Reagent for oxidative degradation of lignin and method for efficiently removing lignin

By using a system composed of hydrogen peroxide solution with a concentration of 8 to 15 wt%, an alkyl acetate and a hydrolysis catalyst, peracetic acid is generated in situ, which solves the problem of safety hazards in the use of peracetic acid in the prior art, and achieves an efficient and safe lignin removal effect.

CN119663662AActive Publication Date: 2025-03-21NANJING FORESTRY UNIV
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Patent Information

Application Number
CN202411816724.3
Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Filing Date
2024-12-11
Publication Date
2025-03-21
Estimated Expiration
2044-12-11

AI Technical Summary

Technical Problem

In the prior art, there are safety risks when using peracetic acid to oxidize and degrade lignin, such as explosive explosion and high storage and transportation costs, and it is difficult to efficiently remove lignin.

Method used

A hydrogen peroxide-alkyl acetate system consisting of a hydrogen peroxide solution with a concentration of 8 to 15 wt%, an alkyl acetate and a hydrolysis catalyst is used to form peracetic acid in situ through the hydrolysis catalyst, and oxidation treatment is carried out to remove lignin.

Benefits of technology

It achieves safe delignin without stress and explosion hazards, and can remove lignin highly selectively, improving the efficiency of lignin removal.

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Abstract

The invention provides a reagent for oxidative degradation of lignin and a method for efficiently removing lignin, and belongs to the technical field of agricultural and forestry biomass degradation and conversion. The invention provides a reagent for oxidative degradation of lignin. The reagent is prepared from the following raw materials: a hydrogen peroxide solution, alkyl acetate and a hydrolysis catalyst, the concentration of the hydrogen peroxide solution is 8-15 wt%; the volume ratio of the hydrogen peroxide solution to the alkyl acetate is (4-6): (6-4); the volume of the hydrolysis catalyst accounts for 1.0-1.5% of the total volume of the hydrogen peroxide solution and the alkyl acetate. According to the method, a hydrogen peroxide-alkyl acetate system is established with the hydrogen peroxide solution with the concentration of 8-15 wt%, peracetic acid can be generated in situ, the reaction system is free of pressure and potential safety hazards during oxidation, and wood lignin can be removed with high selectivity under the condition that the temperature is larger than or equal to 60 DEG C.
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Description

Technical Field

[0001] The invention belongs to the technical field of agricultural and forestry biomass degradation and conversion, and particularly relates to a reagent for oxidative degradation of lignin and a method for efficiently removing lignin. Background Art

[0002] At present, in the biorefining of lignocellulose, the carbohydrate platform of cellulose and hemicellulose can be used as raw materials for preparing bioenergy and pulp and paper, nanocellulose, and the biochemical conversion of cellulose raw materials can be used to synthesize ethanol, glycerol, propionic acid and succinic acid, and the nanocellulose extracted from lignocellulose has attractive properties such as high strength, excellent stiffness and high surface area. In addition, nanocellulose contains a large number of hydroxyl groups, which can be used for surface modification. However, lignin is considered to be an important obstacle to biomass bioconversion, which prevents enzymes or chemical reagents from approaching cellulose and causes inhibition during bioconversion. Biorefining technology based on carbohydrate platforms needs to preferentially degrade lignin components to break the anti-degradation barrier of lignocellulose. And in the field of pulp and paper, lignin is considered to have an adverse effect on the durability of paper. Therefore, lignin needs to be removed.

[0003] In the prior art, lignin is removed by oxidative depolymerization of lignin, which exhibits relatively mild reaction conditions (80°C) and high selectivity. Among them, peracetic acid reacts with lignin as an electrophilic reagent, resulting in oxidation and subsequent degradation. Peracetic acid is considered to be environmentally friendly and has a high oxidation potential (1.748v). It is a promising selective agent for delignification. The principle is that peracetic acid-mediated oxidation of lignin can cleave CC and CO bonds connected to aromatic rings and phenylpropane units connected to ethers. However, peracetic acid is expensive, extremely unstable, and prone to explosion when the concentration is too high. This safety hazard increases the storage and transportation costs of peracetic acid. For example, there is a technical solution that uses 30% hydrogen peroxide and acetic acid solution to synthesize peracetic acid in situ at 80° C. to treat poplar wood, and its lignin removal rate can reach 86%. Although this system can synthesize peracetic acid in situ, due to the high concentrations of acetic acid and 30% hydrogen peroxide, and the high dosages of hydrogen peroxide and acetic acid in the finally prepared hydrogen peroxide-acetic acid solution (hydrogen peroxide concentration is 12wt%, acetic acid concentration is 40wt%), the decomposition process of hydrogen peroxide and peracetic acid in the system leads to high pressure and is prone to explosion, posing a safety hazard. Summary of the invention

[0004] The purpose of the present invention is to provide a reagent for oxidative degradation of lignin and a method for efficiently removing lignin. The present invention adopts a hydrogen peroxide solution with a concentration of 8 to 15wt% to prepare a hydrogen peroxide-ethyl acetate system. The system has no pressure and explosion hazards during oxidation treatment, and can achieve safe delignification.

[0005] In order to achieve the purpose of the present invention, the present invention provides the following technical solutions:

[0006] A reagent for oxidative degradation of lignin, the preparation raw materials comprising: hydrogen peroxide solution, alkyl acetate and a hydrolysis catalyst;

[0007] The concentration of the hydrogen peroxide solution is 8-15 wt %; the volume ratio of the hydrogen peroxide solution to the alkyl acetate is 4-6:6-4;

[0008] The volume of the hydrolysis catalyst accounts for 1.0-1.5% of the total volume of the hydrogen peroxide solution and the alkyl acetate.

[0009] Preferably, the alkyl acetate includes one or more of methyl acetate, ethyl acetate and propyl acetate.

[0010] Preferably, the hydrolysis catalyst comprises one or more of sulfuric acid, hydrochloric acid and nitric acid.

[0011] The present invention also provides a method for efficiently removing lignin, comprising the following steps:

[0012] Mixing wood and the reagent for oxidative degradation of lignin described in the above technical solution, performing oxidation treatment, and obtaining holocellulose residue from which lignin has been removed after solid-liquid separation;

[0013] The temperature of the oxidation treatment is ≥ 60°C.

[0014] Preferably, the solid-liquid ratio of the wood and the reagent for oxidative degradation of lignin is 1 g:5-12 mL.

[0015] Preferably, the oxidation treatment time is 4 to 12 hours.

[0016] Preferably, the method further comprises enzymatically hydrolyzing the holocellulose residue to obtain an enzymatic hydrolyzate containing glucose.

[0017] Preferably, the enzyme reagent used for the enzymolysis is cellulase; the enzyme amount of the enzyme reagent is 5 to 20 FPU / g.

[0018] Preferably, the enzymatic hydrolysis temperature is 40-60°C and the time is 24-72 hours.

[0019] The present invention provides a reagent for oxidative degradation of lignin, and the raw materials for preparation include: hydrogen peroxide solution, alkyl acetate and hydrolysis catalyst; the concentration of the hydrogen peroxide solution is 8-15wt%; the volume ratio of the hydrogen peroxide solution to the alkyl acetate is 4-6:6-4; the volume of the hydrolysis catalyst accounts for 1.0-1.5% of the total volume of the hydrogen peroxide solution and the alkyl acetate. The present invention uses a hydrogen peroxide solution with a concentration of 8-15wt% to establish a hydrogen peroxide-alkyl acetate system, decomposes the alkyl acetate into acetic acid through a hydrolysis catalyst, and catalyzes hydrogen peroxide and acetic acid to generate peracetic acid in situ, and gradually synthesizes peracetic acid. The reaction system is pressure-free and has no safety hazards during oxidation, and can remove lignin with high selectivity.

[0020] The present invention also provides a method for removing lignin efficiently, and the present invention can remove lignin with high selectivity at ≥60°C. Furthermore, the holocellulose residue obtained by solid-liquid separation can be directly used to prepare bioenergy, chemicals and chemical materials, or the holocellulose residue from which lignin is removed can be enzymatically hydrolyzed to obtain an enzymatic hydrolyzate containing glucose; the liquid obtained by solid-liquid separation can be subsequently separated into quinone and carboxylic acid compounds such as 2,6-dimethoxy-1,4-benzoquinone, p-benzoquinone, malonic acid, maleic anhydride and propionic acid, which can be used in the field of producing platform chemicals (such as luminal, barbiturate) and pharmaceutical intermediates. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0022] Figure 1 The present invention is a flow chart of the method for efficiently removing lignin. DETAILED DESCRIPTION

[0023] The present invention provides a reagent for oxidative degradation of lignin, the preparation raw materials comprising: hydrogen peroxide solution, alkyl acetate and a hydrolysis catalyst;

[0024] The concentration of the hydrogen peroxide solution is 8-15 wt %; the volume ratio of the hydrogen peroxide solution to the alkyl acetate is 4-6:6-4;

[0025] The volume of the hydrolysis catalyst accounts for 1.0-1.5% of the total volume of the hydrogen peroxide solution and the alkyl acetate.

[0026] In the present invention, unless otherwise specified, all raw materials are commercially available products well known to those skilled in the art.

[0027] In the present invention, the concentration of the hydrogen peroxide solution is 8-15wt%, and in a specific embodiment, it can be 8wt%, 10wt% or 15wt%; the alkyl acetate includes one or more of methyl acetate, ethyl acetate and propyl acetate, and in a specific embodiment, it can be ethyl acetate; the volume ratio of the hydrogen peroxide solution to the alkyl acetate is 4-6:6-4, and in a specific embodiment, it can be 5:5. The present invention establishes a hydrogen peroxide-alkyl acetate system with a hydrogen peroxide solution with a concentration of 5-15wt%, and peracetic acid can be generated in situ. The reaction system is pressure-free and has no safety hazards during oxidation, and can remove wood lignin with high selectivity.

[0028] In the present invention, the hydrolysis catalyst includes one or more of sulfuric acid, hydrochloric acid and nitric acid, and in a specific embodiment, it can be sulfuric acid; the concentration of the sulfuric acid is 50-98.3wt%, and in a specific embodiment, it can be 50wt%, 70wt% or 98.3wt%; the volume of the hydrolysis catalyst accounts for 1.0-1.5% of the total volume of the hydrogen peroxide solution and the alkyl acetate, and in a specific embodiment, it can be 1.0%, 1.2% or 1.5%. In the present invention, the hydrolysis catalyst is a bifunctional catalyst that decomposes ethyl acetate into acetic acid and catalyzes hydrogen peroxide and acetic acid to generate peracetic acid.

[0029] The present invention also provides a method for efficiently removing lignin, comprising the following steps:

[0030] Mixing wood and the reagent for oxidative degradation of lignin described in the above technical solution, performing oxidation treatment, and obtaining holocellulose residue from which lignin has been removed after solid-liquid separation;

[0031] The temperature of the oxidation treatment is ≥ 60°C.

[0032] In the present invention, the wood includes coniferous wood and / or broad-leaved wood. In a specific embodiment, the broad-leaved wood can be bamboo. The wood is screened before use. The mesh size of the sieve used for screening is 40 to 80 meshes.

[0033] In the present invention, the solid-to-liquid ratio of the wood and the reagent for oxidative degradation of lignin is 1 g:5-12 mL, and in a specific embodiment, it can be 1 g:6 mL, 1 g:8 mL or 1 g:10 mL.

[0034] In the present invention, the temperature of the oxidation treatment is ≥60°C, and in a specific embodiment, it can be 70°C or 80°C; the time of the oxidation treatment is 4 to 12 hours, and in a specific embodiment, it can be 6 hours, 7 hours, 9 hours or 11 hours.

[0035] In the present invention, the solid-liquid separation method may be suction filtration.

[0036] In the present invention, a treated liquid is obtained after the solid-liquid separation; the treated liquid includes lignin oxidation products and acetic acid and ethanol solvents, and the treated liquid can be subsequently separated into quinones and carboxylic acid compounds such as 2,6-dimethoxy-1,4-benzoquinone, p-benzoquinone, malonic acid, maleic anhydride and propionic acid, which can be used in the production of platform chemicals (luminal, barbiturate) and drug intermediates; the subsequent separation methods of the treated liquid include: lipophilic organic solvent extraction method: chloroform and benzene and other lipophilic organic solvents are used to extract quinone substances; alkali extraction and acid precipitation method: quinone substances are extracted by alkali solution, and then acidified to precipitate them; steam distillation method: separation of volatile small molecular benzoquinone compounds in lignin oxidation products.

[0037] In the present invention, the holocellulose residue from which lignin is removed obtained after solid-liquid separation can be used to prepare bioenergy, chemicals and chemical materials.

[0038] In the present invention, the holocellulose residue from which lignin has been removed is subjected to organic acid hydrolysis to obtain xylo-oligosaccharides; or the holocellulose residue from which lignin has been removed is modified and cross-linked using a chemical cross-linking agent to obtain a packaging film.

[0039] The present invention further comprises enzymolyzing the holocellulose residue to obtain an enzymolyzate containing glucose; preferably, the enzyme reagent used for the enzymolysis is cellulase, and in a specific embodiment, it can be cellulase; the enzyme amount of the enzyme reagent is 5 to 20 FPU / g, and in a specific embodiment, it can be 10 FPU / g or 15 FPU / g; the enzyme amount of the present invention refers to the amount of cellulase used for enzymolysis per gram of dry cellulose residue material.

[0040] In the present invention, the temperature of the enzymatic hydrolysis is 40-60°C, and in a specific embodiment, it can be 40°C, 50°C or 60°C; the time is 24-72h, and in a specific embodiment, it can be 48h or 72h; the enzymatic hydrolysis is carried out under stirring conditions; the stirring rate is 100-200r / min, and in a specific embodiment, it can be 150r / min.

[0041] In order to further illustrate the present invention, the reagent for oxidative degradation of lignin and the method for efficient removal of lignin provided by the present invention are described in detail below in conjunction with the accompanying drawings and examples, but they should not be construed as limiting the scope of protection of the present invention.

[0042] Example 1

[0043] according to Figure 1 The flow chart shown in the figure removes lignin, and the specific steps are:

[0044] Measure 30 wt % hydrogen peroxide solution and dilute it to a concentration of 15 wt %, and mix the 15 wt % hydrogen peroxide solution with ethyl acetate in a volume ratio of 5:5 to obtain a hydrogen peroxide-ethyl acetate system;

[0045] Weigh 1 g of bamboo powder (cellulose content 35.4%, hemicellulose content 17.2%, lignin content 28.9%), mix with the above 10 mL of hydrogen peroxide-ethyl acetate system and 0.1 mL of 98.3 wt% sulfuric acid, oxidize and remove lignin at 60 ° C for 6 h, and filter to obtain holocellulose residue after removal.

[0046] The components of the treated holocellulose residue were analyzed by NREL method, and the results were as follows: cellulose recovery rate was 90.3%, hemicellulose recovery rate was 68.5%, and lignin removal rate was 93.6%.

[0047] According to the enzyme content of 10 FPU / g, the above holocellulose residue and cellulase were mixed, and oscillated and enzymolyzed at 50°C and 150 r / min for 72 hours to obtain an enzymolysis solution containing glucose; the glucose yield was 88.1%.

[0048] Example 2

[0049] Measure 30 wt % hydrogen peroxide solution and dilute it to a concentration of 15 wt %, and mix the 15 wt % hydrogen peroxide solution with ethyl acetate in a volume ratio of 5:5 to obtain a hydrogen peroxide-ethyl acetate system;

[0050] 1 g of bamboo powder, 10 mL of the above hydrogen peroxide-ethyl acetate system and 0.1 mL of 98.3 wt% sulfuric acid were mixed, and oxidative removal of lignin was performed at 60° C. for 4 h. After the removal, the holocellulose residue was filtered out.

[0051] The components of the treated holocellulose residue were analyzed by NREL method, and the results were as follows: cellulose recovery rate was 92.4%, hemicellulose recovery rate was 78.1%, and lignin removal rate was 85.6%.

[0052] According to the enzyme content of 10 FPU / g, the above holocellulose residue and cellulase were mixed, and oscillated and enzymolyzed at 50°C and 150 r / min for 72 hours to obtain an enzymolysis solution containing glucose; the glucose yield was 83.4%.

[0053] Example 3

[0054] Measure 30 wt % hydrogen peroxide solution and dilute it to a concentration of 10 wt %, and mix the 10 wt % hydrogen peroxide solution with ethyl acetate in a volume ratio of 5:5 to obtain a hydrogen peroxide-ethyl acetate system;

[0055] 1 g of bamboo powder, 10 mL of the above hydrogen peroxide-ethyl acetate system and 0.1 mL of 98.3 wt% sulfuric acid were mixed, and oxidative removal of lignin was performed at 60° C. for 6 h. After the removal, the holocellulose residue was filtered out.

[0056] The components of the treated holocellulose residue were analyzed by NREL method, and the results were as follows: cellulose recovery rate was 91.2%, hemicellulose recovery rate was 72.5%, and lignin removal rate was 88.7%.

[0057] According to the enzyme content of 10 FPU / g, the above holocellulose residue and cellulase were mixed, and oscillated and enzymolyzed at 50°C and 150 r / min for 72 hours to obtain an enzymolysis solution containing glucose; the glucose yield was 79.3%.

[0058] Example 4

[0059] Measure 30 wt % hydrogen peroxide solution and dilute it to a concentration of 15 wt %, and mix the 15 wt % hydrogen peroxide solution with ethyl acetate in a volume ratio of 4:6 to obtain a hydrogen peroxide-ethyl acetate system;

[0060] 1 g of bamboo powder, 10 mL of the above hydrogen peroxide-ethyl acetate system and 0.1 mL of 98.3 wt% sulfuric acid were mixed, and oxidative removal of lignin was performed at 60° C. for 6 h. After the removal, the holocellulose residue was filtered out.

[0061] The components of the treated holocellulose residue were analyzed by NREL method, and the results were as follows: cellulose recovery rate was 89.3%, hemicellulose recovery rate was 71.2%, and lignin removal rate was 87.0%.

[0062] According to the enzyme content of 10 FPU / g, the above holocellulose residue and cellulase were mixed, and oscillated and enzymolyzed at 50°C and 150 r / min for 72 hours to obtain an enzymolysis solution containing glucose; the glucose yield was 88.1%.

[0063] Example 5

[0064] Measure 30 wt % hydrogen peroxide solution and dilute it to a concentration of 10 wt %, and mix the 10 wt % hydrogen peroxide solution with ethyl acetate in a volume ratio of 5:5 to obtain a hydrogen peroxide-ethyl acetate system;

[0065] 1 g of bamboo powder, 10 mL of the above hydrogen peroxide-ethyl acetate system and 0.15 mL of 98.3 wt % sulfuric acid were mixed, and oxidative removal of lignin was performed at 60° C. for 6 h. After the removal, the holocellulose residue was filtered out.

[0066] The components of the treated holocellulose residue were analyzed by NREL method, and the results were as follows: cellulose recovery rate was 90.5%, hemicellulose recovery rate was 70.6%, and lignin removal rate was 91.3%.

[0067] According to the enzyme content of 10 FPU / g, the above holocellulose residue and cellulase were mixed, and oscillated and enzymolyzed at 50°C and 150 r / min for 72 hours to obtain an enzymolysis solution containing glucose; the glucose yield was 79.3%.

[0068] Example 6

[0069] Measure 30 wt % hydrogen peroxide solution and dilute it to a concentration of 8 wt %, and mix the 8 wt % hydrogen peroxide solution with ethyl acetate in a volume ratio of 6:4 to obtain a hydrogen peroxide-ethyl acetate system;

[0070] 1 g of bamboo powder, 10 mL of the above hydrogen peroxide-ethyl acetate system and 0.12 mL of 98.3 wt % sulfuric acid were mixed, and oxidative removal of lignin was performed at 70° C. for 8 h. After the removal, the holocellulose residue was filtered out.

[0071] The components of the treated holocellulose residue were analyzed by NREL method, and the results were as follows: cellulose recovery rate was 91.3%, hemicellulose recovery rate was 72.6%, and lignin removal rate was 90.1%.

[0072] According to the enzyme content of 10 FPU / g, the above holocellulose residue and cellulase were mixed, and oscillated and enzymolyzed at 50°C and 150 r / min for 72 hours to obtain an enzymolysis solution containing glucose; the glucose yield was 84.5%.

[0073] Comparative Example 1

[0074] Measure 30 wt % hydrogen peroxide solution and dilute it to a concentration of 15 wt %, and mix the 15 wt % hydrogen peroxide solution with ethyl acetate in a volume ratio of 7:3 to obtain a hydrogen peroxide-ethyl acetate system;

[0075] 1 g of bamboo powder was weighed, mixed with the above 10 mL of hydrogen peroxide-ethyl acetate system and 0.1 mL of 98.3 wt % sulfuric acid, and oxidatively removed the lignin at 50° C. for 8 h. After the removal, the holocellulose residue was filtered out.

[0076] The components of the treated holocellulose residue were analyzed by NREL method, and the results were as follows: cellulose recovery rate was 95.6%, hemicellulose recovery rate was 94.7%, and lignin removal rate was 37.5%.

[0077] According to the enzyme content of 10 FPU / g, the above holocellulose residue and cellulase were mixed, and oscillated and enzymolyzed at 50°C and 150 r / min for 72 hours to obtain an enzymolysis solution containing glucose; the glucose yield was 69.3%.

[0078] Comparative Example 2

[0079] Measure 30 wt % hydrogen peroxide solution and dilute it to a concentration of 15 wt %, and mix the 15 wt % hydrogen peroxide solution with ethyl acetate at a volume ratio of 5:5 to obtain a hydrogen peroxide-ethyl acetate system;

[0080] 1 g of bamboo powder, 10 mL of the above hydrogen peroxide-ethyl acetate system and 0.1 mL of 98.3 wt % sulfuric acid were mixed, and oxidative removal of lignin was performed at 50° C. for 4 h. After the removal, the holocellulose residue was filtered out.

[0081] The components of the treated holocellulose residue were analyzed by NREL method, and the results were as follows: cellulose recovery rate was 94.4%, hemicellulose recovery rate was 92.2%, and lignin removal rate was 42.6%.

[0082] According to the enzyme content of 10 FPU / g, the above holocellulose residue and cellulase were mixed, and oscillated and enzymolyzed at 50°C and 150 r / min for 72 hours to obtain an enzymolysis solution containing glucose; the glucose yield was 72.5%.

[0083] Comparative Example 3

[0084] Measure 30 wt % hydrogen peroxide solution and dilute it to a concentration of 15 wt %, and mix the 15 wt % hydrogen peroxide solution with ethyl acetate at a volume ratio of 5:5 to obtain a hydrogen peroxide-ethyl acetate system;

[0085] 1 g of bamboo powder, 10 mL of the above hydrogen peroxide-ethyl acetate system and 0.05 mL of 98.3 wt% sulfuric acid were mixed, and oxidative removal of lignin was performed at 60° C. for 8 h. After the removal, the holocellulose residue was filtered out.

[0086] The components of the treated holocellulose residue were analyzed by NREL method, and the results were as follows: cellulose recovery rate was 93.7%, hemicellulose recovery rate was 83.5%, and lignin removal rate was 65.3%.

[0087] According to the enzyme content of 10 FPU / g, the above holocellulose residue and cellulase were mixed, and oscillated and enzymolyzed at 50°C and 150 r / min for 72 hours to obtain an enzymolysis solution containing glucose; the glucose yield was 79.5%.

[0088] Comparative Example 4

[0089] Measure 30 wt % hydrogen peroxide solution and dilute it to a concentration of 5 wt %, and mix the 5 wt % hydrogen peroxide solution with ethyl acetate in a volume ratio of 5:5 to obtain a hydrogen peroxide-ethyl acetate system;

[0090] 1 g of bamboo powder, 10 mL of the above hydrogen peroxide-ethyl acetate system and 0.1 mL of 98.3 wt% sulfuric acid were mixed, and oxidative removal of lignin was performed at 60° C. for 6 h. After the removal, the holocellulose residue was filtered out.

[0091] The components of the treated holocellulose residue were analyzed by NREL method, and the results were as follows: cellulose recovery rate was 95.6%, hemicellulose recovery rate was 78.2%, and lignin removal rate was 81.4%.

[0092] According to the enzyme content of 10 FPU / g, the above holocellulose residue and cellulase were mixed, and oscillated and enzymolyzed at 50°C and 150 r / min for 72 hours to obtain an enzymolysis solution containing glucose; the glucose yield was 76.1%.

[0093] According to the above specific examples 1 to 6 and comparative examples 1 to 4, the hydrogen peroxide solution-ethyl acetate oxidation system provided by the present invention can efficiently and selectively remove bamboo lignin, when the concentration of the hydrogen peroxide solution is 8 to 15 wt%, the volume ratio of the hydrogen peroxide solution to the ethyl acetate is 4 to 6:6 to 4; the amount of sulfuric acid catalyst is 1.0 to 1.5% (v / v), and the reaction temperature is ≥ Under the conditions of 60℃ and treatment time of 4 to 12h, the lignin removal rate in bamboo is as high as 85.6 to 93.6%, the cellulose recovery rate is 89.3 to 92.4%, the hemicellulose recovery rate is 68.5 to 78.1%, and the glucose yield by enzymatic hydrolysis is 79.3 to 88.1%.

[0094] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. People can also obtain other embodiments based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A reagent for oxidative degradation of lignin, characterized in that The preparation raw materials include: hydrogen peroxide solution, alkyl acetate and hydrolysis catalyst; The concentration of the hydrogen peroxide solution is 8-15 wt %; the volume ratio of the hydrogen peroxide solution to the alkyl acetate is 4-6:6-4; The volume of the hydrolysis catalyst accounts for 1.0-1.5% of the total volume of the hydrogen peroxide solution and the alkyl acetate.

2. The reagent according to claim 1, characterized in that The alkyl acetate includes one or more of methyl acetate, ethyl acetate and propyl acetate.

3. The reagent according to claim 1, characterized in that The hydrolysis catalyst includes one or more of sulfuric acid, hydrochloric acid and nitric acid.

4. A method for efficiently removing lignin, characterized in that: The following steps are involved: Mixing wood and the agent for oxidative degradation of lignin according to any one of claims 1 to 3, performing oxidation treatment, and obtaining holocellulose residue from which lignin has been removed after solid-liquid separation; The temperature of the oxidation treatment is ≥ 60°C.

5. The method according to claim 4, characterized in that The solid-liquid ratio of the wood and the reagent for oxidative degradation of lignin is 1g:5-12mL.

6. The method according to claim 4, characterized in that The oxidation treatment time is 4 to 12 hours.

7. The method according to claim 4, characterized in that The method also includes enzymatically hydrolyzing the holocellulose residue to obtain an enzymatic hydrolyzate containing glucose.

8. The method according to claim 7, characterized in that The enzyme reagent used for the enzymolysis is cellulase; the enzyme amount of the enzyme reagent is 5-20 FPU / g.

9. The method according to claim 7, characterized in that: The temperature of the enzymolysis is 40-60° C., and the time is 24-72 hours.

Citation Information

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