized water, and airing at room temperature to obtain the catalyst.
50ml of the fresh modified resin catalyst is loaded into a fixed bed reactor with the inner diameter of 10mm and the length of 1000mm for the synthesis reaction of the ethylene glycol tert-butyl ether, the reaction pressure value is 1.2MPa, the molar ratio of the ethylene glycol to the isobutene is 4:1, and the space velocity is 4h-1The reaction temperature was 80 ℃ and the conversion of isobutylene was 90.55% and the selectivity was 91.41% as measured.
Referring to examples 5 and 6, the modified catalyst has excellent catalytic activity and has the technical potential of improving the space velocity and the production efficiency on the premise of ensuring the conversion rate of isobutene.
In each of the above examples, the acetone or butanone may be replaced by a mixture of acetone and butanone in the same amount as that of each example.
As the method for synthesizing ethylene glycol t-butyl ether in each of the above examples, the production method described in CN105061160A was used. The following is a comparative example of the resin catalyst prepared by applying the record of CN101935371 in the preparation method, and the modified catalyst and the unmodified resin catalyst in the technical scheme are examined and compared to compare the catalytic capability of the modified catalyst and the unmodified resin catalyst applied to the synthesis reaction of the methyl tert-butyl ether.
Comparative example:
50ml of the resin catalyst prepared by the method is placed in a fixed bed reactor with the inner diameter of 10mm and the length of 1000mm and applied to the synthesis reaction of the methyl tert-butyl ether, the reaction pressure is 1.2MPa, the molar ratio of the ethylene glycol to the isobutene is 2:1, and the space velocity is 2h-1The reaction temperature was 70 ℃. The isobutene conversion was found to be 83.43% with a selectivity of 85.59%.
The physical property index data of the resin catalysts of the above examples and comparative examples are shown in table 1:
Claims (3)
1. a resin catalyst for synthesizing and preparing ethylene glycol tert-butyl ether is obtained by modifying and purifying a polystyrene hydrogen type cation resin catalyst, and is characterized in that:
①, modification treatment, namely putting a dry polystyrene hydrogen type cationic resin catalyst into a stainless steel stirring kettle, adding one or a mixture of acetone and butanone into the kettle, heating the kettle to 40-50 ℃ after the liquid surface is submerged in the resin catalyst, filling hydrogen chloride gas into the kettle, stirring and reacting for 8-10 hours at the temperature of 70-80 ℃ under the pressure of 0.2-0.5 MPa, and filtering out liquid;
②, purification treatment:
the resin catalyst modified in the step ① is put into deionized water at the temperature of 80-95 ℃, and is boiled under reduced pressure for 3-6 hours under the pressure of-0.090-0.095 MPa, and then is washed by the deionized water and is dried at room temperature.
2. The resin catalyst for ethylene glycol t-butyl ether synthesis production according to claim 1, characterized in that the dried styrene hydrogen type cationic resin catalyst has a water content of not more than 10%.
3. A method for modifying a resin catalyst for the synthesis preparation of ethylene glycol t-butyl ether according to any one of claims 1 to 2.
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| CN201710245084.9A CN106944134B (en) | 2017-04-14 | 2017-04-14 | Resin catalyst for synthesis and preparation of ethylene glycol tert-butyl ether and modification method thereof |
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| CN106944134B true CN106944134B (en) | 2020-06-02 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1048921C (en) * | 1995-12-02 | 2000-02-02 | 中国石化齐鲁石油化工公司 | Preparation method of macroporous strong acid type cation exchange resin catalyst |
| CN100427447C (en) * | 2003-11-17 | 2008-10-22 | 萨索尔溶剂德国有限公司 | Condensation and hydrogenation reactions for the preparation of carbonyl-containing products |
| CN101696162B (en) * | 2009-10-30 | 2013-01-02 | 华南理工大学 | Method for preparing glutaric acid from dimethyl glutarate |
| CN101935371B (en) * | 2010-08-10 | 2013-04-03 | 丹东明珠特种树脂有限公司 | Large-particle cross-linked polystyrene resin catalyst and polymerized preparation method thereof |
| CN105061160A (en) * | 2015-07-22 | 2015-11-18 | 珠海飞扬新材料股份有限公司 | Diol tertiary butyl ether production method |
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