CN113321204A - Two-step method for degrading lignocellulose raw material to prepare phenolic chemicals and carbon quantum dots - Google Patents
Two-step method for degrading lignocellulose raw material to prepare phenolic chemicals and carbon quantum dots Download PDFInfo
- Publication number
- CN113321204A CN113321204A CN202110667262.3A CN202110667262A CN113321204A CN 113321204 A CN113321204 A CN 113321204A CN 202110667262 A CN202110667262 A CN 202110667262A CN 113321204 A CN113321204 A CN 113321204A
- Authority
- CN
- China
- Prior art keywords
- quantum dots
- carbon quantum
- solid
- raw material
- lignin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a two-step method for degrading lignocellulose raw materials to prepare phenolic chemicals and carbon quantum dots, which combines lignin degradation with biomass component separation and subsequent conversion of carbohydrates, firstly carries out catalytic hydrogenation reduction on lignin in the biomass raw materials to convert the lignin into a phenol compound taking 3-methoxy-4-hydroxy phenylpropyl alcohol and 3, 5-dimethoxy-4-hydroxy phenylpropyl alcohol as main products, and then prepares the carbon quantum dots from solid carbohydrate residues obtained by catalytic conversion through a one-step hydrothermal method, thereby realizing high-value conversion and utilization of the whole components of the lignocellulose biomass. The preparation method has the advantages of simple preparation process, mild reaction conditions and good industrial popularization prospect.
Description
Technical Field
The invention belongs to the technical field of biomass energy chemical industry, and relates to a method for preparing chemicals and materials by comprehensively utilizing all components of a lignocellulose raw material, in particular to a method for preparing phenolic chemicals and carbon quantum dots by degrading the lignocellulose raw material by a two-step method.
Background
The global energy demand mainly depends on fossil fuels such as petroleum, coal and natural gas, and the consumption of the fossil fuels accounts for 81 percent of the total primary energy supply in 2016 years. Their combustion causes the emission of pollutants such as COx, NOx, SOx, CxHy, dust, and particulate matter, thereby causing a series of problems such as thermal pollution, greenhouse effect, and environmental pollution. Therefore, the development and utilization of renewable energy sources to replace the existing fossil energy sources have become a hot research focus in countries around the world. Among them, lignocellulosic biomass, as the only renewable carbon source in nature, can be converted into energy, chemicals and materials, and is considered as an important method and approach for solving the energy crisis.
At present, the main method for refining lignocellulose is to utilize carbohydrates through technical means such as sulfite, sulfate and organic solvent pretreatment. Lignin is used as a byproduct associated in the biomass pretreatment process, and the beta-O-4 skeleton structure of the lignin generates an irreversible bond breaking-condensation reaction in the treatment process to form industrial lignin with serious condensation and low reaction activity. Most industrial lignin provides heat value through modes such as combustion and the like, so that a large amount of industrial lignin resources are wasted.
Lignin, the largest natural aromatic compound, accounts for 15-40% of lignocellulosic biomass. Depolymerization of lignin into phenolic monomeric compounds is an important technical means for realizing high-value utilization of lignin. The high-value utilization of the lignin can not only improve the economic benefit of the biomass refining industry, but also maximally utilize various components of the biomass and completely convert the components into valuable products.
At present, a great deal of research is carried out on catalytic conversion of lignin into phenolic monomer compounds by taking forest biomass as a raw material. Zhang et al catalytically degraded lignin in bamboo into 4-propoxyl guaiacol and 4-propoxyl syringol using Pd/C catalyst, enzymatically hydrolyzed cellulose and hemicellulose components in the remaining carbohydrates into monosaccharides with yields of glucose and xylose reaching 90% and 85%, respectively (Bioresource. technol., 2019, 285: 121335). Chen et al also catalyzed the degradation of eucalyptus lignin to phenolic monomeric compounds using Pd/C catalysts with a maximum monomer yield of 49.8 wt% and the retained carbohydrate syrup was catalyzed with a Lewis acid catalyst to convert it to levulinic acid and furfural (Biotechnol. Biofuels, 2020, 13(1): 1-10). Van den Bosch et Al used Ni-Al2O3 catalyst for catalytic hydrogenolysis of birch to 44% yield of lignin to phenolic monomers, simultaneous saccharification and fermentation of the remaining carbohydrates for bioethanol production (Green chem., 2017, 19: 3313-3326.). The previous research realizes that the yield of the lignin catalytically converted into the phenol monomer reaches the theoretical monomer yield by regulating and controlling the conditions of the type, the dosage, the reaction temperature, the reaction time and the like of the catalyst. However, less research has been conducted on the carbohydrates remaining after the catalytic reaction, and there is a limitation to achieving further high-value conversion of carbohydrates simply by acid catalysis or biological treatment. Therefore, the lignocellulose raw material is directly subjected to catalytic reduction treatment, the degradation of lignin is realized, and the cellulose and hemicellulose components can be basically reserved for subsequent conversion and utilization on the premise that the yield of the phenol monomer reaches the theoretical maximum value. The method explores high-efficiency lignocellulose raw material full-component conversion and utilization, and has important application value for producing chemicals and materials.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a method for preparing chemicals and materials by comprehensively utilizing all components of a lignocellulose raw material, and the lignocellulose raw material is catalytically degraded by a two-step method, so that the aim of efficiently converting all three components of a biomass raw material into high-added-value products such as the chemicals and the materials is fulfilled.
The invention adopts the following technical scheme:
degrading a lignocellulose raw material by a two-step method to prepare phenolic chemicals and carbon quantum dots, combining lignin degradation with biomass component separation and subsequent conversion of carbohydrates, firstly carrying out catalytic hydrogenation reduction on the lignin in the biomass raw material to preferentially degrade the lignin into phenolic compounds, and then preparing the carbon quantum dots from solid carbohydrate residues obtained by catalytic conversion by a one-step hydrothermal method;
the method specifically comprises the following steps:
(1) mixing a lignocellulose raw material with a proper amount of alcohol solvent and a proper amount of metal catalyst, and putting the mixture and a rotor into a stainless steel reactor;
(2) introducing nitrogen into the reactor filled in the step (1), replacing air in a stainless steel reactor, then introducing pressurized hydrogen, putting the reactor into a matched heating device for heating reaction for a certain time, and simultaneously starting magnetic stirring at the stirring speed of 800 rpm;
(3) after the reaction in the step (2) is finished, rapidly cooling the reactor to room temperature by using ice water, and filtering the reaction mixture by using a sand core funnel device to realize solid-liquid separation, wherein the liquid mainly contains a phenol compound after lignin degradation;
(4) adding a proper amount of deionized water into the solid carbohydrate residues obtained in the step (3), carrying out ultrasonic treatment for a certain time to obtain a solution with good dispersibility, and then filling the solution into a polytetrafluoroethylene tube;
(5) heating the mixed solution obtained in the step (4) to a reaction temperature for reacting for a certain time, and preparing carbon quantum dots;
(6) and (5) cooling to room temperature after the reaction is finished, and extracting the carbon quantum dots.
The lignocellulose raw material in the step (1) is firstly crushed to 20-40 meshes of granularity and dried.
The wood fiber raw material in the step (1) comprises at least one raw material of broadleaf wood, softwood and herbaceous plants; the broadleaf wood is at least one of birch, phoenix tree or poplar, the coniferous wood is at least one of masson pine or cedar, and the herbaceous plant is at least one of pennisetum, switchgrass and rice straw.
The alcohol solvent in the step (1) comprises at least one of methanol, tetrahydrofuran/water, isopropanol and water, and the metal catalyst comprises Mo/C, Ru/C, Ni/C, MoOxin/C and Zn/Pd/COne of the wood fiber raw materials is less, the solid-liquid ratio of the wood fiber raw materials to the alcohol solvent is 10-50 g/L, and the dosage of the metal catalyst is 5-40 wt% (based on the dosage of the wood fiber raw materials).
The pressure of the hydrogen in the step (2) is 1-5 MPa, and the reaction temperature is 140-280 MPaoAnd C, the reaction time is 0-20 h.
The liquid obtained in the step (3) mainly contains lignin-degraded phenol compounds, including lignin monomers, dimers and a small amount of polymers, and then contains part of carbohydrate degradation products;
after rotary evaporation of the liquid, the phenol compound was collected by extraction with dichloromethane.
The solid carbohydrate residue obtained in the step (3) is rich in carbohydrate and the solid catalyst added before the reaction, and the solid carbohydrate residue remained in the wood fiber raw material is obtained while the catalyst is recovered by selecting a screening mode with a 300-mesh sieve.
In the step (4), the solid-to-liquid ratio of the solid carbohydrate residues to the deionized water is 10-70 g/L, and the ultrasonic time of the mixture is 20-100 min.
The reaction temperature for preparing the carbon quantum dots in the step (5) is 140-220%oAnd C, the reaction time is 1-36 h.
The step (6) of extracting the carbon quantum dots comprises the following steps:
(6-1) filtering through a 0.22 μm microporous membrane to obtain a supernatant, the prepared carbon quantum dots being present in the brown supernatant;
(6-2) putting the supernatant into a dialysis membrane of 500 Da for dialysis for 72 h for purification;
and (6-3) freeze-drying the purified supernatant to obtain the solid carbon quantum dots.
The beneficial effects obtained by adopting the technical scheme are as follows:
the invention takes the wood fiber biomass as the raw material to directly carry out catalytic reduction, thereby realizing that the lignin in the wood fiber raw material is preferentially degraded into phenol compounds. In the process, cellulose and hemicellulose components in the wood fiber raw material can be basically reserved and used for preparing the carbon quantum dots through a subsequent one-step hydrothermal method, so that high-value utilization of all components of the wood fiber raw material is realized.
According to the invention, through optimization of the catalytic process, the lignin can be preferentially and selectively converted into the phenol compound, the monomer yield reaches the theoretical maximum value, and the development of the technology related to the preparation of fine chemical products by degrading the lignin is promoted.
The method realizes high yield of carbohydrate residues after the catalytic degradation of lignin from the lignocellulose raw material by regulating and controlling reaction conditions in the hydrothermal treatment process, and catalytically degrades the lignocellulose raw material by a two-step method to convert the lignocellulose raw material into a phenol compound taking 3-methoxy-4-hydroxy phenylpropanol and 3, 5-dimethoxy-4-hydroxy phenylpropanol as main products. In the process, cellulose and hemicellulose components can be basically reserved and the carbon quantum dots are prepared by a one-step hydrothermal method, so that high-value conversion and utilization of all components of the lignocellulose biomass are realized.
The preparation method has the advantages of simple preparation process, mild reaction conditions and good industrial popularization prospect.
Drawings
FIG. 1 is a schematic diagram of a two-step process for degrading a lignocellulosic feedstock to produce phenolic chemicals and carbon quantum dots.
Detailed Description
The technical solution in the embodiment of the present invention is clearly and completely described with reference to fig. 1, and it is obvious that the described embodiment is only a part of the embodiment of the present invention, and not a whole embodiment. It should be noted that, based on the embodiments of the present invention, all other embodiments obtained by a person of ordinary skill in the art without any creative effort belong to the protection scope of the present invention.
A method for preparing phenolic chemicals and carbon quantum dots by degrading a lignocellulose raw material by a two-step method combines lignin degradation with separation of biomass components and subsequent conversion of carbohydrates, firstly carries out catalytic hydrogenation reduction on lignin in the biomass raw material, preferentially degrades the lignin into phenolic compounds, and then prepares the carbon quantum dots by a one-step hydrothermal method on solid carbohydrate residues obtained by catalytic conversion.
Example 1
The lignocellulose raw material-birch is firstly crushed to 20-40 meshes of granularity and dried.
(1) Taking 15 g of birch with the particle size of 20-40 meshes, adding 500 mL of methanol and 15 wt% of Mo/C catalyst, and putting the birch into a stainless steel reactor.
(2) Introducing nitrogen to replace air therein, subsequently introducing 2 MPa of hydrogen, and heating the mixture to 250oC, reacting for 4 hours, and simultaneously turning on magnetic stirring at the stirring speed of 800 rpm.
(3) Filtering the reaction mixture obtained in the step (2) by using a sand core funnel device to realize solid-liquid separation, wherein the liquid mainly contains a phenol compound after lignin degradation, including lignin monomers, dimers and a small amount of polymers, and a part of carbohydrate degradation products, and after the liquid is subjected to rotary evaporation, extracting and collecting the phenol compound by using dichloromethane to obtain a phenol compound; the solid carbohydrate residue is rich in carbohydrate and solid catalyst added before reaction, and the solid carbohydrate residue remained in the wood fiber raw material is obtained while the catalyst is recovered by selecting a screening mode with a 300-mesh sieve.
(4) And (3) taking 5.0 g of the solid carbohydrate residue obtained in the step (3), adding 100 mL of deionized water, carrying out ultrasonic treatment on the mixture for 30 min, and filling the mixture into a polytetrafluoroethylene tube.
(5) Heating the mixture obtained in the step (4) to 200 DEGoC, reacting for 5 h, and preparing the carbon quantum dots.
(6) Filtering through a 0.22 mu m microporous membrane after the reaction is finished to obtain supernatant, wherein the prepared carbon quantum dots exist in the brown supernatant; putting the supernatant into a 500 Da dialysis membrane for dialysis for 72 h for purification; and freeze-drying the purified supernatant to obtain the solid carbon quantum dots.
The phenol monomer yield and quantum yield of this example were tested.
Example 2
The lignocellulose raw material-birch is firstly crushed to 20-40 meshes of granularity and dried.
(1) Taking 15 g of birch with the particle size of 20-40 meshes, adding 500 mL of water and 20 wt% of Mo/C catalyst, and putting the birch into a stainless steel reactor.
(2) Introducing nitrogen to replace air therein, and then introducing 2 MPa hydrogen; the resulting mixture was warmed to 250 deg.CoC, reacting for 5 hours, and simultaneously turning on magnetic stirring at the stirring speed of 800 rpm.
(3) Filtering the reaction mixture obtained in the step (2) by using a sand core funnel device to realize solid-liquid separation, wherein the liquid mainly contains a phenol compound after lignin degradation, including lignin monomers, dimers and a small amount of polymers, and a part of carbohydrate degradation products, and after the liquid is subjected to rotary evaporation, extracting and collecting the phenol compound by using dichloromethane to obtain a phenol compound; the solid carbohydrate residue is rich in carbohydrate and solid catalyst added before reaction, and the solid carbohydrate residue remained in the wood fiber raw material is obtained while the catalyst is recovered by selecting a screening mode with a 300-mesh sieve.
(4) And (3) taking 5.0 g of the solid carbohydrate residue obtained in the step (3), adding 100 mL of deionized water, carrying out ultrasonic treatment on the mixture for 30 min, and filling the mixture into a polytetrafluoroethylene tube.
(5) Heating the mixture obtained in the step (4) to 200 DEGoC, reacting for 8 h, and preparing the carbon quantum dots.
(6) Filtering through a 0.22 mu m microporous membrane after the reaction is finished to obtain supernatant, wherein the prepared carbon quantum dots exist in the brown supernatant; putting the supernatant into a 500 Da dialysis membrane for dialysis for 72 h for purification; and freeze-drying the purified supernatant to obtain the solid carbon quantum dots.
The phenol monomer yield and quantum yield of this example were tested.
Example 3
The lignocellulose raw material-poplar wood is firstly crushed to 20-40 meshes of granularity and dried.
(1) Taking 15 g of poplar wood with the particle size of 20-40 meshes, adding 500 mL of tetrahydrofuran/water and 20 wt% of Ru/C catalyst, and placing the mixture into a stainless steel reactor.
(2) Introducing nitrogen to replace air therein, subsequently introducing 2 MPa hydrogen, and heating the mixture to250 oC, reacting for 5 hours, and simultaneously turning on magnetic stirring at the stirring speed of 800 rpm.
(3) Filtering the reaction mixture obtained in the step (2) by using a sand core funnel device to realize solid-liquid separation, wherein the liquid mainly contains a phenol compound after lignin degradation, including lignin monomers, dimers and a small amount of polymers, and a part of carbohydrate degradation products, and after the liquid is subjected to rotary evaporation, extracting and collecting the phenol compound by using dichloromethane to obtain a phenol compound; the solid carbohydrate residue is rich in carbohydrate and solid catalyst added before reaction, and the solid carbohydrate residue remained in the wood fiber raw material is obtained while the catalyst is recovered by selecting a screening mode with a 300-mesh sieve.
(4) And (3) taking 5.0 g of the solid carbohydrate residue obtained in the step (3), adding 100 mL of deionized water, carrying out ultrasonic treatment on the mixture for 30 min, and filling the mixture into a polytetrafluoroethylene tube.
(5) Heating the mixture obtained in the step (4) to 160 DEGoAnd C, reacting for 36 h, and preparing the carbon quantum dots.
(6) Filtering through a 0.22 mu m microporous membrane after the reaction is finished to obtain supernatant, wherein the prepared carbon quantum dots exist in the brown supernatant; putting the supernatant into a 500 Da dialysis membrane for dialysis for 72 h for purification; and freeze-drying the purified supernatant to obtain the solid carbon quantum dots.
The phenol monomer yield and quantum yield of this example were tested.
Example 4
(1) Taking 15 g of birch with the particle size of 20-40 meshes, adding 700 mL of tetrahydrofuran/water and 15 wt% of Zn/Pd/C catalyst, and putting the mixture into a stainless steel reactor
(2) Introducing nitrogen to replace air therein, and then introducing 3 MPa hydrogen; the resulting mixture was warmed to 250 deg.CoC, reacting for 5 hours, and simultaneously turning on magnetic stirring at the stirring speed of 800 rpm.
(3) Filtering the reaction mixture obtained in the step (2) by using a sand core funnel device to realize solid-liquid separation, wherein the liquid mainly contains a phenol compound after lignin degradation, including lignin monomers, dimers and a small amount of polymers, and a part of carbohydrate degradation products, and after the liquid is subjected to rotary evaporation, extracting and collecting the phenol compound by using dichloromethane to obtain a phenol compound; the solid carbohydrate residue is rich in carbohydrate and solid catalyst added before reaction, and the solid carbohydrate residue remained in the wood fiber raw material is obtained while the catalyst is recovered by selecting a screening mode with a 300-mesh sieve.
(4) And (3) taking 5.0 g of the solid carbohydrate residue obtained in the step (3), adding 100 mL of deionized water, carrying out ultrasonic treatment on the mixture for 60 min, and filling the mixture into a polytetrafluoroethylene tube.
(5) Heating the mixture obtained in the step (4) to 220 DEGoC, reacting for 8 h, and preparing the carbon quantum dots.
(6) Filtering through a 0.22 mu m microporous membrane after the reaction is finished to obtain supernatant, wherein the prepared carbon quantum dots exist in the brown supernatant; putting the supernatant into a 500 Da dialysis membrane for dialysis for 72 h for purification; and freeze-drying the purified supernatant to obtain the solid carbon quantum dots.
The phenol monomer yield and quantum yield of this example were tested.
Example 5
(1) Taking 15 g of switchgrass with the particle size of 20-40 meshes, adding 400 mL of water and 10 wt% of Zn/Pd/C catalyst, and putting the mixture into a stainless steel reactor.
(2) Introducing nitrogen to replace air therein, and then introducing 4 MPa hydrogen; the resulting mixture was warmed to 270 deg.CoC, reacting for 3 hours, and simultaneously turning on magnetic stirring at the stirring speed of 800 rpm.
(3) Filtering the reaction mixture obtained in the step (2) by using a sand core funnel device to realize solid-liquid separation, wherein the liquid mainly contains a phenol compound after lignin degradation, including lignin monomers, dimers and a small amount of polymers, and a part of carbohydrate degradation products, and after the liquid is subjected to rotary evaporation, extracting and collecting the phenol compound by using dichloromethane to obtain a phenol compound; the solid carbohydrate residue is rich in carbohydrate and solid catalyst added before reaction, and the solid carbohydrate residue remained in the wood fiber raw material is obtained while the catalyst is recovered by selecting a screening mode with a 300-mesh sieve.
(4) And (3) taking 5.0 g of the solid carbohydrate residue obtained in the step (3), adding 150 mL of deionized water, carrying out ultrasonic treatment on the mixture for 60 min, and filling the mixture into a polytetrafluoroethylene tube.
(5) Heating the mixture obtained in the step (4) to 160 DEGoC, reacting for 24 hours.
(6) Filtering through a 0.22 mu m microporous membrane after the reaction is finished to obtain supernatant, wherein the prepared carbon quantum dots exist in the brown supernatant; putting the supernatant into a 500 Da dialysis membrane for dialysis for 72 h for purification; and freeze-drying the purified supernatant to obtain the solid carbon quantum dots.
The phenol monomer yield and quantum yield of this example were tested.
Example 6
(1) Taking 15 g of masson pine with the particle size of 20-40 meshes, adding 500 mL of isopropanol and 10 wt% of Ru/C catalyst, and placing the mixture into a stainless steel reactor.
(2) Introducing nitrogen to replace air therein, and then introducing 4 MPa hydrogen; the resulting mixture was warmed to 270 deg.CoC, reacting for 3 hours, and simultaneously starting magnetic stirring at the stirring speed of 800 rpm;
(3) filtering the reaction mixture obtained in the step (2) by using a sand core funnel device to realize solid-liquid separation, wherein the liquid mainly contains a phenol compound after lignin degradation, including lignin monomers, dimers and a small amount of polymers, and a part of carbohydrate degradation products, and after the liquid is subjected to rotary evaporation, extracting and collecting the phenol compound by using dichloromethane to obtain a phenol compound; the solid carbohydrate residue is rich in carbohydrate and solid catalyst added before reaction, and the solid carbohydrate residue remained in the wood fiber raw material is obtained while the catalyst is recovered by selecting a screening mode with a 300-mesh sieve.
(4) And (3) taking 5.0 g of the solid carbohydrate residue obtained in the step (3), adding 150 mL of deionized water, carrying out ultrasonic treatment on the mixture for 60 min, and filling the mixture into a polytetrafluoroethylene tube.
(5) Subjecting the product of step (4)Heating the mixture to 160 deg.CoAnd C, reacting for 36 h, and preparing the carbon quantum dots.
(6) Filtering through a 0.22 mu m microporous membrane after the reaction is finished to obtain supernatant, wherein the prepared carbon quantum dots exist in the brown supernatant; putting the supernatant into a 500 Da dialysis membrane for dialysis for 72 h for purification; and freeze-drying the purified supernatant to obtain the solid carbon quantum dots.
The phenol monomer yield and quantum yield of this example were tested.
Example 7
(1) Taking 15 g of poplar wood with the particle size of 20-40 meshes, adding 800 mL of tetrahydrofuran/water and 15 wt% of Mo/C catalyst, and putting the mixture into a stainless steel reactor.
(2) Introducing nitrogen to replace air therein, and then introducing 5 MPa hydrogen; the resulting mixture was warmed to 250 deg.CoC, reacting for 8 hours, and simultaneously turning on magnetic stirring at the stirring speed of 800 rpm.
(3) Filtering the reaction mixture obtained in the step (2) by using a sand core funnel device to realize solid-liquid separation, wherein the liquid mainly contains a phenol compound after lignin degradation, including lignin monomers, dimers and a small amount of polymers, and a part of carbohydrate degradation products, and after the liquid is subjected to rotary evaporation, extracting and collecting the phenol compound by using dichloromethane to obtain a phenol compound; the solid carbohydrate residue is rich in carbohydrate and solid catalyst added before reaction, and the solid carbohydrate residue remained in the wood fiber raw material is obtained while the catalyst is recovered by selecting a screening mode with a 300-mesh sieve.
(4) And (3) taking 5.0 g of the solid carbohydrate residue obtained in the step (3), adding 100 mL of deionized water, carrying out ultrasonic treatment on the mixture for 30 min, and filling the mixture into a polytetrafluoroethylene tube.
(5) Heating the mixture obtained in the step (4) to 180 DEGoC, reacting for 10 h, and preparing the carbon quantum dots.
(6) Filtering through a 0.22 mu m microporous membrane after the reaction is finished to obtain supernatant, wherein the prepared carbon quantum dots exist in the brown supernatant; putting the supernatant into a 500 Da dialysis membrane for dialysis for 72 h for purification; and freeze-drying the purified supernatant to obtain the solid carbon quantum dots.
The phenol monomer yield and quantum yield of this example were tested.
Example 8
(1) Taking 15 g of poplar wood with the particle size of 20-40 meshes, adding 600 mL of isopropanol and 20 wt% of Mo/C catalyst, and putting the mixture into a stainless steel reactor.
(2) Introducing nitrogen to replace air therein, and then introducing 4 MPa hydrogen; the resulting mixture was warmed to 250 deg.CoC, reacting for 6 hours, and simultaneously turning on magnetic stirring at the stirring speed of 800 rpm.
(3) Filtering the reaction mixture obtained in the step (2) by using a sand core funnel device to realize solid-liquid separation, wherein the liquid mainly contains a phenol compound after lignin degradation, including lignin monomers, dimers and a small amount of polymers, and a part of carbohydrate degradation products, and after the liquid is subjected to rotary evaporation, extracting and collecting the phenol compound by using dichloromethane to obtain a phenol compound; the solid carbohydrate residue is rich in carbohydrate and solid catalyst added before reaction, and the solid carbohydrate residue remained in the wood fiber raw material is obtained while the catalyst is recovered by selecting a screening mode with a 300-mesh sieve.
(4) And (3) taking 5.0 g of the solid carbohydrate residue obtained in the step (3), adding 100 mL of deionized water, carrying out ultrasonic treatment on the mixture for 30 min, and filling the mixture into a polytetrafluoroethylene tube.
(5) Heating the mixture obtained in the step (4) to 200 DEGoC, reacting for 7 h, and preparing the carbon quantum dots.
(6) Filtering through a 0.22 mu m microporous membrane after the reaction is finished to obtain supernatant, wherein the prepared carbon quantum dots exist in the brown supernatant; putting the supernatant into a 500 Da dialysis membrane for dialysis for 72 h for purification; and freeze-drying the purified supernatant to obtain the solid carbon quantum dots.
The phenol monomer yield and quantum yield of this example were tested.
Example 9
(1) Taking 15 g of phoenix tree with the particle size of 20-40 meshes, adding 500 mL of water and 30 wt% of Zn/Pd/C catalyst, and putting the mixture into a stainless steel reactor.
(2) Introducing nitrogen to replace air therein, and then introducing 2 MPa hydrogen; the resulting mixture was warmed to 200 deg.CoC, reacting for 12 hours, and simultaneously turning on magnetic stirring at the stirring speed of 800 rpm.
(3) Filtering the reaction mixture obtained in the step (2) by using a sand core funnel device to realize solid-liquid separation, wherein the liquid mainly contains a phenol compound after lignin degradation, including lignin monomers, dimers and a small amount of polymers, and a part of carbohydrate degradation products, and after the liquid is subjected to rotary evaporation, extracting and collecting the phenol compound by using dichloromethane to obtain a phenol compound; the solid carbohydrate residue is rich in carbohydrate and solid catalyst added before reaction, and the solid carbohydrate residue remained in the wood fiber raw material is obtained while the catalyst is recovered by selecting a screening mode with a 300-mesh sieve.
(4) And (3) taking 5.0 g of the solid carbohydrate residue obtained in the step (3), adding 150 mL of deionized water, carrying out ultrasonic treatment on the mixture for 60 min, and filling the mixture into a polytetrafluoroethylene tube.
(5) Heating the mixture obtained in the step (4) to 200 DEGoC, reacting for 10 hours; and dialyzing and freeze-drying the supernatant obtained after the reaction to obtain the carbon quantum dots, wherein the carbon quantum dots are used for preparing the carbon quantum dots.
(6) Filtering through a 0.22 mu m microporous membrane after the reaction is finished to obtain supernatant, wherein the prepared carbon quantum dots exist in the brown supernatant; putting the supernatant into a 500 Da dialysis membrane for dialysis for 72 h for purification; and freeze-drying the purified supernatant to obtain the solid carbon quantum dots.
The phenol monomer yield and quantum yield of this example were tested.
Example 10
(1) Taking 15 g of pennisetum alopecuroides with the particle size of 20-40 meshes, adding 500 mL of methanol and 10 wt% of Ru/C catalyst, and putting the mixture into a stainless steel reactor.
(2) Introducing nitrogen to replace air therein, and then introducing 3 MPa hydrogen; the resulting mixture was warmed to 220 deg.CoC, reacting for 10 hours, and simultaneously starting magnetic stirring at a stirring speedAt 800 rpm.
(3) Filtering the reaction mixture obtained in the step (2) by using a sand core funnel device to realize solid-liquid separation, wherein the liquid mainly contains a phenol compound after lignin degradation, including lignin monomers, dimers and a small amount of polymers, and a part of carbohydrate degradation products, and after the liquid is subjected to rotary evaporation, extracting and collecting the phenol compound by using dichloromethane to obtain a phenol compound; the solid carbohydrate residue is rich in carbohydrate and solid catalyst added before reaction, and the solid carbohydrate residue remained in the wood fiber raw material is obtained while the catalyst is recovered by selecting a screening mode with a 300-mesh sieve.
(4) 5.0 g of the solid carbohydrate residue obtained in step (3) was taken, 200 mL of deionized water was added, the mixture was subjected to ultrasonic treatment for 90 min, and the mixture was charged into a polytetrafluoroethylene tube.
(5) Heating the mixture obtained in the step (4) to 220 DEGoC, reacting for 10 h, and preparing the carbon quantum dots.
(6) Filtering through a 0.22 mu m microporous membrane after the reaction is finished to obtain supernatant, wherein the prepared carbon quantum dots exist in the brown supernatant; putting the supernatant into a 500 Da dialysis membrane for dialysis for 72 h for purification; and freeze-drying the purified supernatant to obtain the solid carbon quantum dots.
The phenol monomer yield and quantum yield of this example were tested.
Example 11
(1) Taking 15 g of cypress with the particle size of 20-40 meshes, adding 600 mL of methanol and 20 wt% of Mo/C catalyst, and putting the materials into a stainless steel reactor.
(2) Introducing nitrogen to replace air therein, and then introducing 3 MPa hydrogen; the resulting mixture was warmed to 250 deg.CoC, reacting for 10 hours, and simultaneously turning on magnetic stirring at the stirring speed of 800 rpm.
(3) Filtering the reaction mixture obtained in the step (2) by using a sand core funnel device to realize solid-liquid separation, wherein the liquid mainly contains a phenol compound after lignin degradation, including lignin monomers, dimers and a small amount of polymers, and a part of carbohydrate degradation products, and after the liquid is subjected to rotary evaporation, extracting and collecting the phenol compound by using dichloromethane to obtain a phenol compound; the solid carbohydrate residue is rich in carbohydrate and solid catalyst added before reaction, and the solid carbohydrate residue remained in the wood fiber raw material is obtained while the catalyst is recovered by selecting a screening mode with a 300-mesh sieve.
(4) 5.0 g of the solid carbohydrate residue obtained in step (3) was taken, 200 mL of deionized water was added, the mixture was subjected to ultrasonic treatment for 90 min, and the mixture was charged into a polytetrafluoroethylene tube.
(5) Heating the mixture obtained in the step (4) to 200 DEGoC, reacting for 10 h, and preparing the carbon quantum dots.
(6) Filtering through a 0.22 mu m microporous membrane after the reaction is finished to obtain supernatant, wherein the prepared carbon quantum dots exist in the brown supernatant; putting the supernatant into a 500 Da dialysis membrane for dialysis for 72 h for purification; and freeze-drying the purified supernatant to obtain the solid carbon quantum dots.
The phenol monomer yield and quantum yield of this example were tested.
Example 12
(1) Taking 15 g of straw with the particle size of 20-40 meshes, adding 700 mL of tetrahydrofuran/water and 25 wt% of Ru/C catalyst, and placing the mixture into a stainless steel reactor.
(2) Introducing nitrogen to replace air therein, and then introducing 3 MPa hydrogen; the resulting mixture was warmed to 270 deg.CoC, reacting for 2 hours, and simultaneously turning on magnetic stirring at the stirring speed of 800 rpm.
(3) Filtering the reaction mixture obtained in the step (2) by using a sand core funnel device to realize solid-liquid separation, wherein the liquid mainly contains a phenol compound after lignin degradation, including lignin monomers, dimers and a small amount of polymers, and a part of carbohydrate degradation products, and after the liquid is subjected to rotary evaporation, extracting and collecting the phenol compound by using dichloromethane to obtain a phenol compound; the solid carbohydrate residue is rich in carbohydrate and solid catalyst added before reaction, and the solid carbohydrate residue remained in the wood fiber raw material is obtained while the catalyst is recovered by selecting a screening mode with a 300-mesh sieve.
(4) And (3) taking 5.0 g of the solid carbohydrate residue obtained in the step (3), adding 150 mL of deionized water, carrying out ultrasonic treatment on the mixture for 60 min, and filling the mixture into a polytetrafluoroethylene tube.
(5) Heating the mixture obtained in the step (4) to 140 DEGoC, reacting for 24 h, and preparing the carbon quantum dots.
(6) Filtering through a 0.22 mu m microporous membrane after the reaction is finished to obtain supernatant, wherein the prepared carbon quantum dots exist in the brown supernatant; putting the supernatant into a 500 Da dialysis membrane for dialysis for 72 h for purification; and freeze-drying the purified supernatant to obtain the solid carbon quantum dots.
The phenol monomer yield and quantum yield of this example were tested.
Example 13
(1) Taking 15 g of poplar with the particle size of 20-40 meshes, adding 600 mL of isopropanol and 15 wt% of Ru/C catalyst, and placing the mixture into a stainless steel reactor.
(2) Introducing nitrogen to replace air therein, and then introducing 5 MPa hydrogen; the resulting mixture was warmed to 250 deg.CoC, reacting for 10 hours, and simultaneously turning on magnetic stirring at the stirring speed of 800 rpm.
(3) Filtering the reaction mixture obtained in the step (2) by using a sand core funnel device to realize solid-liquid separation, wherein the liquid mainly contains a phenol compound after lignin degradation, including lignin monomers, dimers and a small amount of polymers, and a part of carbohydrate degradation products, and after the liquid is subjected to rotary evaporation, extracting and collecting the phenol compound by using dichloromethane to obtain a phenol compound; the solid carbohydrate residue is rich in carbohydrate and solid catalyst added before reaction, and the solid carbohydrate residue remained in the wood fiber raw material is obtained while the catalyst is recovered by selecting a screening mode with a 300-mesh sieve.
(4) And (3) taking 5.0 g of the solid carbohydrate residue obtained in the step (3), adding 100 mL of deionized water, carrying out ultrasonic treatment on the mixture for 30 min, and filling the mixture into a polytetrafluoroethylene tube.
(5) Heating the mixture obtained in the step (4) to 200 DEGoC, reacting for 10 h, and preparing the carbon quantum dots.
(6) Filtering through a 0.22 mu m microporous membrane after the reaction is finished to obtain supernatant, wherein the prepared carbon quantum dots exist in the brown supernatant; putting the supernatant into a 500 Da dialysis membrane for dialysis for 72 h for purification; and freeze-drying the purified supernatant to obtain the solid carbon quantum dots.
The phenol monomer yield and quantum yield of this example were tested.
Example 14
(1) Taking 15 g of poplar with the particle size of 20-40 meshes, adding 700 mL of isopropanol and 10 wt% of Ru/C catalyst, and placing the mixture into a stainless steel reactor.
(2) Introducing nitrogen to replace air therein, and then introducing 5 MPa hydrogen; the resulting mixture was warmed to 200 deg.CoC, reacting for 14 h while turning on magnetic stirring at the stirring speed of 800 rpm.
(3) Filtering the reaction mixture obtained in the step (2) by using a sand core funnel device to realize solid-liquid separation, wherein the liquid mainly contains a phenol compound after lignin degradation, including lignin monomers, dimers and a small amount of polymers, and a part of carbohydrate degradation products, and after the liquid is subjected to rotary evaporation, extracting and collecting the phenol compound by using dichloromethane to obtain a phenol compound; the solid carbohydrate residue is rich in carbohydrate and solid catalyst added before reaction, and the solid carbohydrate residue remained in the wood fiber raw material is obtained while the catalyst is recovered by selecting a screening mode with a 300-mesh sieve.
(4) And (3) taking 5.0 g of the solid carbohydrate residue obtained in the step (3), adding 100 mL of deionized water, carrying out ultrasonic treatment on the mixture for 30 min, and filling the mixture into a polytetrafluoroethylene tube.
(5) Heating the mixture obtained in the step (4) to 200 DEGoC, reacting for 12 h, and preparing the carbon quantum dots.
(6) Filtering through a 0.22 mu m microporous membrane after the reaction is finished to obtain supernatant, wherein the prepared carbon quantum dots exist in the brown supernatant; putting the supernatant into a 500 Da dialysis membrane for dialysis for 72 h for purification; and freeze-drying the purified supernatant to obtain the solid carbon quantum dots.
The phenol monomer yield and quantum yield of this example were tested.
TABLE 2 phenol monomer yield and Quantum yield in examples 1-14
| Phenolic monomer/%) | Quantum yield/% | |
| Example 1 | 36.2 | 21.0 |
| Example 2 | 34.8 | 21.4 |
| Example 3 | 37.6 | 16.2 |
| Example 4 | 38.9 | 20.6 |
| Example 5 | 27.3 | 18.4 |
| Example 6 | 23.6 | 19.7 |
| Example 7 | 40.1 | 20.8 |
| Example 8 | 42.5 | 20.6 |
| Example 9 | 26.6 | 21.8 |
| Example 10 | 28.4 | 19.1 |
| Example 11 | 29.1 | 22.4 |
| Example 12 | 25.4 | 12.1 |
| Example 13 | 39.6 | 21.5 |
| Example 14 | 28.9 | 17.6 |
Table 1 is a comparison table of reaction conditions for preparing phenolic chemicals and carbon quantum dots by degrading lignocellulose raw materials by a two-step method in examples 1-14. Table 2 shows the yield and quantum yield of phenol monomer in examples 1 to 14. The invention preferentially degrades lignin in the wood fiber raw material by regulating and controlling the catalytic reduction reaction condition, and converts the lignin into a phenol compound which takes 3-methoxy-4-hydroxy phenylpropanol and 3, 5-dimethoxy-4-hydroxy phenylpropanol as main products. Meanwhile, the carbohydrate residues after the catalytic degradation of the lignin by the wood fiber raw material can be basically reserved and the carbon quantum dots are prepared by a one-step hydrothermal method, so that the high-value conversion and utilization of the whole components of the wood fiber biomass are realized.
The preparation method has the advantages of simple preparation process and mild reaction conditions, can ensure the yield and the quantum yield of the phenol monomer, and has better industrial popularization prospect.
It should be understood, however, that the description herein of specific embodiments is not intended to limit the invention to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The method is characterized in that lignin degradation, biomass component separation and subsequent conversion of carbohydrates are combined, firstly, lignin in the biomass raw material is subjected to catalytic hydrogenation reduction, and is preferentially degraded into phenol compounds, and then solid carbohydrate residues obtained by catalytic conversion are subjected to one-step hydrothermal method to prepare the carbon quantum dots;
the method specifically comprises the following steps:
(1) mixing a lignocellulose raw material with a proper amount of alcohol solvent and a proper amount of metal catalyst, and putting the mixture and a rotor into a stainless steel reactor;
(2) introducing nitrogen into the reactor filled in the step (1), replacing air in a stainless steel reactor, then introducing pressurized hydrogen, putting the reactor into a matched heating device for heating reaction for a certain time, and simultaneously starting magnetic stirring at the stirring speed of 800 rpm;
(3) after the reaction in the step (2) is finished, rapidly cooling the reactor to room temperature by using ice water, and filtering the reaction mixture by using a sand core funnel device to realize solid-liquid separation, wherein the liquid mainly contains a phenol compound after lignin degradation;
(4) adding a proper amount of deionized water into the solid carbohydrate residues obtained in the step (3), carrying out ultrasonic treatment for a certain time to obtain a solution with good dispersibility, and then filling the solution into a polytetrafluoroethylene tube;
(5) heating the mixed solution obtained in the step (4) to a reaction temperature for reacting for a certain time, and preparing carbon quantum dots;
(6) and (5) cooling to room temperature after the reaction is finished, and extracting the carbon quantum dots.
2. The two-step method for degrading the lignocellulose raw material to prepare the phenolic chemicals and the carbon quantum dots according to the claim 1, wherein the lignocellulose raw material in the step (1) is firstly crushed to 20-40 meshes of granularity and dried.
3. The two-step method for degrading a lignocellulosic feedstock to produce phenolic chemicals and carbon quantum dots according to claims 1 and 2, wherein the lignocellulosic feedstock in step (1) comprises at least one of hardwood, softwood, and herbaceous plants; the broadleaf wood is at least one of birch, phoenix tree or poplar, the coniferous wood is at least one of masson pine or cedar, and the herbaceous plant is at least one of pennisetum, switchgrass and rice straw.
4. The two-step method for degrading lignocellulose raw material to prepare phenolic chemicals and carbon quantum dots according to claim 1, wherein the alcohol solvent in the step (1) comprises at least one of methanol, tetrahydrofuran/water, isopropanol and water, and the metal catalyst comprises Mo/C, Ru/C, Ni/C, MoOxAt least one of/C and Zn/Pd/C, lignocellulosic feedstockThe solid-liquid ratio of the catalyst to the alcohol solvent is 10-50 g/L, and the amount of the metal catalyst is 5-40 wt%.
5. The two-step method for degrading the lignocellulose raw material to prepare the phenolic chemicals and the carbon quantum dots according to the claim 1, wherein the pressure of the hydrogen in the step (2) is 1-5 MPa, and the reaction temperature is 140-280 MPaoAnd C, the reaction time is 0-20 h.
6. The two-step method for degrading a lignocellulose raw material to prepare a phenolic chemical and a carbon quantum dot according to claim 1, wherein the liquid obtained in the step (3) mainly comprises lignin-degraded phenol compounds, including lignin monomers, dimers and a small amount of polymers, and secondly comprises a part of carbohydrate degradation products;
after rotary evaporation of the liquid, the phenol compound was collected by extraction with dichloromethane.
7. The two-step method for degrading lignocellulosic feedstock to produce phenolic chemicals and carbon quantum dots according to claim 1, wherein the solid carbohydrate residue obtained in step (3) is rich in carbohydrate and the solid catalyst added before the reaction, and the solid carbohydrate residue remaining in the lignocellulosic feedstock is obtained while recovering the catalyst by sieving with a 300 mesh sieve.
8. The two-step method for degrading the lignocellulose raw material to prepare the phenolic chemicals and the carbon quantum dots according to the claim 1, wherein the solid-to-liquid ratio of the solid carbohydrate residue to the deionized water in the step (4) is 10-70 g/L, and the ultrasonic time of the mixture is 20-100 min.
9. The two-step method for degrading the lignocellulose raw material to prepare the phenolic chemicals and the carbon quantum dots according to the claim 1, wherein the reaction temperature for preparing the carbon quantum dots in the step (5) is 140-220%oAnd C, the reaction time is 1-36 h.
10. The two-step method for degrading the lignocellulose raw material to prepare the phenolic chemicals and the carbon quantum dots according to the claim 1, wherein the step (6) of extracting the carbon quantum dots comprises the following steps:
(6-1) filtering through a 0.22 μm microporous membrane to obtain a supernatant, the prepared carbon quantum dots being present in the brown supernatant;
(6-2) putting the supernatant into a dialysis membrane of 500 Da for dialysis for 72 h for purification;
and (6-3) freeze-drying the purified supernatant to obtain the solid carbon quantum dots.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110667262.3A CN113321204A (en) | 2021-06-16 | 2021-06-16 | Two-step method for degrading lignocellulose raw material to prepare phenolic chemicals and carbon quantum dots |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110667262.3A CN113321204A (en) | 2021-06-16 | 2021-06-16 | Two-step method for degrading lignocellulose raw material to prepare phenolic chemicals and carbon quantum dots |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113321204A true CN113321204A (en) | 2021-08-31 |
Family
ID=77421320
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110667262.3A Pending CN113321204A (en) | 2021-06-16 | 2021-06-16 | Two-step method for degrading lignocellulose raw material to prepare phenolic chemicals and carbon quantum dots |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113321204A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106629661A (en) * | 2016-12-22 | 2017-05-10 | 泉州师范学院 | Process for preparing carbon nanospheres from bagasse |
| CN107840783A (en) * | 2017-09-15 | 2018-03-27 | 北京林业大学 | A kind of method of molybdenum oxide catalyst catalytic degradation biomass |
| CN108059149A (en) * | 2017-12-29 | 2018-05-22 | 华南理工大学 | A kind of biomass fluorescent carbon quantum dot and preparation method thereof |
| CN108584916A (en) * | 2018-06-05 | 2018-09-28 | 桂林理工大学 | The method for preparing the luminous water-solubility fluorescent carbon quantum dot of visible region with sisal fiber |
| CN109110747A (en) * | 2018-11-06 | 2019-01-01 | 湖南农业大学 | It is a kind of using extract oil residue as raw material prepare fluorescent carbon point method and its manufactured fluorescent carbon point |
| CN110304992A (en) * | 2019-06-27 | 2019-10-08 | 北京林业大学 | The method that lignocellulosic full constituent higher value application prepares chemicals |
-
2021
- 2021-06-16 CN CN202110667262.3A patent/CN113321204A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106629661A (en) * | 2016-12-22 | 2017-05-10 | 泉州师范学院 | Process for preparing carbon nanospheres from bagasse |
| CN107840783A (en) * | 2017-09-15 | 2018-03-27 | 北京林业大学 | A kind of method of molybdenum oxide catalyst catalytic degradation biomass |
| CN108059149A (en) * | 2017-12-29 | 2018-05-22 | 华南理工大学 | A kind of biomass fluorescent carbon quantum dot and preparation method thereof |
| CN108584916A (en) * | 2018-06-05 | 2018-09-28 | 桂林理工大学 | The method for preparing the luminous water-solubility fluorescent carbon quantum dot of visible region with sisal fiber |
| CN109110747A (en) * | 2018-11-06 | 2019-01-01 | 湖南农业大学 | It is a kind of using extract oil residue as raw material prepare fluorescent carbon point method and its manufactured fluorescent carbon point |
| CN110304992A (en) * | 2019-06-27 | 2019-10-08 | 北京林业大学 | The method that lignocellulosic full constituent higher value application prepares chemicals |
Non-Patent Citations (1)
| Title |
|---|
| 陈文新: "基于生物质甘蔗渣的荧光碳量子点制备", 《暨南大学学报(自然科学与医学版)》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Song et al. | Recent advances and challenges of inter-disciplinary biomass valorization by integrating hydrothermal and biological techniques | |
| Huang et al. | Removal of fermentation inhibitors from pre-hydrolysis liquor using polystyrene divinylbenzene resin | |
| Sannigrahi et al. | Cellulosic biorefineries—unleashing lignin opportunities | |
| Trinh et al. | Aqueous acidified ionic liquid pretreatment for bioethanol production and concentration of produced ethanol by pervaporation | |
| CN103113187B (en) | By the method for acetic acid ethanol co-production ethyl acetate | |
| WO2016192404A1 (en) | Process for hydrothermal carbonization of biomass with co-generation of bio-oil | |
| Du et al. | Iron based catalysts in biomass processing | |
| Chen et al. | Rice husk-based solid acid for efficient hydrolysis and saccharification of corncob | |
| CN111500658B (en) | Method for multi-way value-added utilization of biomass | |
| JP2021524869A (en) | Comprehensive usage for fiber-based biomass | |
| KR102136842B1 (en) | Methods for Pretreating Lignocellulosic Biomass | |
| CN102516209A (en) | Method for coproducing furfural, ethanol and lignin from corncob | |
| CN105152854A (en) | Method for converting lignin into liquid fuel through one-step method | |
| CN111423399B (en) | Method for converting holocellulose into furfural platform compound | |
| CN111393279A (en) | Method for converting cellulose into levulinic acid through catalytic degradation | |
| CN101445736A (en) | Method of using biomass to prepare gas used for synthesizing alcohol ether in biomass preparation and device therefor | |
| Manivannan et al. | Valorization of fruit waste using DES pretreatment and hydrolysis over a heterogeneous catalyst for bioethanol production | |
| CN112844379B (en) | Method for preparing monophenol chemicals by catalyzing lignin depolymerization through ruthenium loaded on metal organic framework material derivative | |
| Gong et al. | A novel deep eutectic solvent–mediated Fenton-like system for pretreatment of water hyacinth and biobutanol production | |
| CN102399204A (en) | Process for preparing furfural by using hydrolyzate for wood chips for dissolving pulp through sulfuric acid continuous method | |
| CN110304992B (en) | Method for preparing chemicals by utilizing full components of lignocellulose in high-value manner | |
| CN113321204A (en) | Two-step method for degrading lignocellulose raw material to prepare phenolic chemicals and carbon quantum dots | |
| CN109628652B (en) | Method for preparing xylose by one-step catalysis of hemicellulose in corn straws | |
| CN116888270A (en) | Method for converting lignocellulosic biomass into sugars, biochemicals, biofuels and biomaterials | |
| CN102532068A (en) | Process for preparing furfural byintermittent production with wood chip hydrolysate as raw material and acetic acid as catalytic agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210831 |