CN111250166B - Heteropolyacid supported sulfonic acid catalyst and preparation method and application thereof - Google Patents
Heteropolyacid supported sulfonic acid catalyst and preparation method and application thereof Download PDFInfo
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- CN111250166B CN111250166B CN202010215970.9A CN202010215970A CN111250166B CN 111250166 B CN111250166 B CN 111250166B CN 202010215970 A CN202010215970 A CN 202010215970A CN 111250166 B CN111250166 B CN 111250166B
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- 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
- B01J31/0215—Sulfur-containing compounds
- B01J31/0229—Sulfur-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0214
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- 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
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- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
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- C07C45/60—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in six-membered rings
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Abstract
The invention provides a heteropoly acid supported sulfonic acid catalyst, and also provides a preparation method, wherein propane sultone is added into toluene, pyridine is added, stirring and filtering are carried out, precipitate is washed, vacuum drying is carried out, sulfonated pyridine is obtained, the sulfonated pyridine is dissolved in methanol, heteropoly acid aqueous solution is dropwise added, reflux, vacuum reduced pressure drying and washing are carried out, and the heteropoly acid supported sulfonic acid catalyst is obtained. Also provided is the use in a reaction for catalysing the depolymerisation of paraldehyde to acetaldehyde. The heteropoly acid supported sulfonic acid catalyst can well catalyze the paraldehyde depolymerization reaction, is used for catalyzing the reaction of depolymerizing paraldehyde into acetaldehyde, has high catalytic activity, can be recycled for multiple times after the catalytic reaction, and can still keep good catalytic activity.
Description
Technical Field
The invention belongs to the technical field of catalyst materials, and particularly relates to a heteropolyacid supported sulfonic acid catalyst, and a preparation method and application thereof.
Background
Acetaldehyde is a common chemical reagent and an important chemical raw material, and downstream products using acetaldehyde as a raw material are many, for example: crotonaldehyde, 3-hydroxybutyraldehyde, butyraldehyde, crotonic acid, 1, 3-butanediol, chloral, pentaerythritol, and the like. Most of the commercially available acetaldehyde reagents are aqueous solutions of acetaldehyde, and in chemical synthesis of acetaldehyde as a starting material, it is often required that acetaldehyde is freshly distilled acetaldehyde [1]. And because the chemical property of the acetaldehyde is active, the acetaldehyde is easy to hydrate in the aqueous solution, an azeotrope is formed between the acetaldehyde and water during distillation, and the pure acetaldehyde is difficult to obtain by a redistillation method. Acetaldehyde is produced in chemical laboratories and industrial processes using a variety of methods for the depolymerization of paraldehyde. The paraldehyde is a cyclic trimer of acetaldehyde, is more stable than acetaldehyde, and can undergo depolymerization reaction to generate acetaldehyde under the action of an acidic catalyst.
Over an acidic catalyst (HCl, HBr, H) 2 SO 4 、H 3 PO 4 、CCl 3 COOH、CHCl 2 COOH) is used, the solvent such as benzene and nitrobenzene is used for accelerating the depolymerization reaction rate and improving the acetaldehyde yield, the solvent used in the method is toxic, the used liquid phase acid can corrode production equipment, and more seriously, the catalyst is not easy to recover, so that acid waste liquid is generated. The method overcomes the defects of the liquid-phase acid catalyst, however, the solid acid catalyst is easy to deposit, so that the catalytic activity is weakened, and the reaction conversion rate is not ideal. In order to solve these problems, it is desirable to design a highly effective solid catalyst that is non-toxic and harmless and can be recycled. Therefore, it is still of great importance to develop a catalyst which is simple in preparation process and which is capable of depolymerizing paraldehyde with high efficiency under normal conditions.
Disclosure of Invention
Aiming at the defects of the prior art, the technical problem to be solved by the invention is to provide the heteropoly acid supported sulfonic acid catalyst, and the preparation method and the application thereof.
In order to solve the technical problems, the invention adopts the following technical scheme: a heteropolyacid-supported sulfonic acid catalyst having the structural formula:
wherein X is heteropolyacid radical, and the heteropolyacid radical is phosphotungstic acid radical or phosphomolybdic acid radical.
The invention also provides a method for preparing the heteropolyacid supported sulfonic acid catalyst, which comprises the following steps:
s1, adding propane sultone into toluene to obtain toluene solution of propane sultone, adding pyridine into the toluene solution of propane sultone, stirring for 6-18 h, filtering, washing the precipitate with diethyl ether for 3 times, and drying in vacuum to obtain sulfonated pyridine;
s2, dissolving the sulfonated pyridine obtained in the S1 in methanol to obtain a mixed solution a, dripping the heteropolyacid aqueous solution into the mixed solution a, refluxing for 18-24 hours at the temperature of 100 ℃, drying under vacuum and decompressing, and washing with acetone to obtain a heteropolyacid-loaded sulfonic acid catalyst; the heteropoly acid in the heteropoly acid aqueous solution is phosphotungstic acid or phosphomolybdic acid.
Preferably, the ratio of propane sultone to toluene used in S1 is 0.1mol:50mL.
Preferably, the molar ratio of propane sultone to pyridine in S1 is 1:1.
Preferably, the concentration of the sulfonated pyridine in the mixed solution a in the S2 is 2mol/L to 10mol/L.
Preferably, the concentration of the heteropolyacid aqueous solution in S2 is 0.1mol/L to 0.5mol/L.
Preferably, the dosage ratio of the heteropolyacid aqueous solution to the mixed solution a in the S2 is 5:1.
the invention also provides application of the heteropoly acid supported sulfonic acid catalyst, wherein the heteropoly acid supported sulfonic acid catalyst is used for catalyzing the reaction of depolymerizing paraldehyde to generate acetaldehyde.
Compared with the prior art, the invention has the following advantages:
the heteropoly acid supported sulfonic acid catalyst can well catalyze the paraldehyde depolymerization reaction, the heteropoly acid supported sulfonic acid catalyst prepared by the method has no corrosiveness to equipment, the preparation process is simple, the condition is mild, high-temperature and high-pressure reaction is not needed, the heteropoly acid supported sulfonic acid catalyst is used for catalyzing the reaction of depolymerizing paraldehyde to generate acetaldehyde, the catalytic activity is high, the heteropoly acid supported sulfonic acid catalyst after the catalytic reaction can be recycled for multiple times, and the good catalytic activity can still be maintained.
The invention is described in further detail below with reference to the drawings and examples.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a heteropolyacid-supported sulfonic acid catalyst of example 1 of the present invention.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the heteropolyacid-supported sulfonic acid catalyst of example 2 of the present invention.
Detailed Description
Example 1
The structural formula of the heteropolyacid supported sulfonic acid catalyst in this embodiment is:
the embodiment also provides a method for preparing the heteropolyacid supported sulfonic acid catalyst, which comprises the following steps:
s1, adding 0.1mol of propane sultone into 50mL of toluene to obtain a toluene solution of propane sultone, adding 0.1mol of pyridine into the toluene solution of propane sultone, stirring for 6 hours, filtering, washing a precipitate with diethyl ether for 3 times, and drying in vacuum to obtain sulfonated pyridine;
s2, dissolving the sulfonated pyridine obtained in the S1 in methanol to obtain a mixed solution a, dripping 50mL of heteropolyacid water solution with the concentration of 2mol/L into 10mL of the mixed solution a, refluxing for 18 hours at the temperature of 100 ℃, drying under vacuum and decompression, and washing with acetone to obtain a heteropolyacid-loaded sulfonic acid catalyst; the heteropoly acid in the heteropoly acid aqueous solution is phosphotungstic acid.
The structure of the prepared heteropolyacid supported sulfonic acid catalyst is detected, and the catalyst is characterized by adopting a nuclear magnetic resonance spectrometer, wherein the nuclear magnetic resonance hydrogen spectrogram is shown in figure 1, and the analysis of the nuclear magnetic resonance hydrogen spectrogram shows that the structure of the heteropolyacid supported sulfonic acid catalyst is shown in the specification.
The present example also provides the use of the heteropoly acid supported sulfonic acid catalyst described above in a reaction for catalyzing the depolymerization of paraldehyde to acetaldehyde, 50g of paraldehyde, 1mL of water and 1g of the heteropoly acid supported sulfonic acid catalyst prepared in the present example were added to a reactor, thoroughly mixed, heated to elevated temperature, distilled for 2 hours at a reaction temperature of 60 ℃, and the acetaldehyde yield was 99%. After the reaction is completed, the heteropoly acid supported sulfonic acid catalyst of this example can be recycled, 50g of paraldehyde and 0.5mL of water are continuously added, and distillation is carried out for 2 hours at a reaction temperature of 60 ℃, and the yield of acetaldehyde is 99%. The cycle was used 14 times, and the acetaldehyde yield was unchanged.
The heteropoly acid supported sulfonic acid catalyst of the embodiment is used for catalyzing the reaction of depolymerizing paraldehyde to generate acetaldehyde, and the catalyst is used for 14 times in a circulating way, so that the catalytic efficiency is not obviously reduced.
The heteropoly acid supported sulfonic acid catalyst of the embodiment can well catalyze the paraldehyde depolymerization reaction, the heteropoly acid supported sulfonic acid catalyst prepared by the embodiment has no corrosiveness to equipment, the preparation process is simple, the condition is mild, high-temperature and high-pressure reaction is not needed, the heteropoly acid supported sulfonic acid catalyst of the embodiment is used for catalyzing the reaction of depolymerizing paraldehyde to generate acetaldehyde, the catalytic activity is high, the heteropoly acid supported sulfonic acid catalyst after the catalytic reaction can be recycled for multiple times, and the good catalytic activity can still be maintained.
The heteropolyacid supported sulfonic acid catalyst prepared by the embodiment is an efficient and stable heterogeneous strong acid solid catalyst, belongs to a solid strong acid resin catalyst, can well catalyze the paraldehyde depolymerization reaction, has no corrosiveness to equipment, and is stable to water and air.
Example 2
The structural formula of the heteropolyacid supported sulfonic acid catalyst in this embodiment is:
the embodiment also provides a method for preparing the heteropolyacid supported sulfonic acid catalyst, which comprises the following steps:
s1, adding 0.1mol of propane sultone into 50mL of toluene to obtain a toluene solution of propane sultone, adding 0.1mol of pyridine into the toluene solution of propane sultone, stirring for 18h, filtering, washing a precipitate with diethyl ether for 3 times, and drying in vacuum to obtain sulfonated pyridine;
s2, dissolving the sulfonated pyridine obtained in the S1 in methanol to obtain a mixed solution a, dripping 50mL of heteropolyacid water solution with the concentration of 10mol/L into 10mL of the mixed solution a, refluxing for 24 hours at the temperature of 100 ℃, drying under vacuum and decompression, and washing with acetone to obtain a heteropolyacid-loaded sulfonic acid catalyst; the heteropoly acid in the heteropoly acid aqueous solution is phosphomolybdic acid.
The structure of the prepared heteropolyacid supported sulfonic acid catalyst is detected, and the catalyst is characterized by adopting a nuclear magnetic resonance spectrometer, wherein the nuclear magnetic resonance hydrogen spectrogram is shown in figure 2, and the analysis of the nuclear magnetic resonance hydrogen spectrogram shows that the structure of the heteropolyacid supported sulfonic acid catalyst is proved to be the above.
The present example also provides the use of the heteropoly acid supported sulfonic acid catalyst described above in the reaction for catalyzing the depolymerization of paraldehyde to acetaldehyde, 50g of paraldehyde, 1mL of water and 1g of the heteropoly acid supported sulfonic acid catalyst prepared in the present example were added to a reactor, thoroughly mixed, heated and warmed, distilled for 3 hours at a reaction temperature of 55 ℃, and the yield of acetaldehyde was 99%. After the reaction is completed, the heteropoly acid supported sulfonic acid catalyst of this example can be recycled, 50g of paraldehyde and 0.5mL of water are continuously added, and distillation is carried out for 3 hours at a reaction temperature of 55 ℃, and the yield of acetaldehyde is 99%. The cycle was used 14 times, and the acetaldehyde yield was unchanged.
The heteropoly acid supported sulfonic acid catalyst of the embodiment is used for catalyzing the reaction of depolymerizing paraldehyde to generate acetaldehyde, and the catalyst is used for 14 times in a circulating way, so that the catalytic efficiency is not obviously reduced.
The heteropoly acid supported sulfonic acid catalyst of the embodiment can well catalyze the paraldehyde depolymerization reaction, the heteropoly acid supported sulfonic acid catalyst prepared by the embodiment has no corrosiveness to equipment, the preparation process is simple, the condition is mild, high-temperature and high-pressure reaction is not needed, the heteropoly acid supported sulfonic acid catalyst of the embodiment is used for catalyzing the reaction of depolymerizing paraldehyde to generate acetaldehyde, the catalytic activity is high, the heteropoly acid supported sulfonic acid catalyst after the catalytic reaction can be recycled for multiple times, and the good catalytic activity can still be maintained.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention. Any simple modification, variation and equivalent variation of the above embodiments according to the technical substance of the invention still fall within the scope of the technical solution of the invention.
Claims (1)
1. The application of the heteropoly acid supported sulfonic acid catalyst is characterized in that the heteropoly acid supported sulfonic acid catalyst is used for catalyzing the reaction of depolymerizing paraldehyde to generate acetaldehyde;
the structural formula of the heteropolyacid supported sulfonic acid catalyst is as follows:
wherein X is heteropolyacid radical, and the heteropolyacid radical is phosphotungstic acid radical or phosphomolybdic acid radical;
the preparation method of the heteropolyacid supported sulfonic acid catalyst comprises the following steps:
s1, adding propane sultone into toluene to obtain toluene solution of propane sultone, adding pyridine into the toluene solution of propane sultone, stirring for 6-18 h, filtering, washing the precipitate with diethyl ether for 3 times, and drying in vacuum to obtain sulfonated pyridine; the dosage ratio of propane sultone and toluene in S1 is 0.1mol:50mL; the molar ratio of the propane sultone to the pyridine in the S1 is 1:1;
s2, dissolving the sulfonated pyridine obtained in the S1 in methanol to obtain a mixed solution a, dripping the heteropolyacid aqueous solution into the mixed solution a, refluxing for 18-24 hours at the temperature of 100 ℃, drying under vacuum and decompressing, and washing with acetone to obtain a heteropolyacid-loaded sulfonic acid catalyst; the heteropoly acid in the heteropoly acid aqueous solution is phosphotungstic acid or phosphomolybdic acid; s2, the concentration of sulfonated pyridine in the mixed solution a is 2 mol/L-10 mol/L; the concentration of the heteropoly acid aqueous solution in the S2 is 0.1 mol/L-5.0 mol/L; the dosage ratio of the heteropoly acid aqueous solution to the mixed solution a in the S2 is 5:1.
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