CN115518685A - Carbon-supported p-toluenesulfonic acid catalyst and preparation method and application thereof - Google Patents

Carbon-supported p-toluenesulfonic acid catalyst and preparation method and application thereof Download PDF

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CN115518685A
CN115518685A CN202211135178.8A CN202211135178A CN115518685A CN 115518685 A CN115518685 A CN 115518685A CN 202211135178 A CN202211135178 A CN 202211135178A CN 115518685 A CN115518685 A CN 115518685A
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toluenesulfonic acid
carbon
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roasting
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CN115518685B (en
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王建国
程家旭
邵方君
马帆冬
江文杰
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Zhejiang University of Technology ZJUT
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0215Sulfur-containing compounds
    • B01J31/0225Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
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    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/08Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
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Abstract

The invention discloses a carbon-supported p-toluenesulfonic acid catalyst, and a preparation method and application thereof, wherein the preparation method comprises the following steps: under an infrared lamp, slowly dropwise adding an ethanol solution of sodium hydroxide onto the activated carbon, carrying out physical grinding until the ethanol is completely evaporated, and then carrying out N-phase grinding 2 Roasting in the atmosphere, and carrying out hole expanding treatment on the activated carbon; washing the expanded active carbon with deionized water to neutrality, filtering, activating in a vacuum drying oven, adding the activated active carbon into p-toluenesulfonic acid solution, ultrasonically dispersing uniformly, stirring for 10-24h, and processingFiltering, washing, drying in vacuum drying oven, and adding N 2 And roasting in the atmosphere to obtain the carbon-supported p-toluenesulfonic acid catalyst. According to the invention, the heterogeneous catalyst is obtained by loading the p-toluenesulfonic acid on the active carbon subjected to pore expanding treatment, so that the problems that equipment is easily corroded by using concentrated sulfuric acid as the catalyst, acidic waste liquid treatment is easily caused and the like are solved, and the catalyst is recycled and reused.

Description

Carbon-supported p-toluenesulfonic acid catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a carbon-supported p-toluenesulfonic acid catalyst, and a preparation method and application thereof.
Background
The low molecular weight carboxylic ester compound is a common organic solvent and is also commonly applied to industries such as spices, essences, cosmetics, soaps, medicines and the like. Such as ethyl acetate, has excellent dissolving power, is an excellent industrial solvent, and can also be used as an eluent for column chromatography. Can be used as top note for improving fresh fruit fragrance of small amount of essence such as magnolia, cananga odorata, sweet osmanthus, conyza blinii flower, floral water, fruit fragrance type essence, etc., and especially used in perfume essence with round-cooked effect. Methyl formate is used as an important organic synthesis intermediate, can be directly used as a fumigant and a bactericide for processing tobacco, dried fruits, grains and the like, is also commonly used as a solvent of nitrocellulose and cellulose acetate, and is also commonly used as a synthesis raw material of medicaments such as sulfonic acid methyl pyrimidine, sulfonic acid methoxypyrimidine, antitussive agent methaphen and the like in medicine. Other analogs are ethyl formate, isopropyl acetate, n-propyl acetate, and the like.
In the current industrial production, ester compounds with low molecular weight generally adopt concentrated sulfuric acid as a catalyst for esterification reaction, the method has high yield, but the concentrated sulfuric acid can corrode equipment, the sulfuric acid is difficult to recycle, the treatment of the sulfuric acid is complicated, a large amount of acidic waste liquid can be generated to pollute the environment, and the treatment cost is increased.
In order to overcome the above disadvantages, various environment-friendly catalysts have been developed, such as acidic resins, heteropoly acids, modified molecular sieves, etc., which have good esterification effects, but these methods still have the following problems: the activation and regeneration of the acidic resin are complicated; the preparation of heteropoly acid and solid super acid is complex, and the production cost is high; poor stability of molecular sieves, complicated preparation process, and the like; in addition, the method uses the water-carrying agent, so that high yield can be achieved, but raw material consumption is increased, the production process is simplified, and the production cost is increased.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention aims to provide a carbon-supported p-toluenesulfonic acid catalyst suitable for synthesis of lower lipids, and a preparation method and application thereof.
In order to achieve the purpose, the following technical scheme is provided:
a preparation method of a carbon-supported p-toluenesulfonic acid catalyst comprises the following steps:
1) Under an infrared lamp, slowly dropwise adding an ethanol solution of sodium hydroxide onto the activated carbon, carrying out physical grinding until the ethanol is completely evaporated, and then carrying out N-phase grinding 2 Roasting in the atmosphere, performing hole expanding treatment on the activated carbon, and activating the activated carbon by using sodium hydroxide, so that the specific surface area of the activated carbon can be increased, and the loading capacity of p-toluenesulfonic acid can be increased;
2) Washing the active carbon subjected to hole expanding in the step 1) to be neutral by using deionized water, filtering, and placing in a vacuum drying oven for activation treatment;
3) Adding activated carbon into p-toluenesulfonic acid solution, ultrasonically dispersing uniformly, stirring for 10-24h, filtering, washing, drying in a vacuum drying oven, and finally drying in N 2 And roasting in the atmosphere to obtain the carbon-supported p-toluenesulfonic acid catalyst.
Further, the adding amount of the sodium hydroxide in the step 1) is 10.0-50.0 wt% of the mass of the activated carbon.
Further, the activated carbon in the step 1) is N 2 And (3) roasting under the atmosphere at the temperature rise rate of 5 ℃/min to 600 to 1000 ℃, and roasting for 5 to 7h.
Further, in step 3) at N 2 When the mixture is roasted in the atmosphere, the temperature is raised to 200 to 300 ℃ at the temperature raising rate of 5 ℃/min, and the mixture is roasted for 2 to 5 hours.
Further, the dropping speed of the ethanol solution of the sodium hydroxide in the step 1) is 3ml/min-5 ml/min.
The carbon-supported p-toluenesulfonic acid catalyst prepared by the preparation method has a p-toluenesulfonic acid loading amount of 5-30 wt%.
The application of carbon supported p-toluenesulfonic acid catalyst in synthesis of lower lipid comprises methyl formate, methyl acetate, ethyl acetate, propyl acetate, n-propyl acetate, isopropyl acetate and ethyl propionate.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention obtains the heterogeneous catalyst by loading the p-toluenesulfonic acid on the active carbon subjected to reaming treatment, avoids the problems that concentrated sulfuric acid is used as the catalyst in the traditional process and is easy to corrode equipment, the acidic waste liquid is treated and the like, realizes the recovery and the reutilization of the catalyst, and simultaneously the catalyst has excellent catalytic activity and product yield for the synthesis of the carboxylic ester compounds with low molecular weight.
Drawings
FIG. 1 is an SEM image of a 30wt% p-toluenesulfonic acid/AC catalyst prepared in example 2;
FIG. 2 is an elemental distribution diagram of a 30wt% p-toluenesulfonic acid/AC catalyst prepared in example 2.
Detailed Description
The technical solution of the present invention is further described below with reference to the following examples and the drawings of the specification, but the scope of the present invention is not limited thereto.
Example 1
(1) Preparation of carbon-supported p-toluenesulfonic acid catalyst:
100.0mg of sodium hydroxide are dissolved in 10.0ml of ethanol solution, slowly added dropwise to 1.0g of activated carbon under an infrared lamp at a rate of 4ml/min, continuously ground until the ethanol has completely evaporated, and then added under N 2 Roasting at 800 ℃ for 5h at the heating rate of 5 ℃/min under the atmosphere, cooling to room temperature, washing the activated carbon to be neutral by deionized water, and placing in a vacuum drying oven for overnight drying at 60 ℃. Dissolving 300.0mg of p-toluenesulfonic acid in 50ml of deionized water, adding pretreated activated carbon, and performing ultrasonic treatmentDispersing uniformly, coating with preservative film, stirring for 24 hr, filtering, washing, vacuum drying at 60 deg.C overnight, and drying in N 2 Roasting for 2h at the temperature rise rate of 5 ℃/min and the temperature rise rate of 200 ℃ under the atmosphere to obtain the target catalyst of 30wt% of p-toluenesulfonic acid/AC.
(2) The application of the catalyst comprises the following steps:
4.6g of ethanol and 9.0g of acetic acid were weighed into a reaction kettle, 100.0mg of the p-toluenesulfonic acid/AC catalyst prepared by the above method was added, reflux was carried out at 125 ℃ for 40min, and then distillation was carried out to collect fractions, thereby obtaining an ethyl acetate crude product.
Example 2
(1) Preparation of carbon-supported p-toluenesulfonic acid catalyst:
300.0mg of sodium hydroxide are dissolved in 10.0ml of ethanol solution, slowly added dropwise to 1.0g of activated carbon under an infrared lamp at a rate of 4ml/min, continuously ground until the ethanol has completely evaporated, and then added under N 2 Roasting at 800 ℃ for 5h at the heating rate of 5 ℃/min under the atmosphere, cooling to room temperature, washing the activated carbon to be neutral by using deionized water, and placing in a vacuum drying oven for overnight drying at 60 ℃. Dissolving 300.0mg of p-toluenesulfonic acid in 50ml of deionized water, adding pretreated activated carbon, uniformly dispersing by ultrasonic wave, coating with a preservative film, stirring for 24h, filtering, washing, drying in a vacuum drying oven at 60 ℃ overnight, and then drying in N 2 Roasting for 2h at the temperature rise rate of 5 ℃/min and 300 ℃ under the atmosphere to obtain the target catalyst of 30wt% of p-toluenesulfonic acid/AC.
(2) The application of the catalyst comprises the following steps:
4.6g of ethanol and 9.0g of acetic acid were weighed into a reaction kettle, 100.0mg of the p-toluenesulfonic acid/AC catalyst prepared by the above method was added, reflux was carried out at 125 ℃ for 40min, and then distillation was carried out to collect fractions, thereby obtaining an ethyl acetate crude product.
Example 3
(1) Preparation of carbon-supported p-toluenesulfonic acid catalyst:
dissolving 500.0mg sodium hydroxide in 10.0ml ethanol solution, slowly dripping onto 1.0g activated carbon under infrared lamp at 4ml/min, and continuously grinding until ethanol is completely evaporatedThen at N 2 Roasting at 800 ℃ for 5h at the heating rate of 5 ℃/min under the atmosphere, cooling to room temperature, washing the activated carbon to be neutral by using deionized water, and placing in a vacuum drying oven for overnight drying at 60 ℃. Dissolving 300.0mg of p-toluenesulfonic acid in 50ml of deionized water, adding pretreated activated carbon, uniformly dispersing by ultrasonic wave, coating with a preservative film, stirring for 24h, filtering, washing, drying in a vacuum drying oven at 60 ℃ overnight, and then drying in N 2 Roasting for 2h at the temperature rise rate of 5 ℃/min and 300 ℃ under the atmosphere to obtain the target catalyst of 30wt% of p-toluenesulfonic acid/AC.
(2) The application of the catalyst comprises the following steps:
4.6g of ethanol and 9.0g of acetic acid were weighed into a reaction kettle, 100.0mg of the p-toluenesulfonic acid/AC catalyst prepared by the above method was added, reflux was carried out at 125 ℃ for 40min, and then distillation was carried out to collect fractions, thereby obtaining an ethyl acetate crude product.
Example 4
(1) Preparation of carbon-supported p-toluenesulfonic acid catalyst:
300.0mg of sodium hydroxide are dissolved in 10.0ml of ethanol solution, slowly added dropwise to 1.0g of activated carbon under an infrared lamp at a rate of 4ml/min, continuously ground until the ethanol has completely evaporated, and then added under N 2 Roasting at 1000 ℃ for 5h at the heating rate of 5 ℃/min under the atmosphere, cooling to room temperature, washing the activated carbon to be neutral by using deionized water, and placing in a vacuum drying oven for overnight drying at 60 ℃. Dissolving 300.0mg of p-toluenesulfonic acid in 50ml of deionized water, adding pretreated activated carbon, uniformly dispersing by ultrasonic waves, coating with a preservative film, stirring for 24 hours, filtering, washing, putting in a vacuum drying oven for overnight drying at 60 ℃, and then drying in N 2 Roasting for 2h at the temperature rise rate of 5 ℃/min and the temperature rise rate of 200 ℃ under the atmosphere to obtain the target catalyst of 30wt% of p-toluenesulfonic acid/AC.
(2) The application of the catalyst comprises the following steps:
4.6g of ethanol and 9.0g of acetic acid were weighed into a reaction kettle, 100.0mg of the p-toluenesulfonic acid/AC catalyst prepared by the above method was added, reflux was carried out at 125 ℃ for 40min, and then distillation was carried out to collect fractions, thereby obtaining an ethyl acetate crude product.
Example 5:
(1) Preparation of carbon-supported p-toluenesulfonic acid catalyst:
300.0mg of sodium hydroxide are dissolved in 10.0ml of ethanol solution, slowly added dropwise to 1.0g of activated carbon under an infrared lamp at a rate of 4ml/min, continuously ground until the ethanol has completely evaporated, and then subjected to N 2 Roasting at 600 ℃ for 5h at the heating rate of 5 ℃/min under the atmosphere, cooling to room temperature, washing the activated carbon to be neutral by deionized water, and placing in a vacuum drying oven for overnight drying at 60 ℃. Dissolving 300.0mg of p-toluenesulfonic acid in 50ml of deionized water, adding pretreated activated carbon, uniformly dispersing by ultrasonic wave, coating 0 with a preservative film, stirring for 24h, filtering, washing, drying in a vacuum drying oven at 60 ℃ overnight, and then drying in N 2 Roasting for 2h at the temperature rise rate of 5 ℃/min and the temperature rise rate of 200 ℃ under the atmosphere to obtain the target catalyst of 30wt% of p-toluenesulfonic acid/AC.
(2) The application of the catalyst comprises the following steps:
weighing 4.6g of ethanol and 9.0g of acetic acid, putting the ethanol and the acetic acid into a reaction kettle, adding 100.0mg of the p-toluenesulfonic acid/AC catalyst prepared by the method, refluxing for 40min at 125 ℃, then distilling, and collecting fractions to obtain a crude product of ethyl acetate.
Example 6:
(1) Preparation of carbon-supported p-toluenesulfonic acid catalyst:
300.0mg of sodium hydroxide are dissolved in 10.0ml of ethanol solution, slowly added dropwise to 1.0g of activated carbon under an infrared lamp at a rate of 4ml/min, continuously ground until the ethanol has completely evaporated, and then added under N 2 Roasting at 800 ℃ for 7h at the heating rate of 5 ℃/min under the atmosphere, cooling to room temperature, washing the activated carbon to be neutral by using deionized water, and placing in a vacuum drying oven for overnight drying at 60 ℃. Dissolving 100.0mg of p-toluenesulfonic acid in 50ml of deionized water, adding pretreated activated carbon, uniformly dispersing by ultrasonic wave, coating with a preservative film, stirring for 24h, filtering, washing, drying in a vacuum drying oven at 60 ℃ overnight, and then drying in N 2 Roasting for 2h at the temperature rise rate of 5 ℃/min and the temperature rise rate of 200 ℃ under the atmosphere to obtain the target catalyst of 10wt% of p-toluenesulfonic acid/AC.
(2) The application of the catalyst comprises the following steps:
weighing 4.6g of ethanol and 9.0g of acetic acid, putting the ethanol and the acetic acid into a reaction kettle, adding 100.0mg of the p-toluenesulfonic acid/AC catalyst prepared by the method, refluxing for 40min at 125 ℃, then distilling, and collecting fractions to obtain a crude product of ethyl acetate.
Example 7:
(1) Preparation of carbon-supported p-toluenesulfonic acid catalyst:
300.0mg of sodium hydroxide are dissolved in 10.0ml of ethanol solution, slowly added dropwise to 1.0g of activated carbon under an infrared lamp at a rate of 4ml/min, continuously ground until the ethanol has completely evaporated, and then added under N 2 Roasting at 800 ℃ for 7h at the heating rate of 5 ℃/min under the atmosphere, cooling to room temperature, washing the activated carbon to be neutral by deionized water, and placing in a vacuum drying oven for overnight drying at 60 ℃. Dissolving 300.0mg of p-toluenesulfonic acid in 50ml of deionized water, adding pretreated activated carbon, uniformly dispersing by ultrasonic waves, coating with a preservative film, stirring for 12 hours, filtering, washing, putting into a vacuum drying oven for overnight drying at 60 ℃, and then drying in N 2 Roasting for 4h at the temperature rise rate of 5 ℃/min and 300 ℃ under the atmosphere to obtain the target catalyst of 30wt% of p-toluenesulfonic acid/AC.
(2) The application of the catalyst comprises the following steps:
4.6g of ethanol and 9.0g of acetic acid were weighed into a reaction kettle, 100.0mg of the p-toluenesulfonic acid/AC catalyst prepared by the above method was added, reflux was carried out at 125 ℃ for 40min, and then distillation was carried out to collect fractions, thereby obtaining an ethyl acetate crude product.
Example 8:
(1) Preparation of carbon-supported p-toluenesulfonic acid catalyst:
300.0mg of sodium hydroxide are dissolved in 10.0ml of ethanol solution, slowly added dropwise to 1.0g of activated carbon under an infrared lamp at a rate of 4ml/min, continuously ground until the ethanol has completely evaporated, and then added under N 2 Roasting at 800 ℃ for 7h at the heating rate of 5 ℃/min under the atmosphere, cooling to room temperature, washing the activated carbon to be neutral by deionized water, and placing in a vacuum drying oven for overnight drying at 60 ℃. 300.0mg of p-toluenesulfonic acid was dissolved in 50ml of deionized water, and then the pretreatment was addedThe active carbon is evenly dispersed by ultrasonic, coated by a preservative film, stirred for 24 hours, filtered, washed, put into a vacuum drying oven for overnight drying at 60 ℃, and then dried in N 2 Roasting for 2h at the temperature rise rate of 5 ℃/min and the temperature rise rate of 200 ℃ under the atmosphere to obtain the target catalyst of 30wt% of p-toluenesulfonic acid/AC.
(2) The application of the catalyst comprises the following steps:
4.6g of ethanol and 9.0g of acetic acid were weighed into a reaction kettle, 50.0mg of the p-toluenesulfonic acid/AC catalyst prepared by the above method was added, reflux was carried out at 125 ℃ for 40min, and then distillation was carried out to collect fractions, thereby obtaining an ethyl acetate crude product.
Example 9:
(1) Preparation of carbon-supported p-toluenesulfonic acid catalyst:
10.0ml of ethanol solution was slowly added dropwise to 1.0g of activated carbon under an infrared lamp at 4ml/min, continuously ground until the ethanol had completely evaporated, and then added under N 2 Roasting at 800 ℃ for 7h at the heating rate of 5 ℃/min under the atmosphere, cooling to room temperature, washing the activated carbon to be neutral by deionized water, and placing in a vacuum drying oven for overnight drying at 60 ℃. Dissolving 300.0mg of p-toluenesulfonic acid in 50ml of deionized water, adding pretreated activated carbon, uniformly dispersing by ultrasonic wave, coating with a preservative film, stirring for 24h, filtering, washing, drying in a vacuum drying oven at 60 ℃ overnight, and then drying in N 2 Roasting for 2h at the temperature rise rate of 5 ℃/min and the temperature rise rate of 200 ℃ under the atmosphere to obtain the target catalyst of 30wt% of p-toluenesulfonic acid/AC.
(2) The application of the catalyst comprises the following steps:
4.6g of ethanol and 9.0g of acetic acid are weighed into a reaction kettle, 300.0mg of p-toluenesulfonic acid/AC catalyst prepared by the method is added, reflux is carried out at 125 ℃ for 40min, and then distillation is carried out to collect fractions, so as to obtain a crude ethyl acetate product.
Example 10:
(1) Preparation of carbon-supported p-toluenesulfonic acid catalyst:
300.0mg of sodium hydroxide are dissolved in 10.0ml of ethanol solution and slowly added dropwise to 1.0g of activated carbon under an infrared lamp at a rate of 4ml/min, continuously grinding until the ethanol is completely evaporatedThen in N 2 Roasting at 800 ℃ for 7h at the heating rate of 5 ℃/min under the atmosphere, cooling to room temperature, washing the activated carbon to be neutral by deionized water, and placing in a vacuum drying oven for overnight drying at 60 ℃. Dissolving 300.0mg of p-toluenesulfonic acid in 50ml of deionized water, adding pretreated activated carbon, uniformly dispersing by ultrasonic wave, coating with a preservative film, stirring for 24h, filtering, washing, drying in a vacuum drying oven at 60 ℃ overnight, and then drying in N 2 Roasting for 2h at the temperature rise rate of 5 ℃/min and 300 ℃ under the atmosphere to obtain the target catalyst of 30wt% of p-toluenesulfonic acid/AC.
(2) The application of the catalyst comprises the following steps:
3.2g of methanol and 4.6g of formic acid were weighed out and placed in a reaction vessel, 100.0mg of p-toluenesulfonic acid/AC catalyst prepared by the above method was added, and the mixture was refluxed at 125 ℃ for 40min, then distilled, and the distillate was collected to obtain a crude methyl formate.
Example 11
The application of the catalyst comprises the following steps:
6.0g of n-propanol and 9.0g of acetic acid were weighed into a reaction vessel, 100.0mg of the p-toluenesulfonic acid/AC catalyst obtained in example 10 was added, and the mixture was refluxed at 125 ℃ for 40min, then distilled, and the distillate was collected to obtain a crude n-propyl acetate product.
Example 12
The application of the catalyst comprises the following steps:
6.0g of isopropyl alcohol and 9.0g of acetic acid were weighed into a reaction vessel, 100.0mg of p-toluenesulfonic acid/AC catalyst obtained in example 10 was added, and the mixture was refluxed at 125 ℃ for 40min, then distilled, and the distillate was collected to obtain a crude product of isopropyl acetate.
Example 13
4.6g of ethanol and 11.1g of propionic acid were weighed into a reaction kettle, 100.0mg of p-toluenesulfonic acid/AC catalyst obtained in example 10 was added, and the mixture was refluxed at 125 ℃ for 40min, and then distilled to collect fractions, thereby obtaining a crude ethyl propionate product.
TABLE 1 catalytic Performance of the catalysts of the examples
Figure DEST_PATH_IMAGE001
Fig. 1 and 2 are SEM and element distribution diagrams of 30wt% p-toluenesulfonic acid/AC catalyst prepared by the above method in example 2, and it can be seen from fig. 1 and 2 that there is no Na element remaining on the surface of activated carbon, and furthermore, p-toluenesulfonic acid was successfully supported on activated carbon by impregnation, and the deviation from the theoretical supporting amount was not large. Table 2 shows the p-toluenesulfonic acid/AC catalysts prepared in examples 1 to 13 under different conditions and their catalytic properties. It can be seen that in a certain range, the activity of the catalyst can be improved to a certain extent by carrying out pore-expanding treatment on the activated carbon by using sodium hydroxide, and when the using amount of the sodium hydroxide is excessive, the surface of the activated carbon is likely to be alkalescent and reacts with p-toluenesulfonic acid loaded later, so that the activity of the catalyst is reduced. The calcination temperature has a great influence on the activity of the catalyst by changing the preparation conditions of the catalyst, and the best effect can be achieved when the calcination temperature is 800 ℃, probably because the pore-expanding effect is not obvious when the temperature is too low, and the pore channels of the activated carbon collapse and the specific surface area is reduced when the calcination temperature is too high. The loading amount of the p-toluenesulfonic acid, the stirring time and the addition amount during the reaction also have great influence on the activity of the catalyst, and the higher the loading amount of the p-toluenesulfonic acid is, the longer the stirring time is, the higher the activity of the catalyst is. In addition, the catalyst has good catalytic activity when synthesizing carboxylic ester compounds with low molecular weight.

Claims (7)

1. A preparation method of a carbon-supported p-toluenesulfonic acid catalyst is characterized by comprising the following steps:
1) Under an infrared lamp, slowly dropwise adding an ethanol solution of sodium hydroxide onto the activated carbon, carrying out physical grinding until the ethanol is completely evaporated, and then carrying out N-phase grinding 2 Roasting in the atmosphere, and carrying out hole expanding treatment on the activated carbon;
2) Washing the active carbon subjected to hole expanding in the step 1) to be neutral by using deionized water, filtering, and placing in a vacuum drying oven for activation treatment;
3) Will be subjected to activation treatmentAdding the activated carbon into a p-toluenesulfonic acid solution, stirring for 10-24h after uniform ultrasonic dispersion, filtering, washing, drying in a vacuum drying oven, and finally adding N 2 And roasting in the atmosphere to obtain the carbon-supported p-toluenesulfonic acid catalyst.
2. The preparation method of claim 1, wherein the sodium hydroxide in step 1) is added in an amount of 10.0wt% to 50.0wt% based on the mass of the activated carbon.
3. The method of claim 1, wherein the activated carbon in step 1) is at N 2 The temperature of the roasting is raised to 600 to 1000 ℃ at the temperature rising rate of 5 ℃/min under the atmosphere, and the roasting is carried out for 5 to 7h.
4. The method of claim 1, wherein in step 3) N is 2 When the roasting is carried out under the atmosphere, the temperature is raised to 200 to 300 ℃ at the heating rate of 5 ℃/min, and the roasting is carried out for 2 to 5 hours.
5. The method of claim 1, wherein the dropping rate of the ethanol solution of sodium hydroxide in step 1) is 3ml/min to 5ml/min.
6. The carbon-supported p-toluenesulfonic acid catalyst prepared by the method of claim 1, wherein the p-toluenesulfonic acid loading is 5wt% to 30wt%.
7. Use of the carbon-supported p-toluenesulfonic acid catalyst of claim 5 in the synthesis of lower lipids, wherein the lower lipids comprise methyl formate, methyl acetate, ethyl acetate, propyl acetate, n-propyl acetate, isopropyl acetate and ethyl propionate.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104445181A (en) * 2014-11-19 2015-03-25 福州大学 Activated carbon and preparation method thereof
CN109174180A (en) * 2018-09-30 2019-01-11 浙江工业大学上虞研究院有限公司 A kind of preparation method and applications of the loaded catalyst based on sulfonating reaction
CN110639567A (en) * 2019-10-10 2020-01-03 浙江工业大学 Carbon-supported ruthenium phosphide nanocluster bifunctional catalyst and preparation method and application thereof
CN110776443A (en) * 2018-12-14 2020-02-11 瑞孚信江苏药业股份有限公司 Preparation method of p-methylsulfonyl phenyl serine ethyl ester
CN114560770A (en) * 2022-03-23 2022-05-31 广西金源生物化工实业有限公司 Method for preparing ethyl sorbate by catalysis of supported p-toluenesulfonic acid

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104445181A (en) * 2014-11-19 2015-03-25 福州大学 Activated carbon and preparation method thereof
CN109174180A (en) * 2018-09-30 2019-01-11 浙江工业大学上虞研究院有限公司 A kind of preparation method and applications of the loaded catalyst based on sulfonating reaction
CN110776443A (en) * 2018-12-14 2020-02-11 瑞孚信江苏药业股份有限公司 Preparation method of p-methylsulfonyl phenyl serine ethyl ester
CN110639567A (en) * 2019-10-10 2020-01-03 浙江工业大学 Carbon-supported ruthenium phosphide nanocluster bifunctional catalyst and preparation method and application thereof
CN114560770A (en) * 2022-03-23 2022-05-31 广西金源生物化工实业有限公司 Method for preparing ethyl sorbate by catalysis of supported p-toluenesulfonic acid

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CUIPING WANG ET AL.: "Bio-oil upgrading by reactive distillation using p-toluene sulfonic acid catalyst loaded on biomass activated carbon", 《BIOMASS AND BIOENERGY》, vol. 56, pages 405 - 411, XP028684698, DOI: 10.1016/j.biombioe.2013.04.026 *
朱蕾等: "活性炭固载对甲苯磺酸催化合成乙酸正丁酯", 《化工时刊》, vol. 20, no. 1, pages 43 *

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