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 PDFInfo
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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
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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 146
- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 104
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 80
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 57
- 238000001035 drying Methods 0.000 claims abstract description 32
- 238000001291 vacuum drying Methods 0.000 claims abstract description 26
- 238000005406 washing Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 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 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000011068 loading method Methods 0.000 claims abstract description 7
- 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 19
- 230000007935 neutral effect Effects 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 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
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 4
- 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
- 150000002632 lipids Chemical class 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 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
- 230000000630 rising effect Effects 0.000 claims 1
- 238000001132 ultrasonic dispersion Methods 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 8
- 230000002378 acidificating effect Effects 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 230000003213 activating effect Effects 0.000 abstract description 2
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 39
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000001816 cooling Methods 0.000 description 10
- 239000003755 preservative agent Substances 0.000 description 10
- 230000002335 preservative effect Effects 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000012043 crude product Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 238000004821 distillation Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- -1 carboxylic ester compound Chemical class 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000686 essence Substances 0.000 description 4
- 239000000047 product Substances 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
- 239000003814 drug Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 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
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 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
- 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
- 238000005303 weighing Methods 0.000 description 2
- VTSWSQGDJQFXHB-UHFFFAOYSA-N 2,4,6-trichloro-5-methylpyrimidine Chemical compound CC1=C(Cl)N=C(Cl)N=C1Cl VTSWSQGDJQFXHB-UHFFFAOYSA-N 0.000 description 1
- YLZYSVYZMDJYOT-UHFFFAOYSA-N 2-methoxypyrimidine Chemical compound COC1=NC=CC=N1 YLZYSVYZMDJYOT-UHFFFAOYSA-N 0.000 description 1
- 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
- 240000007436 Cananga odorata Species 0.000 description 1
- 235000007571 Cananga odorata Nutrition 0.000 description 1
- 241000446281 Eschenbachia blinii Species 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
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 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
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- 235000011869 dried fruits Nutrition 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003480 eluent 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
- 239000002808 molecular sieve Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002304 perfume 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
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 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
- 235000013599 spices Nutrition 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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
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
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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