CN112121818B - Magnetic carbon-based catalyst, preparation method and application - Google Patents
Magnetic carbon-based catalyst, preparation method and application Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 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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- 239000002041 carbon nanotube Substances 0.000 claims description 16
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 16
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- 238000003756 stirring Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
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- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
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- 239000001913 cellulose Substances 0.000 claims description 6
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- 238000003786 synthesis reaction Methods 0.000 claims description 6
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- 238000001816 cooling Methods 0.000 claims description 5
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
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- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 13
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- 240000008042 Zea mays Species 0.000 description 4
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- 238000000227 grinding Methods 0.000 description 4
- 229930091371 Fructose Natural products 0.000 description 3
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 3
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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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
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- 230000003213 activating effect Effects 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
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- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
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- 238000004128 high performance liquid chromatography Methods 0.000 description 2
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- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- 150000002772 monosaccharides Chemical class 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B01J35/33—
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of high-valued utilization of biomass waste, and particularly relates to a magnetic carbon-based catalyst, a preparation method and application thereof. The preparation method comprises the steps of sulfonating a carbon-based carrier, and then loading a magnetic substance on the sulfonated carbon-based carrier by a precipitation method to obtain the magnetic carbon-based catalyst. The invention also relates to application of the magnetic carbon-based catalyst in directionally preparing 5-hydroxymethylfurfural through microwave catalytic liquefaction of cellulosic biomass. 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-valued utilization of biomass waste, and particularly relates to a magnetic carbon-based catalyst, a preparation method and application thereof.
Background
Petroleum, coal and natural gas are all primary energy sources which are mainly used worldwide today. However, with the increasing demands of people on energy and quality thereof, the efficient development and effective utilization of novel energy are important. Biomass is becoming more and more attractive as a new energy source, and the synthesis of energy products and high value-added chemicals using renewable biomass resources has gradually become a hotspot for research by researchers around the world in recent years. Furfural, one of the most competitive biomass-based platform compounds identified by the United states department of energy, is currently the only important chemical raw material obtained by completely utilizing agriculture and forestry waste extraction.
Although the higher reactivity of the 5-hydroxymethylfurfural has wide application prospect, the method has the advantages of low yield, poor selectivity and high energy consumption in the reproduction process. Many studies have been made by researchers to solve the above problems. Yan et al prepare and obtain carbon solid acid catalyst by taking corn straw as raw materialAnd studied in ionic liquids [ Bmim][Cl]The one-step method is used for catalyzing corn stalks to prepare 5-hydroxymethylfurfural, and when the corn stalks react for 30min at 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, and then combining MIP with H 2 S0 4 Carrying out synchronous hydrothermal carbonization and sulfonation to obtain the macroporous carbon solid acid catalyst with a multi-level pore structure, when [ Bmim ]][C1]As a solvent, the conversion of the catalytic cellulose can obtain the yield of the 5-hydroxymethylfurfural which is up to 43.1 percent, and the selectivity of the product is 57.7 percent. It can be seen that the two methods have the problems that the preparation method is complex, the catalyst is mixed with the reaction residues after the reaction is finished, the catalyst is difficult to separate, the catalyst cannot be recycled, and the ionic liquid is used as the reaction solvent, so that the cost is high, the application effect is poor, and the like.
The invention comprises the following steps:
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 disperse uniformly on the carrier, and has certain catalytic activity, thus being suitable for being used as the carrier of reaction; the carbon-based carriers such as carbon nano tubes, activated carbon and the like are loaded with iron element, so that the catalyst has low price and high acidity, is magnetic, and overcomes the problem that the catalyst cannot be recovered; 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 invention provides that carbon-based carriers such as carbon nano tubes, biochar and activated carbon are magnetic 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 problem that the catalyst is difficult to recycle, has the characteristics of difficult cooperation of the catalytic activity and the microwave absorption capacity of the catalyst, and the like, has simple preparation method, can effectively recycle the magnetic carbon-based catalyst, has high selectivity on the target product 5-hydroxymethylfurfural, and has good industrial application prospect.
The preparation method of the magnetic carbon-based catalyst is characterized by comprising the following steps:
placing a carbon-based carrier in concentrated sulfuric acid, magnetically stirring 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 with deionized water in a conical flask at room temperature to form a stable uniform system, mixing with a certain mass of sulfonated carbon-based carrier, and uniformly stirring; heating in water bath to 50-60deg.C under certain stirring speed, dropwise adding concentrated ammonia water to adjust pH to 7-8, maintaining for 1 hr, and maintaining in water bath at 70-80deg.C for 4-5 hr; after cooling, the reaction mixture was repeatedly rinsed with deionized water to remove Cl introduced during the synthesis - 、NH 4 + Then magnetically separating from the aqueous solution, and drying at 70-90 ℃ to obtain the magnetic carbon-based catalyst.
The concentration of the concentrated sulfuric acid is 1mol/L; the carbon-based carrier is carbon nanotube, biochar or active carbon.
The temperature of the magnetic stirring treatment is 70-80 ℃, the time is 4-5h, and the rotating speed is 200r/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 mass of the ferric dichloride tetrahydrate to the mass of the sulfonated carbon-based carrier is 1:5.
The certain stirring speed is 200r/min.
Adding cellulosic 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 aid 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; the filtrate is distilled, and the product 5-hydroxymethylfurfural and the reaction solvent are obtained by gradual separation.
The certain mesh number is 50-100 meshes.
The temperature of the oven is 70-80 ℃ and the drying time is 12h.
The mass ratio of the fine powder of the reaction raw materials, 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 rising refers to a process of using the microwave reactor of fig. 9, wherein parameters of the reactor can be set by itself and heating a reaction system by microwaves, and the set parameters are as follows: the reaction temperature T=120-240 ℃, the reaction time t=10-50 min and the microwave power P=10-180W.
The method for reactivating the catalyst comprises the following steps: the recovered catalyst was washed with water and acetone a number of times until the filtrate was clear, and then dried in an oven at 80 ℃.
The step separation refers to distillation separation by utilizing the difference of boiling points of a product and a solvent.
Pretreatment of raw materials: adding a certain mass of cellulosic biomass into a crushing grinder, grinding to a certain mesh number, placing the fine powder into an oven, and drying for a certain time.
The reaction: adding a certain mass of fine powder of a reaction raw material and a certain mass of magnetic carbon-based catalyst into a microwave reactor, and heating by microwave assistance to obtain a crude product.
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; the filtrate is distilled, and the product 5-hydroxymethylfurfural and the organic solvent are obtained by gradual separation.
The prepared iron-modified carbon-based catalyst maintains the advantages of stable chemical property, high catalytic activity and the like of the carbon-based carrier, and the catalyst is more suitable for hydrolysis of cellulosic 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:
the preparation method is characterized by comprising the steps of.
The beneficial effects are that:
1. the invention takes cellulose biomass as raw material, has wide sources, low price and simple and efficient pretreatment. The target product 5-hydroxymethylfurfural has good selectivity and high possibility of being put into production;
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 the unique characteristics of heat and mass transfer, 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 is a graph showing the effect of different reaction conditions on the preparation of 5-hydroxymethylfurfural by corncob microwave catalytic liquefaction under the action of sulfonated carbon nanotubes; t=180 ℃, p=150w, m=0.05 g; b: t=30 min, p=150 w, m=0.05 g.
FIG. 3 is a graph showing the effect of different reaction conditions on the preparation of 5-hydroxymethylfurfural by corncob microwave catalytic liquefaction under the action of sulfonated carbon nanotubes; t=20 ℃, t=30 min, p=150W; t=200 ℃, t=30 min, m=0.03 g.
FIG. 4 is a graph showing the effect of different solvents on the formation of 5-hydroxymethylfurfural by cob microwave catalytic liquefaction under the action of a magnetic carbon nanotube catalyst;
FIG. 5 is a graph showing the effect of different 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 is an illustration of the effect of different magnetic carbon-based catalysts on the preparation of 5-hydroxymethylfurfural by cob microwave catalytic liquefaction conversion; the solvent is dimethyl sulfoxide.
FIG. 7 is the effect of solvent circulation on the preparation of 5-hydroxymethylfurfural by cob microwave catalytic conversion; the catalyst is magnetic carbon nano tube.
FIG. 8 is a schematic illustration of a magnetic carbon nanotube catalyst;
fig. 9 is a schematic diagram of a microwave catalytic liquefaction reactor.
Reference numeral 8 illustrates:
1-a nitrogen cylinder; 2-an air control valve; 3-a microwave reaction device; 4-a computer; 5-a pressure sensor; 6-a microwave generating device; 7-a reaction kettle; 8-a display screen and an operating keyboard; 9-a remote sensing infrared sensor; 10-fiber probe
Detailed Description
The technical scheme of the invention is further described in detail below with reference to the accompanying drawings and specific embodiments.
Example one
Placing 2g of carbon nano tube in concentrated sulfuric acid, magnetically stirring at 70 ℃ for 5 hours, filtering, washing the sulfonated carbon nano tube with deionized water until the pH value is 7, preparing an aqueous solution containing ferric trichloride (1.2 g) and ferric dichloride tetrahydrate (0.8 g) into a conical flask with deionized water at room temperature to form a stable uniform system, mixing with 2g of sulfonated carbon nano tube, and uniformly stirring; heating the water bath to 50-60 ℃ at the rotating speed of 200r/min, dropwise adding concentrated ammonia water to adjust the pH to 7-8, preserving heat for 1h, and preserving heat in a water bath kettle at 80 ℃ for 4h; after cooling, the reaction mixture was repeatedly rinsed with deionized water to remove Cl introduced during the synthesis - 、NH 4 + Then magnetically separating from the aqueous solution, and drying at 90 ℃ to obtain the magnetic carbon nanotube catalyst, as shown in figure 8.
To verify the results of the synthesized catalyst, BET characterization analysis was performed.
TABLE 1 structural characterization of carbon nanotubes and magnetic carbon nanotube catalysts
Table 1 shows that the specific surface area and the void volume of the magnetic carbon nanotubes are increased, which indicates that the magnetic substance is successfully loaded on the surface of the carbon nanotubes, and the pore size is almost unchanged, which indicates that the carbon nanotube skeleton is not broken in the preparation process.
Example two
Taking 2g of biochar (obtained by cracking corn straw with microwaves, grinding to the mesh number of 40-50), placing in concentrated sulfuric acid, magnetically stirring at 80 ℃ for 4 hours, carrying out suction filtration, washing the sulfonated biochar with deionized water to pH 7, preparing an aqueous solution containing ferric trichloride (1.2 g) and ferric dichloride tetrahydrate (0.8 g) in a conical flask with deionized water at room temperature to form a stable uniform system, mixing with 2g of sulfonated biochar, and uniformly stirring; heating the water bath to 50-60 ℃ at the rotating speed of 200r/min, dropwise adding concentrated ammonia water to adjust the pH to 7-8, preserving heat for 1h, and preserving heat in a water bath kettle at 80 ℃ for 4h; after cooling, the reaction mixture was repeatedly rinsed with deionized water to remove Cl introduced during the synthesis - 、NH 4 + Then magnetically separating from the aqueous solution, and drying at 90 ℃ to obtain the magnetic biochar catalyst.
Example three
2g of active carbon (grinding to 40-50 mesh) is put into concentrated sulfuric acid, magnetically stirring is carried out for 5 hours at 70 ℃, suction filtration is carried out, the sulfonated active carbon is washed by deionized water until the pH value is 7, at room temperature, an aqueous solution containing ferric trichloride (1.2 g) and ferric dichloride tetrahydrate (0.8 g) is prepared by the deionized water in an conical flask to form a stable uniform system, and the stable uniform system is mixed with 2g of sulfonated active carbon, and is uniformly stirred; heating the water bath to 50-60 ℃ at the rotating speed of 200r/min, dropwise adding concentrated ammonia water to adjust the pH to 7-8, preserving heat for 1h, and preserving heat in a water bath kettle at 80 ℃ for 4h; after cooling, the reaction mixture was repeatedly rinsed with deionized water to remove Cl introduced during the synthesis - 、NH 4 + Then magnetically separating from the aqueous solution, and drying at 90 ℃ to obtain the magnetic activated carbon catalyst.
Example four
Taking 0.5g of prepared biomass corncob fine powder, 10ml of dimethyl sulfoxide and a magnetic stirring speed of 200rad/min, wherein a catalyst adopts sulfonated carbon nano tubes, and other important parameters are set according to a single factor method. Then, the microwave catalytic liquefaction reaction is carried out. Filtering after the reaction is finished, taking out the catalyst from the filter residue, and activating for later use. And after sampling the filtrate, distilling to obtain a product of 5-hydroxymethylfurfural and a solvent, and carrying out HPLC analysis on the sample.
As can be seen from the results in fig. 2 and 3, the optimal conditions for converting corncob into 5-hydroxymethylfurfural by microwave catalytic liquefaction of sulfonated carbon nanotubes are as follows: the reaction time is 30min, the reaction temperature is 200 ℃, and the catalyst dosage is 0.03g. Wherein the reaction temperature (shown in figure 2B) has the most obvious effect on the catalytic conversion of corncob reaction to 5-hydroxymethylfurfural, and the yield of 5-hydroxymethylfurfural is lower than 5wt.% at the reaction temperature of 120-160 ℃. When the temperature was increased to 180 ℃, the yield of 5-hydroxymethylfurfural reached 12.1wt.% rapidly, and to the optimum temperature of 200 ℃, the yield reached more 12.4wt.%. The possible reason for this reaction temperature being higher than the glucose or fructose conversion temperature is that higher temperatures are required for cob decomposition and polysaccharide hydrolysis. The decrease in yield may then be due to the gradual decomposition of the product 5-hydroxymethylfurfural, with a higher rate of decomposition than the rate of formation. This is consistent with the effect of reaction time on it (as shown in figure 2A). It can be seen from fig. 3C that as the catalyst usage increases, the yield of 5-hydroxymethylfurfural rapidly reaches a maximum of 20.4wt.% and then gradually decreases to 13.4wt.%, indicating that the greater catalyst usage is detrimental to the conversion reaction, which may be that the presence of excess catalyst affects the desorption of the product 5-hydroxymethylfurfural, resulting in a decrease in yield as seen from fig. 3D with an increase in microwave power, with a trend of increasing and then decreasing the yield of 5-hydroxymethylfurfural, and that the maximum yield of 5-hydroxymethylfurfural is 20.4wt.% at a microwave power of 150W.
Example five
Taking 0.5g of biomass raw material fine powder, 10ml of solvent and 10ml of solvent, setting the magnetic stirring speed to 200rad/min, setting the microwave liquefaction reaction temperature to 220 ℃, setting the microwave power to 150W, setting the reaction time to 30min, and setting the magnetic carbon-based catalyst to 0.03g and the solvent to 10ml. Then, the microwave catalytic liquefaction reaction is carried out. Filtering after the reaction is finished, taking out the catalyst from the filter residue, and activating for later use. Sampling the filtrate, distilling to obtain 5-hydroxymethylfurfural and solvent, and performing HPLC analysis
As can be seen from fig. 4, with the carbon-based catalyst, the yield of 5-hydroxymethylfurfural was 11.3wt.% with water as solvent, while under the effect of decalin and dimethyl sulfoxide, the yields of 5-hydroxymethylfurfural were 19.8wt.% and 23.3wt.%, respectively, which may be that both solvents have high boiling acids and both have a certain polarity.
From fig. 5, it can be seen that using pine, corncob, cellulose, glucose and fructose as raw materials, yields of 5-hydroxymethylfurfural were 19.4wt.%,23.3wt.%,33.9wt.%,62.9wt.%,96.4wt.%, respectively. The yield of 5-hydroxymethylfurfural from corncob to fructose of the raw material accords with the mechanism of isomerism and dehydration of saccharide substances obtained by hydrolysis of cellulosic biomass to generate 5-hydroxymethylfurfural, and the pine is used as the raw material, so that the yield of 19.4wt.% of 5-hydroxymethylfurfural is also achieved, which shows that the carbon-based catalyst has universality for agriculture and forestry biomass.
From fig. 6, it can be seen that the use of different magnetic carbon-based catalysts has an obvious catalytic effect on the conversion reaction, and the yields of 5-hydroxymethylfurfural obtained by using magnetic carbon nanotubes, magnetic biomass charcoal and magnetic activated charcoal as catalysts are 23.3wt.%,19.7wt.% and 18.5wt.%, respectively. While the conversion yield without catalyst was only 5.2wt.%.
As can be seen from fig. 7, after the solvent was repeatedly used 3 times, the yields of 5-hydroxymethylfurfural were 23.3wt.%, 24.6wt.% and 23.9wt.%, respectively, with a good circulation effect.
In conclusion, 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 the advantages of the two materials are complementary and synergistic, so that the yield of a target product can be obviously improved in the process of directionally preparing 5-hydroxymethylfurfural by using cellulose biomass to catalyze liquefaction, 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 (3)
1. An application of a magnetic carbon-based catalyst,the method is characterized in that the catalyst is used for converting cellulose biomass into 5-hydroxymethylfurfural in the microwave-assisted liquefaction process; the preparation method of the magnetic carbon-based catalyst comprises the following steps: placing a carbon-based carrier in concentrated sulfuric acid, magnetically stirring 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 with deionized water in a conical flask at room temperature to form a stable uniform system, mixing with a certain mass of sulfonated carbon-based carrier, and uniformly stirring; heating in water bath to 50-60deg.C under certain stirring speed, dropwise adding concentrated ammonia water to adjust pH to 7-8, maintaining temperature at 1-h, and maintaining temperature in water bath at 70-80deg.C at 4-5h; after cooling, the reaction mixture was repeatedly rinsed with deionized water to remove Cl introduced during the synthesis - 、NH4 + Then magnetically separating from the aqueous solution, and drying at 70-90 ℃ to obtain the magnetic carbon-based catalyst; the concentration of the concentrated sulfuric acid is 1mol/L; the carbon-based carrier is a carbon nanotube, biochar or activated carbon; the temperature of the magnetic stirring treatment is 70-80 ℃, the time is 4-5h, and the rotating speed is 200r/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 masses of the ferric trichloride and the ferric dichloride tetrahydrate to the sulfonated carbon-based carrier is 1:5; the certain stirring speed is 200r/min.
2. The use of a magnetic carbon-based catalyst according to claim 1, wherein cellulosic biomass is added to a pulverizer mill, ground to a certain mesh number, and the obtained fine powder of the reaction raw material is placed in an oven and dried 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 aid 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; the filtrate is distilled, and the product 5-hydroxymethylfurfural and the reaction solvent are obtained by gradual separation.
3. The use according to claim 2, wherein the certain mesh number is 50-100 mesh; the temperature of the oven is 70-80 ℃ and the drying time is 12 hours; the mass ratio of the fine powder of the reaction raw materials, 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 with water and acetone a number of times until the filtrate was clear, and then dried in an oven at 80 ℃.
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