CN115627300A - Method for disassembling three major components of wood fiber biomass by acidic two-phase system one-pot method - Google Patents
Method for disassembling three major components of wood fiber biomass by acidic two-phase system one-pot method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K13/00—Sugars not otherwise provided for in this class
- C13K13/002—Xylose
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- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K13/00—Sugars not otherwise provided for in this class
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention belongs to the technical field of biomass chemical preparation, and discloses a method for disassembling three major components of a wood fiber biomass by an acidic two-phase system one-pot method. The method comprises the following operation steps: adding a certain amount of acid and the wood fiber biomass raw material subjected to grinding extraction into a reaction tank, adding a certain amount of aqueous solution and organic solution, packaging in a reactor, heating for reaction, taking out the reaction tank after reaction, and cooling to room temperature to obtain aqueous solution rich in xylose/arabinose, dissolved lignin and organic solution containing a small amount of furfural, and the rest of solid residue rich in cellulose. The method has the characteristics of simple reaction process and high reaction efficiency, the yield of xylose/arabinose is 3.12-100.00%, the removal rate of hemicellulose is 34.25-98.15%, the retention rate of cellulose is 72.26-97.05%, and the removal rate of lignin is 22.59-89.37%.
Description
Technical Field
The invention belongs to the technical field of biomass chemical pretreatment, and particularly relates to a method for high-selectivity disassembly of three major components of a lignocellulosic biomass by an acidic two-phase system one-pot method.
Background
The pretreatment and the disassembly of the lignocellulose and the biomass can provide powerful technical support for the subsequent production of value-added chemicals such as fuel ethanol, gamma-valerolactone and the like, and have very important significance in the development of green energy sources at present.
Usually, the pretreatment of the wood fiber biomass only removes one of the three main components, such as lignin, and the rest component is holocellulose consisting of hemicellulose and cellulose; because the hemicellulose is the most easily removed part of the three major components, the hemicellulose is also selectively hydrolyzed and removed, and the rest components consist of cellulose and lignin. In the above, the three major components cannot be effectively separated and obtained in one step, and all components of the biomass cannot be respectively and fully utilized.
The biomass pretreatment based on a two-phase system can effectively separate three major components of the lignocellulosic biomass, which is called Organocat by research, but the acid used at the moment can only be organic acid, including oxalic acid and furandicarboxylic acid; the organic phase is currently only one of 2-methyltetrahydrofuran (2-MeTHF). Based on the above, no other organic acid or inorganic acid is applied to biomass pretreatment under a two-phase system at present; no other organic solvents from petrochemical sources are applied to the system as an organic phase; and no two-phase system pretreatment concept is proposed.
There is a literature that proposes Organocat pretreatment (Fractionation of lignocellustic biomassuses the organic cat process, green chem.,2015,17,3533), but the acid used is oxalic acid only, the organic solvent is only 2-methyltetrahydrofuran, and the literature does not compare the problem of different solvent volume ratios. The method provided by the document has the defects of large limitation and poor reaction effect.
Disclosure of Invention
In order to make up the defect that the existing wood fiber biomass pretreatment method cannot effectively split and separate the three components of the biomass in one step, the development of one-pot acid hydrolysis pretreatment based on a two-phase system has wide application prospect.
The invention aims to provide a one-pot acid hydrolysis pretreatment method under a two-phase system, which realizes high-selectivity disassembly and oriented component migration of hemicellulose, lignin and cellulose out of phase.
The purpose of the invention is realized by the following technical scheme.
A method for high-selectivity disassembly of three major components of lignocellulosic biomass by an acidic two-phase system one-pot method comprises the following steps:
adding milled and extracted lignocellulose biomass raw material and acid into a reaction tank, adding an organic solvent and an aqueous solution, packaging the reaction tank in a reactor, heating to react, cooling the reaction tank to room temperature after the reaction is finished, and thus obtaining an aqueous solution rich in xylose/arabinose, an organic solution rich in lignin or lignin and furfural, and solid residue rich in cellulose. The final product was a yellow or dark brown layered solution with solid residue dispersed in the bottom.
Preferably, the lignocellulosic biomass feedstock comprises wheat straw, corn stover, wood, shrubs, and the like.
Preferably, the acid is an organic acid or an inorganic acid, wherein the organic acid includes p-toluenesulfonic acid, oxalic acid, furandicarboxylic acid, L-malic acid, malonic acid, maleic acid, tartaric acid, etc., and the inorganic acid includes sulfuric acid, hydrochloric acid, etc.
Preferably, the concentration of the acid is 0.05M to 1M.
Preferably, the organic solvent includes isobutanol, 2-methyltetrahydrofuran, toluene, methyl isobutyl ketone, cyclopentyl methyl ether, 2-butanol, etc.
Preferably, the ratio (volume ratio) of the amounts of the organic solvent and the aqueous solution added is 0.2 to 5.0.
Preferably, the liquid-solid ratio of the addition amount of the lignocellulosic biomass raw material to the total volume of the organic solvent and the aqueous solution is 10 to 30.
Preferably, the reaction temperature is 80-180 ℃, and the reaction time is 0.25-8 h.
Preferably, the reactor can be one of a pressure reaction kettle placed in an oil bath, a reaction kettle with magnetic stirring and a microwave reactor.
The preparation method of the invention has the following advantages and beneficial effects:
(1) The method can be used for high-selectively disassembling three major components of the wood fiber biomass by a one-pot method on the basis of a two-phase system formed by an organic solvent and an aqueous solution. The lignin is dissolved and extracted into an organic solvent, the hemicellulose is hydrolyzed into xylose and arabinose in an aqueous solution, and the cellulose is retained in solid phase residues, so that simultaneous disassembly of three components and directional migration of the components are realized.
(2) The invention can respectively recover and obtain three major components of biomass. The lignin can be recovered in an organic solvent by an anti-solvent method or a distillation method; recovering the cellulose residue by filtration; the xylose and arabinose can be obtained by concentrating and crystallizing from an aqueous solution.
(3) The invention is a reaction system which can be amplified, the reaction conditions can be enlarged in the same proportion for reaction, and the reaction effect is not influenced.
(4) The invention can achieve different separation purposes by changing various conditions of the reaction, and can carry out the reaction by replacing different organic solvents, such as isobutanol, so that more lignin can be removed; the 2-methyltetrahydrofuran can better protect the cellulose; toluene, methyl isobutyl ketone and cyclopentyl methyl ether can selectively achieve high hemicellulose sugar yield, but with less lignin removal.
(5) The invention is a green and efficient wood fiber biomass pretreatment method, and has the characteristics of simple reaction process and high reaction efficiency. The yield of xylose/arabinose is 3.12-100.00%, the yield of hemicellulose sugar is 6.54-81.90%, the yield of furfural is 0.00-50.75%, the removal rate of hemicellulose is 34.25-98.15%, the retention rate of cellulose is 72.26-97.05%, and the removal rate of lignin is 22.59-89.37%.
Drawings
FIG. 1 is a process flow diagram of a method for separating three major components of biomass by one-pot acid hydrolysis pretreatment based on a two-phase system.
FIG. 2 is a high performance liquid chromatogram of the aqueous solution after the reaction of example 1.
FIG. 3 is a scanning electron microscope image of wheat straw feedstock of example 2.
FIG. 4 is a scanning electron micrograph of the residue recovered after the reaction of example 2.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
The identity and quantification of the xylose/arabinose and furfural products obtained in the following examples were determined by HPLC testing.
Examples are given below where the xylose/arabinose concentration y = 0.0029xz (mg/L), where x is the peak area measured by HPLC, y is the xylose/arabinose concentration, and z is the dilution factor of the solution in mg/L.
In the following examples, the furfural concentration b =0.0024a x z (mg/L), where a is the area of the peak measured by HPLC, b is the furfural concentration, and z is the dilution factor of the solution in mg/L.
Example 1
The method for splitting three major components of biomass by one-pot acid hydrolysis pretreatment based on a two-phase system comprises the following specific preparation steps:
1.5g of wheat straw raw material subjected to grinding extraction, 15mL of aqueous solution, 15mL of 2-methyltetrahydrofuran solution and 1M p-toluenesulfonic acid are added into a reaction tank. Packaging in a reaction kettle, putting into an oil bath kettle which is arranged and heated to 120 ℃, taking out the reaction kettle after reacting for 3 hours, putting into an ice water bath, and rapidly cooling to room temperature. Obtaining a water solution rich in xylose/arabinose, an organic solution containing lignin and a small amount of furfural and residual solid residue containing cellulose.
The xylose/arabinose content in the solution was determined by High Performance Liquid Chromatography (HPLC).
Hemicellulose sugar yield = (sum of mass of xylose and arabinose in solution after reaction/sum of mass of xylose and arabinose in raw material before reaction) × 100%
Furfural yield = (molar mass of furfural in solution after reaction/sum of molar mass of xylose and arabinose in raw material before reaction) × 100%
Lignin removal rate = (mass of lignin in raw material before reaction-mass of lignin remaining after reaction)/mass of lignin in raw material before reaction × 100%
Hemicellulose removal rate = (hemicellulose mass in raw material before reaction-hemicellulose mass remaining after reaction)/hemicellulose mass in raw material before reaction x 100%
Cellulose retention = mass of cellulose after reaction/mass of cellulose in raw material before reaction × 100%
The water phase of this example was diluted and tested in the liquid phase, and the peak pattern of the test is shown in FIG. 2. 11.627 is glucose; 12.496 is xylose; 13.477 is arabinose; 49.805 is furfural, and the peak area is substituted into the above formula for calculation, so that 76.15% xylose yield, 100% arabinose yield, 81.90% hemicellulose sugar yield and 3.35% furfural yield can be obtained. And this example has 75.88% lignin removal, 89.37% hemicellulose removal, and 92.37% cellulose retention.
Example 2
The method for splitting three major components of biomass by one-pot acid hydrolysis pretreatment based on a two-phase system comprises the following specific preparation steps:
1.5g of wheat straw raw material subjected to grinding extraction, 15mL of aqueous solution, 15mL of 2-methyltetrahydrofuran solution and 0.2M of p-toluenesulfonic acid are added into a reaction tank. Packaging in a reaction kettle, putting into an oil bath kettle which is arranged and heated to 180 ℃, taking out the reaction kettle after reacting for 3 hours, putting into an ice water bath, and rapidly cooling to room temperature. To obtain a xylose/arabinose-rich aqueous solution, an organic solution containing lignin and furfural and a residual solid residue containing cellulose.
The xylose/arabinose content in the solution was determined by High Performance Liquid Chromatography (HPLC).
Hemicellulose sugar yield = (sum of mass of xylose and arabinose in solution after reaction/mass of sugar in raw material before reaction) × 100%
Furfural yield = (molar mass of furfural in solution after reaction/sum of molar mass of xylose and arabinose in raw material before reaction) × 100%
Lignin removal rate = (mass of lignin in raw material before reaction-mass of lignin remaining after reaction)/mass of lignin in raw material before reaction × 100%
Hemicellulose removal rate = (hemicellulose mass in raw material before reaction-hemicellulose mass remaining after reaction)/hemicellulose mass in raw material before reaction x 100%
Cellulose retention = mass of cellulose after reaction/mass of cellulose in raw material before reaction × 100%
The present example can obtain 32.48% xylose yield, 71.12% arabinose yield, hemicellulose sugar yield of 35.06%, and 50.75% furfural yield; and has lignin removal rate of 78.26%, hemicellulose removal rate of 98.15% and cellulose retention rate of 72.26%. As can be seen from a comparison of fig. 3 and 4: the morphology of fig. 4 is severely damaged, the original fiber morphology cannot be seen, and at this time, the reaction conditions are severe, lignin and hemicellulose in the amorphous region can be sufficiently removed, and more removal of cellulose is caused, and the retention rate is reduced.
Example 3
The method for splitting three major components of biomass through one-pot acid hydrolysis pretreatment based on a two-phase system comprises the following specific preparation steps:
1.5g of wood raw material after grinding extraction, 15mL of aqueous solution, 15mL of 2-methyltetrahydrofuran solution and 0.1M sulfuric acid were added into a polytetrafluoroethylene reaction tank. Packaging in a reaction kettle, putting into a microwave reactor which is arranged and heated to 100 ℃, taking out the reaction kettle after reacting for 0.5h, and putting into an ice water bath for rapidly cooling to room temperature. To obtain an aqueous solution containing xylose/arabinose, an organic solution containing lignin and a residual solid residue containing cellulose.
The xylose/arabinose content in the solution was determined by High Performance Liquid Chromatography (HPLC).
Hemicellulose sugar yield = (sum of mass of xylose and arabinose in solution after reaction/mass of sugar in raw material before reaction) × 100%
Furfural yield = (molar mass of furfural in solution after reaction/sum of molar mass of xylose and arabinose in raw material before reaction) × 100%
Lignin removal rate = (mass of lignin in raw material before reaction-mass of lignin remaining after reaction)/mass of lignin in raw material before reaction × 100%
Hemicellulose removal rate = (mass of hemicellulose in raw material before reaction-mass of hemicellulose remaining after reaction)/mass of hemicellulose in raw material before reaction × 100%
Cellulose retention = mass of cellulose after reaction/mass of cellulose in raw material before reaction × 100%
This example can obtain 38.53% xylose yield, 82.53% arabinose yield, 42.47% hemicellulose sugar yield and 0.00% furfural yield. And has 41.78% lignin removal rate, 67.67% hemicellulose removal rate and 91.81% cellulose retention rate.
Example 4
The method for splitting three major components of biomass by one-pot acid hydrolysis pretreatment based on a two-phase system comprises the following specific preparation steps:
1.5g of wood raw material after grinding extraction, 10mL of aqueous solution, 20mL of isobutanol solution and 0.1M of p-toluenesulfonic acid are added into a polytetrafluoroethylene reaction tank. Packaging in a reaction kettle, putting into a microwave reactor which is arranged and heated to 100 ℃, taking out the reaction kettle after reacting for 1h, putting into an ice water bath, and rapidly cooling to room temperature. To obtain an aqueous solution containing xylose/arabinose, an organic solution containing lignin and a residual solid residue containing cellulose.
The xylose/arabinose content in the solution was determined by High Performance Liquid Chromatography (HPLC).
Hemicellulose sugar yield = (sum of mass of xylose and arabinose in solution after reaction/mass of sugar in raw material before reaction) × 100%
Furfural yield = (molar mass of furfural in solution after reaction/sum of molar mass of xylose and arabinose in raw material before reaction) × 100%
Lignin removal rate = (mass of lignin in raw material before reaction-mass of lignin remaining after reaction)/mass of lignin in raw material before reaction × 100%
Hemicellulose removal rate = (mass of hemicellulose in raw material before reaction-mass of hemicellulose remaining after reaction)/mass of hemicellulose in raw material before reaction × 100%
Cellulose retention = mass of cellulose after reaction/mass of cellulose in raw material before reaction × 100%
This example can obtain 48.06% xylose yield, 95.41% arabinose yield, hemicellulose sugar yield of 51.30%, furfural yield of 0.16%. And has 75.78% lignin removal rate, 65.67% hemicellulose removal rate and 87.81% cellulose retention rate.
Example 5
The method for splitting three major components of biomass through one-pot acid hydrolysis pretreatment based on a two-phase system comprises the following specific preparation steps:
0.5g of ground and extracted corn raw material, 5mL of aqueous solution, 5mL of isobutanol solution and 0.2M oxalic acid are added into a polytetrafluoroethylene reaction tank. Packaging in a reaction kettle, putting into an oil bath kettle which is arranged and heated to 140 ℃, taking out the reaction kettle after reacting for 4 hours, putting into an ice water bath, and rapidly cooling to room temperature. To obtain an aqueous solution containing xylose/arabinose, an organic solution containing lignin and a residual solid residue containing cellulose.
The xylose/arabinose content of the solution was determined by High Performance Liquid Chromatography (HPLC).
Hemicellulose sugar yield = (sum of mass of xylose and arabinose in solution after reaction/mass of sugar in raw material before reaction) × 100%
Furfural yield = (molar mass of furfural in solution after reaction/sum of molar mass of xylose and arabinose in raw material before reaction) × 100%
Lignin removal rate = (mass of lignin in raw material before reaction-mass of lignin remaining after reaction)/mass of lignin in raw material before reaction × 100%
Hemicellulose removal rate = (hemicellulose mass in raw material before reaction-hemicellulose mass remaining after reaction)/hemicellulose mass in raw material before reaction x 100%
Cellulose retention = mass of cellulose after reaction/mass of cellulose in raw material before reaction × 100%
The present example can obtain xylose yield of 16.70%, arabinose yield of 78.22%, hemicellulose sugar yield of 39.27% and furfural yield of 0.00%. And has 47.76% lignin removal rate, 67.24% hemicellulose removal rate and 91.34% cellulose retention rate.
Example 6
The method for splitting three major components of biomass by one-pot acid hydrolysis pretreatment based on a two-phase system comprises the following specific preparation steps:
1.5g of wheat straw raw material subjected to grinding extraction, 15mL of aqueous solution, 15mL of cyclopentyl methyl ether solution and 0.1M of p-toluenesulfonic acid are added into a polytetrafluoroethylene reaction tank. Packaging in a reaction kettle, putting the reaction kettle into a magnetic stirring reaction kettle which is arranged and heated to 140 ℃ for reaction for 3 hours, taking out the reaction kettle, putting the reaction kettle into an ice water bath, and rapidly cooling to room temperature. To obtain an aqueous solution containing xylose/arabinose, an organic solution containing lignin and a residual solid residue containing cellulose.
The xylose/arabinose content in the solution was determined by High Performance Liquid Chromatography (HPLC).
Hemicellulose sugar yield = (sum of mass of xylose and arabinose in solution after reaction/mass of sugar in raw material before reaction) × 100%
Furfural yield = (molar mass of furfural in solution after reaction/sum of molar mass of xylose and arabinose in raw material before reaction) × 100%
Lignin removal rate = (mass of lignin in raw material before reaction-mass of lignin remaining after reaction)/mass of lignin in raw material before reaction × 100%
Hemicellulose removal rate = (mass of hemicellulose in raw material before reaction-mass of hemicellulose remaining after reaction)/mass of hemicellulose in raw material before reaction × 100%
Cellulose retention = mass of cellulose after reaction/mass of cellulose in raw material before reaction × 100%
The present example can obtain xylose yield of 61.41%, arabinose yield of 100%, hemicellulose sugar yield of 65.32%, furfural yield of 0.00%. And has 29.32% lignin removal rate, 80.68% hemicellulose removal rate and 97.05% cellulose retention rate.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for high-selectivity disassembly of three major components of lignocellulosic biomass by an acidic two-phase system one-pot method is characterized by comprising the following steps:
adding milled and extracted lignocellulose biomass raw material and acid into a reaction tank, adding an organic solvent and an aqueous solution, packaging the reaction tank in a reactor, heating to react, cooling the reaction tank to room temperature after the reaction is finished, and thus obtaining an aqueous solution rich in xylose/arabinose, an organic solution rich in lignin or lignin and furfural, and solid residue rich in cellulose.
2. The method for high-selectivity dismantling of three major components of lignocellulosic biomass according to claim 1 by an acidic two-phase system one-pot method, wherein the lignocellulosic biomass raw material comprises wheat straw, corn straw, wood, shrub.
3. The method for high-selectivity resolution of three major components of lignocellulosic biomass according to claim 1, wherein the acid is an organic acid or an inorganic acid, wherein the organic acid is selected from one of p-toluenesulfonic acid, oxalic acid, furandicarboxylic acid, L-malic acid, malonic acid, maleic acid, tartaric acid; the inorganic acid is selected from one of sulfuric acid and hydrochloric acid.
4. The method for high-selectivity disassembly of three major components of lignocellulosic biomass according to claim 1, wherein the concentration of the acid is 0.05M to 1M.
5. The method for high-selectivity disassembly of three major components of lignocellulosic biomass according to claim 1, wherein the organic solvent is one of isobutanol, 2-methyltetrahydrofuran, methyl isobutyl ketone, toluene, cyclopentyl methyl ether, 2-butanol.
6. The method for high-selectivity disassembly of three major components of lignocellulosic biomass according to claim 1, wherein the ratio of the addition amount of the organic solvent to the aqueous solution is 0.2-5.0.
7. The method for high-selectivity disassembly of three major components of lignocellulosic biomass according to claim 1, wherein the liquid-solid ratio of the addition amount of the lignocellulosic biomass raw material to the total volume of the organic solvent and the aqueous solution is 10-30.
8. The method for high-selectivity disassembly of three major components of lignocellulosic biomass according to claim 1, wherein the reaction temperature is 80-180 ℃ and the reaction time is 0.25-8 h.
9. The method for high-selectivity resolution of three major components of lignocellulosic biomass by an acidic two-phase system one-pot method according to claim 1, wherein the reactor is one of a pressure reactor, a reactor with magnetic stirring and a microwave reactor which are placed in an oil bath.
10. The method for high-selectivity disassembly of three major components of lignocellulosic biomass according to any one of claims 1 to 9, wherein the yield of xylose/arabinose is 3.12 to 100.00%, the yield of hemicellulose sugars is 6.54 to 81.90%, the yield of furfural is 0.00 to 50.75%, the removal rate of hemicellulose is 34.25 to 98.15%, the retention rate of cellulose is 72.26 to 97.05%, and the removal rate of lignin is 22.59 to 89.37%.
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| CN113501852A (en) * | 2021-06-30 | 2021-10-15 | 华南理工大学 | Method for preparing xylose, arabinose and formic acid by using hexose |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104292193A (en) * | 2014-09-05 | 2015-01-21 | 中国科学院广州能源研究所 | Method for grading biomass, preparing furfural and preparing levulinic acid through two steps |
| CN107385119A (en) * | 2017-08-28 | 2017-11-24 | 华南理工大学 | A kind of method that corncob rapidly and efficiently prepares xylose hydrolysis fluid |
| CN111395025A (en) * | 2020-04-07 | 2020-07-10 | 齐鲁工业大学 | Comprehensive utilization method of lignocellulose biomass |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104292193A (en) * | 2014-09-05 | 2015-01-21 | 中国科学院广州能源研究所 | Method for grading biomass, preparing furfural and preparing levulinic acid through two steps |
| CN107385119A (en) * | 2017-08-28 | 2017-11-24 | 华南理工大学 | A kind of method that corncob rapidly and efficiently prepares xylose hydrolysis fluid |
| CN111395025A (en) * | 2020-04-07 | 2020-07-10 | 齐鲁工业大学 | Comprehensive utilization method of lignocellulose biomass |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113501852A (en) * | 2021-06-30 | 2021-10-15 | 华南理工大学 | Method for preparing xylose, arabinose and formic acid by using hexose |
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