CN112121818A - Magnetic carbon-based catalyst, preparation method and application - Google Patents
Magnetic carbon-based catalyst, preparation method and application Download PDFInfo
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- CN112121818A CN112121818A CN202011069203.8A CN202011069203A CN112121818A CN 112121818 A CN112121818 A CN 112121818A CN 202011069203 A CN202011069203 A CN 202011069203A CN 112121818 A CN112121818 A CN 112121818A
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- hydroxymethylfurfural
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 41
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 41
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- 230000008569 process Effects 0.000 claims description 7
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
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- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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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
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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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention belongs to the technical field of high-value utilization of biomass wastes, and particularly relates to a magnetic carbon-based catalyst, and a preparation method and application thereof. The preparation method comprises the steps of sulfonating the carbon-based carrier, and then loading the magnetic substance on the sulfonated carbon-based carrier by using a precipitation method to obtain the magnetic carbon-based catalyst. The invention also relates to an application of the magnetic carbon-based catalyst in microwave catalytic liquefaction of cellulose biomass for directionally preparing 5-hydroxymethylfurfural. The invention has the characteristics of simple catalyst preparation process, good selectivity, convenient separation, good recycling effect of partial substances and the like.
Description
Technical Field
The invention belongs to the technical field of high-value utilization of biomass wastes, and particularly relates to a magnetic carbon-based catalyst, and a preparation method and application thereof.
Background
Petroleum, coal and natural gas are primary energy sources mainly used in the world today. However, as the demand of people for energy and the quality thereof are increasing, efficient development and effective utilization of new energy sources are important. As a new energy source, biomass is more and more noticed by people, and the synthesis of energy products and high value-added chemicals by utilizing renewable biomass resources has gradually become a hotspot researched by researchers in various countries in the world in recent years. Furfural is one of the most competitive biomass-based platform compounds identified by the U.S. department of energy, and is one of the only important chemical raw materials which are obtained by fully utilizing agricultural and forestry wastes for refining at present.
Although the high reaction activity of the compound enables 5-hydroxymethylfurfural to have a wide application prospect, the compound has low yield, poor selectivity and high energy consumption in the reproduction process. In order to solve the above problems, researchers have made many studies. Yan et al prepared a carbon solid acid catalyst from corn straw as raw material and studied the use of the catalyst in ionic liquid [ Bmim ]][Cl]The corn straw is catalyzed by a medium-one-step method to prepare 5-hydroxymethylfurfural, and after the reaction is carried out for 30min at the temperature of 150 ℃, the yield of the obtained 5-hydroxymethylfurfural reaches 44.1 percent. Zhang et al prepared a macroporous inorganic, organic hybrid polymer by template method, then MIP and H2S04Performing synchronous hydrothermal carbonization and sulfonation to obtain a macroporous carbon solid acid catalyst with a hierarchical pore structure, namely [ Bmim ]][C1]As a solvent, the catalytic cellulose conversion can obtain the yield of 5-hydroxymethylfurfural of 43.1 percent, and the product selectivity is 57.7 percent. It can be seen that the above two methods both have the problems of complicated preparation method, difficult separation of the catalyst and the reaction residues after the reaction is finished, incapability of recycling the catalyst, high cost and poor application effect due to the use of ionic liquid as the reaction solvent, and the like.
The invention content is as follows:
aiming at the technical problems, the invention provides a magnetic carbon-based catalyst, a preparation method and application thereof.
In the invention, the carbon-based carrier, such as carbon nano tube and active carbon, has large specific surface area, and the active precursor is easy to be uniformly dispersed on the carrier, has certain catalytic activity and is suitable for being used as the characteristic of the carrier of the reaction; iron elements are loaded on carbon-based carriers such as carbon nanotubes, activated carbon and the like, so that the catalyst is low in price and high in acidity, and the catalyst is magnetic, so that the problem that the catalyst cannot be recycled is solved; the carbon-based catalyst reacts under the microwave heating condition, has unique heat and mass transfer effects, and can greatly improve the catalytic effect of the carbon-based catalyst on 5-hydroxymethylfurfural in the microwave-assisted liquefaction process. The patent of the invention proposes that carbon-based carriers such as carbon nano tubes, biochar and activated carbon have magnetism and participate in the reaction of converting cellulose biomass into 5-hydroxymethylfurfural in the microwave-assisted liquefaction process, which is not reported yet. The method overcomes the problems that the catalyst is difficult to recover, the catalytic activity and the microwave absorption capacity of the catalyst are difficult to cooperate, and the like, and has the characteristics of simple preparation method, effective recovery of the magnetic carbon-based catalyst, high selectivity on the target product 5-hydroxymethylfurfural and good industrial application prospect.
The preparation method of the magnetic carbon-based catalyst is characterized by comprising the following steps of:
placing the carbon-based carrier in concentrated sulfuric acid, performing magnetic stirring treatment at a certain temperature, performing suction filtration, washing the sulfonated carbon-based carrier with deionized water until the pH value is 7, preparing a certain amount of aqueous solution containing ferric trichloride and ferric dichloride tetrahydrate in a conical flask by using deionized water at room temperature to form a stable uniform system, mixing the stable uniform system with the sulfonated carbon-based carrier with a certain quality, and uniformly stirring; heating in water bath to 50-60 deg.C under stirring, dropwise adding concentrated ammonia water to adjust pH to 7-8, maintaining for 1 hr, and maintaining in 70-80 deg.C water bath for 4-5 hr; after cooling, the solution is repeatedly rinsed with deionized water to remove Cl introduced during the synthesis process-、NH4 +Then, magnetic separation is carried out from the water solution, and drying is carried out at 70-90 ℃ to obtain the magnetic carbon-based catalyst.
The concentration of the concentrated sulfuric acid is 1 mol/L; the carbon-based carrier is carbon nano tube, biochar or activated carbon.
The temperature of the magnetic stirring treatment is 70-80 ℃, the time is 4-5h, and the rotating speed is 200 r/min.
The molar ratio of the ferric trichloride to the ferric dichloride tetrahydrate is 1:1-1: 3; the mass ratio of the sum of the mass of the ferric trichloride and the ferric dichloride tetrahydrate to the sulfonated carbon-based carrier is 1: 5.
The certain stirring speed refers to 200 r/min.
Adding cellulose biomass into a crushing grinder, grinding to a certain mesh number, placing the obtained reaction raw material fine powder into an oven, and drying for a certain time. Adding a certain mass of reaction raw material fine powder, a certain mass of magnetic carbon-based catalyst and a reaction solvent into a microwave reactor, and heating with the assistance of microwaves to obtain a crude product; filtering to obtain filter residue and filtrate; the magnetic carbon-based catalyst in the filter residue is obtained by magnet adsorption, and the catalyst is activated again for the next use; and distilling the filtrate, and gradually separating to obtain a product 5-hydroxymethylfurfural and a reaction solvent.
The certain mesh number is 50-100 meshes.
The temperature of the oven is 70-80 ℃, and the drying time is 12 h.
The mass ratio of the reaction raw material fine powder, the magnetic carbon-based catalyst and the reaction solvent added into the microwave reactor is 0.5:0.01:11-0.5:0.07: 11; the reaction solvent is water, dimethyl sulfoxide, tetrahydrofuran, decalin or dimethylformamide.
The microwave-assisted temperature rise refers to the use of the microwave reactor of fig. 9, the parameters of the reactor can be set by itself, and the microwave is utilized to heat the reaction system, and the set parameters are as follows: the reaction temperature T is 120-240 ℃, the reaction time T is 10-50min, and the microwave power P is 10-180W.
The method for reactivating the catalyst comprises the following steps: the recovered catalyst was washed several times with water and acetone until the filtrate was clear, and then placed in an oven at 80 ℃ to dry.
The stepwise separation refers to the separation by distillation using the difference in boiling points between the product and the solvent.
Pretreatment of raw materials: adding cellulose biomass with a certain mass into a crushing and grinding machine, grinding to a certain mesh number, placing the fine powder into an oven, and drying for a certain time.
Reaction: adding a certain mass of reaction raw material fine powder and a certain mass of magnetic carbon-based catalyst into a microwave reactor, and raising the temperature with the assistance of microwave to obtain a crude product.
And (3) post-treatment: filtering to obtain filter residue and filtrate. The magnetic carbon-based catalyst in the filter residue is obtained by magnet adsorption, and the catalyst is activated again for the next use; and distilling the filtrate, and gradually separating to obtain a product 5-hydroxymethylfurfural and an organic solvent.
The carbon-based catalyst modified by iron prepared by the invention keeps the advantages of stable chemical property, high catalytic activity and the like of the carbon-based carrier, and is more suitable for hydrolysis of cellulose biomass and conversion of monosaccharide to 5-hydroxymethylfurfural by combining the regulation and control of iron element on acidity and the change of the surface of the catalyst through a precipitation method.
In the whole process, the organic solvent can be recycled, and the catalyst can be effectively separated.
A magnetic carbon-based catalyst, characterized by:
prepared by the process.
Has the advantages that:
1. the invention takes cellulose biomass as raw material, has wide source, low price, simple pretreatment and high efficiency. The target product 5-hydroxymethylfurfural has good selectivity and high production possibility;
2. the microwave reactor has the characteristics of high heating rate, low reaction temperature, short reaction time, less side reaction, promotion of chemical reaction, energy conservation and the like;
3. the microwave heating is combined with the carbon-based catalyst, so that the catalyst has unique heat and mass transfer characteristics, and the catalytic activity of the carbon-based catalyst is effectively improved;
4. the catalyst has high catalytic activity and good hydrothermal stability;
5. the carbon-based catalyst has certain magnetism and is easy to separate and recycle so as to be reused.
Drawings
FIG. 1 is a flow chart of 5-hydroxymethylfurfural production;
FIG. 2 shows the effect of different reaction conditions on the microwave catalytic liquefaction of corncobs to prepare 5-hydroxymethylfurfural under the action of sulfonated carbon nanotubes; t is 180 deg.C, P is 150W, m is 0.05 g; t is 30min, P is 150W, and m is 0.05 g.
FIG. 3 shows the effect of different reaction conditions on the microwave catalytic liquefaction of corncobs to prepare 5-hydroxymethylfurfural under the action of sulfonated carbon nanotubes; c, T is 20 ℃, T is 30min, and P is 150W; t200 ℃, T30 min, m 0.03 g.
FIG. 4 shows the effect of different solvents on the microwave catalytic liquefaction of corn cobs to produce 5-hydroxymethylfurfural under the action of a magnetic carbon nanotube catalyst;
FIG. 5 shows the effect of different raw materials on the preparation of 5-hydroxymethylfurfural by microwave catalytic liquefaction under the action of a magnetic carbon nanotube catalyst; the solvent is dimethyl sulfoxide.
FIG. 6 shows the effect of different magnetic carbon-based catalysts on the preparation of 5-hydroxymethylfurfural by microwave catalytic liquefaction and conversion of corncobs; the solvent is dimethyl sulfoxide.
FIG. 7 is a graph showing the effect of solvent circulation on the microwave catalytic conversion of corn cobs to produce 5-hydroxymethylfurfural; the catalyst is magnetic carbon nanotube.
FIG. 8 is a magnetic carbon nanotube catalyst;
FIG. 9 is a schematic diagram of a microwave catalytic liquefaction reactor.
FIG. 8 depicts a reference:
1-nitrogen gas cylinder; 2-an air control valve; 3-microwave reaction device; 4-a computer; 5-a pressure sensor; 6-a microwave generating device; 7-a reaction kettle; 8-display screen and operation keyboard; 9-remote sensing infrared sensor; 10-optical fiber probe
Detailed Description
The technical solution of the present invention is further described in detail with reference to the accompanying drawings and specific embodiments.
Example one
Placing 2g of carbon nano tube in concentrated sulfuric acid, performing magnetic stirring treatment at 70 ℃ for 5h, performing suction filtration, washing the sulfonated carbon nano tube with deionized water until the pH value is 7, preparing an aqueous solution containing ferric trichloride (1.2g) and ferric dichloride tetrahydrate (0.8g) in a conical flask with deionized water at room temperature to form a stable uniform system, mixing the stable uniform system with 2g of sulfonated carbon nano tube, and uniformly stirring; heating in water bath to 50-60 deg.C at a rotation speed of 200r/min, dropwise adding concentrated ammonia water to adjust pH to 7-8, maintaining the temperature for 1h, and maintaining the temperature in 80 deg.C water bath for 4 h; after cooling, the solution is repeatedly rinsed with deionized water to remove Cl introduced during the synthesis process-、NH4 +Then magnetically separating from the water solution, drying at 90 ℃ to obtain the magnetic carbon nano tube catalystAs shown in fig. 8.
To verify the results of the synthesized catalyst, BET characterization analysis was performed.
TABLE 1 analysis of structural characteristics of carbon nanotube and magnetic carbon nanotube catalysts
Table 1 shows structural characteristic analysis of the carbon nanotube and the magnetic carbon nanotube catalyst, and the results show that the specific surface area and the pore volume of the magnetic carbon nanotube are increased, which indicates that the magnetic substance is successfully loaded on the surface of the carbon nanotube, and the pore size is almost unchanged, which indicates that the carbon nanotube skeleton is not fractured during the preparation process.
Example two
Placing 2g of biochar (obtained by microwave pyrolysis of corn straws and ground to 40-50 meshes) in concentrated sulfuric acid, performing magnetic stirring treatment at 80 ℃ for 4 hours, performing suction filtration, washing sulfonated biochar with deionized water until the pH value is 7, preparing an aqueous solution containing ferric trichloride (1.2g) and ferric dichloride tetrahydrate (0.8g) in a conical flask with deionized water at room temperature to form a stable uniform system, mixing the stable uniform system with 2g of sulfonated biochar, and uniformly stirring; heating in water bath to 50-60 deg.C at a rotation speed of 200r/min, dropwise adding concentrated ammonia water to adjust pH to 7-8, maintaining the temperature for 1h, and maintaining the temperature in 80 deg.C water bath for 4 h; after cooling, the solution is repeatedly rinsed with deionized water to remove Cl introduced during the synthesis process-、NH4 +Then, magnetic separation is carried out from the water solution, and drying is carried out at the temperature of 90 ℃ to obtain the magnetic biochar catalyst.
Example three
Placing 2g of activated carbon (ground to 40-50 meshes) in concentrated sulfuric acid, performing magnetic stirring treatment at 70 ℃ for 5h, performing suction filtration, washing the sulfonated activated carbon with deionized water until the pH value is 7, preparing an aqueous solution containing ferric trichloride (1.2g) and ferric dichloride tetrahydrate (0.8g) in a conical flask with deionized water at room temperature to form a stable uniform system, mixing the stable uniform system with 2g of the sulfonated activated carbon, and uniformly stirring; heating the mixture to 50-60 ℃ in water bath at the rotating speed of 200r/min, and dropwise adding concentrated ammonia waterAdjusting pH to 7-8, keeping the temperature for 1h, and then keeping the temperature for 4h in a water bath kettle at 80 ℃; after cooling, the solution is repeatedly rinsed with deionized water to remove Cl introduced during the synthesis process-、NH4 +Then, magnetic separation is carried out from the water solution, and drying is carried out at the temperature of 90 ℃ to obtain the magnetic activated carbon catalyst.
Example four
Taking 0.5g of prepared biomass corncob fine powder, 10ml of dimethyl sulfoxide, and setting other important parameters according to a single-factor method, wherein the magnetic stirring speed is 200rad/min, and the catalyst adopts sulfonated carbon nanotubes. Then carrying out microwave catalytic liquefaction reaction. And after the reaction is finished, filtering, taking out the catalyst from filter residues, and activating for later use. And (3) after sampling the filtrate, distilling to obtain a product 5-hydroxymethylfurfural and a solvent, and carrying out HPLC analysis on the sample.
As can be seen from the results of FIG. 2 and FIG. 3, the optimal conditions for converting the sulfonated carbon nanotube into the 5-hydroxymethylfurfural by microwave catalytic liquefaction are as follows: the reaction time was 30min, the reaction temperature was 200 ℃ and the catalyst amount was 0.03 g. Wherein the reaction temperature (as shown in FIG. 2B) has the most obvious influence on the catalytic conversion of the corncobs to generate the 5-hydroxymethylfurfural, and the yield of the 5-hydroxymethylfurfural is lower than 5 wt% at the reaction temperature of 120-160 ℃. When the temperature is increased to 180 ℃, the yield of 5-hydroxymethylfurfural rapidly reaches 12.1 wt.%, and when the optimal temperature is reached to 200 ℃, the yield further reaches 12.4 wt.%. The higher temperature of the reaction than the glucose or fructose conversion temperature may be due to the higher temperature required for corncob decomposition and polysaccharide hydrolysis. The yield decrease may then be due to the gradual decomposition of the product 5-hydroxymethylfurfural, with a decomposition rate higher than the production rate. This is consistent with the results of the reaction time effect on it (as shown in figure 2A). It can be seen from fig. 3C that as the amount of catalyst used increases, the yield of 5-hydroxymethylfurfural rapidly reaches the maximum value of 20.4 wt.%, and then gradually decreases to 13.4 wt.%, indicating that the use amount of catalyst is large and unfavorable for the conversion reaction, which may be that the presence of excessive catalyst affects the desorption of the catalyst for the product 5-hydroxymethylfurfural, resulting in a yield decrease as the yield of 5-hydroxymethylfurfural increases with the increase of microwave power, and then decreases, and that when the microwave power is 150W, the maximum yield of 5-hydroxymethylfurfural is 20.4 wt.%.
Example five
Taking 0.5g of biomass raw material fine powder and 10ml of solvent, setting the magnetic stirring speed to be 200rad/min, the microwave liquefaction reaction temperature to be 220 ℃, the microwave power to be 150W, the reaction time to be 30min, 0.03g of magnetic carbon-based catalyst and 10ml of solvent. Then carrying out microwave catalytic liquefaction reaction. And after the reaction is finished, filtering, taking out the catalyst from filter residues, and activating for later use. After the filtrate is sampled, distillation is carried out to obtain a product 5-hydroxymethylfurfural and a solvent, and HPLC analysis is carried out on the sample
It can be seen from fig. 4 that with the carbon-based catalyst, the yield of 5-hydroxymethylfurfural was 11.3 wt.% with water as the solvent, and the yields of 5-hydroxymethylfurfural were 19.8 wt.% and 23.3 wt.% with decalin and dmso, respectively, which is likely that both solvents have high boiling acid and both have a certain polarity.
As can be seen from fig. 5, the yields of 5-hydroxymethylfurfural were 19.4 wt.%, 23.3 wt.%, 33.9 wt.%, 62.9 wt.%, 96.4 wt.%, respectively, using pine, corncob, cellulose, glucose and fructose as raw materials. The yield of 5-hydroxymethylfurfural from corncobs to fructose of the raw material accords with the mechanism of isomerization and dehydration of carbohydrate substances obtained by hydrolysis of cellulosic biomass to generate 5-hydroxymethylfurfural, and the yield of 5-hydroxymethylfurfural is 19.4 wt.% by using pine as the raw material, which shows that the carbon-based catalyst has universality for agriculture and forestry biomass.
As can be seen from fig. 6, different magnetic carbon-based catalysts have significant catalytic effects on the conversion reaction, and yields of 5-hydroxymethylfurfural obtained by using magnetic carbon nanotubes, magnetic biomass carbon and magnetic activated carbon as catalysts are 23.3 wt.%, 19.7 wt.% and 18.5 wt.%, respectively. While the conversion yield without catalyst was only 5.2 wt.%.
From fig. 7, it can be seen that after the solvent is reused 3 times, the yields of 5-hydroxymethylfurfural are 23.3 wt.%, 24.6 wt.% and 23.9 wt.%, respectively, and the recycling effect is better.
The supported magnetic carbon-based catalyst obtained by combining the carbon-based catalyst and the acidic metal oxide has hydrophilicity and strong acidity of the metal oxide catalyst, and can enable the advantages of the two materials to be complementary and have synergistic effects, so that the yield of a target product can be obviously improved in the process of directionally preparing 5-hydroxymethylfurfural by catalyzing, liquefying and reacting cellulose biomass, the magnetic carbon-based catalyst is easy to separate after reaction, the recycling of the catalyst is greatly promoted, and the production cost is reduced.
Claims (5)
1. A preparation method of a magnetic carbon-based catalyst is characterized in that a carbon-based carrier is placed in concentrated sulfuric acid, magnetic stirring treatment is carried out at a certain temperature, then suction filtration is carried out, the sulfonated carbon-based carrier is washed by deionized water until the pH value is 7, a certain amount of aqueous solution containing ferric trichloride and ferric dichloride tetrahydrate is prepared in a conical flask by the deionized water at room temperature to form a stable uniform system, and the stable uniform system is mixed with the sulfonated carbon-based carrier with a certain mass and stirred uniformly; heating in water bath to 50-60 deg.C under stirring, dropwise adding concentrated ammonia water to adjust pH to 7-8, maintaining for 1 hr, and maintaining in 70-80 deg.C water bath for 4-5 hr; after cooling, the solution is repeatedly rinsed with deionized water to remove Cl introduced during the synthesis process-、NH4+Then, magnetic separation is carried out from the water solution, and drying is carried out at 70-90 ℃ to obtain the magnetic carbon-based catalyst.
2. The method according to claim 1, wherein the concentrated sulfuric acid has a concentration of 1 mol/L; the carbon-based carrier is a carbon nano tube, biochar or activated carbon; the temperature of the magnetic stirring treatment is 70-80 ℃, the time is 4-5h, and the rotating speed is 200 r/min; the molar ratio of the ferric trichloride to the ferric dichloride tetrahydrate is 1:1-1: 3; the mass ratio of the sum of the mass of the ferric trichloride and the ferric dichloride tetrahydrate to the sulfonated carbon-based carrier is 1: 5; the certain stirring speed refers to 200 r/min.
3. The use of the magnetic carbon-based catalyst prepared by the preparation method of claim 1, wherein the catalyst is used for converting cellulosic biomass into 5-hydroxymethylfurfural in a microwave-assisted liquefaction process.
4. The use according to claim 3, wherein the cellulose-based biomass is added to a pulverizing mill, ground to a certain mesh number, and the resulting reaction raw material fine powder is placed in an oven and dried for a certain period of time; adding a certain mass of reaction raw material fine powder, a certain mass of magnetic carbon-based catalyst and a reaction solvent into a microwave reactor, and heating with the assistance of microwaves to obtain a crude product; filtering to obtain filter residue and filtrate; the magnetic carbon-based catalyst in the filter residue is obtained by magnet adsorption, and the catalyst is activated again for the next use; and distilling the filtrate, and gradually separating to obtain a product 5-hydroxymethylfurfural and a reaction solvent.
5. The use according to claim 4, wherein the predetermined mesh number is 50-100 mesh; the temperature of the oven is 70-80 ℃, and the drying time is 12 h; the mass ratio of the reaction raw material fine powder, the magnetic carbon-based catalyst and the reaction solvent added into the microwave reactor is 0.5:0.01:11-0.5:0.07: 11; the reaction solvent is water, dimethyl sulfoxide, tetrahydrofuran, decalin or dimethylformamide; the method for reactivating the catalyst comprises the following steps: the recovered catalyst was washed several times with water and acetone until the filtrate was clear, and then placed in an oven at 80 ℃ to dry.
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