CN115518685B - 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 PDFInfo
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- CN115518685B CN115518685B CN202211135178.8A CN202211135178A CN115518685B CN 115518685 B CN115518685 B CN 115518685B CN 202211135178 A CN202211135178 A CN 202211135178A CN 115518685 B CN115518685 B CN 115518685B
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- toluenesulfonic acid
- carbon
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- roasting
- activated carbon
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 110
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 75
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 57
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 28
- 238000001291 vacuum drying Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000005406 washing Methods 0.000 claims abstract description 26
- 239000008367 deionised water Substances 0.000 claims abstract description 23
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 23
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000011068 loading method Methods 0.000 claims abstract description 7
- 230000004913 activation Effects 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 17
- 230000007935 neutral effect Effects 0.000 claims description 12
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 10
- 230000000630 rising effect Effects 0.000 claims description 10
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 8
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 6
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 4
- 229940011051 isopropyl acetate Drugs 0.000 claims description 4
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 150000002632 lipids Chemical class 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 abstract description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 14
- 239000012043 crude product Substances 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 238000004821 distillation Methods 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000003755 preservative agent Substances 0.000 description 9
- 230000002335 preservative effect Effects 0.000 description 9
- -1 carboxylic ester compound Chemical class 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 241000218378 Magnolia Species 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 244000242564 Osmanthus fragrans Species 0.000 description 1
- 235000019083 Osmanthus fragrans Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003434 antitussive agent Substances 0.000 description 1
- 229940124584 antitussives Drugs 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 235000011869 dried fruits Nutrition 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 235000021022 fresh fruits Nutrition 0.000 description 1
- 239000002316 fumigant Substances 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004434 industrial solvent Substances 0.000 description 1
- VBSZTJYIXRUJJV-UHFFFAOYSA-N methyl pyrimidine-2-sulfonate Chemical compound N1=C(N=CC=C1)S(=O)(=O)OC VBSZTJYIXRUJJV-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution 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
- B01J2231/49—Esterification or transesterification
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: slowly dripping ethanol solution of sodium hydroxide onto active carbon under infrared lamp, and physically grinding until ethanol is completely evaporated, and then adding water to the mixture under N 2 Roasting in atmosphere, and reaming the activated carbon; washing the reamed active carbon with deionized water to neutrality, filtering, placing in a vacuum drying oven for activation treatment, adding activated carbon into p-toluenesulfonic acid solution, ultrasonic dispersing uniformly, stirring for 10-24 hr, filtering, washing, placing in a vacuum drying oven for drying, and finally adding N into a catalyst 2 Roasting is carried out in 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 activated carbon subjected to pore expansion treatment, so that the problems of easy corrosion to equipment, acid waste liquid treatment and the like caused by using concentrated sulfuric acid as the catalyst are avoided, and the recovery and recycling of the catalyst are realized.
Description
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 widely applied to industries such as perfume, essence, cosmetics, soap, medicines and the like. For example, ethyl acetate has excellent dissolving capacity, is an excellent industrial solvent, and can also be used as an eluent for column chromatography. Can be used for improving fresh fruit fragrance by using small amounts of essence such as magnolia, ylang, osmanthus fragrans, lager and floral water, fruit fragrance and the like as the top fragrance, and particularly has the effect of being well-done in perfume essence. Methyl formate is used as an important organic synthesis intermediate, and can be directly used as fumigant and bactericide for processing tobacco, dried fruits, grains and the like, and is also used as solvent of nitrocellulose and cellulose acetate, and is also used as synthesis raw material of medicines such as methyl pyrimidine sulfonate, antitussive agent and methafene. Other similar compounds include ethyl formate, isopropyl acetate, n-propyl acetate, and the like.
In the current industrial production, the ester compounds with low molecular weight generally adopt concentrated sulfuric acid as a catalyst for esterification reaction, the method has extremely high yield, but the concentrated sulfuric acid can cause corrosion to equipment, the sulfuric acid is difficult to recycle, the sulfuric acid is more complicated to treat, a large amount of acid waste liquid can be generated to pollute the environment, and the treatment cost is increased. To overcome the above disadvantages, various environment-friendly catalysts have been developed, such as acid resins, heteropolyacids, modified molecular sieves, etc., which achieve good esterification effects, but these methods still have the following problems: the acidic resin is complicated to activate and regenerate; the preparation of the heteropolyacid and the solid superacid is complex, and the production cost is high; the stability of the molecular sieve is poor, the preparation process is complex, and the like; in addition, the method can achieve higher yield by using the water-carrying agent, but increases raw material consumption, increases production process and increases production cost.
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 synthesizing lower lipids, and a preparation method and application thereof.
In order to achieve the above purpose, the following technical scheme is provided:
a preparation method of a carbon-supported p-toluenesulfonic acid catalyst comprises the following steps:
1) Slowly dripping ethanol solution of sodium hydroxide onto active carbon under infrared lamp, and physically grinding until ethanol is completely evaporated, and then adding water to the mixture under N 2 Roasting in atmosphere, reaming the activated carbon, and activating the activated carbon by 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 reamed active carbon in the step 1) to be neutral by deionized water, filtering and placing in a vacuum drying oven for activation treatment;
3) Adding activated carbon into p-toluenesulfonic acid solution, ultrasonic dispersing, stirring for 10-24 hr, filtering, washing, vacuum drying in a vacuum drying oven, and adding N 2 Roasting is carried out in atmosphere to obtain the carbon-supported p-toluenesulfonic acid catalyst.
Further, the addition amount of the sodium hydroxide in the step 1) is 10.0-50.0 wt% of the mass of the activated carbon.
Further, in step 1), the activated carbon is activated in N 2 Roasting in the atmosphere, the temperature is raised to 600-1000 ℃ at the heating rate of 5 ℃/min, and the roasting is carried out for 5-7 h.
Further, in step 3), at N 2 When roasting is carried out under the atmosphere, the temperature is raised to 200-300 ℃ at the heating rate of 5 ℃/min, and the roasting is carried out for 2-5 h.
Further, the dropping speed of the ethanol solution of sodium hydroxide in the step 1) is 3ml/min-5ml/min.
The carbon-supported p-toluenesulfonic acid catalyst prepared by the preparation method has the load of 5-30wt% of p-toluenesulfonic acid.
Use of a carbon supported p-toluenesulfonic acid catalyst in the synthesis of lower lipids including 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:
according to the invention, the heterogeneous catalyst is obtained by loading the p-toluenesulfonic acid on the activated carbon subjected to pore expansion treatment, so that the problems that equipment is easy to corrode, acid waste liquid is easy to treat and the like due to the fact that concentrated sulfuric acid is used as the catalyst in the traditional process are solved, the catalyst is recovered and reused, meanwhile, the catalyst has excellent catalytic activity and product yield for synthesizing the low-molecular-weight carboxylate compound, and the preparation method provided by the invention is simple and controllable, and has a wide application prospect.
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 scheme of the present invention will be further described with reference to examples and drawings, but the scope of the present invention is not limited thereto.
Example 1
(1) Preparation of a carbon supported p-toluenesulfonic acid catalyst:
dissolving 100.0mg of sodium hydroxide in 10.0ml of ethanol solution, slowly dripping onto 1.0g of active carbon at a rate of 4ml/min under an infrared lamp, continuously grinding until ethanol is completely evaporated, and then adding the mixture into N 2 Roasting for 5 hours at 800 ℃ at a heating rate of 5 ℃/min under the atmosphere, cooling to room temperature, washing the activated carbon to be neutral by deionized water, and drying at 60 ℃ overnight in a vacuum drying oven. 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 24 hours, filtering, washing, drying at 60 ℃ overnight in a vacuum drying oven, and then drying in N 2 Roasting for 2 hours at the temperature rising rate of 5 ℃/min and at the temperature of 200 ℃ under the atmosphere to obtain the target catalyst of 30wt% of p-toluenesulfonic acid/AC.
(2) Application of the catalyst:
4.6g of ethanol and 9.0g of acetic acid were weighed out and placed in a reaction kettle, 100.0mg of p-toluenesulfonic acid/AC catalyst prepared by the above method was added, reflux was conducted at 125℃for 40min, then distillation was conducted, and fractions were collected to obtain a crude product of ethyl acetate.
Example 2
(1) Preparation of a carbon supported p-toluenesulfonic acid catalyst:
dissolving 300.0mg of sodium hydroxide in 10.0ml of ethanol solution, slowly dripping onto 1.0g of active carbon at a rate of 4ml/min under an infrared lamp, continuously grinding until ethanol is completely evaporated, and then adding the mixture into N 2 Roasting for 5 hours at 800 ℃ at a heating rate of 5 ℃/min under the atmosphere, cooling to room temperature, washing the activated carbon to be neutral by deionized water, and drying at 60 ℃ overnight in a vacuum drying oven. 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 24 hours, filtering, washing, drying at 60 ℃ overnight in a vacuum drying oven, and then drying in N 2 Roasting for 2 hours at 300 ℃ at a heating rate of 5 ℃/min under the atmosphere to obtain the target catalyst of 30wt% of p-toluenesulfonic acid/AC.
(2) Application of the catalyst:
4.6g of ethanol and 9.0g of acetic acid were weighed out and placed in a reaction kettle, 100.0mg of p-toluenesulfonic acid/AC catalyst prepared by the above method was added, reflux was conducted at 125℃for 40min, then distillation was conducted, and fractions were collected to obtain a crude product of ethyl acetate.
Example 3
(1) Preparation of a carbon supported p-toluenesulfonic acid catalyst:
dissolving 500.0mg sodium hydroxide in 10.0ml ethanol solution, slowly dripping onto 1.0g active carbon at 4ml/min under infrared lamp, grinding until ethanol is completely evaporated, and adding into N 2 Roasting for 5 hours at 800 ℃ at a heating rate of 5 ℃/min under the atmosphere, cooling to room temperature, washing the activated carbon to be neutral by deionized water, and drying at 60 ℃ overnight in a vacuum drying oven. 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 24 hours, filtering, washing, drying at 60 ℃ overnight in a vacuum drying oven, and then drying in N 2 Roasting for 2 hours at 300 ℃ at a heating rate of 5 ℃/min under the atmosphere to obtain the target catalyst of 30wt% of p-toluenesulfonic acid/AC.
(2) Application of the catalyst:
4.6g of ethanol and 9.0g of acetic acid were weighed out and placed in a reaction kettle, 100.0mg of p-toluenesulfonic acid/AC catalyst prepared by the above method was added, reflux was conducted at 125℃for 40min, then distillation was conducted, and fractions were collected to obtain a crude product of ethyl acetate.
Example 4
(1) Preparation of a carbon supported p-toluenesulfonic acid catalyst:
dissolving 300.0mg of sodium hydroxide in 10.0ml of ethanol solution, slowly dripping onto 1.0g of active carbon at a rate of 4ml/min under an infrared lamp, continuously grinding until ethanol is completely evaporated, and then adding the mixture into N 2 Roasting for 5 hours at the temperature rising rate of 5 ℃/min and 1000 ℃ under the atmosphere, washing the activated carbon to be neutral by deionized water after cooling to room temperature, and drying at 60 ℃ overnight in a vacuum drying oven. 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 24 hours, filtering, washing, drying at 60 ℃ overnight in a vacuum drying oven, and then drying in N 2 Roasting for 2 hours at the temperature rising rate of 5 ℃/min and at the temperature of 200 ℃ under the atmosphere to obtain the target catalyst of 30wt% of p-toluenesulfonic acid/AC.
(2) Application of the catalyst:
4.6g of ethanol and 9.0g of acetic acid were weighed out and placed in a reaction kettle, 100.0mg of p-toluenesulfonic acid/AC catalyst prepared by the above method was added, reflux was conducted at 125℃for 40min, then distillation was conducted, and fractions were collected to obtain a crude product of ethyl acetate.
Example 5:
(1) Preparation of a carbon supported p-toluenesulfonic acid catalyst:
dissolving 300.0mg of sodium hydroxide in 10.0ml of ethanol solution, slowly dripping onto 1.0g of active carbon at a rate of 4ml/min under an infrared lamp, continuously grinding until ethanol is completely evaporated, and then adding the mixture into N 2 Roasting for 5 hours at the temperature rising rate of 5 ℃/min and 600 ℃ under the atmosphere, washing the activated carbon to be neutral by deionized water after cooling to room temperature, and drying at 60 ℃ overnight in a vacuum drying oven. Dissolving 300.0mg of p-toluenesulfonic acid in 50ml of deionized water, adding pretreated activated carbon, and performing ultrasonic dispersionUniformly coating 0 with fresh-keeping film, stirring for 24 hr, filtering, washing, vacuum drying at 60deg.C overnight, and drying under N 2 Roasting for 2 hours at the temperature rising rate of 5 ℃/min and at the temperature of 200 ℃ under the atmosphere to obtain the target catalyst of 30wt% of p-toluenesulfonic acid/AC.
(2) Application of the catalyst:
4.6g of ethanol and 9.0g of acetic acid were weighed out and placed in a reaction kettle, 100.0mg of p-toluenesulfonic acid/AC catalyst prepared by the above method was added, reflux was conducted at 125℃for 40min, then distillation was conducted, and fractions were collected to obtain a crude product of ethyl acetate.
Example 6:
(1) Preparation of a carbon supported p-toluenesulfonic acid catalyst:
dissolving 300.0mg of sodium hydroxide in 10.0ml of ethanol solution, slowly dripping onto 1.0g of active carbon at a rate of 4ml/min under an infrared lamp, continuously grinding until ethanol is completely evaporated, and then adding the mixture into N 2 Roasting for 7 hours at 800 ℃ at a heating rate of 5 ℃/min under the atmosphere, washing the activated carbon to be neutral by deionized water after cooling to room temperature, and drying at 60 ℃ overnight in a vacuum drying oven. 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 24 hours, filtering, washing, drying at 60 ℃ overnight in a vacuum drying oven, and then drying in N 2 Roasting for 2 hours at the temperature rising rate of 5 ℃/min and at the temperature of 200 ℃ under the atmosphere to obtain the target catalyst of 10wt% of p-toluenesulfonic acid/AC.
(2) Application of the catalyst:
4.6g of ethanol and 9.0g of acetic acid were weighed out and placed in a reaction kettle, 100.0mg of p-toluenesulfonic acid/AC catalyst prepared by the above method was added, reflux was conducted at 125℃for 40min, then distillation was conducted, and fractions were collected to obtain a crude product of ethyl acetate.
Example 7:
(1) Preparation of a carbon supported p-toluenesulfonic acid catalyst:
dissolving 300.0mg of sodium hydroxide in 10.0ml of ethanol solution, slowly dripping onto 1.0g of active carbon at a rate of 4ml/min under an infrared lamp, and continuously grinding until reaching BThe alcohol is completely evaporated, then in N 2 Roasting for 7 hours at 800 ℃ at a heating rate of 5 ℃/min under the atmosphere, washing the activated carbon to be neutral by deionized water after cooling to room temperature, and drying at 60 ℃ overnight in a vacuum drying oven. 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 12 hours, filtering, washing, drying at 60 ℃ overnight in a vacuum drying oven, and then drying in N 2 Roasting for 4 hours at 300 ℃ at a heating rate of 5 ℃/min under the atmosphere to obtain the target catalyst of 30wt% of p-toluenesulfonic acid/AC.
(2) Application of the catalyst:
4.6g of ethanol and 9.0g of acetic acid were weighed out and placed in a reaction kettle, 100.0mg of p-toluenesulfonic acid/AC catalyst prepared by the above method was added, reflux was conducted at 125℃for 40min, then distillation was conducted, and fractions were collected to obtain a crude product of ethyl acetate.
Example 8:
(1) Preparation of a carbon supported p-toluenesulfonic acid catalyst:
dissolving 300.0mg of sodium hydroxide in 10.0ml of ethanol solution, slowly dripping onto 1.0g of active carbon at a rate of 4ml/min under an infrared lamp, continuously grinding until ethanol is completely evaporated, and then adding the mixture into N 2 Roasting for 7 hours at 800 ℃ at a heating rate of 5 ℃/min under the atmosphere, washing the activated carbon to be neutral by deionized water after cooling to room temperature, and drying at 60 ℃ overnight in a vacuum drying oven. 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 24 hours, filtering, washing, drying at 60 ℃ overnight in a vacuum drying oven, and then drying in N 2 Roasting for 2 hours at the temperature rising rate of 5 ℃/min and at the temperature of 200 ℃ under the atmosphere to obtain the target catalyst of 30wt% of p-toluenesulfonic acid/AC.
(2) Application of the catalyst:
4.6g of ethanol and 9.0g of acetic acid were weighed out and placed in a reaction kettle, 50.0mg of p-toluenesulfonic acid/AC catalyst prepared by the above method was added, reflux was conducted at 125℃for 40min, then distillation was conducted, and fractions were collected to obtain a crude product of ethyl acetate.
Example 9:
(1) Preparation of a carbon supported p-toluenesulfonic acid catalyst:
10.0ml of ethanol solution was slowly added dropwise to 1.0g of activated carbon at 4ml/min under an infrared lamp and continuously ground until the ethanol had evaporated completely, then added under N 2 Roasting for 7 hours at 800 ℃ at a heating rate of 5 ℃/min under the atmosphere, washing the activated carbon to be neutral by deionized water after cooling to room temperature, and drying at 60 ℃ overnight in a vacuum drying oven. 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 24 hours, filtering, washing, drying at 60 ℃ overnight in a vacuum drying oven, and then drying in N 2 Roasting for 2 hours at the temperature rising rate of 5 ℃/min and at the temperature of 200 ℃ under the atmosphere to obtain the target catalyst of 30wt% of p-toluenesulfonic acid/AC.
(2) Application of the catalyst:
4.6g of ethanol and 9.0g of acetic acid were weighed out and placed in a reaction kettle, 300.0mg of p-toluenesulfonic acid/AC catalyst prepared by the above method was added, reflux was conducted at 125℃for 40min, then distillation was conducted, and fractions were collected to obtain a crude product of ethyl acetate.
Example 10:
(1) Preparation of a carbon supported p-toluenesulfonic acid catalyst:
dissolving 300.0mg of sodium hydroxide in 10.0ml of ethanol solution, slowly dripping onto 1.0g of active carbon at a rate of 4ml/min under an infrared lamp, continuously grinding until ethanol is completely evaporated, and then adding the mixture into N 2 Roasting for 7 hours at 800 ℃ at a heating rate of 5 ℃/min under the atmosphere, washing the activated carbon to be neutral by deionized water after cooling to room temperature, and drying at 60 ℃ overnight in a vacuum drying oven. 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 24 hours, filtering, washing, drying at 60 ℃ overnight in a vacuum drying oven, and then drying in N 2 Roasting for 2 hours at 300 ℃ at a heating rate of 5 ℃/min under the atmosphere to obtain the target catalyst of 30wt% of p-toluenesulfonic acid/AC.
(2) Application of the catalyst:
3.2g of methanol and 4.6g of formic acid were weighed out and placed in a reaction kettle, 100.0mg of p-toluenesulfonic acid/AC catalyst prepared by the above method was added, reflux was conducted at 125℃for 40min, then distillation was conducted, and fractions were collected to obtain a crude product of methyl formate.
Example 11
Application of the catalyst:
6.0g of n-propanol and 9.0g of acetic acid were weighed into a reaction vessel, 100.0mg of p-toluenesulfonic acid/AC catalyst prepared by example 10 was added, refluxed at 125℃for 40 minutes, then distilled, and fractions were collected to obtain an n-propyl acetate crude product.
Example 12
Application of the catalyst:
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 prepared by example 10 was added, refluxed at 125℃for 40min, then distilled, and the fraction was collected to obtain isopropyl acetate crude product.
Example 13
4.6g of ethanol and 11.1g of propionic acid were weighed into a reaction vessel, 100.0mg of p-toluenesulfonic acid/AC catalyst prepared by example 10 was added, refluxed at 125℃for 40 minutes, then distilled, and the fraction was collected to obtain a crude ethyl propionate product.
Table 1 catalytic performance of the catalysts of the examples
| Group of | Conversion rate | Yield is good |
| Example 1 | 89.7％ | 87.1％ |
| Example 2 | 93.3％ | 89.6％ |
| Example 3 | 81.9％ | 73.3％ |
| Example 4 | 87.0％ | 87.4％ |
| Example 5 | 80.2％ | 86.1％ |
| Example 6 | 92.4％ | 88.5％ |
| Example 7 | 92.7％ | 88.1％ |
| Example 8 | 92.9％ | 87.9％ |
| Example 9 | 86.4％ | 87.4％ |
| Example 10 | 92.1％ | 91.6％ |
| Example 11 | 92.4％ | 90.6％ |
| Example 12 | 93.8％ | 90.3％ |
| Example 13 | 92.9％ | 89.6％ |
Fig. 1 and 2 are SEM images and element distribution diagrams of the 30wt% p-toluenesulfonic acid/AC catalyst prepared by the above-described method in example 2, and it can be seen from fig. 1 and 2 that the activated carbon surface has no Na element residue, and in addition, p-toluenesulfonic acid was successfully supported on the activated carbon by impregnation, and deviation from theoretical loading was not large. Table 1 shows the p-toluenesulfonic acid/AC catalysts and their catalytic performances prepared under different conditions in examples 1-13. It can be seen that in a certain range, the catalyst activity can be improved to a certain extent by adopting sodium hydroxide to perform reaming treatment on the activated carbon, and when the dosage of the sodium hydroxide is excessive, the surface of the activated carbon is possible to be alkalescent and react with p-toluenesulfonic acid loaded later, so that the catalyst activity is reduced. Changing the preparation conditions of the catalyst finds that the calcination temperature has a great influence on the activity of the catalyst, and when the calcination temperature is 800 ℃, the optimal effect can be achieved, which is probably due to the fact that when the temperature is too low, the hole expanding effect is not obvious, and when the calcination temperature is too high, the pore channels of the activated carbon collapse, and the specific surface area of the activated carbon is reduced. The loading capacity, stirring time and the adding amount during the reaction of the p-toluenesulfonic acid have great influence on the activity of the catalyst, and the larger the loading capacity and the longer the stirring time of the p-toluenesulfonic acid are, the higher the activity of the catalyst is. In addition, the catalyst has good catalytic activity when synthesizing the carboxylic ester compound with low molecular weight.
Claims (5)
1. The preparation method of the carbon-supported p-toluenesulfonic acid catalyst is characterized by comprising the following steps of:
1) Slowly dripping ethanol solution of sodium hydroxide onto active carbon under infrared lamp, and physically grinding until ethanol is completely evaporated, and then adding water to the mixture under N 2 Roasting in atmosphere, and reaming the activated carbon;
2) Washing the reamed active carbon in the step 1) to be neutral by deionized water, filtering and placing in a vacuum drying oven for activation treatment;
3) Adding activated carbon into p-toluenesulfonic acid solution, ultrasonic dispersing, stirring for 10-24 hr, filtering, washing, vacuum drying in a vacuum drying oven, and adding N 2 Roasting in the atmosphere to obtain a carbon-supported p-toluenesulfonic acid catalyst;
the loading amount of the p-toluenesulfonic acid of the carbon-loaded p-toluenesulfonic acid catalyst is 5-30wt%;
the ratio of the addition amount of sodium hydroxide to the mass of the activated carbon in the step 1) is 300mg:1g;
activated carbon in step 1) under N 2 Roasting under atmosphere, wherein the temperature rising rate of 5 ℃/min is increased to 800 ℃, and roasting is performed for 5-7 h.
2. The process according to claim 1, wherein in step 3) N 2 And (3) when roasting is carried out under the atmosphere, the temperature rising rate of 5 ℃/min is increased to 200-300 ℃, and roasting is carried out for 2-5 h.
3. The method according to claim 1, wherein the dropping speed of the ethanol solution of sodium hydroxide in step 1) is 3ml/min to 5ml/min.
4. A carbon-supported p-toluenesulfonic acid catalyst prepared by the preparation process according to claim 1.
5. Use of a carbon supported p-toluenesulfonic acid catalyst as claimed in claim 4 in the synthesis of lower lipids including methyl formate, methyl acetate, ethyl acetate, propyl acetate, n-propyl acetate, isopropyl acetate and ethyl propionate.
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