CN115138392B - Multifunctional biochar catalyst rich in oxygen-containing functional groups and preparation method thereof - Google Patents
Multifunctional biochar catalyst rich in oxygen-containing functional groups and preparation method thereof Download PDFInfo
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 125000000524 functional group Chemical group 0.000 title claims abstract description 34
- 239000001301 oxygen Substances 0.000 title claims abstract description 34
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
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- 229940009827 aluminum acetate Drugs 0.000 claims description 6
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- 230000035484 reaction time Effects 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
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- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
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- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 15
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- 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
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
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- 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
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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Abstract
The invention relates to a multifunctional biochar catalyst rich in oxygen-containing functional groups and a preparation method thereof, wherein lignin is pyrolyzed at different temperatures to obtain a lignin-based carbon material; mixing the lignin-based carbon material, a Bronsted acid precursor and a Lewis acid precursor, and performing ball milling treatment; oxidizing the ball-milled material, wherein the Bronsted acid precursor is one of thiomalic acid, cysteine and thioglycolic acid; the Lewis acid precursor is one of aluminum-containing metal salts. The invention takes the biomass lignin as a carbon source, has low cost and rich oxygen-containing functional groups; the ball milling method is adopted for functional modification, the reaction efficiency is high, no organic solvent is involved in the synthesis process, and the method is green and efficient. The results of the examples show that glucose can be directly catalytically converted into ethyl levulinate and 5-ethoxymethylfurfural in an ethanol solution, the preparation method of the catalyst is simpler, more efficient, more environment-friendly than the traditional method, the raw materials are cheap and easily available, and the whole process is green and more efficient.
Description
Technical Field
The invention relates to the technical field of solid catalysts, in particular to a multifunctional biochar catalyst rich in oxygen-containing functional groups and a preparation method thereof.
Background
The rapid development of global economy and the increasing population size have led to a global energy crisis. Meanwhile, the problems of environmental pollution, ecological damage and the like are increasingly highlighted due to the large exploitation and use of non-renewable fossil energy. Therefore, it is urgent to develop renewable, environmentally friendly new energy sources. Among them, lignocellulose biomass is the most abundant organic matter on earth, has many advantages of wide sources, renewability, environmental friendliness and the like, is expected to replace the traditional fossil energy, and is widely concerned by countries in the world. Among the numerous biomass-based derivatives, ethyl levulinate and 5-ethoxymethylfurfural are not only important biomass fuels but also one of important platform compounds, and can be further converted into biofuels and other high value-added chemicals, such as:
eLactones, 2, 5-furandicarboxylic acid, and the like.
At present, the method for producing ethyl levulinate and 5-ethoxymethylfurfural by using biomass as a raw material is mainly a chemical catalysis method. The traditional liquid catalyst has high efficiency, but has the problems of strong corrosion to equipment, more byproducts, difficult recycling and the like. Accordingly, solid catalysts are receiving increasing attention. Unlike other biomass catalytic conversion processes, ethyl levulinate and 5-ethoxymethylfurfural are produced from glucose by heterogeneous catalytic conversion with lewis acids. Moreover, the solid acid is insoluble in ethanol, so that the reaction time is long and the catalytic efficiency is low. This results in a high design requirement for the catalyst. The traditional preparation method of the Bronsted acid-Lewis acid multifunctional catalyst usually needs strong corrosive acid, alkali or a large amount of organic solvent, and has the problems of longer preparation process, higher synthesis temperature and high production cost. For example, chinese patent document CN108658904A, applied to the production of ethyl levulinate and 5-ethoxymethylfurfural by the catalytic conversion of glucose. The method involves a large amount of organic solvents, and has the advantages of high raw material cost, complex synthesis process and difficult expansion of production.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the multifunctional biochar catalyst which is high in efficiency, low in cost and environment-friendly and is rich in oxygen-containing functional groups and the preparation method.
In order to achieve the purpose, the invention provides the following technical scheme:
a multifunctional biochar catalyst rich in oxygen-containing functional groups is characterized in that: comprises lignin-based carbon material and sulfonic acid group, binding state Al and carboxyl which are grafted on the lignin-based carbon material in a covalent bond mode.
A preparation method of a multifunctional biochar catalyst rich in oxygen-containing functional groups comprises the following specific steps:
pyrolyzing lignin to obtain a lignin-based carbon material;
mixing a lignin-based carbon material, a Bronsted acid precursor and a Lewis acid precursor, and performing ball milling treatment to obtain a ball-milled carbon material;
oxidizing the carbon material subjected to ball milling to obtain a multifunctional biochar catalyst rich in oxygen-containing functional groups;
the Bronsted acid precursor is one of thiomalic acid, cysteine and thioglycollic acid;
the Lewis acid precursor is one of aluminum-containing metal salts.
And the mass ratio of the Lewis acid precursor is 2-4:0-4:4-0, and the sum of the mass ratios of the Bronsted acid precursor and the Lewis acid precursor is 4.
And the mass ratio of the lignin-based carbon material, the Bronsted acid precursor and the Lewis acid precursor is 2:1.3:2.7, the Bronsted acid precursor is cysteine, and the Lewis acid precursor is aluminum acetate.
And the mass ratio of the lignin-based carbon material, the Bronsted acid precursor and the Lewis acid precursor is 2:2.5:1.5.
moreover, the rotating speed of the ball milling treatment is 5-20Hz; the ball milling treatment time is 1-5h; the diameter of the ball milling beads for ball milling treatment is 5-20mm, and the mass ratio of ball materials for ball milling treatment is 10-50:2-6.
And the Lewis acid precursor is one of aluminum acetate, aluminum chloride or aluminum nitrate.
A method for preparing ethyl levulinate and 5-ethoxymethylfurfural by catalyzing glucose comprises the steps of mixing a biochar catalyst, glucose and ethanol, and carrying out isomerization, dehydration and esterification on the glucose under the catalytic action of the biochar catalyst to obtain ethyl levulinate and 5-ethoxymethylfurfural.
Moreover, the reaction temperature is 115-150 ℃ and the reaction time is 1-24h.
Moreover, the mass concentration of glucose in the mixed solution obtained by mixing the biochar catalyst, the glucose and the ethanol is 1-5wt%; the mass ratio of the biochar catalyst to the glucose is 1-9:5-15.
The invention has the following advantages and beneficial effects:
the catalyst prepared by the invention is free of organic solvent intervention in the synthesis process, is green and efficient, and the results of the embodiment show that the multifunctional biochar catalyst prepared by the mechanical ball milling method is rich in oxygen-containing functional groups, contains Bronsted acid and Lewis acid multifunctional catalytic sites, is high in thermal stability, can be used for directly catalytically converting glucose into ethyl levulinate and 5-ethoxymethylfurfural in an alcohol solution, and is simple, efficient and environment-friendly in preparation method compared with the traditional method, the raw materials are cheap and easy to obtain, and the whole process is green and efficient.
The preparation method of the multifunctional biochar catalyst rich in oxygen-containing functional groups, which is provided by the invention, takes lignin-based carbon materials as carriers, so that the cost is low; the ball milling method is adopted for functional modification, so that the use of organic solvents is avoided. Under the action of strong tensile force, shearing force and the like provided by ball milling, oxygen-containing functional groups such as-COOH and-OH in the Bronsted acid precursor and the Lewis acid precursor and the lignin-based carbon material are grafted to the lignin-based carbon material in a covalent bond manner, and Bronsted acid precursor (-SH) and Lewis acid (Al) catalytic sites are formed on the lignin-based carbon material.
The multifunctional biochar catalyst rich in oxygen-containing functional groups prepared by the method is good in thermal stability, contains a Bronsted acid catalytic site and a Lewis acid catalytic site, and is rich in oxygen-containing functional groups.
In an ethanol phase, when glucose is directly catalyzed to generate 5-ethoxymethylfurfural and ethyl levulinate, lewis acid sites are beneficial to isomerization of the glucose into fructose, and Broenss acid sites further convert the fructose into final products of the 5-ethoxymethylfurfural and the ethyl levulinate, so that the high-efficiency catalytic reaction is realized, the yield of the 5-ethoxymethylfurfural can reach 33.1%, the sum of the yields of the 5-hydroxymethylfurfural, the 5-ethoxymethylfurfural and the ethyl levulinate can reach 57.0%, and the multifunctional carbon catalyst can still maintain high reaction activity after being repeatedly used for 5 times.
Drawings
FIG. 1 is a scanning electron micrograph of the multifunctional carbon catalyst prepared in example 3;
FIG. 2 is an XPS spectrum (AL ions) of the multifunctional carbon catalyst prepared in example 3;
FIG. 3 is an XPS spectrum (containing S groups) of the multifunctional carbon catalyst prepared in example 3;
FIG. 4 is a FT-IR spectrum of the multifunctional carbon catalyst prepared in examples 1-5;
FIG. 5 is a graph showing the reaction product yield of catalytically converted glucose in an ethanol solvent as a function of reaction time for catalysts prepared in example 1 under different reaction temperature conditions.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
A multifunctional biochar catalyst rich in oxygen-containing functional groups comprises a lignin-based carbon material and sulfonic acid groups, bonded Al and carboxyl groups which are grafted on the lignin-based carbon material in a covalent bond manner, or comprises the lignin-based carbon material and Bronsted acid (sulfonic acid groups) and Lewis acid (metals and carboxyl groups) which are grafted on the lignin-based carbon material in a covalent bond manner.
The invention provides a preparation method of a multifunctional biochar catalyst rich in oxygen-containing functional groups, which comprises the following specific steps: mixing a lignin-based carbon material, a Bronsted acid precursor and a Lewis precursor to obtain a mixture; ball-milling and oxidizing the mixture to obtain the Bronsted acid-Lewis acid multifunctional carbon catalyst; the Bronsted acid precursor is one of thiomalic acid/cysteine/thioglycolic acid; the Lewis acid precursor is one of aluminum-containing metal salts (such as aluminum acetate). The invention has no special requirements on the sources of the lignin, the Bronsted acid precursor and the Lewis acid precursor, and can be prepared by adopting a commercial product. The Bronsted acid-Lewis acid multifunctional carbon catalyst comprises lignin-based functional carbon and a Bronsted acid monomer and a Lewis acid monomer which are grafted on the lignin-based biochar in a covalent bond mode. The ball mill has no special requirements on the equipment in the ball milling process, and a ball mill known by a person skilled in the art can be adopted, and in the embodiment of the invention, a planetary ball mill is adopted for ball milling.
A preparation method of a multifunctional biochar catalyst rich in oxygen-containing functional groups comprises the following specific steps:
(1) pyrolyzing lignin at different temperatures to obtain a lignin-based carbon material; mixing the carbon material, the Bronsted acid precursor and the Lewis acid precursor, and performing ball milling treatment; the lignin-based carbon material is preferably one or more lignin-based carbon materials obtained by carbonizing lignin at 300 ℃, 400 ℃ and 500 ℃; and lignin-based carbon material obtained by carbonizing lignin at 300 deg.C is preferred.
(2) Oxidizing the ball-milled material to obtain a multifunctional biochar catalyst rich in oxygen-containing functional groups; the rotation speed of the ball milling is 5-20Hz, and the preferred rotation speed is 10-15Hz; the time is 1 to 5 hours, and the preferable time is 2 to 3 hours; the diameter of the ball milling beads for ball milling is 5-20mm, more preferably 10-15mm, and the ball-to-material ratio is 10-50:2-6; further preferably 10 to 20:3-4.
The mass ratio of the lignin-based carbon material to the Broensted acid precursor to the Lewis acid precursor is 2-4:0-4:4-0 (note: the sum of the masses of the bronsted acid precursor and the lewis acid precursor is 4). After the mixture is obtained, the mixture is subjected to ball milling to obtain the Bronsted acid-Lewis acid multifunctional carbon catalyst. The Bronsted acid precursor is one of thiomalic acid, cysteine and thioglycolic acid, and is preferably thiomalic acid; the Lewis acid precursor is one of aluminum-containing metal salts, preferably aluminum acetate.
The multifunctional carbon material catalyst obtained by the invention is rich in oxygen-containing functional groups; the specific surface area of the catalyst is
(ii) a The metal content of the catalyst is 0.22-3.52mmol/g, and the sulfate radical content is 0.47-0.85mmol/g.
The preparation method of the Bronsted acid-Lewis acid multifunctional biochar catalyst provided by the invention takes a lignin-based functional carbon material as a carrier and adopts a ball milling method to carry out functional modification. A lignin-based carbon material and a Bronsted acid monomer and a Lewis acid monomer covalently grafted to the lignin-based carbon material. The reaction efficiency is high, no organic solvent is involved in the synthesis process, the method is green and efficient, and the specific reaction schematic diagram is shown in figure 2. And washing, oxidizing and drying the obtained ball-milling material formulation after the ball milling is finished to obtain the Bronsted acid-Lewis acid multifunctional carbon catalyst. The washing solvent is preferably water, more preferably deionized water; the washing solvent is preferably used in an amount of 20 to 50mL, more preferably 20 to 35mL. The number of washing steps in the present invention is preferably 3 to 5.
In the invention, the specific process of washing is as follows: mixing the ball milling material and the washing solvent, stirring and filtering, wherein the stirring time is preferably 1-2h, and the stirring speed is preferably 500rmp. The drying temperature is preferably 55-85 ℃, more preferably 60-75 ℃, and the drying time is preferably 10-24h, more preferably 12-15h. In the present invention, the drying is preferably oven drying; the invention has no special requirements on the drying equipment, and can be realized by adopting a common drying box.
The invention also provides a method for catalyzing glucose to generate 5-ethoxymethylfurfural and ethyl levulinate in a liquid phase by using the catalyst, which comprises the following steps:
mixing the Bronsted acid-Lewis acid multifunctional carbon catalyst, glucose and ethanol, and carrying out isomerization-dehydration-esterification reaction to obtain 5-ethoxymethylfurfural and ethyl levulinate. The invention has no special requirements on the mixing process and can achieve uniform mixing.
The mass concentration of glucose in a mixed solution obtained by mixing the multifunctional biochar catalyst (also called as Bronsted acid-Lewis acid multifunctional carbon catalyst) rich in oxygen-containing functional groups, glucose and ethanol is 1-5wt%; the mass ratio of the Broenss-Lewis acid multifunctional solid carbon catalyst to the glucose is 1-9:5-15. The temperature of the catalytic reaction is preferably 115-150 ℃, the time of the catalytic reaction is preferably 0.5-24h, the catalytic reaction is preferably carried out under the condition of magnetic stirring, and the rotating speed of the magnetic stirring is preferably 500rmp. The equipment for the catalytic reaction is not particularly required by the invention, and glucose catalytic isomerization-dehydration-esterification reaction equipment well known to those skilled in the art can be adopted, and in the embodiment of the invention, the catalytic reaction is preferably carried out in a reaction kettle.
After the catalytic reaction is finished, preferably, post-treating the mixture of the catalytic reaction, wherein the post-treating specifically comprises: taking out the catalytic reaction mixture, rapidly washing and cooling the reaction mixture by water, filtering the obtained mixture by using a filter membrane, and taking filtrate, namely the solution of the product 5-Ethoxymethylfurfural (EMF) and Ethyl Levulinate (EL).
And (3) performing liquid chromatography on the product-containing solution to determine products, and calculating the conversion rate of glucose and the yield of reaction products fructose, 5-hydroxymethylfurfural, 5-ethoxymethylfurfural and ethyl levulinate, wherein the conditions of the liquid chromatography are as follows: mobile phase
Column temperature 30 o C, flow rate 0.5mL/min, differential detector.
Example 1
A multifunctional biochar catalyst rich in oxygen-containing functional groups and a preparation method thereof comprise the following specific steps:
(1) uniformly mixing 2g of lignin-based carbon material pyrolyzed at 300 ℃ and 4g of Lewis acid precursor, and transferring the mixture into a 50mL ball milling tank;
(2) adding 30g of steel ball grinding beads with the diameter of 5mm into a ball milling tank, and carrying out mechanical ball milling under the ball milling condition; the rotating speed is 10Hz, and the time is 3h;
(3) and after the ball milling is finished, washing with deionized water, wherein the using amount of the deionized water is 40mL, performing suction filtration, and repeating for 6 times. Finally at 65 o C, drying for 12 hours;
(4) mixing 1g of dried lignin-based biomass charcoal material containing Lewis acid precursor with 25mL of hydrogen peroxide solution with mass concentration (30 wt%), and stirring at the rotating speed of 500 r/min for 24h to carry out oxidation reaction; then filtering, washing by distilled water, drying at the constant temperature of 60 ℃ in vacuum for 12h to remove all water, and obtaining the Bronsted acid-Lewis acid multifunctional carbon catalyst.
The total specific surface area of the Bronsted acid-Lewis acid multifunctional carbon catalyst is calculated after being tested by a measuring instrument (a nitrogen adsorption and desorption instrument, an element analyzer, a Fourier infrared analyzer or ICP-OES)
The Al concentration of the catalyst was 3.5mmol/g. XPS and FT-IR analysis showed that the surface of the material prepared in this example is rich in oxygen-containing functional groups (-COOH, -OH, -C = O), al active sites (FIG. 4).
Example 2
A multifunctional biochar catalyst rich in oxygen-containing functional groups and a preparation method thereof comprise the following specific steps:
(1) uniformly mixing 2g of lignin-based carbon material pyrolyzed at 300 ℃, 1.0g of Broenstic acid precursor and 3.0g of Lewis acid precursor, and transferring the mixture into a 50mL ball milling tank;
(2) adding 30g of steel ball grinding beads with the diameter of 5mm into the ball milling tank, and carrying out mechanical ball milling under the following conditions: the rotating speed is 10Hz, and the time is 3h;
(3) and after the ball milling is finished, washing with deionized water, wherein the using amount of the deionized water is 40mL, performing suction filtration, and repeating for 6 times. Finally at 65 o C, drying for 12 hours under the condition of C,
(4) mixing 1g of dried lignin-based carbon material containing a Bronsted acid precursor and a Lewis acid precursor with 25mL of hydrogen peroxide solution with the mass concentration (30 wt%), and stirring at the rotating speed of 500 r/min for 24h to carry out oxidation reaction; then filtering, washing by distilled water, drying at the constant temperature of 60 ℃ in vacuum for 12h to remove all water, and obtaining the Bronsted acid-Lewis acid multifunctional carbon catalyst.
The total specific surface area of the Bronsted acid-Lewis acid multifunctional carbon catalyst is calculated after being tested by a measuring instrument (a nitrogen adsorption and desorption instrument, an element analyzer, a Fourier infrared analyzer or an ICP-OES)
The Al concentration of the catalyst is 1.7mmol/g,
the concentration was 0.75mmol/g. XPS and FT-IR analysis showed that the surface of the material prepared in this example is rich in oxygen-containing functional groups (-COOH, -OH, -C = O), -SH, -SOx,
and-C = C-functional group.
Example 3
A multifunctional biochar catalyst rich in oxygen-containing functional groups and a preparation method thereof comprise the following specific steps:
(1) uniformly mixing 2g of lignin-based carbon material pyrolyzed at 300 ℃, 1.3g of Broenstic acid precursor and 2.7g of Lewis acid precursor, and transferring the mixture into a 50mL ball milling tank;
(2) adding 30g of steel ball grinding balls with the diameter of 5mm into the ball milling tank, and carrying out mechanical ball milling under the following ball milling conditions: the rotating speed is 10Hz, and the time is 3h;
(3) and after the ball milling is finished, washing with deionized water, wherein the using amount of the deionized water is 40mL, performing suction filtration, and repeating for 6 times. Finally at 65 o And (5) drying for 12h under C.
(4) Mixing 1g of dried lignin-based biomass charcoal material containing a Broenstic acid precursor and a Lewis acid precursor with 25mL of hydrogen peroxide solution with the mass concentration (30 wt%), and stirring at the rotating speed of 500 revolutions per minute for 24 hours to carry out oxidation reaction; then filtering, washing by distilled water, drying at the constant temperature of 60 ℃ in vacuum for 12h to remove all water, and obtaining the Bronsted acid-Lewis acid multifunctional carbon catalyst.
The scanning electron micrograph of the obtained multifunctional carbon catalyst containing Bronsted acid and Lewis acid is shown in FIG. 1, and is calculated by adopting a measuring instrument (nitrogen adsorption and desorption instrument, element analyzer, fourier infrared analyzer or ICP-OES) to measure, wherein the total specific surface area of the multifunctional carbon catalyst containing Bronsted acid and Lewis acid is smaller than that of the multifunctional carbon catalyst containing Bronsted acid and Lewis acid
The Al concentration of the catalyst is 1.4mmol/g,
the concentration was 0.8mmol/g. XPS and FT-IR analysis showed that the material prepared in this example is rich in oxygen-containing functional groups (-COOH, -OH, -C = O), -SH, and,
、
and-C = C-functional group (fig. 4).
Example 4
A multifunctional biochar catalyst rich in oxygen-containing functional groups and a preparation method thereof comprise the following specific steps:
(1) uniformly mixing 2g of lignin-based carbon material pyrolyzed at 300 ℃, 2.5g of Broenstic acid precursor and 1.5g of Lewis acid precursor, and transferring the mixture into a 50mL ball milling tank;
(2) adding 30g of steel ball grinding balls with the diameter of 5mm into the ball milling tank, and carrying out mechanical ball milling under the following ball milling conditions: the rotating speed is 10Hz, and the time is 3h.
(3) And after the ball milling is finished, washing with deionized water, wherein the using amount of the deionized water is 40mL, performing suction filtration, and repeating for 6 times. Finally at 65 o C, drying for 12 hours;
(4) mixing 1g of dried lignin-based biomass charcoal material containing a Broenstic acid precursor and a Lewis acid precursor with 25mL of hydrogen peroxide solution with the mass concentration (30 wt%), and stirring at the rotating speed of 500 revolutions per minute for 24 hours to carry out oxidation reaction; then filtering, washing by distilled water, drying at the constant temperature of 60 ℃ in vacuum for 12h to remove all water, and obtaining the Bronsted acid-Lewis acid multifunctional carbon catalyst.
The total specific surface area of the Bronsted acid-Lewis acid multifunctional carbon catalyst is less than 9m and is calculated after being tested by a measuring instrument (a nitrogen adsorption and desorption instrument, an element analyzer, a Fourier infrared analyzer or an ICP-OES) 2 Al concentration of the catalyst is 1.2mmol/g,
the concentration was 0.77mmol/g. XPS and FT-IR analysis showed that the compound of this example was preparedThe surface of the material is rich in oxygen-containing functional groups (-COOH, -OH, -C = O), -SH, and,
、
and-C = C-functional group.
Example 5
A multifunctional biochar catalyst rich in oxygen-containing functional groups and a preparation method thereof are disclosed, which comprises the following specific steps:
(1) uniformly mixing 2g of lignin-based carbon material pyrolyzed at 300 ℃ and 4.0g of Broenstic acid precursor, and transferring the mixture into a 50mL ball milling tank;
(2) adding 30g of steel ball milling beads with the diameter of 5mm, and carrying out mechanical ball milling under the following ball milling conditions: the rotating speed is 10Hz, and the time is 3h;
(3) and after the ball milling is finished, washing with deionized water, wherein the using amount of the deionized water is 40mL, performing suction filtration, and repeating for 6 times. Finally at 65 o And (5) drying for 12h under C. (ii) a
(4) Mixing 1g of dried lignin-based biomass charcoal material containing a Broenstic acid precursor and a Lewis acid precursor with 25mL of hydrogen peroxide solution with the mass concentration (30 wt%), and stirring at the rotating speed of 500 revolutions per minute for 24 hours to carry out oxidation reaction; then filtering, washing by distilled water, drying at the constant temperature of 60 ℃ in vacuum for 12h to remove all water, and obtaining the Bronsted acid-Lewis acid multifunctional carbon catalyst.
The total specific surface area of the Bronsted acid-Lewis acid multifunctional carbon catalyst is less than 9m and is calculated after being tested by a measuring instrument (a nitrogen adsorption and desorption instrument, an element analyzer or ICP-OES) 2 Per g, catalyst-SO 3 The H concentration was 0.8mmol/g. XPS and FT-IR analysis showed that the material prepared in this example is rich in oxygen-containing functional groups (-COOH, -OH, -C = O), -SH, and,
、
and-C = C-functional group.
Example 6
A multifunctional biochar catalyst rich in oxygen-containing functional groups and a preparation method thereof comprise the following specific steps:
(1) uniformly mixing 2g of commercial non-lignin biochar pyrolyzed at 300 ℃, 1.3g of Bronsted acid precursor and 2.7g of Lewis acid precursor, and transferring the mixture into a 50mL ball milling tank; the procedure was as in example 3, and the results are shown in Table 1.
Application example 1
A process for the catalytic production of 5-ethoxymethylfurfural and ethyl levulinate from glucose in the liquid phase using the catalyst of example 1, comprising the steps of:
0.05g of the Lewis acid-based functional carbon solid catalyst obtained in example 1, 0.05g of glucose and 5mL of ethanol are uniformly mixed, and then the mixture is transferred into a reaction kettle, the magnetic stirring speed is 500rmp, and the reaction kettle is 132 o C, reacting for 0.5h, 1h, 2h, 3h, 4h and 6h, setting different reaction time points to take reaction mixtures, rapidly washing and cooling the reaction mixtures by water, filtering the obtained mixtures by a filter membrane, and taking supernate to perform liquid chromatography to determine products.
The conversion of glucose, the yield of fructose, the yield of 5-Hydroxymethylfurfural (HMF), the yield of 5-Ethoxymethylfurfural (EMF) and the yield of Ethyl Levulinate (EL) were calculated. The yield calculation formula is as follows:
the conditions of the liquid chromatography were: mobile phase
Column temperature 30 o C, flow rate 0.5mL/min, differential detector.
The experimental results are shown in FIG. 4, from which it can be seen from FIG. 4 that the catalyst obtained in example 1 of the present invention was 135 o Under the condition of C, glucose can be isomerized into fructose, after 30min, the glucose conversion rate is more than 90 percent, and the maximum fructose yield is more than40 percent. However, the yields of 5-Hydroxymethylfurfural (HMF), 5-Ethoxymethylfurfural (EMF) and Ethyl Levulinate (EL) were less than 20% throughout the reaction. Probably because the Lewis acid base functional carbon solid catalyst obtained in the example 1 is rich in Lewis acid active sites, and promotes the generation of by-product humic acid.
Application example 2
A process for the catalytic production of 5-ethoxymethylfurfural and ethyl levulinate from glucose in the liquid phase using the catalyst of example 12, comprising the steps of:
0.05g of the Bronsted acid-Lewis acid multifunctional carbon catalyst obtained in example 2, 0.05g of glucose and 5mL of ethanol are mixed uniformly and then transferred into a reaction kettle with the magnetic stirring speed of 500rmp at 132 o C, reacting for 6 hours, after the reaction is finished, rapidly washing with water to cool the reaction mixture, filtering the obtained mixture with a filter membrane, taking supernate, and measuring the product by liquid chromatography, wherein the conversion rate of glucose is 94%, the yield of fructose is 11.2%, the yield of 5-Hydroxymethylfurfural (HMF) is 12.5%, the yield of 5-Ethoxymethylfurfural (EMF) is 23.1% and the yield of Ethyl Levulinate (EL) is 18.6% by calculation.
Application example 3
A process for the catalytic production of 5-ethoxymethylfurfural and ethyl levulinate from glucose in the liquid phase using the catalyst of example 3, comprising the steps of:
0.05g of the Bronsted acid-Lewis acid multifunctional carbon catalyst obtained in example 3, 0.05g of glucose and 5mL of ethanol are mixed uniformly and then transferred into a reaction kettle with the magnetic stirring speed of 500rmp at 132 o C, reacting for 4 hours, after the reaction is finished, rapidly washing and cooling the reaction mixture by water, filtering the obtained mixture by using a filter membrane, taking supernate, and measuring the product by using liquid chromatography, wherein the conversion rate of glucose is 98.2%, the yield of fructose is 5.3%, the yield of 5-Hydroxymethylfurfural (HMF) is 3.5%, the yield of 5-Ethoxymethylfurfural (EMF) is 33.1% and the yield of Ethyl Levulinate (EL) is 20.4%.
Application example 4
A method for catalyzing glucose to generate 5-ethoxymethylfurfural and ethyl levulinate in a liquid phase by using the catalyst of example 4 comprises the following steps:
0.05g of the Bronsted acid-Lewis acid multifunctional carbon catalyst obtained in example 4, 0.05g of glucose and 5mL of ethanol are uniformly mixed, and then the mixture is transferred into a reaction kettle, the magnetic stirring speed is 500rmp, and the reaction kettle is 132 o C for 6 hours, after the reaction is finished, quickly flushing water to cool the reaction mixture, filtering the obtained mixture by using a filter membrane, taking supernate, and measuring the product by using liquid chromatography, wherein the conversion rate of glucose is 100%, the yield of fructose is 9.7%, the yield of 5-Hydroxymethylfurfural (HMF) is 2.7%, the yield of 5-Ethoxymethylfurfural (EMF) is 26.7% and the yield of Ethyl Levulinate (EL) is 39.8%.
Application example 5
A method for catalyzing glucose to generate 5-ethoxymethylfurfural and ethyl levulinate in a liquid phase by using the catalyst of example 5 comprises the following steps:
0.05g of the Bronsted acid-based functional carbon solid catalyst obtained in example 5, 0.05g of glucose and 5mL of ethanol are uniformly mixed, and then the mixture is transferred into a reaction kettle, the magnetic stirring speed is 500rmp, and the reaction kettle is 132 o C, reacting for 6 hours, after the reaction is finished, rapidly washing and cooling the reaction mixture by water, filtering the obtained mixture by a filter membrane, and taking supernatant fluid to perform liquid chromatography to determine products.
The conversion of glucose was calculated to be 100% and the yields of fructose, 5-Hydroxymethylfurfural (HMF), 5-Ethoxymethylfurfural (EMF) and Ethyl Levulinate (EL) were all less than 10%. The main reason for this may be that the material in example 5 does not contain Lewis acid sites and glucose cannot isomerize efficiently to fructose, further yielding 5-Ethoxymethylfurfural (EMF) and Ethyl Levulinate (EL)
Application example 6
A process for the production of 5-ethoxymethylfurfural and ethyl levulinate from glucose in the liquid phase using the catalyst of example 6 under the same conditions as in application example 5, and the results are shown in Table 2.
From the results of examples 1-6 and application examples 1-6 above, it can be seen that the bronsted acid-lewis acid multifunctional carbon catalyst obtained by the mechanical ball milling method provided by the present invention is rich in oxygen-containing functional groups, and contains both bronsted acid and lewis acid active sites, and the catalyst can directly convert glucose into 5-hydroxymethylfurfural (hmf), 5-Ethoxymethylfurfural (EMF) and Ethyl Levulinate (EL) in ethanol solution. Compared with the traditional method, the preparation method of the catalyst is simple, efficient, environment-friendly, cheap and easily available in raw materials, and green and efficient in the whole process.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (8)
1. A preparation method of a multifunctional biochar catalyst rich in oxygen-containing functional groups and used for catalyzing glucose to prepare ethyl levulinate and 5-ethoxymethylfurfural is characterized by comprising the following steps:
the method comprises the following specific steps:
pyrolyzing lignin to obtain a lignin-based carbon material;
mixing a lignin-based carbon material, a Bronsted acid precursor and a Lewis acid precursor, and performing ball milling treatment to obtain a ball-milled carbon material;
oxidizing the ball-milled carbon material to obtain a multifunctional biochar catalyst rich in oxygen-containing functional groups; the catalyst comprises a lignin-based carbon material, and a sulfonic acid group, a combined Al and a carboxyl group which are grafted on the lignin-based carbon material in a covalent bond manner;
the Bronsted acid precursor is one of thiomalic acid, cysteine and thioglycolic acid;
the Lewis acid precursor is one of aluminum-containing metal salts;
the mass ratio of the lignin-based carbon material to the Bronsted acid precursor to the Lewis acid precursor is 2-4:0-4:4-0, and the sum of the mass ratio of the Bronsted acid precursor to the Lewis acid precursor is 4.
2. The method of claim 1, wherein: the mass ratio of the lignin-based carbon material to the Bronsted acid precursor to the Lewis acid precursor is 2:1.3:2.7, the Bronsted acid precursor is cysteine, and the Lewis acid precursor is aluminum acetate.
3. The method of claim 1, wherein: the mass ratio of the lignin-based carbon material to the Broensted acid precursor to the Lewis acid precursor is 2:2.5:1.5.
4. the method of claim 1, wherein: the rotating speed of the ball milling treatment is 5-20Hz; the ball milling treatment time is 1-5h; the diameter of the ball milling beads for ball milling treatment is 5-20mm, and the mass ratio of ball materials for ball milling treatment is 10-50:2-6.
5. The method of claim 1, wherein: the Lewis acid precursor is one of aluminum acetate, aluminum chloride or aluminum nitrate.
6. A method for preparing ethyl levulinate and 5-ethoxymethylfurfural by catalyzing glucose is characterized by comprising the following steps: mixing the biochar catalyst prepared by the preparation method of claim 1, glucose and ethanol, and carrying out isomerization, dehydration and esterification reaction on the glucose under the catalytic action of the biochar catalyst to obtain ethyl levulinate and 5-ethoxymethylfurfural.
7. The method of claim 6, wherein: the reaction temperature is 115-150 ℃ and the reaction time is 1-24h.
8. The method of claim 6, wherein: the mass concentration of glucose in a mixed solution obtained by mixing the biochar catalyst, glucose and ethanol is 1-5wt%; the mass ratio of the biochar catalyst to glucose is 1-9:5-15.
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