CN109289870B - Sulfonated carbon and preparation method and application thereof - Google Patents
Sulfonated carbon and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to sulfonated carbon and a preparation method and application thereof, wherein the preparation method comprises the following steps of 1, preparing carbohydrate acidolysis by-products by acidolysis of carbohydrates with sulfuric acid; step 2, cracking the carbohydrate acidolysis by-products at high temperature under the inert gas atmosphere to obtain high-temperature carbide: and 3, sulfonating the high-temperature carbide by using a sulfonating agent to obtain sulfonated carbon. The application of sulfonated carbon in catalyzing esterification reaction of levulinic acid and n-butyl alcohol, wherein the molar ratio of the levulinic acid to the butyl alcohol is 1: (3-6), reacting for 4 hours at 80-120 ℃ with the mass ratio of the sulfonated carbon to the levulinic acid being 10-40%. The amorphous sulfonated carbon obtained by the preparation method of the invention improves the catalytic reaction effect of the sulfonated carbon during the catalytic reaction, is easy to separate and can be used for multiple times, plays a perfect role in the comprehensive utilization of resources and the comprehensive utilization of biomass, and improves the added value of the acidolysis carbohydrate solid waste.
Description
Technical Field
The invention relates to the technical field of preparation of solid acid catalysts, in particular to a solid acid catalyst prepared by hydrolyzing wastes generated by carbohydrates through acid, and specifically relates to sulfonated carbon and a preparation method and application thereof.
Background
With the continuous consumption of fossil resources and the need for environmental protection, the development and utilization of renewable energy sources are receiving more and more attention, and lignocellulose is one of the most abundant biomass resources. The lignocellulose can be converted into small molecular platform compounds such as saccharides and furans by chemical catalysis. In this process, acid hydrolysis is the first step of breaking the structure of the lignocellulose and reducing its degree of polymerization. Lignocellulose can be hydrolyzed into cellulose and hemicellulose through acid catalysis, the cellulose and the hemicellulose are continuously hydrolyzed into carbohydrates such as hexose and pentose through acid catalysis, the hexose comprises glucose, fructose and the like, and the pentose comprises xylose and the like. Further acid-catalyzed dehydration of hexoses will form 5-hydroxymethylfurfural and levulinic acid, while further acid-catalyzed dehydration of pentoses will form furfural. However, lignocellulose produces a large amount of solid insoluble residues during the acid hydrolysis process, especially during the carbohydrate acid hydrolysis process. The yield of the by-product is influenced by various factors such as raw materials, catalysts, reaction media, process parameters and the like, and can reach 30-40% at most.
Therefore, it is necessary to reuse the solid by-products from the acid hydrolysis of carbohydrates, so that the biomass can be fully utilized in the biorefinery process, and the concept of green chemistry can be met. In the past utilization, most of solid byproducts for carbohydrate acidolysis stay in low-added-value applications such as combustion heat and field recovery, and some researchers try to perform value-added utilization on the solid byproducts, which are also called artificial humus, for example, researchers use artificial humus solution to perform impregnation modification on furfural resin to prepare composite Materials for the Building industry, and the composite Materials are specifically published in articles such as "a.mija et al/Construction and Building Materials 139(2017) 594-; artificial humus is also adopted as a phenol substitute, and a modified phenolic adhesive is synthesized by a two-step method, so that the research results are shown in Polymers 2017,9 and 373; 10.3390/polym9080373 "; in addition, although there are some published articles for preparing Carbon Quantum Dots by artificial humus post-treatment, such as "YanRu Zhang, Ning Gao, PBM. huntin-based Carbon Quantum Dots [ J ], No.2,2018", etc., no report has been made on the use of an acid hydrolysis carbohydrate solid by-product as a precursor of a solid acid catalyst for preparing a solid acid catalyst and catalyzing the same.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides sulfonated carbon and a preparation method and application thereof, which have the advantages of low cost, simple preparation process, environmental protection, easy separation and high added value, and improve the added value of lignocellulose acid hydrolysis solid waste.
The invention is realized by the following technical scheme:
a preparation method of sulfonated carbon comprises the following steps:
step 1, preparing carbohydrate acidolysis byproducts;
mixing carbohydrate, sulfuric acid and deionized water, heating to 180-240 ℃ for reaction for 0.5-24h, performing suction filtration washing after the temperature of the obtained mixed solution is reduced to room temperature until the pH value of the filtrate is 7, drying a filter cake obtained by performing suction filtration washing on the mixed solution at 80-105 ℃ for 5-14h, and grinding to obtain a carbohydrate acidolysis byproduct;
step 2, pyrolysis of carbohydrate acidolysis byproducts;
heating the carbohydrate acidolysis by-product obtained in the step 1 to 350-500 ℃ in an inert gas atmosphere for cracking for 4-8h to obtain a high-temperature carbide;
step 3, sulfonating the high-temperature carbide;
mixing the high-temperature carbide obtained in the step 2 with a sulfonating agent according to the weight ratio of 1 g: (10-30) ml, mixing, sulfonating for 10-24h at the temperature of 120-150 ℃, filtering and washing after the temperature of the mixture is reduced to room temperature until the pH value of the filtrate is 7, and drying a filter cake obtained by filtering and washing the mixture for 5-14h at the temperature of 80-105 ℃ to obtain sulfonated carbon.
Preferably, the carbohydrate in step 1 is glucose, fructose, xylose, sucrose or cellulose.
Preferably, the inert gas in step 2 is N2And the flow rate is 200-300 mL/min.
Preferably, the sulfonating agent in step 3 is concentrated sulfuric acid, fuming sulfuric acid or chlorosulfonic acid.
Preferably, the concentration of the carbohydrate in step 1 is 1-2 mol/L.
Preferably, the concentration of the sulfuric acid in the step 1 is 0.01-0.1 mol/L.
Preferably, the reaction described in step 1 is carried out under stirring at a stirring rate of 200-400 rpm.
A sulfonated carbon prepared by the method of any one of the preceding claims.
The application of sulfonated carbon in catalyzing esterification reaction of levulinic acid and n-butyl alcohol, wherein the molar ratio of the levulinic acid to the butyl alcohol is 1: (3-6), reacting for 4 hours at 80-120 ℃ with the mass ratio of the sulfonated carbon to the levulinic acid being 10-40%.
Further, the reaction was carried out under magnetic stirring at a stirring rate of 100 and 200 rpm.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention relates to a preparation method of sulfonated carbon, which is characterized in that the selected raw material is solid waste after carbohydrate acidolysis, after being acidified by sulfuric acid, the solid waste is filtered, washed and filtered until the pH value of the filtrate is 7, so that interfering substances in carbohydrate acidolysis byproducts are removed, and pure carbide is obtained during pyrolysis; after the sulfonation reaction is finished, the mixture is filtered, washed and filtered until the pH value of the filtrate is 7, so that the interference is eliminated, and finally, the pure and amorphous sulfonated carbon is obtained by drying, and the amorphous sulfonated carbon is beneficial to fully contacting with reactants during the catalysis reaction so as to improve the catalysis reaction effect of the sulfonated carbon. The method of the invention plays a perfect role in the comprehensive utilization of resources and the comprehensive utilization of biomass, and improves the added value of the acidolysis carbohydrate solid waste aiming at low-grade treatment modes such as combustion heat and field returning of the acidolysis carbohydrate solid waste. The technical scheme of the invention has the advantages of low cost, simple operation, high catalysis efficiency of the obtained sulfonated carbon, environmental protection and suitability for industrial production.
The sulfonated carbon is applied to catalyzing esterification reaction of levulinic acid and n-butyl alcohol, the sulfonated carbon is used for catalyzing esterification reaction of the levulinic acid and the n-butyl alcohol, the yield of the prepared butyl levulinate can reach 84-99%, the sulfonated carbon is low in cost, easy to separate and capable of being used for multiple times, and the added value of lignocellulose acid hydrolysis solid waste is improved.
Drawings
FIG. 1 is an SEM image of a glucose acidolysis by-product as described in example 1 of the present invention.
FIG. 2 is an SEM photograph of the high temperature carbide of example 1 of the present invention.
FIG. 3 is an SEM image of sulfonated carbon as described in example 1 of the present invention.
FIG. 4a is a schematic representation of the acidolysis by-product of glucose as described in example 1 of the present invention.
FIG. 4b is a schematic diagram of a high temperature carbide according to example 1 of the present invention.
FIG. 4c is a pictorial representation of sulfonated carbon, according to example 1 of the present invention.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The invention aims to solve the problem of low-grade utilization of the solid byproduct of acid hydrolysis of carbohydrate, and provides sulfonated carbon which is prepared by taking the solid byproduct generated by acid hydrolysis of carbohydrate as a raw material, has low cost, simple preparation process, environmental protection, easy separation and high added value, and a preparation method and application thereof.
The invention relates to a method for preparing sulfonated carbon by using carbohydrate acidolysis byproducts and application thereof, wherein the sulfonated carbon is prepared by taking a brownish black solid byproduct generated in the process of preparing platform compounds such as 5-hydroxymethylfurfural, levulinic acid, furfuryl alcohol and the like by acid hydrolysis of cellulose and hemicellulose as a precursor, and the sulfonated carbon is used for catalyzing esterification reaction of levulinic acid and n-butyl alcohol to prepare butyl levulinate.
The carbohydrate acid hydrolysis byproduct is named as artificial humus, and the method for preparing the sulfonated carbon comprises the following steps: step 1, preparation of carbohydrate acidolysis by-products: adding carbohydrate, dilute sulfuric acid and deionized water into a hydrothermal kettle, heating to a certain temperature, stirring for a period of time, reacting, after the reaction is stopped, cooling the mixed solution to room temperature, performing suction filtration and washing, drying a filter cake, and grinding to obtain a carbohydrate acidolysis byproduct; step 2, pyrolysis of carbohydrate acidolysis byproducts: the carbohydrate acidolysis by-products are placed in a tube furnace and flowed N2Heating to a certain temperature in the atmosphere to crack for a period of time to obtain black carbide; and 3, sulfonation of the carbide: mixing the black carbide obtained in the step 2 with a sulfonating agent according to a certain proportion, sulfonating at a certain temperature for a certain time, filtering, washing and re-filtering the reacted mixtureDrying to obtain the solid acid catalyst sulfonated carbon.
The application of preparing butyl levulinate by catalyzing esterification reaction of levulinic acid and n-butanol by using sulfonated carbon comprises the following two steps: firstly, putting sulfonated carbon, levulinic acid and n-butyl alcohol into a reaction kettle for reaction under the condition of stirring; and step two, after the reaction is finished, cooling the mixed system to room temperature, filtering and separating sulfonated carbon and the solution obtained after the reaction, thereby obtaining the butyl levulinate. The sulfonated carbon obtained by post-treating the solid waste generated in the acid hydrolysis process of the lignocellulose by a simple and feasible method is used for catalyzing levulinic acid and n-butyl alcohol, the yield of the prepared butyl levulinate can reach 84-99 percent, and the catalyst sulfonated carbon has low cost, is easy to separate and can be used for multiple times, thereby improving the additional value of the solid waste of the acid hydrolysis of the lignocellulose.
Specifically, the preparation method of the sulfonated carbon comprises the following steps:
step 1, preparing carbohydrate acidolysis byproducts;
adding carbohydrate, dilute sulfuric acid and deionized water into a hydrothermal kettle, heating to 180-240 ℃, stirring for 0.5-24h, after the reaction is stopped, cooling the temperature of the mixed solution to room temperature, adding deionized water, performing suction filtration to wash soluble interfering substances in the carbohydrate acidolysis by-products, performing suction filtration and washing alternately and repeatedly by using boiling deionized water and absolute ethyl alcohol until the pH value of the filtrate is 7, so as to remove sulfuric acid and organic residues in the pore structure of the carbohydrate acidolysis by-products, drying the obtained filter cake for 5-14h at 80-105 ℃, and grinding after drying to obtain the carbohydrate acidolysis by-products;
step 2, pyrolysis of carbohydrate acidolysis byproducts;
putting the carbohydrate acidolysis by-product obtained in the step 1 into a tube furnace and flowing N2Heating to 350-500 ℃ in the atmosphere, and cracking for 4-8h to obtain high-temperature carbide;
step 3, sulfonating the high-temperature carbide;
mixing the high-temperature carbide obtained in the step 2 with a sulfonating agent according to the weight ratio of 1 g: (10-30) ml of the mixture is sulfonated at the temperature of 120-150 ℃ for 10-24h, the reacted mixture is filtered and washed by deionized water after the temperature of the reacted mixture is reduced to room temperature, the filtrate is diluted, filtered and washed by boiling deionized water until the pH value of the filtrate is 7 so as to remove impurities in the sulfonated carbon, and the obtained filter cake is dried at the temperature of 80-105 ℃ for 5-14h to obtain the sulfonated carbon.
In the preferred embodiment, the carbohydrate in step 1 is glucose, fructose, xylose, sucrose or cellulose; n in step 22The flow rate is 200-300 mL/min; and 3, the sulfonating agent is concentrated sulfuric acid, fuming sulfuric acid or chlorosulfonic acid.
The solid acid catalyst sulfonated carbon is used for catalyzing the reaction of preparing butyl levulinate from levulinic acid and n-butanol.
Specifically, the application of the sulfonated carbon to catalyze the esterification reaction of levulinic acid and n-butanol to prepare butyl levulinate comprises the following two steps:
firstly, mixing levulinic acid and n-butanol to obtain a mixed solution of the levulinic acid and the n-butanol, and adding sulfonated carbon into the mixed solution of the levulinic acid and the n-butanol, wherein the molar ratio of the levulinic acid to the butanol is 1: (3-6), stirring and reacting the sulfonated carbon and the levulinic acid for 4 hours at the temperature of 80-120 ℃, wherein the mass ratio of the sulfonated carbon to the levulinic acid is 10-40%;
and step two, cooling the mixed system to room temperature after the reaction is finished, filtering and separating the sulfonated carbon from the solution obtained after the reaction.
In the preferred embodiment, the stirring in the first step is magnetic stirring, and the stirring speed is 100-200 rpm.
Example 1
A method for preparing sulfonated carbon comprises the following steps,
step 1, adding 60ml of deionized water into a 100ml reaction kettle, adding glucose and dilute sulfuric acid into the reaction kettle to ensure that the concentration of the glucose is 1mol/L and the concentration of the sulfuric acid is 0.05mol/L, and mechanically stirring the mixture at 250rpm at 190 ℃ to react for 3 hours; after the reaction is finished, cooling the mixed solution to room temperature, adding deionized water, performing suction filtration and washing alternately and repeatedly by using boiling deionized water and absolute ethyl alcohol until the pH value of the filtrate is 7, finally drying the filter cake in an oven at 80 ℃ for 14h, and grinding to obtain a carbohydrate acidolysis byproduct, wherein a physical diagram of the byproduct is shown in fig. 4 a; and the SEM image is shown in FIG. 1, wherein the lower 10 cells to the right of the middle represent 50 μm, so that the microscopic particle size of the carbohydrate acid hydrolysis by-product obtained by the method can be estimated; as can be seen from FIG. 1, the carbohydrate acid hydrolysis by-products have large differences in particle size and irregular morphology, indicating that the substance is difficult to handle;
step 2, putting the carbohydrate acidolysis by-product obtained in the step 1 into a tubular furnace, heating to 500 ℃ at a heating rate of 10 ℃/min under a nitrogen atmosphere of 300mL/min, and keeping the temperature for 4 hours to obtain a high-temperature carbide, wherein a physical diagram of the high-temperature carbide is shown in FIG. 4 b; and the SEM image is shown in FIG. 2, wherein 10 cells at the lower middle right part represent 50 μm, so that the high-temperature carbide micro-particle size obtained by the method can be estimated. As can be seen from FIG. 2, the particle size of the carbohydrate acid hydrolysis by-product after cracking has not changed significantly compared to FIG. 1, but the particle morphology and size are uniform compared to FIG. 1; the high-temperature carbide obtained in the step (1) is obtained by modifying small-size substances and large-size substances in the carbohydrate acidolysis by-product obtained in the step (1), so that a material basis is provided for the sulfonation of the high-temperature carbide in the next step;
step 3, adding 1g of the high-temperature carbide obtained in the step 2 and 10ml of concentrated sulfuric acid into a reaction kettle, and keeping the temperature at 130 ℃ for 18 hours to perform sulfonation reaction; after the reaction is finished, cooling the temperature of the mixture to room temperature, adding deionized water, performing suction filtration and washing, diluting, performing suction filtration and washing with boiling deionized water until the pH value of the filtrate is 7, drying the obtained filter cake in an oven at 80 ℃ for 14h to obtain solid acid catalyst sulfonated carbon, wherein a physical diagram of the sulfonated carbon is shown in fig. 4 c; and the SEM image is shown in FIG. 3, wherein 10 cells at the lower part, which is right and middle, represent 50 μm, so that the micro-particle size of the sulfonated carbon obtained by the method can be estimated; as can be seen from FIG. 3, the sulfonated carbon obtained by the method does not have the spherical structure of other sulfonated carbons at present, but is bonded with each other, the self characteristics of the carbohydrate acidolysis by-product obtained in the step 1 are fully utilized, and the obtained amorphous sulfonated carbon is beneficial to full contact between the sulfonated carbon and reactants, so that the catalytic reaction effect of the sulfonated carbon is improved;
the application of the sulfonated carbon in catalyzing esterification reaction of levulinic acid and n-butyl alcohol is as follows,
taking 0.174g of prepared sulfonated carbon, 1.16g of levulinic acid and 3.7g of n-butanol, wherein the molar ratio of the levulinic acid to the n-butanol is 1:5, the using amount of the catalyst is 15% of the mass of the levulinic acid, putting 0.174g of the sulfonated carbon, 1.16g of the levulinic acid and 3.7g of the n-butanol into a reaction kettle for reaction at 80 ℃ for 4 hours, magnetically stirring at 200rpm during the reaction process, cooling a mixed system to room temperature after the reaction is finished, and filtering and separating the sulfonated carbon and the solution obtained after the reaction to obtain butyl levulinate.
The gas chromatography quantitative analysis gave a butyl levulinate concentration of 0.057mol/L, whereas the theoretical butyl levulinate concentration should be 0.068mol/L, so the yield of butyl levulinate in this example was 84%.
Example 2
A method for preparing sulfonated carbon comprises the following steps,
step 1, adding 60ml of deionized water into a 100ml reaction kettle, adding fructose and dilute sulfuric acid into the reaction kettle to ensure that the concentration of the fructose is 2mol/L and the concentration of the sulfuric acid is 0.01mol/L, and mechanically stirring the mixture at 180 ℃ and 200rpm to react for 0.5 h; after the reaction is finished, cooling the mixed solution to room temperature, adding deionized water, performing suction filtration and washing, repeatedly performing suction filtration and washing by using boiling deionized water and absolute ethyl alcohol until the pH value of the filtrate is 7, finally drying the filter cake in an oven at 85 ℃ for 14h, and grinding to obtain a carbohydrate acidolysis byproduct;
step 2, putting the carbohydrate acidolysis by-product obtained in the step 1 into a tube furnace, heating to 350 ℃ at a heating rate of 10 ℃/min under a nitrogen atmosphere of 200mL/min, and keeping the temperature for 8 hours to obtain a high-temperature carbide;
step 3, adding 1g of the high-temperature carbide obtained in the step 2 and 15ml of concentrated sulfuric acid into a reaction kettle, and keeping the temperature at 120 ℃ for 24 hours to perform sulfonation reaction; and after the reaction is finished, cooling the mixture to room temperature, adding deionized water, performing suction filtration washing, diluting, performing suction filtration washing by using boiling deionized water until the pH value of the filtrate is 7, and drying the obtained filter cake in an oven at 85 ℃ for 14h to obtain the solid acid catalyst sulfonated carbon.
The application of the sulfonated carbon in catalyzing esterification reaction of levulinic acid and n-butyl alcohol is as follows,
taking 0.116g of prepared sulfonated carbon, 1.16g of levulinic acid and 2.22g of n-butanol, wherein the molar ratio of the levulinic acid to the n-butanol is 1:3, the using amount of the catalyst is 10 percent of the mass of the levulinic acid, putting 0.116g of the sulfonated carbon, 1.16g of the levulinic acid and 2.22g of the n-butanol into a reaction kettle for reacting for 4 hours at 90 ℃, magnetically stirring 180rpm in the reaction process, cooling a mixed system to room temperature after the reaction is finished, filtering and separating the sulfonated carbon and the solution obtained after the reaction to obtain butyl levulinate.
The gas chromatography quantitative analysis gave a butyl levulinate concentration of 0.064mol/L, whereas the theoretical amount of butyl levulinate should be 0.069mol/L, so the yield of butyl levulinate in this example was 93%.
Example 3
A method for preparing sulfonated carbon comprises the following steps,
step 1, adding 60ml of deionized water into a 100ml reaction kettle, adding xylose and dilute sulfuric acid into the reaction kettle to ensure that the concentration of the xylose is 1.2mol/L and the concentration of the sulfuric acid is 0.06mol/L, and mechanically stirring the mixture at 300rpm at 200 ℃ to react for 8 hours; after the reaction is finished, cooling the mixed solution to room temperature, adding deionized water, performing suction filtration washing, repeatedly performing suction filtration washing by using boiling deionized water and absolute ethyl alcohol until the pH value of the filtrate is 7, finally drying the filter cake in a 90 ℃ oven for 12 hours, and grinding to obtain a carbohydrate acidolysis byproduct;
step 2, putting the carbohydrate acidolysis by-product obtained in the step 1 into a tube furnace, heating to 450 ℃ at a heating rate of 10 ℃/min under a nitrogen atmosphere of 280mL/min, and keeping the temperature for 6 hours to obtain a high-temperature carbide;
step 3, adding 1g of the high-temperature carbide obtained in the step 2 and 20ml of chlorosulfonic acid into a reaction kettle, and keeping the temperature at 130 ℃ for 18 hours to perform sulfonation reaction; and after the reaction is finished, cooling the mixture to room temperature, adding deionized water, performing suction filtration washing, diluting, performing suction filtration washing by using boiling deionized water until the pH value of the filtrate is 7, and drying the obtained filter cake in a 90 ℃ drying oven for 12 hours to obtain the solid acid catalyst sulfonated carbon.
The application of the sulfonated carbon in catalyzing esterification reaction of levulinic acid and n-butyl alcohol is as follows,
taking 0.232g of prepared sulfonated carbon, 1.16g of levulinic acid and 4.44g of n-butanol, wherein the molar ratio of the levulinic acid to the n-butanol is 1:6, the using amount of the catalyst is 20 percent of the mass of the levulinic acid, putting 0.232g of the sulfonated carbon, 1.16g of the levulinic acid and 4.44g of the n-butanol into a reaction kettle, reacting for 4 hours at 100 ℃, magnetically stirring at 140rpm in the reaction process, cooling to room temperature after the reaction is finished, and filtering and separating the sulfonated carbon and the solution obtained after the reaction to obtain butyl levulinate.
The gas chromatography quantitative analysis gave a butyl levulinate concentration of 0.070mol/L, whereas the theoretical amount of butyl levulinate should be 0.074mol/L, so the yield of butyl levulinate in this example was 95%.
Example 4
A method for preparing sulfonated carbon comprises the following steps,
step 1, adding 60ml of deionized water into a 100ml reaction kettle, adding sucrose and dilute sulfuric acid into the reaction kettle to ensure that the concentration of the sucrose is 1.8mol/L and the concentration of the sulfuric acid is 0.08mol/L, and mechanically stirring the mixture at 350rpm at 220 ℃ to react for 12 hours; after the reaction is finished, cooling the mixed solution to room temperature, adding deionized water, performing suction filtration washing, repeatedly performing suction filtration washing by using boiling deionized water and absolute ethyl alcohol until the pH value of the filtrate is 7, finally drying the filter cake in a 100 ℃ oven for 8 hours, and grinding to obtain a carbohydrate acidolysis byproduct;
step 2, putting the carbohydrate acidolysis by-product obtained in the step 1 into a tube furnace, heating to 400 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere of 240mL/min, and keeping the temperature for 5 hours to obtain a high-temperature carbide;
step 3, adding 1g of the high-temperature carbide obtained in the step 2 and 25ml of fuming sulfuric acid into a reaction kettle, and keeping the temperature at 140 ℃ for 14 hours to carry out sulfonation reaction; and after the reaction is finished, cooling the mixture to room temperature, adding deionized water, performing suction filtration washing, diluting, performing suction filtration washing by using boiling deionized water until the pH value of the filtrate is 7, and drying the obtained filter cake in a 100 ℃ drying oven for 8h to obtain the solid acid catalyst sulfonated carbon.
The application of the sulfonated carbon in catalyzing esterification reaction of levulinic acid and n-butyl alcohol is as follows,
taking 0.348g of prepared sulfonated carbon, 1.16g of levulinic acid and 2.96g of n-butanol, wherein the molar ratio of the levulinic acid to the n-butanol is 1:4, the using amount of the catalyst is 30% of the mass of the levulinic acid, putting 0.348g of the sulfonated carbon, 1.16g of the levulinic acid and 2.96g of the n-butanol into a reaction kettle, reacting for 4 hours at 110 ℃, magnetically stirring at 100rpm in the reaction process, cooling a mixed system to room temperature after the reaction is finished, and filtering and separating the sulfonated carbon and the solution obtained after the reaction to obtain butyl levulinate.
The gas chromatography quantitative analysis gave a butyl levulinate concentration of 0.071mol/L, whereas the theoretical amount of butyl levulinate should be 0.073mol/L, so the yield of butyl levulinate in this example was 97%.
Example 5
A method for preparing sulfonated carbon comprises the following steps,
step 1, adding 60ml of deionized water into a 100ml reaction kettle, adding cellulose and dilute sulfuric acid into the reaction kettle to ensure that the concentration of the cellulose is 1.5mol/L and the concentration of the sulfuric acid is 0.1mol/L, and mechanically stirring the mixture at the temperature of 240 ℃ and the rpm of 400 to react for 24 hours; after the reaction is finished, cooling the mixed solution to room temperature, adding deionized water, performing suction filtration washing, repeatedly performing suction filtration washing by using boiling deionized water and absolute ethyl alcohol until the pH value of the filtrate is 7, finally drying the filter cake in a drying oven at 105 ℃ for 5 hours, and grinding to obtain a carbohydrate acidolysis byproduct;
step 2, putting the carbohydrate acidolysis by-product obtained in the step 1 into a tubular furnace, heating to 500 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere of 300mL/min, and keeping the temperature for 4 hours to obtain a high-temperature carbide;
step 3, adding 1g of the high-temperature carbide obtained in the step 2 and 30ml of fuming sulfuric acid into a reaction kettle, and keeping the temperature at 150 ℃ for 10 hours to carry out sulfonation reaction; and after the reaction is finished, cooling the mixture to room temperature, adding deionized water, performing suction filtration washing, diluting, performing suction filtration washing by using boiling deionized water until the pH value of the filtrate is 7, and drying the obtained filter cake in a 105 ℃ drying oven for 5 hours to obtain the solid acid catalyst sulfonated carbon.
The application of the sulfonated carbon in catalyzing esterification reaction of levulinic acid and n-butyl alcohol is as follows,
taking 0.464g of prepared sulfonated carbon, 1.16g of levulinic acid and 4.44g of n-butanol, wherein the molar ratio of the levulinic acid to the n-butanol is 1:6, the using amount of the catalyst is 40% of the mass of the levulinic acid, putting 0.464g of the sulfonated carbon, 1.16g of the levulinic acid and 4.44g of the n-butanol into a reaction kettle, reacting for 4 hours at 120 ℃, magnetically stirring at 100rpm in the reaction process, cooling a mixed system to room temperature after the reaction is finished, filtering and separating the sulfonated carbon and the solution obtained after the reaction to obtain butyl levulinate.
Gas chromatography quantitative analysis gave a butyl levulinate concentration of 0.0742mol/L, whereas theoretical butyl levulinate should be 0.0748mol/L, so the yield of butyl levulinate in this example was 99%.
Claims (8)
1. The preparation method of the sulfonated carbon is characterized by comprising the following steps:
step 1, preparing carbohydrate acidolysis byproducts;
mixing carbohydrate, sulfuric acid and deionized water, heating to 180-240 ℃ for reaction for 0.5-24h, performing suction filtration washing after the temperature of the obtained mixed solution is reduced to room temperature until the pH value of the filtrate is 7, drying a filter cake obtained by performing suction filtration washing on the mixed solution at 80-105 ℃ for 5-14h, and grinding to obtain a carbohydrate acidolysis byproduct;
step 2, pyrolysis of carbohydrate acidolysis byproducts;
heating the carbohydrate acidolysis by-product obtained in the step 1 to 350-500 ℃ in an inert gas atmosphere for cracking for 4-8h to obtain a high-temperature carbide;
step 3, sulfonating the high-temperature carbide;
mixing the high-temperature carbide obtained in the step 2 with a sulfonating agent according to the weight ratio of 1 g: (10-30) ml, mixing, sulfonating for 10-24h at the temperature of 120-150 ℃, filtering and washing after the temperature of the mixture is reduced to room temperature until the pH value of the filtrate is 7, and drying a filter cake obtained by filtering and washing the mixture for 5-14h at the temperature of 80-105 ℃ to obtain sulfonated carbon.
2. The method for preparing sulfonated carbon according to claim 1, wherein the carbohydrate in step 1 is glucose, fructose, xylose, sucrose or cellulose.
3. The method of claim 1, wherein the inert gas in step 2 is N2And the flow rate is 200-300 mL/min.
4. The method of claim 1, wherein the sulfonating agent in step 3 is concentrated sulfuric acid, fuming sulfuric acid or chlorosulfonic acid.
5. The method of claim 1, wherein the carbohydrate concentration of the mixture of the carbohydrate, the sulfuric acid and the deionized water in step 1 is 1-2 mol/L.
6. The method for preparing sulfonated carbon according to claim 1, wherein the concentration of sulfuric acid in step 1 is 0.01 to 0.1 mol/L.
7. The method as claimed in claim 1, wherein the reaction in step 1 is performed under stirring at a stirring speed of 200-400 rpm.
8. A sulfonated carbon prepared by the process of any one of claims 1 to 7.
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