CN109046381B - Sulfur-carbon based solid acid catalyst - Google Patents
Sulfur-carbon based solid acid catalyst Download PDFInfo
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- 239000011973 solid acid Substances 0.000 title claims abstract description 89
- 239000003054 catalyst Substances 0.000 title claims abstract description 79
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- 229910052799 carbon Inorganic materials 0.000 claims abstract description 59
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 56
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
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- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
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- 241000282414 Homo sapiens Species 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QTJOIXXDCCFVFV-UHFFFAOYSA-N [Li].[O] Chemical compound [Li].[O] QTJOIXXDCCFVFV-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
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- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
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- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical group OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
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- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K1/00—Glucose; Glucose-containing syrups
- C13K1/02—Glucose; Glucose-containing syrups obtained by saccharification of cellulosic materials
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- Emergency Medicine (AREA)
- General Health & Medical Sciences (AREA)
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Abstract
A sulfur-carbon based solid acid catalyst which is loaded with acidic group-SO3H, -COOH and phenol-OH, and further through bridge bonds-O-, -CH2-S-S-linkage constitutes a sulfur-carbon material. The solid acid catalyst has high sulfur content, exists on the aromatic carbon sheet layer in diversified forms, has a more regular and ordered structure, obviously increases the specific surface area and the pore volume, and has excellent catalytic activity and cycling stability.
Description
Technical Field
The invention relates to a sulfur-carbon based solid acid catalyst, in particular to a carbon based solid acid catalyst in a polysulfide form.
Background
Acid catalytic reaction is always an important catalytic reaction type in chemical industry, the traditional acid catalyst is liquid acid such as sulfuric acid, hydrofluoric acid and the like, the catalytic activity of the liquid acid is good, but a series of problems occur in the using process; for example, the catalyst has strong corrosion to equipment, is difficult to separate from a reaction system, is difficult to recycle, is easy to generate a large amount of industrial wastewater to pollute the environment, and the like, people are forced to search for a more excellent catalyst which meets the value requirements of human beings, and thus the solid acid catalyst is produced at the same time.
The solid acid catalyst perfectly overcomes various defects of the acid catalyst, and the currently known solid acid catalysts have the defects; metal oxides, metal sulfates, metal phosphates, zeolites, carbon-based solid acids, and the like, wherein the carbon-based solid acids are gradually paid attention to because of the advantages of wide raw material sources, controllable acid amount, containing hydrophilic groups such as hydroxyl, sulfonic acid group, carboxyl, and the like.
A carbon-based solid acid which is prepared by loading an acid group-SO3H, -COOH and phenol-OH with the aliphatic side chain-CH3, -OCH3The aromatic carbon sheets are connected by a bridge bond-O-, -CH2A carbon material in which the sulfonic acid groups are present in the sole form of sulfur (M Hara et al, Angewandte Chemie International Edition, 2004, 43 (22): 2955-2958).
Many studies on carbon-based solid acids are carried out, and people beginning to research on preparation of carbon-based solid acids only focus on selection of different carbon sources to prepare the carbon-based solid acids, wherein the selection of the carbon sources mainly comprises saccharides, substances containing benzene rings or condensed ring carbon sheet layers and biomass.
For example, CN101249447B is prepared by selecting starch or soluble sugar as carbon source, using porous high temperature resistant medium as carrier, adding soluble sugar or starch solution, evaporating to dryness several times, igniting, washing with water, oven drying, reacting with concentrated sulfuric acid, washing with hot water to neutrality, filtering, and drying.
CN102069001B, the coking phenol slag is taken as raw material, the coking phenol slag is heated to 400 ℃ and 600 ℃ for carbonization for 1-13h under the protective atmosphere to obtain carbon carrier, the carbon carrier is crushed and added with sulfonating agent, the mixture is sulfonated for 0.01-13h at the temperature of 20-160 ℃ to obtain mixture, and then the mixture is filtered, washed by hot water and dried to obtain the carbon-based solid acid catalyst.
CN104624206B, taking alkali lignin as a main raw material, stirring and dissolving the alkali lignin, alkali and water according to a certain mass ratio at room temperature, adding epoxy chloropropane with a certain mass, stirring for a certain time, obtaining lignin gel at a proper temperature, soaking the lignin gel in a hydrochloric acid aqueous solution, washing the lignin gel to be neutral, and performing vacuum drying to obtain lignin xerogel; carbonizing the dried gel at a certain temperature, sulfonating and washing the dried gel with a sulfonating agent to be neutral, and drying in vacuum to obtain the carbon-based solid acid catalyst.
In recent years, heteroatom doping of carbon-based solid acids has become one of new directions for carbon-based solid acid research, and carbon materials doped with heteroatoms often have more new groups and characteristics. For example, CN103691483B introduces chlorine atoms into carbon-based solid acid during the preparation of carbon-based solid acid, and a carbon-based solid acid catalyst containing chlorine is prepared, for example, CN 103071476A introduces titanium atoms into a carbon support, which can significantly improve the specific surface area and catalytic performance of the catalyst; for example, CN105358481B introduces boron atoms into the carbon carrier, which can remarkably improve the catalytic activity and stability of the catalyst; for example, CN 104923296A uses a nitrogen-doped mesoporous carbon material as a carrier, introduces magnetic ferroferric oxide particles by a dipping and roasting method, and introduces perfluorosulfonic acid groups to the surface of the magnetic ferroferric oxide particles by a liquid phase deposition method; for example, CN 102078823B is prepared by soaking metal oxide in organic solution, evaporating to dryness to obtain carbon-oxide compound, carbonizing the carbon-oxide compound to obtain carbon carrier, and sulfonating to obtain carbon-based solid acid catalyst (Ti/Al/Si) containing metal.
The sulfur-doped porous carbon has attracted wide attention in the last years, and is proved to be a multifunctional functional material with wide potential application space, including heterogeneous catalysis, adsorption and energy conversion and storage fields, the application of sulfur-doped carbon materials is mainly focused on electrochemistry aspects, such as redox reaction, lithium ion batteries, lithium oxygen battery cathodes, electrodes for super capacitors and the like, research results show that S doping improves the catalytic performance, sulfur in thiophene (-C-S-C-) configuration may be active sites for promoting the redox reaction, but research is not carried out at present, carbon materials after sulfur doping are used as carriers, and acidic groups such as sulfonated loaded sulfonic groups are used for preparing carbon-based solid acid.
Disclosure of Invention
The invention obtains a novel sulfur-carbon based solid acid catalyst by sulfonating a sulfur-containing carbon material, so as to improve the hydrolysis activity, esterification activity and reutilization property of cellulose catalyzed by the carbon-based solid acid catalyst, and provides the sulfur-carbon based solid acid catalyst.
The technical scheme adopted by the invention for solving the problems is as follows.
A sulfur-carbon based solid acid catalyst, which is characterized in that: the sulfur-carbon based solid acid is loaded with an acid group-SO3Sulfur-containing aromatic carbon sheet layers of H, -COOH and phenol-OH, said carbon sheet layers being further bonded to each other via a bridge-O-, -CH2-S-is linked to form a sulfur-carbon material;
wherein: removing sulfonic acid group-SO in the form of sulfur3And in addition to H, one or more of thiophene C-S-C, sulfone O = S = O, sulfoxide S = O and disulfide bond-S-S-.
The additional technical scheme is as follows.
A sulfur-carbon based solid acid catalyst, which is characterized in that: the sulfur content of the sulfur-carbon-based solid acid catalyst is 1-60% by mass.
A sulfur-carbon based solid acid catalyst, which is characterized in that: the content of total acid in the sulfur-carbon based solid acid catalyst is 2-6 mmol/g.
A sulfur-carbon based solid acid catalyst, which is characterized in that: the preparation method of the sulfur-carbon based solid acid catalyst comprises the steps of firstly, uniformly mixing a sulfur source and a carbon source according to the mass ratio of 1: 20-10: 1, then, co-carbonizing to prepare a carbon carrier, and then, sulfonating by using a sulfonating agent; after cooling to room temperature, repeatedly washing with distilled water until the filtrate has no sulfate radical; and finally, drying the filter residue, taking out the filter residue, and grinding and sieving the obtained black solid to obtain the sulfur-carbon based solid acid catalyst.
A sulfur-carbon based solid acid catalyst, which is characterized in that: the carbon source is one or more of glucose, cellulose and starch.
A sulfur-carbon based solid acid catalyst, which is characterized in that: the sulfur source is one of sulfur, sodium thiosulfate and 4, 4-thiodiphenol.
A sulfur-carbon based solid acid catalyst, which is characterized in that: the sulfur-carbon based solid acid catalyst is used for catalyzing one of cellulose hydrolysis reaction and esterification reaction.
By implementing the technical scheme, compared with the cellulose-based carbon-based solid acid catalyst, the sulfur-carbon-based solid acid catalyst has the 002 peak corresponding to the 002 peak2θCorner (2θ 002 ) Increase of interlayer spacingd 002 And aromatic carbon sheet diameterL a Reduced, yet stacking heightL c And degree of aromaticityf a The sulfur-carbon-based solid acid is increased, so that compared with the carbon-based solid acid prepared by the same method, the sulfur-carbon-based solid acid has a more regular structure and better stability, and the catalytic hydrolysis and esterification activities are reduced by only 10% after three times of circulation; meanwhile, the sulfur-carbon based solid acid catalyst has a micropore and mesoporous structure, the specific surface area is further enlarged, the adsorption performance is further improved, and the performance of catalyzing cellulose hydrolysis at 150 ℃, 6h and esterification 70 ℃ and 2h is improved by 30-40%.
Drawings
FIG. 1 is a chart of experiments conducted in examples 5 to 7 of the present invention.
FIG. 2 is a table showing the experiments in examples 11 to 13 of the present invention.
FIG. 3 is a schematic diagram of the structure of a sulfur-carbon based solid acid catalyst of the present invention.
Fig. 4 is an infrared spectrum of the sulfur-carbon based solid acid catalyst of the present invention, which shows that the sulfur-carbon based solid acid catalyst possesses a different sulfur existing form from the conventional carbon based solid acid catalyst.
Fig. 5 is an XRD chart of the sulfur-carbon based solid acid catalyst, which shows that the structure of the sulfur-carbon based solid acid catalyst is more regular.
FIG. 6 is an XPS peak profile of the sulfur-based solid acid catalyst showing the presence of sulfur in the sulfur-based solid acid catalyst.
Detailed Description
The following further describes embodiments of the present invention.
A sulfur-carbon based solid acid catalyst is prepared by mixing a carbon source and a sulfur source uniformly according to a certain proportion and then carbonizing, wherein the carbonization process is set to be two-stage, and the first stage is heated from room temperature to a certain temperature of 300-460 ℃ at a heating rate of 3 DEG/min; and a second stage: and standing at the temperature for 3-6 h for carbonization, taking out after the carbonization is finished, cooling to room temperature, grinding and sieving to obtain black solid, namely the sulfur-containing carbon carrier.
Adding concentrated sulfuric acid and the sulfur-containing carbon carrier at a ratio of 20 mL: 1 g in an oil bath at 150 deg.C for 6h, sulfonating, cooling to room temperature, vacuum filtering, and repeatedly washing with boiling distilled water until no SO is detected4 2-And stopping suction filtration, and finally drying the filter residue at 80 ℃ for 12h to obtain the sulfur-carbon based solid acid catalyst.
The obtained sulfur-carbon based solid acid catalyst is characterized in that an acid group-SO is loaded3Sulfur-containing aromatic carbon sheet layers of H, -COOH and phenol-OH, said carbon sheet layers being further bonded to each other via a bridge-O-, -CH2-S-S-linkage constitutes a sulfur-carbon material.
Wherein: the sulfur is present in the form of desulfonation-SO3H is one or more of thiophene C-S-C, sulfone O = S = O, sulfoxide S = O and disulfide bond-S-S-; wherein the mass content of sulfur is 1-60%. The structure schematic diagram of the prepared sulfur-carbon based solid acid catalyst is shown in figure 3, the infrared spectrum of the catalyst is shown in figure 4, the XRD spectrum is shown in figure 5, and the existence form of sulfur is shown in figure 6.
Specific embodiments of the present invention are further illustrated by the following examples.
Example 1
Preparation of sulfur-carbon based solid acid catalyst
Taking a certain amount of cellulose and sodium thiosulfate, mixing and carbonizing according to the ratio of 1: 1, wherein the carbonization process is set to be two-stage, the first stage is: heating from room temperature to 440 ℃ at a heating rate of 3 ℃/min; and a second stage: staying at 440 ℃ for 8h, taking out after the carbonization process is finished, cooling to room temperature, grinding and sieving to obtain black solid, namely the carbon carrier; keeping concentrated sulfuric acid and a sulfur-containing carbon carrier at a ratio of 20mL to 1 g at 150 ℃ for 6h for sulfonation, taking out, cooling to room temperature, performing suction filtration, and repeatedly washing with boiled distilled water until the filtrate is free of sulfate radicals; and finally drying the filter residue at 80 ℃ for 12h, and taking out the obtained black solid, namely the sulfur-carbon based solid acid catalyst.
After XPS scanning and peak separation of S2 p, the sulfur content is 17.28 percent, and the sulfur content is SO3The results of H3.78%, O = S = O1.80%, S = O1.71%, C-S-C6.84%, S-S3.15% indicate that most of the sulfur is present in the aromatic carbon sheet layer.
The specific surface area was measured by a specific surface analyzer, and as a result, it was found that the specific surface area of the sulfur-carbon-based solid acid catalyst was doubled as compared with that of the carbon support.
Example 2
Sulfur-carbon based solid acid catalyst
Uniformly mixing glucose and sulfur according to a certain mass ratio of 1: 1, and then carbonizing; then sulfonating, washing and drying to obtain the sulfur-carbon based solid acid catalyst.
After XPS scanning and peak separation of S2 p, the sulfur content is 34.28 percent, and the sulfur contents are respectively SO3The results of H1.86%, O = S = O0%, S = O2.58%, C-S-C18.78%, S-S11.06% indicated that most of the sulfur was present in the aromatic carbon sheet layer.
Example 3
Uniformly mixing starch and sodium thiosulfate according to a certain mass ratio of 1: 7, and then carbonizing; then sulfonating, washing and drying to obtain the sulfur-carbon based solid acid catalyst.
After XPS scanning and peak separation of S2 p, the sulfur content is 55.86%, and the sulfur contents are SO respectively3The results of H3.54%, O = S = O7.21%, S = O10.13%, C-S-C21.48%, S-S13.50% indicate that most of the sulfur is present in the aromatic carbon sheet layer.
Example 4
Hydrolyzed cellulose
Preparation of sulfur-carbon based solid acid catalyst: uniformly mixing cellulose and sodium thiosulfate according to a certain mass ratio of 1: 1, and then carbonizing; then sulfonating, washing and drying to obtain the sulfur-carbon based solid acid catalyst.
After XPS scanning and peak separation of S2 p, the sulfur content is 17.28 percent, and the sulfur content is SO3H3.78%, O = S = O1.80%, S = O1.71%,the results, C-S-C6.84%, with S-S accounting for 3.15%, indicate that most of the sulfur is present in the aromatic carbon sheet.
The catalytic hydrolysis reaction effect is as follows: mixing a certain amount of cellulose and a sulfur-carbon based solid acid catalyst, placing the mixture into a reaction kettle, adding a certain amount of distilled water, and hydrolyzing at 150 ℃ for 6 hours to obtain the reducing sugar with the yield of 76.89% according to a test.
Examples 5 to 7
The results of the cycle number effect on the catalytic cellulose hydrolysis reaction after recovery of the catalyst of example 4 are shown in FIG. 1, except that the following differences are used.
The influence of the recycling times of the catalyst on the hydrolysis reaction effect of the cellulose.
Example 8
Catalytic esterification
Preparation of sulfur-carbon based solid acid catalyst: uniformly mixing cellulose and 4, 4-thiodiphenol according to a certain mass ratio of 2: 1, and carbonizing; then sulfonating, washing and drying to obtain the sulfur-carbon based solid acid catalyst.
After XPS scanning and peak separation of S2 p, the sulfur content is 7.82 percent, and the sulfur content is SO3The results of H1.41%, O = S = O0.82%, S = O0.43%, C-S-C2.23%, S-S2.93% indicate that most of the sulfur is present in the aromatic carbon sheet layer.
The esterification reaction effect is as follows: 0.2g of sulfur-carbon based solid acid and 5 g of oleic acid are weighed in a single-neck flask and reacted in a water bath kettle at the temperature of 70 ℃ for 2 hours, and the esterification rate is calculated to be 63.85 percent.
Example 9
Catalytic esterification
Preparation of sulfur-carbon based solid acid catalyst: uniformly mixing cellulose and sodium thiosulfate according to a certain mass ratio of 1: 1, and then carbonizing; then sulfonating, washing and drying to obtain the sulfur-carbon based solid acid catalyst.
After XPS scanning and peak separation of S2 p, the sulfur content is 17.28 percent, and the sulfur content is SO3The results of H3.78%, O = S = O1.80%, S = O1.71%, C-S-C6.84%, S-S3.15% indicate that most of the sulfur is present in the aromatic hydrocarbonIn the fragrant carbon sheet layer.
The esterification reaction effect is as follows: 0.2g of sulfur-carbon based solid acid and 5 g of oleic acid are weighed in a single-neck flask and reacted in a water bath kettle at the temperature of 70 ℃ for 2 hours, and the esterification rate is calculated to be 72.17 percent.
Example 10
Catalytic esterification
Preparation of sulfur-carbon based solid acid catalyst: the cellulose and sodium thiosulfate are evenly mixed according to a certain mass ratio of 1: 2 and then carbonized. Then sulfonating, washing and drying to obtain the sulfur-carbon based solid acid catalyst.
After XPS scans S2 p to separate peaks, the sulfur content is 21.92 percent, and the contents of various kinds of sulfur are SO respectively3The results of H3.11%, O = S = O1.74%, S = O2.40%, C-S-C8.26%, S-S6.41% indicate that most of the sulfur is present in the aromatic carbon sheet layer.
The esterification reaction effect is as follows: 0.2g of sulfur-carbon based solid acid and 5 g of oleic acid are weighed in a single-neck flask and reacted for 2 hours in a water bath kettle at the temperature of 70 ℃, and the esterification rate is calculated to be 71.94 percent.
Examples 11 to 13
The catalyst of example 10 was recovered and the results of the number of cycles affecting the catalytic esterification reaction are shown in FIG. 2, except that the following differences were used.
The influence of the recycling times of the catalyst on the catalytic esterification reaction effect.
Claims (7)
1. A sulfur-carbon based solid acid catalyst, which is characterized in that: the sulfur-carbon based solid acid is loaded with an acid group-SO3Sulfur-containing aromatic carbon sheet layers of H, -COOH and phenol-OH, said carbon sheet layers being further bonded to each other via a bridge-O-, -CH2-S-is linked to form a sulfur-carbon material;
wherein: removing sulfonic acid group-SO in the form of sulfur3And in addition to H, one or more of thiophene C-S-C, sulfone O = S = O, sulfoxide S = O and disulfide bond-S-S-.
2. The sulfur-carbon based solid acid catalyst according to claim 1, wherein: the sulfur content of the sulfur-carbon-based solid acid catalyst is 1-60% by mass.
3. The sulfur-carbon based solid acid catalyst according to claim 1, wherein: the content of total acid in the sulfur-carbon based solid acid catalyst is 2-6 mmol/g.
4. The sulfur-carbon based solid acid catalyst according to claim 1, wherein: the preparation method of the sulfur-carbon based solid acid catalyst comprises the steps of firstly, uniformly mixing a sulfur source and a carbon source according to the mass ratio of 1: 20-10: 1, then, co-carbonizing to prepare a carbon carrier, and then, sulfonating by using a sulfonating agent; after cooling to room temperature, repeatedly washing with distilled water until the filtrate has no sulfate radical; and finally, drying the filter residue, taking out the filter residue, and grinding and sieving the obtained black solid to obtain the sulfur-carbon based solid acid catalyst.
5. The sulfur-carbon based solid acid catalyst according to claim 4, wherein: the carbon source is one or a mixture of more of any carbon-containing substances such as glucose, cellulose and starch.
6. The sulfur-carbon based solid acid catalyst according to claim 4, wherein the sulfur source is one of sulfur, sodium thiosulfate and 4, 4-thiodiphenol.
7. The sulfur-carbon based solid acid catalyst according to claim 4, wherein: the sulfur-carbon based solid acid catalyst is used for catalyzing one of cellulose hydrolysis reaction and esterification reaction.
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