CN116283846A - Method for high-valued agricultural residues by ternary deep eutectic solvent system - Google Patents
Method for high-valued agricultural residues by ternary deep eutectic solvent system Download PDFInfo
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- 239000002904 solvent Substances 0.000 title claims abstract description 51
- 230000005496 eutectics Effects 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 30
- 229920005610 lignin Polymers 0.000 claims abstract description 88
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 78
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 64
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- 239000001913 cellulose Substances 0.000 claims abstract description 38
- 239000007787 solid Substances 0.000 claims abstract description 38
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
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- 238000000967 suction filtration Methods 0.000 claims abstract description 27
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- 229960003178 choline chloride Drugs 0.000 claims description 13
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical group CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 9
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 9
- 241000209140 Triticum Species 0.000 claims description 5
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- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical group [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 3
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- 239000000126 substance Substances 0.000 abstract description 5
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 34
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- 239000002028 Biomass Substances 0.000 description 6
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- 238000000354 decomposition reaction Methods 0.000 description 3
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- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
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- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 1
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- 229920002472 Starch Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
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- 150000002240 furans Chemical class 0.000 description 1
- -1 furfural and 5-HMF Chemical class 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
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- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
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- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 description 1
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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
- C07D307/48—Furfural
- C07D307/50—Preparation from natural products
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
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- Biochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Polymers & Plastics (AREA)
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Abstract
A method for preparing agricultural residues by ternary deep eutectic solvent system high value comprises the steps of mixing two hydrogen bond donors and hydrogen bond acceptors, heating and stirring to prepare ternary deep eutectic solvent; mixing agricultural waste powder, ternary deep eutectic solvent, water and organic solvent, and heating for reaction; after the reaction is finished, cooling the reactor to room temperature, and collecting a reaction phase and an extraction phase to prepare furfural; adding acetone and water into the solid-liquid mixture for washing, and collecting filtrate; placing the filtrate into an oil bath pot, evaporating acetone, adding deionized water for washing, and performing suction filtration and drying to obtain lignin; washing the solid obtained after suction filtration by deionized water, and drying to obtain cellulose; mixing and stirring the extracted lignin and ferric salt, evaporating to dryness, and calcining at a high temperature to obtain the lignin-based graphitized carbon-based catalyst. The method can effectively separate the tri-macrophylla, simultaneously convert hemicellulose into high-value platform chemical furfural, enhance the enzymolysis efficiency of cellulose and realize the high-value utilization of agricultural wastes.
Description
Technical Field
The invention belongs to the technical field of comprehensive utilization of biomass resources, and particularly relates to a method for high-valued straw raw materials by using ternary deep eutectic solvents.
Background
With the shortage of non-renewable energy sources such as petroleum, coal and the like and the worsening of global environmental problems, the development and utilization of renewable energy sources are becoming research hotspots. Second generation biofuels are becoming more and more important than first generation biofuels. The starting material for the first generation of biofuels is edible starch, while the starting material for the second generation of biofuels is very wide, especially pesticide residues of lignocellulosic biomass. The straw is one of main agricultural residues, and has low cost and large available amount. It is estimated that wheat, rice and corn stover produced annually in China as agricultural residues are 6.5X10 8 Ton, but not utilized effectively. The wheat straw mainly comprises cellulose (30-35%), hemicellulose (15-25%) and lignin (10-25%). The cellulosic and hemicellulose fractions can be hydrolyzed and dehydrated to furans, such as furfural and 5-HMF, and then synthetically upgraded to fuels and chemicals, lignin for combustion power generation, conversion to phenolic compounds, or lignin-based materials. To resist microorganisms and enzymatic hydrolysis, lignocellulose has a tough structure, i.e. lignin-carbohydrate complex, limiting the separation of the three components and the production of subsequent value added products. In order to realize the efficient utilization of agricultural wastes, the three components are firstly separated by adopting a green and environment-friendly means. Biomass pretreatment is one of the most common techniques for removal and lignin modification in biorefinery, disrupting lignin-carbohydrate structure by altering the interactions of its components cellulose, hemicellulose and lignin. The pretreatment can not only improve the enzyme hydrolysis efficiency of the carbohydrate, but also effectively recycle cellulose, hemicellulose and lignin to realize the increment of biomass.
Various pretreatment methods have been developed to overcome the recalcitrance of lignocellulose in decomposition, such as dilute acid, alkali treatment, sulfite, organic solvent methods, but the above methods have disadvantages of damaging the environment, expensive cost, and damaging equipment. Abboot et al in 2004 discovered a novel solvent with similar physical and chemical properties to ionic liquids, named Deep Eutectic Solvent (DES). The deep eutectic solvent has the advantages of low cost, no toxicity, easy preparation, biodegradability, easy recovery and the like. They are composed of Hydrogen Bond Acceptors (HBAs) and Hydrogen Bond Donors (HBDs), which form complexes through hydrogen bonds, and have been widely used in the fields of catalysis, organic synthesis, electrochemistry, biomass processing, and the like. The deep eutectic solvent has high selectivity to the dissolved lignin, and is beneficial to regenerating lignin and retaining high-value utilization of cellulose. P-toluene sulfonic acid (p-TSA), an aromatic acid, is a hydrotrope with excellent delignification properties at low temperatures below the boiling point of water and can serve as an acidic hydrogen bond donor for DES. The acid hydrogen bond donor of the deep eutectic solvent can effectively separate cellulose, hemicellulose and lignin from lignocellulose. Para-toluene sulfonic acid can depolymerize lignin by ether bond cleavage and can separate carbohydrate-free lignin from lignocellulose. Whereas the less performing ethylene glycol is used as neutral HBD. DES containing three components, one HBA and two HBDs, have proven to be more effective in biomass deconstruction.
Chinese invention (CN 110218335 a) discloses a method for extracting lignin using ternary deep eutectic solvents. The method comprises the following steps: mixing the raw materials with ternary deep eutectic solvent for reaction, cooling to room temperature after the reaction is completed to obtain a reaction product, adding absolute ethyl alcohol into the reaction product, stirring, washing with the ethanol, filtering, concentrating, adding water, standing to obtain a precipitate containing lignin, filtering and drying to obtain lignin. This approach does not mention the subsequent use of trimangulin, and does not meet the expectations of the art.
The invention of China (CN 113956299A) discloses a method for preprocessing eucalyptus fractionated lignin and combining furfural by a double-phase system based on DES. The method comprises the steps of mixing raw materials, DES, an organic solvent and a catalyst, adding the mixture into a reaction kettle for reaction, cooling after the reaction is finished to obtain a solvent and an extract containing furfural, and washing and drying a deep eutectic reaction mixture by an acetone/water solution to obtain lignin. The invention realizes the co-production of furfural and lignin, but needs to add a catalyst in the reaction process, has complicated separation steps and does not accord with the principle of economy and environmental protection.
The invention of China (CN 106495132A) discloses a method for preparing graphene from lignin, which comprises the steps of firstly purifying lignin raw materials by adopting special enzyme treatment to obtain high-purity lignin; on the basis, high-quality graphene is obtained through oxidation, carbonization, graphitization and other processes. The method has complicated steps when purifying lignin, and side reactions such as decomposition, dehydration, esterification and the like are easy to generate in the purification process.
Disclosure of Invention
The technical problems to be solved are as follows: in view of the problems of the prior art that full component utilization of agricultural residues is not realized, the obtained product is relatively single, the added value is low, and the environment is not friendly, and the problem of difficult three-main-element separation due to the intractability of lignin-carbohydrate complex (LCC) bonds in biomass decomposition is solved. The deep eutectic solvent has the capability of cracking ester bonds between lignin and hemicellulose without affecting CC bonds in lignin, and the invention provides a method for high-valued agricultural residues by a ternary deep eutectic solvent system. The method can effectively separate the tri-macroprotein, simultaneously convert hemicellulose into high-value platform chemical furfural, enhance the enzymolysis efficiency of cellulose, and prepare the lignin-based graphitized carbon-based catalyst after mixing and pyrolyzing the extracted lignin and ferric salt, thereby realizing the high-value utilization of agricultural wastes.
The technical scheme is as follows: a method for high valued agricultural residues from a ternary deep eutectic solvent system, comprising the steps of: (1) Mixing two hydrogen bond donors and hydrogen bond acceptors, heating and stirring to obtain ternary deep eutectic solvent; the hydrogen bond acceptor is choline chloride, the two hydrogen bond donors are p-toluenesulfonic acid and ethylene glycol respectively, and the molar ratio of the choline chloride to the p-toluenesulfonic acid to the ethylene glycol is 1:1:0.2-0.5; (2) Mixing agricultural waste powder, ternary deep eutectic solvent, water and organic solvent, wherein the mass ratio of the agricultural waste powder to the ternary deep eutectic solvent is 1 (10-100), and the reaction is carried out for 0.5-2 h at the temperature of 80-120 ℃; (3) After the reaction is finished, cooling the reactor to room temperature, and collecting a reaction phase and an extraction phase to prepare furfural; (4) Adding acetone and water into the solid-liquid mixture in the step (3), washing, wherein the ratio of the acetone to the water is (1-4): 1, and collecting filtrate; (5) Placing the filtrate into an oil bath pot, evaporating acetone, adding deionized water for washing, and performing suction filtration and drying to obtain lignin; (6) Washing the solid obtained after suction filtration in the step (4) with deionized water, and drying to obtain cellulose; (7) Mixing and stirring the extracted lignin and ferric salt, wherein the mass ratio of the lignin to the ferric salt is 1 (0.2-2), evaporating the water, and calcining at a high temperature to obtain the lignin-based graphitized carbon-based catalyst.
Preferably, in step (1): p-toluenesulfonic acid, choline chloride and ethylene glycol are mixed according to a molar ratio of 1:1:0.3.
Preferably, in step (2): the agricultural waste is wheat straw or corn straw, and the grain size is 40-400 meshes.
Preferably, in step (2): the organic solvent is methyl isobutyl ketone, the reaction target temperature is 100 ℃, and the reaction time is 1h.
Preferably, in step (4): the ratio of the acetone to the water is 1:1.
Preferably, in step (7): the iron salt is ferric acetate.
Preferably, in step (7): the high-temperature calcination is carried out at 600-1000 ℃.
Preferably, in step (7): the mass ratio of lignin to ferric salt is 1:0.2.
The beneficial effects are that: (1) Compared with other traditional pretreatment methods or binary deep eutectic solvents, the method can improve the availability and extraction rate of the three main elements when the straws are treated, and can convert hemicellulose into high-value platform chemicals. (2) The lignin obtained by the extraction method can be used with ferric salt to obtain lignin-based graphitized carbon-based catalyst through carbonization, graphitization and other processes, and the advanced oxidation technology is shown. (3) The existing binary deep eutectic solvent treatment technology has the defects that only one hydrogen bond donor is insufficient to occupy all sites of a hydrogen bond acceptor, so that the formed hydrogen bond is weak in capability, and the solubility of lignin and hemicellulose is low in the process of separating and utilizing the trimangrin. After the straw is treated by the ternary deep eutectic solvent, the solubility and the utilization rate of lignin and hemicellulose can be enhanced, the complete cellulose can be reserved, and the enzymolysis efficiency of the cellulose is enhanced. (4) Compared with the traditional organic solvent and inorganic acid-base treatment method, the extraction method disclosed by the invention has the advantages of small environmental damage, low cost and high economic benefit, and accords with the development concept of green and environment protection.
Drawings
FIG. 1 is an XRD pattern of a lignin-based graphitized carbon-based catalyst prepared in accordance with the present invention;
FIG. 2 shows the reaction results of the lignin-based graphitized carbon-based catalyst prepared by the invention for degrading tetracycline in wastewater through Fenton reaction;
FIG. 3 shows the effect of the extraction method used in the present invention on the crystallinity of cellulose.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
Example 1
(1) Deep eutectic solvent preparation
The dried p-toluenesulfonic acid, choline chloride and ethylene glycol were mixed in a molar ratio of 1:1:0.3 and heated and stirred at 80 ℃ for 1h until all solids dissolved as a clear and transparent solution.
(2) Lignocellulose pretreatment and furfural testing
The straw is sieved by a 40-mesh sieve, and then dried to constant weight in a 60 ℃ oven. Adding the dried straw powder, methyl isobutyl ketone, water and deep eutectic solvent into a reactor, mixing the materials according to a solid-liquid ratio of 1:10, and heating the mixture for 1h at 100 ℃. After the reaction was completed, the reaction was cooled to room temperature, and deionized water was added to mix. The reactant is subjected to vacuum filtration, and solid residues and pretreatment liquid are separated. The furfural yield was measured to be 69.43%.
(3) Extraction and purification of lignin and cellulose
And adding 80mL of mixed solution of acetone and water into the solid residue, wherein the volume ratio of the mixed solution of the acetone and the water is 1:1, stirring uniformly, and then carrying out vacuum filtration for 3 times. Washing the cellulose solid subjected to suction filtration with deionized water for 3 times, and then putting the cellulose solid into an oven at 80 ℃ for drying. Mixing the filtrates obtained by 3 times of suction filtration, placing into an oil bath pan at 80deg.C, and evaporating acetone. 200mL of deionized water is added into the filtrate, the mixture is placed into a magnetic stirrer and stirred for 2 hours, and the pressure reduction and suction filtration are carried out for 3 times until the mixture is neutral. The extracted lignin was placed in an oven at 80 ℃ until constant weight.
(4) Preparation of lignin-based graphitized carbon-based catalyst
Dissolving ferric nitrate in 50mL of water, stirring until the ferric nitrate is dissolved, adding extracted lignin, soaking for 12 hours, evaporating the water in an oil bath at 80 ℃, and drying in an oven, wherein the mass ratio of the ferric acetate to the lignin is 1:0.2. Calcining at 2 ℃/min and 1000 ℃ for 1 hour to obtain the lignin-based catalyst.
Example 2
(1) Deep eutectic solvent preparation
The dried p-toluenesulfonic acid, choline chloride and ethylene glycol were mixed in a molar ratio of 1:1:0.6 and heated and stirred at 80 ℃ for 1h until all solids dissolved as a clear and transparent solution.
(2) Lignocellulose pretreatment
The straws are sieved by a 80-mesh sieve and then dried to constant weight in a 60 ℃ oven. Adding the dried straw powder, methyl isobutyl ketone, water and deep eutectic solvent into a reactor, mixing the materials according to a solid-liquid ratio of 1:20, and heating the mixture for 1h at 100 ℃. After the reaction was completed, the reaction was cooled to room temperature, and deionized water was added to mix. The reactant is subjected to vacuum filtration, and solid residues and pretreatment liquid are separated. The furfural yield was measured to be 57.45%.
(3) Extraction and purification of lignin and cellulose
And adding 80mL of mixed solution of acetone and water into the solid residue, wherein the volume ratio of the mixed solution of the acetone and the water is 2:1, stirring uniformly, and then carrying out vacuum filtration for 3 times. Washing the cellulose solid subjected to suction filtration with deionized water for 3 times, and then putting the cellulose solid into an oven at 80 ℃ for drying. Mixing the filtrates obtained by 3 times of suction filtration, placing into an oil bath pan at 80deg.C, and evaporating acetone. 200mL of deionized water is added into the filtrate, the mixture is placed into a magnetic stirrer and stirred for 2 hours, and the pressure reduction and suction filtration are carried out for 3 times until the mixture is neutral. The extracted lignin was placed in an oven at 80 ℃ until constant weight.
(4) Preparation of lignin-based graphitized carbon-based catalyst
Dissolving ferric oxalate in 50mL of water, stirring until the ferric oxalate is dissolved, adding extracted lignin, soaking for 12 hours, evaporating the water in an oil bath at 80 ℃, and drying in an oven, wherein the mass ratio of the ferric oxalate to the lignin is 1:0.5. Calcining at 2 ℃/min and 900 ℃ for 2 hours to obtain the lignin-based catalyst.
Example 3
(1) Deep eutectic solvent preparation
The dried p-toluenesulfonic acid, choline chloride and ethylene glycol were mixed in a molar ratio of 1:1:1 and heated and stirred at 80 ℃ for 1h until all solids dissolved as a clear and transparent solution.
(2) Lignocellulose pretreatment
The straws are sieved by a 120-mesh sieve and then dried to constant weight in a 60 ℃ oven. Adding the dried straw powder, methyl isobutyl ketone, water and deep eutectic solvent into a reactor, mixing the materials according to a solid-liquid ratio of 1:40, and heating the mixture for 1h at 100 ℃. After the reaction was completed, the reaction was cooled to room temperature, and deionized water was added to mix. The reactant is subjected to vacuum filtration, and solid residues and pretreatment liquid are separated. The furfural yield was measured to be 58.79%.
(3) Extraction and purification of lignin and cellulose
And adding 80mL of mixed solution of acetone and water into the solid residue, wherein the volume ratio of the mixed solution of the acetone and the water is 3:1, stirring uniformly, and then carrying out vacuum filtration for 3 times. Washing the cellulose solid subjected to suction filtration with deionized water for 3 times, and then putting the cellulose solid into an oven at 80 ℃ for drying. Mixing the filtrates obtained by 3 times of suction filtration, placing into an oil bath pan at 80deg.C, and evaporating acetone. 200mL of deionized water is added into the filtrate, the mixture is placed into a magnetic stirrer and stirred for 2 hours, and the pressure reduction and suction filtration are carried out for 3 times until the mixture is neutral. The extracted lignin was placed in an oven at 80 ℃ until constant weight.
(4) Preparation of lignin-based graphitized carbon-based catalyst
Dissolving ferric nitrate in 50mL of water, stirring until the ferric nitrate is dissolved, adding extracted lignin, soaking for 12 hours, evaporating the water in an oil bath at 80 ℃, and drying in an oven, wherein the mass ratio of the ferric nitrate to the lignin is 1:1.5. Calcining at 2 ℃/min and 800 ℃ for 2 hours to obtain the lignin-based catalyst.
Example 4
(1) Deep eutectic solvent preparation
The dried p-toluenesulfonic acid, choline chloride and ethylene glycol were mixed in a molar ratio of 1:1:0.3 and heated and stirred at 80 ℃ for 1h until all solids dissolved as a clear and transparent solution.
(2) Lignocellulose pretreatment
The straws are sieved by a 200-mesh sieve and then dried to constant weight in a 60 ℃ oven. Adding the dried straw powder, methyl isobutyl ketone, water and deep eutectic solvent into a reactor, mixing the materials according to a solid-liquid ratio of 1:100, and heating the mixture for 0.5h at 120 ℃. After the reaction was completed, the reaction was cooled to room temperature, and deionized water was added to mix. The reactant is subjected to vacuum filtration, and solid residues and pretreatment liquid are separated. The furfural yield was found to be 57.47%.
(3) Extraction and purification of lignin and cellulose
And adding 80mL of mixed solution of acetone and water into the solid residue, wherein the volume ratio of the mixed solution of the acetone and the water is 4:1, stirring uniformly, and then carrying out vacuum filtration for 3 times. Washing the cellulose solid subjected to suction filtration with deionized water for 3 times, and then putting the cellulose solid into an oven at 80 ℃ for drying. Mixing the filtrates obtained by 3 times of suction filtration, placing into an oil bath pan at 80deg.C, and evaporating acetone. 200mL of deionized water is added into the filtrate, the mixture is placed into a magnetic stirrer and stirred for 2 hours, and the pressure reduction and suction filtration are carried out for 3 times until the mixture is neutral. The extracted lignin was placed in an oven at 80 ℃ until constant weight.
(4) Preparation of lignin-based graphitized carbon-based catalyst
Dissolving ferric nitrate in 50mL of water, stirring until the ferric nitrate is dissolved, adding extracted lignin, soaking for 12 hours, evaporating the water in an oil bath at 80 ℃, and drying in an oven, wherein the mass ratio of the ferric nitrate to the lignin is 1:1. Calcining at 2 ℃/min and 1000 ℃ for 2 hours to obtain the lignin-based catalyst.
Example 5
(1) Deep eutectic solvent preparation
The dried p-toluenesulfonic acid, choline chloride and ethylene glycol were mixed in a molar ratio of 1:1:0.3 and heated and stirred at 80 ℃ for 1h until all solids dissolved as a clear and transparent solution.
(2) Lignocellulose pretreatment
The straws are sieved by a 200-mesh sieve and then dried to constant weight in a 60 ℃ oven. Adding the dried straw powder, methyl isobutyl ketone, water and deep eutectic solvent into a reactor, mixing the materials according to a solid-liquid ratio of 1:80, and heating the mixture at 100 ℃ for 1.5h. After the reaction was completed, the reaction was cooled to room temperature, and deionized water was added to mix. The reactant is subjected to vacuum filtration, and solid residues and pretreatment liquid are separated. The furfural yield was measured to be 47.47%.
(3) Extraction and purification of lignin and cellulose
And adding 80mL of mixed solution of acetone and water into the solid residue, wherein the volume ratio of the mixed solution of the acetone and the water is 4:1, stirring uniformly, and then carrying out vacuum filtration for 3 times. Washing the cellulose solid subjected to suction filtration with deionized water for 3 times, and then putting the cellulose solid into an oven at 80 ℃ for drying. Mixing the filtrates obtained by 3 times of suction filtration, placing into an oil bath pan at 80deg.C, and evaporating acetone. 200mL of deionized water is added into the filtrate, the mixture is placed into a magnetic stirrer and stirred for 2 hours, and the pressure reduction and suction filtration are carried out for 3 times until the mixture is neutral. The extracted lignin was placed in an oven at 80 ℃ until constant weight.
(4) Preparation of lignin-based graphitized carbon-based catalyst
Dissolving ferric nitrate in 50mL of water, stirring until the ferric nitrate is dissolved, adding extracted lignin, soaking for 12 hours, evaporating the water in an oil bath at 80 ℃, and drying in an oven, wherein the mass ratio of the ferric nitrate to the lignin is 1:2. Calcining at the temperature of 1000 ℃ for 3 hours at the speed of 2 ℃/min to obtain the lignin-based catalyst.
Example 6
(1) Deep eutectic solvent preparation
The dried p-toluenesulfonic acid, choline chloride and ethylene glycol were mixed in a molar ratio of 1:1:0.3 and heated and stirred at 80 ℃ for 1h until all solids dissolved as a clear and transparent solution.
(2) Lignocellulose pretreatment
The straws are sieved by a 200-mesh sieve and then dried to constant weight in a 60 ℃ oven. Adding the dried straw powder, methyl isobutyl ketone, water and deep eutectic solvent into a reactor, mixing the materials according to a solid-liquid ratio of 1:80, and heating the mixture for 0.5h at 100 ℃. After the reaction was completed, the reaction was cooled to room temperature, and deionized water was added to mix. The reactant is subjected to vacuum filtration, and solid residues and pretreatment liquid are separated. The furfural yield was measured to be 62.93%.
(3) Extraction and purification of lignin and cellulose
And adding 80mL of mixed solution of acetone and water into the solid residue, wherein the volume ratio of the mixed solution of the acetone and the water is 4:1, stirring uniformly, and then carrying out vacuum filtration for 3 times. Washing the cellulose solid subjected to suction filtration with deionized water for 3 times, and then putting the cellulose solid into an oven at 80 ℃ for drying. Mixing the filtrates obtained by 3 times of suction filtration, placing into an oil bath pan at 80deg.C, and evaporating acetone. 200mL of deionized water is added into the filtrate, the mixture is placed into a magnetic stirrer and stirred for 2 hours, and the pressure reduction and suction filtration are carried out for 3 times until the mixture is neutral. The extracted lignin was placed in an oven at 80 ℃ until constant weight.
(4) Preparation of lignin-based graphitized carbon-based catalyst
Dissolving ferric nitrate in 50mL of water, stirring until the ferric nitrate is dissolved, adding extracted lignin, soaking for 12 hours, evaporating the water in an oil bath at 80 ℃, and drying in an oven, wherein the mass ratio of the ferric nitrate to the lignin is 1:1. Calcining at 2 ℃/min and 1000 ℃ for 1 hour to obtain the lignin-based catalyst.
Example 7
(1) Deep eutectic solvent preparation
The dried p-toluenesulfonic acid, choline chloride and ethylene glycol were mixed in a molar ratio of 1:1:0.1 and heated and stirred at 80 ℃ for 1h until all solids dissolved as a clear and transparent solution.
(2) Lignocellulose pretreatment
The straws are sieved by a 200-mesh sieve and then dried to constant weight in a 60 ℃ oven. Adding the dried straw powder, methyl isobutyl ketone, water and deep eutectic solvent into a reactor, mixing the materials according to a solid-liquid ratio of 1:60, and heating the mixture for 1h at 100 ℃. After the reaction was completed, the reaction was cooled to room temperature, and deionized water was added to mix. The reactant is subjected to vacuum filtration, and solid residues and pretreatment liquid are separated. The furfural yield was measured to be 65.13%.
(3) Extraction and purification of lignin and cellulose
And adding 80mL of mixed solution of acetone and water into the solid residue, wherein the volume ratio of the mixed solution of the acetone and the water is 4:1, stirring uniformly, and then carrying out vacuum filtration for 3 times. Washing the cellulose solid subjected to suction filtration with deionized water for 3 times, and then putting the cellulose solid into an oven at 80 ℃ for drying. Mixing the filtrates obtained by 3 times of suction filtration, placing into an oil bath pan at 80deg.C, and evaporating acetone. 200mL of deionized water is added into the filtrate, the mixture is placed into a magnetic stirrer and stirred for 2 hours, and the pressure reduction and suction filtration are carried out for 3 times until the mixture is neutral. The extracted lignin was placed in an oven at 80 ℃ until constant weight.
(4) Preparation of lignin-based graphitized carbon-based catalyst
Dissolving ferric nitrate in 50mL of water, stirring until the ferric nitrate is dissolved, adding extracted lignin, soaking for 12 hours, evaporating the water in an oil bath at 80 ℃, and drying in an oven, wherein the mass ratio of the ferric nitrate to the lignin is 1:1. Calcining at 2 ℃/min and 900 ℃ for 2 hours to obtain the lignin-based catalyst.
Performance testing
HPLC tests are carried out on the ternary deep eutectic solvents with different molar ratios and the furfurals prepared under experimental conditions of different temperatures and times, and test results are shown in table 1, and as can be seen from table 1, hemicellulose can be efficiently converted into furfurals, and the highest fural yield can reach 69.43%.
Table 1 ternary deep eutectic solvent treatment of wheat straw to prepare furfural yield
XRD test was performed on the prepared lignin-based graphitized carbon-based catalyst, the test results are shown in FIG. 1, and it can be seen from FIG. 1 that the diffraction peak at 43.74 DEG is attributed to Fe 3 C(JCPDS:35–0772)，Fe 3 The presence of C also demonstrates that the iron salt is reduced during carbothermic reduction; diffraction peaks at 44.64 ° and 65 ° are due toα-Fe(JCPDS：06-0696)。
The Fenton reaction performance test is carried out on the prepared graphitized carbon material, and the test method comprises the following steps: 6mg of tetracycline is weighed and dissolved in 100mL of water, and a proper amount of HCl solution is added to adjust the pH to about 3, and an initial sample is taken. 10mg of catalyst was added and stirred for 1h, with samples taken every 30 min. To add 20 mu L H 2 O 2 The time of (2) is the origin of the reaction timing, and samples are taken every 5min with a syringe. The absorbance of TC was then measured with an ultraviolet-visible spectrophotometer at a maximum wavelength of 357 nm. The test results are shown in fig. 2, and it can be seen from fig. 2 that the degradation rate can reach 88.4% in a shorter time, which advantageously proves that the catalyst has a higher oxidation technology.
XRD testing of the pretreated cellulose showed that the crystallinity of the cellulose after treatment with the ternary deep eutectic solvent was significantly increased as seen in FIG. 3, which clearly demonstrates the ability of DES to remove lignin while retaining a fairly complete cellulose structure. And crystallinity of the cellulosic material is an important criterion for assessing the suitability of cellulose for enzymatic hydrolysis, an increase in crystallinity being indicative of an increase in cellulase hydrolysis efficiency.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered in the scope of the claims of the present invention.
Claims (8)
1. A method for high-valued agricultural residues by a ternary deep eutectic solvent system, which is characterized by comprising the following steps: (1) Mixing two hydrogen bond donors and hydrogen bond acceptors, heating and stirring to obtain ternary deep eutectic solvent; the hydrogen bond acceptor is choline chloride, the two hydrogen bond donors are p-toluenesulfonic acid and ethylene glycol respectively, and the molar ratio of the choline chloride to the p-toluenesulfonic acid to the ethylene glycol is 1:1:0.2-0.5; (2) Mixing agricultural waste powder, ternary deep eutectic solvent, water and organic solvent, wherein the mass ratio of the agricultural waste powder to the ternary deep eutectic solvent is 1 (10-100), and the reaction is carried out for 0.5-2 h at the temperature of 80-120 ℃; (3) After the reaction is finished, cooling the reactor to room temperature, and collecting a reaction phase and an extraction phase to prepare furfural; (4) Adding acetone and water into the solid-liquid mixture in the step (3), washing, wherein the ratio of the acetone to the water is (1-4): 1, and collecting filtrate; (5) Placing the filtrate into an oil bath pot, evaporating acetone, adding deionized water for washing, and performing suction filtration and drying to obtain lignin; (6) Washing the solid obtained after suction filtration in the step (4) with deionized water, and drying to obtain cellulose; (7) Mixing and stirring the extracted lignin and ferric salt, wherein the mass ratio of the lignin to the ferric salt is 1 (0.2-2), evaporating the water, and calcining at a high temperature to obtain the lignin-based graphitized carbon-based catalyst.
2. The method for high valued agricultural residues from a ternary deep eutectic solvent system according to claim 1, wherein in step (1): p-toluenesulfonic acid, choline chloride and ethylene glycol are mixed according to a molar ratio of 1:1:0.3.
3. The method for high valued agricultural residues from a ternary deep eutectic solvent system according to claim 1, wherein in step (2): the agricultural waste is wheat straw or corn straw, and the grain size is 40-400 meshes.
4. The method for high valued agricultural residues from a ternary deep eutectic solvent system according to claim 1, wherein in step (2): the organic solvent is methyl isobutyl ketone, the reaction target temperature is 100 ℃, and the reaction time is 1h.
5. The method for high valued agricultural residues from a ternary deep eutectic solvent system according to claim 1, wherein in step (4): the ratio of the acetone to the water is 1:1.
6. The method of high valued agricultural residues from a ternary deep eutectic solvent system according to claim 1, wherein in step (7): the iron salt is ferric acetate.
7. The method of high valued agricultural residues from a ternary deep eutectic solvent system according to claim 1, wherein in step (7): and the high-temperature calcination is carried out at the temperature of 600-1000 ℃.
8. The method of high valued agricultural residues from a ternary deep eutectic solvent system according to claim 1, wherein in step (7): the mass ratio of lignin to ferric salt is 1:0.2.
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| CN117447318B (en) * | 2023-10-26 | 2024-10-15 | 南京林业大学 | Deep eutectic solvent for co-producing phloretin and fermenting woody protein feed by utilizing apple tree pruning branches, and fermentation method and application thereof |
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