CN108465487B - Polyion liquid-based heteropolyacid catalyst for olefin epoxidation reaction, preparation method and application thereof - Google Patents
Polyion liquid-based heteropolyacid catalyst for olefin epoxidation reaction, preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a polyion liquid-based heteropoly acid catalyst for olefin epoxidation reaction, a preparation method and application thereof, belonging to the field of chemical catalysis. The preparation method of the catalyst provided by the invention comprises the following steps: by ion exchange reaction of H3PW12O40And adding heteropoly acid into the piperidine functionalized polyion liquid solution to obtain white solid particles, filtering, washing and drying to obtain the product. The obtained catalyst is used in olefin epoxidation reaction, and the reaction result is detected by GC, so that the conversion rate can reach 100 percent, and the selectivity can reach 97 percent. The catalyst has the advantages that after the piperidine functionalized ionic liquid cation is combined with the heteropolyanion, the charge transfer in the catalyst molecule can be effectively improved, the reaction is accelerated, the yield of the epoxy compound is improved, the catalyst is insoluble in a system in the reaction, the catalyst can be repeatedly used through simple filtration, the catalytic activity is high, and the service life is long.
Description
Technical Field
The invention belongs to the field of chemical catalysis, and particularly relates to a polyion liquid-based heteropoly acid catalyst for olefin epoxidation reaction; the invention also relates to a preparation method and application of the catalyst.
Background
Epoxy compounds are important organic intermediates for the preparation of epoxy coatings, pesticides, rubber accelerators, pharmaceuticals, fuels and the like, and are also used for the preparation of surfactants and polymer modulators. Olefin epoxidation is the most straightforward route to epoxides and has received considerable attention from academia and industry and has been extensively studied. Hydrogen peroxide is an ideal environmentally friendly source of oxygen because it has active oxygen and produces water after reaction that is not harmful to the environment. In recent years, the development of catalytic olefin epoxidation systems using hydrogen peroxide as an oxygen source has been leading and has made great progress in the field of epoxidation research.
The catalyst for epoxidation reaction is mainly based on catalyst containing metal elements (Al, Mn, W, Ti, Fe, Mo, etc.), and heteropoly acid (also called polyoxometallate) is a metal oxygen cluster compound commonly bridged by metal ions of vanadium, molybdenum, tungsten, etc. and oxygen, and has strong oxidizability because the metal atom is usually in the highest valence state, wherein Keggin type phosphotungstic heteropoly acid has been proved to be a very effective olefin epoxidation catalyst. However, during the process of catalyzing olefin epoxidation reaction, Keggin type structure of heteropoly acid is often degraded into PW step by step due to the addition of hydrogen peroxide4，PW3，PW2And the active species of the peroxypolyacid present the behavior of the catalyst dissolved in the reaction system, which brings difficulty to the recovery and reuse of the catalyst. In recent years, a reaction control phase separation catalytic system and a liquid-liquid two-phase catalytic system appear in succession, a new method is provided for recycling the heteropoly acid catalyst, and the problems that active groups are easy to lose, the catalyst recycling step is complex after the reaction is finished and the like still exist.
Currently, Keggin-type anions such as [ XM12O40]3-5(X＝P5+Or Si4+And M ═ W6+，Mo6+) Novel organic-inorganic hybrid materials composed in combination with room temperature ionic liquids have attracted the attention of researchers. In the catalytic aspect, some catalysts combining imidazolium ionic liquid precursors with heteropolyacids have been reported for olefin epoxidation reactions. Chinese patent CN106975522A discloses a preparation of phosphomolybdotungstic heteropoly acid and its application in catalyzing olefin epoxidation, the yield of epoxide obtained by catalyzing with the catalyst can reach 99%, but the catalyst is difficult to be recovered after finishing catalyzing, and the utilization rate is low.
Therefore, obtaining the ionic liquid type heteropolyacid catalyst which has high activity, is easy to recover and can be repeatedly and stably used is still a difficult problem which needs to be solved urgently.
Disclosure of Invention
The invention aims to provide a polyion liquid heteropoly acid catalyst for olefin epoxidation reaction based on the prior art.
Another object of the present invention is to provide a process for preparing the above catalyst.
The third purpose of the invention is to provide the application of the catalyst.
The technical scheme of the invention is as follows:
a polyion liquid heteropoly acid catalyst for olefin epoxidation reaction, which has the following structural formula:
the catalyst is named as IMPD-IMDO-PW, wherein the ratio of x to y is 1: 0.9-1.1, and the catalyst is prepared by ion exchange of a cation precursor and an anion precursor in an aqueous solution. In the invention, the cation precursor is obtained by polymerizing piperidyl functionalized ionic liquid and dodecyl functionalized ionic liquid, and the anion precursor is H3PW12O40。
Preferably, in the present invention, the molar ratio of the cationic precursor to the anionic precursor is 1.5:1 to 2.0: 1.
A preparation method of a polyion liquid-based heteropoly acid catalyst for olefin epoxidation reaction comprises the following steps:
(1) preparing a piperidine functionalized ionic liquid: mixing 1-vinylimidazole, N- (2-chloroethyl) piperidine hydrochloride and absolute ethyl alcohol, refluxing and stirring, and washing to obtain piperidyl functionalized ionic liquid;
(2) preparation of dodecane functionalized ionic liquid: mixing 1-vinylimidazole, bromododecane and absolute ethyl alcohol, refluxing and stirring, removing a solvent, and washing to obtain dodecyl functionalized ionic liquid;
(3) preparing a cation precursor: mixing the product obtained in the step (1) and the step (2), azodiisobutyronitrile and a solvent, refluxing and stirring, removing the solvent, washing, adding KOH, and removing HCl to obtain a cation precursor;
(4) preparation of polyion liquid based heteropoly acid catalyst: mixing the product obtained in the step (3) with H3PW12O40Stirring in water solution, and filtering.
In a preferable scheme, in the step (1), the mixture is refluxed and stirred for 24-60 hours under the protection of nitrogen and then washed by dichloromethane.
In another preferable scheme, in the step (2), after reflux stirring is carried out for 12-48 h under the protection of nitrogen, the solvent is removed by rotary evaporation, and then washing is carried out by using diethyl ether.
In a more preferable scheme, in the step (3), azodiisobutyronitrile is used as an initiator, absolute ethyl alcohol is used as a solvent, and the reflux stirring is carried out for 12-48 hours under the protection of nitrogen. Then the product obtained in the step (3) is mixed with H3PW12O40Stirring in water solution at normal temperature, filtering, washing and drying.
The application of the polyion liquid-based heteropoly acid catalyst for olefin epoxidation reaction is characterized in that olefin is used as a raw material, hydrogen peroxide is used as an oxidant, acetonitrile is used as a solvent, the polyion liquid-based heteropoly acid is used as the catalyst, reflux reaction is carried out, and the polyion liquid-based heteropoly acid catalyst is recovered after filtration and is recycled.
Preferably, the olefin is cyclooctene or cyclohexene. The dosage of the solvent is 10ml, the reaction time is 2-6h, the dosage of the hydrogen peroxide is 2-12mmol, and the dosage of the catalyst is 0.1 g. The catalyst recovery rate is 82-89%.
After the reaction is finished, the catalyst and the product can be separated by filtration or centrifugation. The reaction solution was analyzed by gas chromatography.
By adopting the technical scheme of the invention, the advantages are as follows:
the polyion liquid-based heteropoly acid catalyst for olefin epoxidation provided by the invention takes acetonitrile as a solvent and hydrogen peroxide as an oxidant, the reaction process is heterogeneous catalytic oxidation, and the catalyst can be recycled and reused by simple filtration after the reaction is finished. The whole reaction system is green and efficient, the reaction conditions are mild, the utilization rate of hydrogen peroxide is high, and the industrial application is favorably realized.
Drawings
FIG. 1 is an infrared spectrum of a polyion liquid-based heteropolyacid catalyst of the present invention;
FIG. 2 is an infrared spectrum of the polyion liquid-based heteropoly acid catalyst after recovery after the reaction is finished;
FIG. 3 is a thermogravimetric spectrum of the polyion liquid-based heteropoly acid catalyst of the present invention.
Detailed Description
The polyion liquid-based heteropolyacid catalyst for olefin epoxidation reaction, the preparation method and the application thereof according to the present invention will be further illustrated by the following examples in conjunction with the accompanying drawings, but these examples do not limit the present invention in any way.
Example 1
1. Preparation of polyion liquid group heteropoly acid catalyst
(1) Preparation of piperidine functionalized ionic liquid
Respectively weighing 9.89g of 1-vinyl imidazole and 18.40g of N- (2-chloroethyl) piperidine hydrochloride, adding into a 150mL flask, adding 40mL of absolute ethyl alcohol, uniformly mixing, refluxing and stirring for 48h under the protection of nitrogen, cooling to room temperature after reaction is finished, separating out a white solid, carrying out suction filtration, washing for 2-3 times by using dichloromethane, and drying for 2h at 80 ℃ to obtain white powdery solid particles IMPD.
(2) Preparation of dodecane functionalized ionic liquid
4.7592g (0.05mol) of 1-vinyl imidazole and 12.5529g (0.05mol) of bromododecane are respectively weighed and mixed into a 100mL round-bottom flask, 40mL of absolute ethyl alcohol is added, the mixture is uniformly mixed and stirred under reflux for 24h under the protection of nitrogen, the solvent is removed by rotary evaporation to obtain light yellow liquid, the light yellow liquid is washed by ethyl ether for 3 times, and then the light yellow liquid is dried for 2 hours at 80 ℃ to obtain light yellow oily liquid IMDO which turns into white solid when the temperature is lower.
(3) Cationic precursor preparation
Weighing the obtained product IMPD (1g) and IMDO (1.23g) into a 100mL flask, adding 50mL of absolute ethyl alcohol, uniformly mixing, slowly adding 0.05g of azobisisobutyronitrile, refluxing and stirring for 24 hours under the protection of nitrogen, removing the solvent by rotary evaporation to obtain a light yellow viscous liquid, adding proper distilled water for dissolving, slowly adding KOH, adjusting the pH to 10, continuously stirring for 2 hours, removing water by rotary evaporation, adding proper ethyl alcohol for removing KCl, and obtaining the cation precursor IMPD-IMDO.
(4) Preparation of polyion liquid group heteropoly acid catalyst
IMPD-IMDO, as obtained above, was added 30ml of distilled water, and 2g H was added3PW12O40Dissolving the mixture in another 30ml of distilled water at a molar ratio of 1.5: 1-2.0: 1, mixing, immediately generating solid precipitate, stirring for 24h at normal temperature, filtering, washing with deionized water for 2-3 times, and drying at 80 ℃ for 2h to obtain white powdery solid IMPD-IMDO-PW.
2. Application of IMPD-IMDO-PW of polyion liquid-based heteropoly acid catalyst
Weighing 0.82g of 10mmol of cyclohexene, 10ml of acetonitrile and 0.1g of catalyst IMPD-IMDO-PW, adding the cyclohexene into a 25ml round-bottom flask, placing the flask in a water bath kettle with a temperature controller at 75 ℃, stirring by using a magnetic stirrer, slowly dropping 6mmol of hydrogen peroxide into a reaction system, and finishing the reaction for 5 hours. After the reaction is finished, the mixture is centrifugally separated, the upper layer solution is taken to analyze the composition of the mixture by gas chromatography, and the lower layer solid can be used for the next reaction after being recovered. The recovery rate of the catalyst is 83 percent, the conversion rate of the cyclohexene is 100 percent, and the selectivity is 91.8 percent.
Example 2
According to the application of the polyion liquid-based heteropoly acid catalyst in the example 1, the reactants are changed, and the specific method is as follows:
weighing 1.08g of 10mmol of cyclooctene, 10ml of acetonitrile and 0.1g of catalyst IMPD-IMDO-PW, adding the materials into a 25ml round-bottom flask, placing the flask into a 75 ℃ water bath kettle of a temperature controller, stirring by using a magnetic stirrer, slowly dropwise adding 8mmol of hydrogen peroxide into a reaction system, and finishing the reaction for 5 hours. After the reaction is finished, the mixture is centrifugally separated, the upper layer solution is taken to analyze the composition of the mixture by gas chromatography, and the lower layer solid can be used for the next reaction after being recovered. The catalyst recovery rate is 86%, the cyclohexene conversion rate is 100%, and the selectivity is 97.4%.
Comparative example 1
The catalyst IMPD-ACAM-PW was prepared according to the procedure for the preparation of polyion liquid-based heteropoly acid catalyst of example 1, substituting acrylamide for IMDO. The specific method comprises the following steps:
(1) preparation of IMPD-ACAM
Weighing the obtained product IMPD (0.01mol) and acrylamide (0.01mol) into a 100mL flask, adding 50mL of absolute ethyl alcohol, uniformly mixing, slowly adding 0.05g of azobisisobutyronitrile, refluxing and stirring for 24h under the protection of nitrogen, removing the solvent by rotary evaporation to obtain a light yellow viscous liquid, adding proper distilled water for dissolving, slowly adding KOH, adjusting the pH to 10, continuously stirring for 2h, removing water by rotary evaporation, adding proper ethyl alcohol for removing KCl, and obtaining the cation precursor IMPD-ACAM.
(2)IMPD-ACAM-PW
Adding 30ml distilled water into the IMPD-ACAM obtained as above, adding 2g H3PW12O40Dissolving the mixture in another 30ml of distilled water at a molar ratio of 1.5: 1-2.0: 1, mixing, immediately generating solid precipitate, stirring for 24 hours at normal temperature, filtering, washing with deionized water for 2-3 times, and drying for 2 hours at 80 ℃ to obtain white powdery solid IMPD-ACAM-PW.
(3) Application of catalytic IMPD-ACAM-PW in olefin epoxidation reaction
Weighing 0.82g of 10mmol cyclohexene, 10ml acetonitrile and 0.1g catalyst IMPD-ACAM-PW, adding the mixture into a 25ml round-bottom flask, placing the flask in a water bath kettle with a temperature controller at 75 ℃, stirring by using a magnetic stirrer, slowly dropping 6mmol hydrogen peroxide into the reaction system, and finishing the reaction for 5 hours. After the reaction is finished, the mixture is centrifugally separated, the upper layer solution is taken to analyze the composition of the mixture by gas chromatography, and the lower layer solid can be used for the next reaction after being recovered. The catalyst recovery rate is 82%, the cyclohexene conversion rate is 89.9%, and the selectivity is 57.6%.
Claims (7)
1. A polyion liquid heteropoly acid catalyst for olefin epoxidation reaction, which is characterized in that the structural formula of the catalyst is as follows:
wherein the ratio of x to y is 1: 0.9-1.1;
the catalyst is prepared by ion exchange of a cation precursor and an anion precursor in an aqueous solution; the cation precursor is obtained by polymerizing piperidyl functionalized ionic liquid and dodecyl functionalized ionic liquid; the anion precursor is H3PW12O40(ii) a The molar ratio of the cation precursor to the anion precursor is 1.5: 1-2.0: 1.
2. A process for the preparation of a polyionic liquid-based heteropolyacid catalyst for olefin epoxidation according to claim 1, which comprises the steps of:
(1) preparing a piperidine functionalized ionic liquid: mixing 1-vinylimidazole, N- (2-chloroethyl) piperidine hydrochloride and absolute ethyl alcohol, refluxing and stirring, and washing to obtain piperidyl functionalized ionic liquid;
(2) preparation of dodecane functionalized ionic liquid: mixing 1-vinylimidazole, bromododecane and absolute ethyl alcohol, refluxing and stirring, removing a solvent, and washing to obtain dodecyl functionalized ionic liquid;
(3) preparing a cation precursor: mixing the product obtained in the step (1) and the step (2), azodiisobutyronitrile and a solvent, refluxing and stirring, removing the solvent, washing, adding KOH, and removing HCl to obtain a cation precursor;
(4) preparation of polyion liquid based heteropoly acid catalyst: mixing the product obtained in the step (3) with H3PW12O40Stirring in water solution, and filtering.
3. The preparation method of the polyion liquid-based heteropoly acid catalyst for olefin epoxidation reaction according to claim 2, wherein in the step (1), the mixture is refluxed and stirred for 24-60 h under the protection of nitrogen, and then washed with dichloromethane.
4. The preparation method of the polyion liquid-based heteropoly acid catalyst for olefin epoxidation reaction according to claim 2, wherein in the step (2), after reflux stirring is performed for 12-48 h under the protection of nitrogen, the solvent is removed by rotary evaporation, and then washing is performed with diethyl ether.
5. The preparation method of the polyion liquid-based heteropoly acid catalyst for olefin epoxidation reaction according to claim 2, wherein in the step (3), azobisisobutyronitrile is used as an initiator, absolute ethyl alcohol is used as a solvent, and the mixture is refluxed and stirred for 12-48 h under the protection of nitrogen.
6. The method for preparing polyion liquid-based heteropolyacid catalyst for olefin epoxidation according to claim 2, wherein in the step (4), the product obtained in the step (3) is reacted with H3PW12O40Stirring in water solution at normal temperature, filtering, washing and drying.
7. The application of the polyion liquid-based heteropolyacid catalyst for olefin epoxidation reaction as claimed in claim 1, wherein cyclooctene or cyclohexene is used as a raw material, hydrogen peroxide is used as an oxidant, acetonitrile is used as a solvent, the polyion liquid-based heteropolyacid is used as a catalyst, reflux reaction is carried out, and the polyion liquid-based heteropolyacid catalyst is recovered after filtration and is recycled.
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| CN102671700A (en) * | 2012-06-07 | 2012-09-19 | 江南大学 | Organic heteropoly acid hybrid catalyst for alcohol oxidation reaction and preparation method thereof |
| CN106881151A (en) * | 2017-04-07 | 2017-06-23 | 辽宁大学 | A kind of heterocycle rhenium ionic liquid and preparation method thereof and the application in EPOXIDATION OF ALKENES CATALYZED BY |
| CN106975522A (en) * | 2017-04-17 | 2017-07-25 | 辽宁大学 | A kind of preparation of heteropoly phosphorus molybdenum tungstic acid and its application on catalyzing expoxidation of olefines |
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| CN102671700A (en) * | 2012-06-07 | 2012-09-19 | 江南大学 | Organic heteropoly acid hybrid catalyst for alcohol oxidation reaction and preparation method thereof |
| CN106881151A (en) * | 2017-04-07 | 2017-06-23 | 辽宁大学 | A kind of heterocycle rhenium ionic liquid and preparation method thereof and the application in EPOXIDATION OF ALKENES CATALYZED BY |
| CN106975522A (en) * | 2017-04-17 | 2017-07-25 | 辽宁大学 | A kind of preparation of heteropoly phosphorus molybdenum tungstic acid and its application on catalyzing expoxidation of olefines |
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