CN108212196B - Preparation method and application of composite catalyst for synthesizing propylene glycol ether - Google Patents
Preparation method and application of composite catalyst for synthesizing propylene glycol ether Download PDFInfo
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- B01J29/00—Catalysts comprising molecular sieves
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Abstract
The invention relates to the technical field of chemical catalysis, and provides a preparation method of a composite catalyst for synthesizing propylene glycol ether, which comprises the following steps: preparing amino modified mesoporous nano silicon dioxide spheres; reacting the amino modified mesoporous nano silicon dioxide with succinic anhydride to obtain a carboxylated silicon carrier; and carrying out condensation reaction on the carboxylated silicon carrier and carbon points with amino groups on the surface to obtain the composite catalyst for catalytically synthesizing propylene glycol ether. The invention also provides the application of the composite catalyst for catalytically synthesizing the propylene glycol ether in preparing the propylene glycol ether by catalyzing alcohol and propylene oxide. The catalyst has the advantages of high activity, high selectivity, easy recovery, low energy consumption, reusability and the like.
Description
Technical Field
The invention belongs to the field of chemical catalysis, and particularly relates to a preparation method and application of a composite catalyst for synthesizing propylene glycol ether.
Background
The propylene glycol ether compound is a fine chemical with excellent performance and is also an environment-friendly high-grade solvent, two functional groups with strong solubility, namely hydroxyl and ether bond, are arranged in the structure of the propylene glycol ether compound, the former has hydrophilicity, and the latter has lipophilicity, so that the propylene glycol ether compound has strong dissolving capacity, is called as a universal solvent, and is widely applied to the industries of coatings, printing ink, paint, printing and the like. The propylene glycol ether compound is mainly synthesized by the reaction of propylene oxide and low-carbon alcohol, however, due to the steric effect of the propylene oxide, the ring-opening positions of the propylene glycol ether compound can be different under the conditions of acid and alkali, so that different alcohol ether products can be obtained, wherein the alkali generates 1-methoxy-2-propanol, and the acid generates 2-methoxy-1-propanol. Alcohol ether products catalyzed by bases are more environmentally friendly and are more and more concerned by people. At present, the synthesis routes of propylene glycol ether mainly comprise: williamson synthesis, acetal method, alkoxyepoxypropane method, epoxypropane method, and the like. The propylene oxide method, as a green and efficient synthesis method, has the advantages of high atom utilization rate, low operation risk and the like, and is the only synthesis route which is the most active in development and research and has already realized industrialization at present. The reaction system for synthesizing propylene glycol ether by propylene oxide method can be divided into homogeneous reaction system and heterogeneous reaction system. The homogeneous catalysis process is the method which is generally adopted in the industry at present, and the technology is relatively mature. The main homogeneous acidic catalysts are sulfuric acid, boron trifluoride and the like, while the basic catalysts are sodium hydroxide, sodium methoxide and the like. Homogeneous catalysts can achieve better yield and relatively narrow product distribution, but still face huge challenges due to problems of complex process, corrosion and the like. The heterogeneous catalysts are large at present and mainly comprise molecular sieves, montmorillonite, metal oxides and the like. Although the equipment is not corroded, the process flow is relatively simple, the reaction conditions are relatively harsh, and the product distribution is not uniform.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art and provide a preparation method and application of a composite catalyst for synthesizing propylene glycol ether.
The invention provides a preparation method of a composite catalyst for synthesizing propylene glycol ether, which comprises the following steps:
preparing amino modified mesoporous nano silicon dioxide spheres;
reacting the amino modified mesoporous nano silicon dioxide with succinic anhydride to obtain a carboxylated silicon carrier;
and carrying out condensation reaction on the carboxylated silicon carrier and carbon points with amino groups on the surface to obtain the composite catalyst for catalytically synthesizing propylene glycol ether.
The invention also provides the application of the composite catalyst for catalytically synthesizing the propylene glycol ether in preparing the propylene glycol ether by catalyzing alcohol and propylene oxide.
The composite catalyst obtained by the preparation method of the nano carbon dots for catalytically synthesizing propylene glycol ether provided by the invention has the advantages of high activity, high selectivity, easiness in recovery, low energy consumption, easiness in separation and the like. Compared with the existing solid catalyst, the catalyst has high efficiency and few byproducts. In addition, the catalyst has simple preparation process and low production cost, and is suitable for industrial production.
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FIG. 1 is a transmission electron microscope photograph of a composite catalyst for the catalytic synthesis of propylene glycol ether obtained in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a preparation method of a composite catalyst for catalytically synthesizing propylene glycol ether, which comprises the following steps:
preparing amino modified mesoporous nano silicon dioxide spheres;
reacting the amino modified mesoporous nano silicon dioxide with succinic anhydride to obtain a carboxylated silicon carrier;
and carrying out condensation reaction on the carboxylated silicon carrier and carbon points with amino groups on the surface to obtain the composite catalyst for catalytically synthesizing propylene glycol ether.
Specifically, the amino-modified mesoporous nano-silica spheres can be obtained by the existing method, such as aminated MCM-41 and the like, and preferably, the diameter of the amino-modified mesoporous nano-silica spheres is 200-400 nm, the mesoporous size is distributed in the range of 4-10 nm, and if the size is too small, the carbon dot loading rate is reduced, the products are accumulated, and the catalytic effect is poor. The size of the carbon dots with amino groups on the surface is less than 5nm, and the small size of the carbon dots can improve the surface alkalinity and improve the catalytic effect.
More specifically, the preparation method of the amino modified mesoporous nano-silica spheres comprises the following steps:
adding hexadecyl trimethyl ammonium bromide into water, sequentially adding ammonia water, diethyl ether and ethanol after dissolving, uniformly stirring, adding tetraethoxysilane and 3-aminopropyl triethoxysilane, reacting for 4 hours at 20-25 ℃, centrifuging, washing and drying to obtain the amino modified mesoporous nano-silica spheres.
Preferably, the amino-modified mesoporous nano-silica reacts with succinic anhydride, specifically, the amino-modified mesoporous nano-silica is added into dimethyl sulfoxide, succinic anhydride and triethylamine are added, and stirring is carried out at 40 ℃ for 24-48 hours, so as to obtain the carboxylated silicon carrier.
Specifically, the preparation steps of the carbon dots with the amino groups on the surface are as follows:
dissolving alanine, ethylenediamine and/or polyethyleneimine in water to obtain a mixed solution, wherein the mass ratio of the alanine to the ethylenediamine and/or polyethyleneimine is (1-4): 1;
and placing the mixed solution in a closed reaction container, heating to 180-240 ℃, keeping for 6-24 hours, cooling, and drying a product to obtain the carbon dots with the amino groups on the surface.
Preferably, the mass ratio of the alanine to the ethylenediamine and/or the polyethyleneimine is 2-3: 1. specifically, the mixed solution is placed in a closed reaction container, and is preferably heated to 200 to 220 ℃. After cooling, the organic impurities are preferably removed by dialysis and then dried. More preferably, the carbon dots are made from alanine and ethylenediamine.
Dispersing the carboxylated silicon carrier and carbon points with amino groups on the surface in water, adding a (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) and an N-hydroxysuccinimide (NHS) coupling agent, reacting for 2-12 h, or dispersing the carboxylated silicon carrier and the carbon points with amino groups on the surface in an organic solvent, adding Dicyclohexylcarbodiimide (DCC), and obtaining the composite catalyst for catalytically synthesizing propylene glycol ether.
The invention also provides the application of the composite catalyst for synthesizing the propylene glycol ether in preparing the propylene glycol ether by catalyzing alcohol and propylene oxide.
Specifically, propylene oxide and alcohol are fed into a reactor to contact with the composite catalyst, and are heated to 80-160 ℃ in a closed environment to obtain the propylene glycol ether. Wherein the mass ratio of the composite catalyst to the propylene oxide is 1: 10 to 1000.
Preferably, the heating mode is microwave heating, and the molar ratio of the propylene oxide to the alcohol is 1: 1-10, wherein the mass ratio of the composite catalyst to the propylene oxide is 1: 10-500, and the reaction time is 30-300 min. The pressure is usually between 0.1 and 1 MPa. More preferably, the molar ratio of the propylene oxide to the alcohol is 1: 3-5, and the mass ratio of the catalyst to the propylene oxide is 1: 20 to 100. Compared with the existing catalyst, the propylene glycol ether yield can be higher by adding 0.025-0.5 percent of the propylene oxide by mass. The alcohol is C1～C8Any one of alcohols. Compared with the existing solid catalyst, the composite catalyst has the advantages of greatly improved conversion rate of propylene oxide and selectivity of propylene glycol ether, reusability and low cost.
The preparation method and application of the composite catalyst for synthesizing propylene glycol ether are illustrated by the following specific examples. The raw materials in the following examples can be directly prepared according to the existing methods, and of course, the raw materials in other examples can also be directly purchased from the market, and are not limited thereto.
Example 1:
adding 2.5g of hexadecyl trimethyl ammonium bromide into 350mL of water, sequentially adding 4mL of ammonia water (30%), 75mL of diethyl ether and 25mL of ethanol after dissolving, stirring uniformly, adding 12.5mL of ethyl orthosilicate and 0.5mL of 3-aminopropyl triethoxysilane, reacting for 4 hours at 20-25 ℃, adding 1mL of concentrated hydrochloric acid to stop the reaction, immediately centrifuging and washing, and drying to obtain the amino modified mesoporous nano silicon dioxide ball.
2.67g of alanine was dissolved in 30mL of ultrapure water, and then 0.8mL of ethylenediamine was added while stirring, and then the above solution was transferred to a 50mL high-temperature reaction tank and heated to 200 ℃. After 6 hours of reaction, the reaction mixture was cooled at room temperature, and the product was placed in a dialysis bag (1000MWCO), dialyzed for 48 hours, and freeze-dried to obtain the carbon dots having amino groups on the surface.
And adding 90mg of amino modified mesoporous nano-silica spheres into 10mL of DMSO solution containing 40mg of succinic anhydride and 40mg of triethylamine, stirring for 48 hours at 40 ℃, centrifuging, and washing with ethanol to obtain the carboxylated silicon carrier.
80mg of the carboxylated silicon carrier was added to 6mL of an aqueous solution containing 50mg of EDC and 20mg of NHS, and then 6mg of carbon dots containing amino groups on the surface were added at room temperature and stirred for 8 hours for centrifugation to obtain the composite catalyst for synthesizing propylene glycol ether, which is shown in FIG. 1 in a transmission electron microscope.
Adding the composite catalyst of the epoxy propane, the methanol and the synthetic propylene glycol ether into a microwave reaction tube, wherein the molar ratio of the epoxy propane to the methanol is 1: 7, the mass ratio of the composite catalyst to the propylene oxide is 1: 30. heating to 120 ℃ in a microwave reactor, and reacting for 120 min. A part of the obtained mixture was centrifuged, and the composition of the obtained liquid phase mixture was measured by gas chromatography to calculate that the conversion of propylene oxide was 88% and the selectivity of propylene glycol monomethyl ether was 90%.
Example 2:
adding 90mg of amino modified mesoporous nano-silica MCM-41 into 10mL of DMSO solution containing 40mg of succinic anhydride and 40mg of triethylamine, stirring for 48 hours at 40 ℃, centrifuging, and washing with ethanol to obtain the silicon carboxyl carrier.
80mg of the silicon oxide support is added into 6mL of aqueous solution containing 50mg of EDC and 20mg of NHS, and then 6mg of carbon dots containing amino groups on the surface are added at room temperature, stirred for 8 hours and centrifuged to obtain the composite catalyst for synthesizing the propylene glycol ether.
Adding the composite catalyst of the epoxy propane, the methanol and the synthetic propylene glycol ether into a microwave reaction tube, wherein the molar ratio of the epoxy propane to the methanol is 1: 7, the mass ratio of the composite catalyst to the propylene oxide is 1: 30. heating to 120 ℃ in a microwave reactor, and reacting for 120 min. A part of the obtained mixture was centrifuged, and the composition of the obtained liquid phase mixture was measured by gas chromatography to calculate that the conversion of propylene oxide was 70% and the selectivity of propylene glycol monomethyl ether was 80%.
Example 3:
2.5g of hexadecyltrimethylammonium bromideDissolving in 350mL of water, and sequentially adding 4mL of NH3H2O (30%), 75mL of diethyl ether and 25mL of ethanol, stirring uniformly, adding 12.5mL of ethyl orthosilicate and 0.5mL of 3-aminopropyltriethoxysilane, reacting for 4h at 20-25 ℃, adding 1mL of concentrated HCl to terminate the reaction, immediately centrifuging and washing, and drying to obtain the amino-modified mesoporous nano-silica spheres.
2.67g of alanine was dissolved in 30mL of ultrapure water, and then 0.8mL of ethylenediamine was added while stirring, and then the above solution was transferred to a 50mL high-temperature reaction tank and heated to 200 ℃. After 6 hours of reaction, the reaction mixture was cooled at room temperature, and the product was placed in a dialysis bag (1000MWCO), dialyzed for 48 hours, and freeze-dried to obtain the carbon dots having amino groups on the surface.
And adding 90mg of amino modified mesoporous nano-silica spheres into 10mL of DMSO solution containing 40mg of succinic anhydride and 40mg of triethylamine, stirring for 48 hours at 40 ℃, centrifuging, and washing with ethanol to obtain the carboxylated silicon carrier.
80mg of the carboxylated silicon carrier was added to 6mL of an aqueous solution containing 50mg of EDC and 20mg of NHS, and then 6mg of carbon dots containing amino groups on the surface were added at room temperature and stirred for 8 hours for centrifugation to obtain the composite catalyst for synthesizing propylene glycol ether, which is shown in FIG. 1 in a transmission electron microscope.
Adding the composite catalyst of the epoxy propane, the methanol and the synthetic propylene glycol ether into a microwave reaction tube, wherein the molar ratio of the epoxy propane to the methanol is 1:3, the mass ratio of the composite catalyst to the propylene oxide is 1: 100. heating to 120 ℃ in a microwave reactor, and reacting for 120 min. A part of the obtained mixture was centrifuged, and the composition of the obtained liquid phase mixture was measured by gas chromatography to calculate that the conversion of propylene oxide was 82% and the selectivity of propylene glycol monomethyl ether was 88%.
Example 4:
2.5g hexadecyl trimethyl ammonium bromide was added to 350mL of water, and after dissolution, 4mL of NH were added in sequence3H2O (30%), 75mL of diethyl ether and 25mL of ethanol, stirring uniformly, adding 12.5mL of ethyl orthosilicate and 0.5mL of 3-aminopropyltriethoxysilane, reacting for 4h at 20-25 ℃, finally adding 1mL of concentrated HCl to terminate the reaction, and immediately stopping the reactionAnd (4) centrifugally washing and drying to obtain the amino modified mesoporous nano silicon dioxide spheres.
2.67g of alanine was dissolved in 30mL of ultrapure water, and then 0.8mL of ethylenediamine was added while stirring, and then the above solution was transferred to a 50mL high-temperature reaction tank and heated to 200 ℃. After 6 hours of reaction, the reaction mixture was cooled at room temperature, and the product was placed in a dialysis bag (1000MWCO), dialyzed for 48 hours, and freeze-dried to obtain the carbon dots having amino groups on the surface.
And adding 90mg of amino modified mesoporous nano-silica spheres into 10mL of DMSO solution containing 40mg of succinic anhydride and 40mg of triethylamine, stirring for 48 hours at 40 ℃, centrifuging, and washing with ethanol to obtain the carboxylated silicon carrier.
80mg of the carboxylated silicon carrier was added to 6mL of an aqueous solution containing 50mg of EDC and 20mg of NHS, and then 6mg of carbon dots containing amino groups on the surface were added at room temperature and stirred for 8 hours for centrifugation to obtain the composite catalyst for synthesizing propylene glycol ether, which is shown in FIG. 1 in a transmission electron microscope.
Adding the composite catalyst of the epoxy propane, the methanol and the synthetic propylene glycol ether into a microwave reaction tube, wherein the molar ratio of the epoxy propane to the methanol is 1: 2, the mass ratio of the composite catalyst to the propylene oxide is 1: 10. heating to 120 ℃ in a microwave reactor, and reacting for 120 min. A part of the obtained mixture was centrifuged, and the composition of the obtained liquid phase mixture was measured by gas chromatography to calculate that the conversion of propylene oxide was 90% and the selectivity of propylene glycol monomethyl ether was 92%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The preparation method of the composite catalyst for synthesizing the propylene glycol ether is characterized by comprising the following steps of:
preparing amino modified mesoporous nano silicon dioxide spheres;
reacting the amino modified mesoporous nano silicon dioxide with succinic anhydride to obtain a carboxylated silicon carrier;
and carrying out condensation reaction on the carboxylated silicon carrier and carbon points with amino groups on the surface to obtain the composite catalyst for catalytically synthesizing propylene glycol ether.
2. The method for preparing a composite catalyst for synthesizing propylene glycol ether according to claim 1, wherein the diameter of the amino-modified mesoporous nano silica spheres is 200 to 400nm, and the mesoporous size is distributed between 4nm and 10 nm.
3. The method for preparing the composite catalyst for synthesizing propylene glycol ether according to claim 1, wherein the method for preparing the amino-modified mesoporous nano-silica spheres comprises the following steps: adding hexadecyl trimethyl ammonium bromide into water, sequentially adding ammonia water, diethyl ether and ethanol after dissolving, uniformly stirring, adding tetraethoxysilane and 3-aminopropyl triethoxysilane, reacting for 4 hours at 20-25 ℃, centrifuging, washing and drying to obtain the amino modified mesoporous nano-silica spheres.
4. The method for preparing a composite catalyst for synthesizing propylene glycol ether according to claim 1, wherein the carbon dots having amino groups on the surface are prepared by the steps of:
dissolving alanine, ethylenediamine and/or polyethyleneimine in water to obtain a mixed solution, wherein the mass ratio of the alanine to the ethylenediamine and/or polyethyleneimine is (1-4): 1;
and placing the mixed solution in a closed reaction container, heating to 180-240 ℃, keeping for 6-24 hours, cooling, and drying a product to obtain the carbon dots with the amino groups on the surface.
5. The method for preparing the composite catalyst for synthesizing propylene glycol ether according to claim 4, wherein the mass ratio of alanine to ethylenediamine and/or polyethyleneimine is 2-3: 1.
6. the method for preparing a composite catalyst for synthesizing propylene glycol ether according to claim 1, wherein the size of the carbon dots having amino groups on the surface is less than 5 nm.
7. The use of the composite catalyst for synthesizing propylene glycol ether according to claim 1 to 6 in the preparation of propylene glycol ether by catalyzing alcohol and propylene oxide.
8. The use of the composite catalyst of claim 7 for catalyzing an alcohol and propylene oxide to produce propylene glycol ether, wherein the alcohol is C1～C8Any one of alcohols.
9. The use of the composite catalyst of claim 7 in catalyzing alcohol and propylene oxide to prepare propylene glycol ether, wherein the composite catalyst is used in catalyzing alcohol and propylene oxide to prepare propylene glycol ether by feeding propylene oxide and alcohol into a reactor to contact with the nanocarbon point, and heating to 80-160 ℃ in a closed environment to obtain propylene glycol ether, wherein the mass ratio of the nanocarbon point to propylene oxide is 1: 10 to 500.
10. The use of the composite catalyst of claim 7 in catalyzing alcohol and propylene oxide to produce propylene glycol ether, wherein the mass ratio of the composite catalyst to propylene oxide is 1: 20 to 100.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1775355A (en) * | 2005-12-01 | 2006-05-24 | 中国科学院山西煤炭化学研究所 | Organic solid base catalyst for synthesizing propylene glycol ether and its preparing method and use |
| CN101172228A (en) * | 2006-11-02 | 2008-05-07 | 中国石油化工股份有限公司 | Catalyzer for propylene glycol aether preparation with epoxypropane |
| CN105921172A (en) * | 2016-05-20 | 2016-09-07 | 中国科学院过程工程研究所 | Application of ionic liquid in synthesis of propylene glycol ether and propylene glycol ether synthesis method |
| CN107096567A (en) * | 2017-05-23 | 2017-08-29 | 中国科学院过程工程研究所 | The composite catalyst and preparation method of synthesis of propylene glycol |
| WO2017197857A1 (en) * | 2016-05-20 | 2017-11-23 | 中国科学院过程工程研究所 | Application of ionic liquid in propylene glycol ether synthesis and method for synthesizing propylene glycol ether |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1775355A (en) * | 2005-12-01 | 2006-05-24 | 中国科学院山西煤炭化学研究所 | Organic solid base catalyst for synthesizing propylene glycol ether and its preparing method and use |
| CN101172228A (en) * | 2006-11-02 | 2008-05-07 | 中国石油化工股份有限公司 | Catalyzer for propylene glycol aether preparation with epoxypropane |
| CN105921172A (en) * | 2016-05-20 | 2016-09-07 | 中国科学院过程工程研究所 | Application of ionic liquid in synthesis of propylene glycol ether and propylene glycol ether synthesis method |
| WO2017197857A1 (en) * | 2016-05-20 | 2017-11-23 | 中国科学院过程工程研究所 | Application of ionic liquid in propylene glycol ether synthesis and method for synthesizing propylene glycol ether |
| CN107096567A (en) * | 2017-05-23 | 2017-08-29 | 中国科学院过程工程研究所 | The composite catalyst and preparation method of synthesis of propylene glycol |
Non-Patent Citations (1)
| Title |
|---|
| 环氧丙烷醚化反应合成丙二醇醚的研究进展;赵聪 等;《河南化工》;20170331;第4卷(第3期);全文 * |
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