CN112029112A - Method for preparing high-yield high-aryl ether bond structure lignin from wood fiber biomass - Google Patents
Method for preparing high-yield high-aryl ether bond structure lignin from wood fiber biomass Download PDFInfo
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Abstract
The invention discloses a method for preparing high-yield high-aryl ether bond structure lignin from wood fiber biomass, and belongs to the technical field of value-added conversion and utilization of lignin resources. The method comprises the steps of crushing pretreatment, ball milling, homogenization, enzymolysis, separation washing and the like, wherein the yield of the obtained lignin is more than or equal to 95 percent, and the relative proportion of aryl ether bonds contained in the lignin is more than or equal to 90 percent. Aiming at the current situation that the content of carbon-carbon bonds in lignin obtained by the existing extraction method is high, the lignin obtained by the method has the advantages of low carbon-carbon bond proportion, simple and efficient preparation method, short time consumption, simple operation and low cost, and has good popularization potential and industrialization value.
Description
Technical Field
The invention belongs to the technical field of lignin resource value-added conversion and utilization, and particularly relates to a method for preparing high-yield high-aryl ether bond structure lignin from wood fiber biomass.
Background
Lignin is a natural aromatic ring polymer, and mainly comprises syringyl (S) units, guaiacyl (G) units and p-hydroxyphenyl (H) units. In addition, the lignin structure also contains other precursor structures, such as p-hydroxybenzoic acid, p-coumaric acid, ferulic acid, etc. In the wood fiber, the natural lignin is mainly polymerized by the monomers in the form of aryl ether bond (beta-O-4) and a small amount of carbon-carbon bond (beta-5, beta-beta and the like), and forms a macromolecular lignin polymer together. As the only aromatic ring resource in the wood fiber, the utilization value of the lignin is extremely high.
However, as the most important industry for utilizing wood fiber at present, the pulping and papermaking industry, lignin is subjected to the harsh conditions of delignification during pulping, so that a large number of aryl ether bonds (C-O bonds) in the lignin are broken, and condensation reaction is simultaneously carried out, so that more carbon-carbon bonds (C-C bonds) are formed. Compared with a large amount of C-O bonds existing in the original lignin, the C-C bonds formed by condensation in the preparation process of the industrial lignin cause the lignin to have more complex molecular structure, reduce the chemical reaction activity and increase the heterogeneity and the polydispersity, further limit the subsequent processing and utilization of the lignin and seriously influence the high-value utilization of the lignin. It is estimated that the global industrial lignin currently yields 7000 million tons, with chinese yields exceeding 1000 more than ten thousand tons. The lignin (sulfate lignin, lignosulfonate and alkali lignin) obtained by pulping and delignification has low purity and a complex structure. Only a small portion of high quality industrial lignin (lignosulfonate) has been developed as a surfactant and the like, and about 95% or more of lignin is directly used for combustion to obtain heat, which causes a great waste of resources and creates environmental problems.
In recent years, different lignin separation methods have appeared in the field of biomass refining and biomass pretreatment, including acid method, alkaline method, organic solvent method, green solvent method and the like. However, most of these delignification methods selectively partially break the C — O bond in the lignin, fragment the lignin, separate and dissolve out the lignin in the lignocellulosic raw material by the process of solution dissolution, and the obtained lignin also has the phenomenon that the aryl ether bond content is not high and the carbon-carbon bond content is high.
Due to the aromatic ring nature of native lignin, researchers have focused their attention on the field of production and development of lignin-based aromatic ring chemicals. In the field, researchers generally adopt a mode of combining high temperature and high pressure with a catalyst to realize maximum breakage of C-O bonds in lignin, so that aromatic ring chemicals are obtained by hydrogenation. Therefore, the higher the content of aryl ether linkages contained in the lignin, the corresponding increase in yield and efficiency of conversion of lignin to aromatic ring chemicals will occur.
Therefore, the development of a method for producing lignin from lignocellulosic biomass to achieve high yield and high aryl ether linkage structure has become a problem that needs to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the present invention provides a method for obtaining high yield and high aryl ether bond structure lignin from lignocellulosic biomass.
In order to achieve the above purpose, the invention provides the following technical scheme:
a method for preparing high-yield lignin with high aryl ether bond structure from lignocellulose biomass comprises the following steps:
1) crushing pretreatment: crushing and sieving the wood fiber biomass to obtain a crushed biomass raw material, and drying for later use;
2) ball milling: performing ball milling treatment on the crushed biomass raw material obtained in the step 1), and controlling the particle size of the material to be 200-300 meshes;
3) homogenizing: homogenizing the raw material obtained in the step 2) in a homogenizer, controlling the operation pressure to be 100-150MPa, the concentration of the homogenized sample injection to be 1-5%, and the homogenization frequency to be 5-10 times, and further homogenizing and dissociating the raw material into finer powder;
4) enzymolysis: performing cellulose enzymolysis treatment on the raw material obtained in the step 3);
5) separation and washing: and 4) carrying out centrifugal separation on the mixed system obtained in the step 4), and washing and freeze-drying the precipitate obtained after separation to obtain a residual lignin sample.
Industrial lignin, which is common, includes alkali lignin, kraft lignin, lignosulfonate, and the like. Due to the use of acid-base treatment and other chemical treatments in the existing preparation process, the structure of lignin is seriously changed, and condensation of the lignin structure is generated, so that the carbon-carbon bond content of the lignin is high, the aromatic ether bond content is relatively insufficient, and further the industrial development of preparing aromatic ring chemicals in the downstream of the industry is hindered. Meanwhile, due to the fact that the content of salt and carbohydrate impurities in a large amount of lignin raw materials is high, the problems of low lignin purity and poor dispersity exist, and the subsequent utilization cost is high.
In addition, in the field of biomass refining, the lignin obtained in the existing pretreatment process also has the problems of serious structural change, serious aryl ether bond breakage, easy secondary condensation and poor uniformity. Meanwhile, due to the wide sources of biomass raw materials, different pretreatment methods and different specific strengths, the obtained lignin has larger structural difference. Even the same biomass raw material and the same pretreatment method have larger difference in structure due to different pretreatment conditions. This further limits the progress of lignin production and development of aromatic ring chemicals.
In contrast, the method adopts the crushing pretreatment, avoids the use of acid-base reagents, ensures the retention of aryl ether bonds in the wood structure, has better uniformity and is not easy to generate secondary condensation. On the basis, the method also carries out the refining treatment on the fibers by the combination of ball milling and homogenizing technologies, and breaks the potential connection among cellulose, hemicellulose and lignin in the cell walls of the wood fiber raw material through the physical action. Meanwhile, the crystal structure of the cellulose is damaged by ball milling and homogenization, and the invention can easily remove most of the cellulose and hemicellulose and reserve the lignin as the residue by continuously adopting a cellulose complex enzyme mode.
Preferably, the lignocellulosic biomass comprises: any one of waste bamboo and manila hemp in the processing process of balsawood, moso bamboo parenchyma cells and moso bamboo recombined materials.
It is worth noting that only a few representative native lignin (MWL, CEL, EMAL) samples used for structural analysis of native lignin in lignocellulosic biomass have high aryl ether linkages (typically 70-80% of the lignin linkages). However, the current industrial lignin separation method is to obtain lignin components with different yields by breaking the connecting bonds between ether bonds and other groups contained in lignin and then using chemical dissolution. In this case, the ether bond contained in lignin itself cannot be effectively retained due to the cleavage of the ether bond, so that the desired lignin with high ether bond cannot be obtained in the subsequent aromatic ring compound processing and preparation field. Moreover, the representative original lignins generally have the problems of long preparation time, complex process, multiple purification steps, high cost and yield of only 10-50% of the mass of the lignins in the raw materials, and are not suitable for large-scale preparation.
The invention breaks through the limitation of bond breaking and dissolving, and realizes the retention and separation of lignin with high aryl ether bond structure in various wood fiber biomasses. In addition, aiming at the lignin raw material containing a high aryl ether bond structure, the invention not only provides the limitation of the type of the lignin raw material, but also avoids the damage of the separation preparation method to the aryl ether bond contained in the lignin raw material.
Preferably, the fineness of the pulverized lignocellulosic biomass in the step 1) is 10 to 100 meshes.
Preferably, the enzymolysis conditions in the step 4) are as follows: enzymolysis is carried out for 24-72 hours, the enzyme activity is 10-50 FPU/g substrate, and the enzymolysis temperature is 40-60 ℃.
More preferably, the cellulase used in the invention is a cellulose complex enzyme, comprising
CTec2、
CTec3 or Celluclast.
Preferably, the yield of the lignin is more than or equal to 95 percent, and the proportion of the obtained lignin containing aryl ether bonds in the total chain links is more than or equal to 90 percent.
Compared with the prior art, the invention has the advantages that:
1. the invention firstly provides a lignin preparation method with ultrahigh yield (more than or equal to 95 percent) and aryl ether bond content (more than or equal to 90 percent);
2. compared with the current situation that the lignin obtained by the current common lignin extraction method has low aryl ether bond and high carbon-carbon bond content, the lignin obtained by the invention only contains 1 to 10 percent of carbon-carbon bond;
3. the preparation method disclosed by the invention is simple and efficient, short in time consumption, simple to operate and low in cost, has better application in the original field of basic research on lignin structural analysis and lignin catalytic degradation, and has certain popularization potential and industrial utilization value.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a flow chart of a method for producing high yield high aryl ether linkage lignin from lignocellulosic biomass as disclosed herein.
FIG. 2 is a two-dimensional single quantum hydrocarbon correlation spectrum (2D-HSQC) spectrum of lignin obtained in example 1 of the present invention.
FIG. 3 is a two-dimensional single quantum hydrocarbon correlation spectrum (2D-HSQC) spectrum of lignin obtained in example 2 of the present invention.
FIG. 4 is a two-dimensional single quantum hydrocarbon correlation spectrum (2D-HSQC) spectrum of lignin obtained in example 3 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A method for preparing high-yield lignin with high aryl ether bond structure from lignocellulose biomass comprises the following steps:
1) pretreatment: removing impurities from the balsawood raw material, crushing the balsawood raw material to 20-60 meshes of fineness, and drying the balsawood raw material to obtain a wood fiber biomass raw material for later use;
2) ball milling: carrying out ball milling on the lignocellulose raw material obtained in the step 1) at 450rpm for 2h for later use;
3) homogenizing: homogenizing the crushed raw materials obtained in the step 2) in a homogenizer, controlling the operation pressure to be 150MPa, controlling the concentration of the homogenized sample to be 2.5%, and controlling the homogenization frequency to be 10 times, wherein the obtained sample is reserved;
4) enzymolysis: adding the raw material obtained in the step 3) into a sodium acetate buffer solution with the pH value of 4.8, then adding 35FPU cellulase/g substrate, and carrying out enzymolysis for 48h at the temperature of 50 ℃.
5) Separation and washing: and 4) carrying out centrifugal separation on the mixed system obtained in the step 4) to remove carbohydrate, repeatedly washing the precipitate obtained by centrifugation with water, and freeze-drying to obtain the lignin sample.
The lignin sample is characterized through a two-dimensional single-quantum hydrocarbon correlation spectrum (2D-HSQC), the types of chemical composition units and connecting bonds of the lignin are identified, meanwhile, integration is assisted, and the proportion of each connecting bond is obtained through calculation.
Example 2
A method for preparing high-yield lignin with high aryl ether bond structure from lignocellulose biomass comprises the following steps:
1) pretreatment: removing impurities from the moso bamboo parenchyma cell raw material, crushing to 20-60 meshes, and drying to obtain a wood fiber biomass raw material for later use;
2) ball milling: ball-milling the lignocellulose raw material obtained in the step 1) at 400rpm for 2.5 hours for later use;
3) homogenizing: homogenizing the crushed raw material obtained in the step 2) in a homogenizer, controlling the operation pressure to be 130MPa, the concentration of the homogenized sample injection to be 1.5 percent, and homogenizing for 8 times to obtain a sample for later use;
4) enzymolysis: adding the raw material obtained in the step 3) into a sodium acetate buffer solution with the pH value of 5.0, then adding 30FPU cellulase/g substrate, and carrying out enzymolysis for 48h at the temperature of 45-55 ℃.
5) Separation and washing: and 4) carrying out centrifugal separation on the mixed system obtained in the step 4) to remove carbohydrate, repeatedly washing the precipitate obtained by centrifugation with water, and freeze-drying to obtain the lignin sample.
The lignin sample is characterized through a two-dimensional single-quantum hydrocarbon correlation spectrum (2D-HSQC), the types of chemical composition units and connecting bonds of the lignin are identified, meanwhile, integration is assisted, and the proportion of each connecting bond is obtained through calculation.
Example 3
A method for preparing high-yield lignin with high aryl ether bond structure from lignocellulose biomass comprises the following steps:
1) pretreatment: removing impurities from the manila hemp raw material, crushing to the fineness of 100-mesh and 150-mesh, and drying to obtain a wood fiber biomass raw material for later use;
2) ball milling: ball-milling the lignocellulose raw material obtained in the step 1) at 500rpm for 3.5 hours for later use;
3) homogenizing: homogenizing the crushed raw materials obtained in the step 2) in a homogenizer, controlling the operation pressure to be 140MPa, the concentration of the homogenized sample injection to be 1%, and the homogenization frequency to be 10 times, wherein the obtained sample is reserved;
4) enzymolysis: adding the raw material obtained in the step 3) into a sodium acetate buffer solution with the pH value of 5.5, then adding 50FPU cellulase/g substrate, and carrying out enzymolysis for 72h at the temperature of 45 ℃.
5) Separation and washing: and 4) carrying out centrifugal separation on the mixed system obtained in the step 4) to remove carbohydrate, repeatedly washing the precipitate obtained by centrifugation with water, and freeze-drying to obtain the lignin sample.
The lignin sample is characterized through a two-dimensional single-quantum hydrocarbon correlation spectrum (2D-HSQC), the types of chemical composition units and connecting bonds of the lignin are identified, meanwhile, integration is assisted, and the proportion of each connecting bond is obtained through calculation.
To further verify the excellent effects of the present invention, the inventors also conducted the following comparative experiments:
comparative example 1
A method for preparing high-yield lignin with high aryl ether bond structure from lignocellulose biomass comprises the following steps:
1) pretreatment: removing impurities from the balsawood raw material, crushing to the fineness of 100-plus 150 meshes, and drying to obtain a wood fiber biomass raw material for later use;
2) ball milling: ball-milling the lignocellulose raw material obtained in the step 1) at 500rpm for 5 hours for later use;
3) enzymolysis: adding the raw material obtained in the step 2) into a sodium acetate buffer solution with the pH value of 4.8, then adding 50FPU cellulase/g substrate, and carrying out enzymolysis for 72h at the temperature of 50 ℃.
4) Separation and washing: and 3) carrying out centrifugal separation on the mixed system obtained in the step 3) to remove carbohydrate, repeatedly washing the precipitate obtained by centrifugation with water, and freeze-drying to obtain the lignin sample.
Comparative example 2
A method for preparing high-yield lignin with high aryl ether bond structure from lignocellulose biomass comprises the following steps:
1) pretreatment: removing impurities from the moso bamboo parenchyma cell raw material, crushing to 40-60 meshes, and drying to obtain a wood fiber biomass raw material for later use;
2) ball milling: ball-milling the lignocellulose raw material obtained in the step 1) at 400rpm for 4.5 hours for later use;
3) enzymolysis: adding the raw material obtained in the step 2) into a sodium acetate buffer solution with the pH value of 5.0, then adding 50FPU cellulase/g substrate, and carrying out enzymolysis for 48h at the temperature of 55 ℃.
4) Separation and washing: and 3) carrying out centrifugal separation on the mixed system obtained in the step 3) to remove carbohydrate, repeatedly washing the precipitate obtained by centrifugation with water, and freeze-drying to obtain the lignin sample.
Comparative example 3
A method for preparing high-yield lignin with high aryl ether bond structure from lignocellulose biomass comprises the following steps:
1) pretreatment: removing impurities from the manila hemp raw material, crushing to the fineness of 100-mesh and 150-mesh, and drying to obtain a wood fiber biomass raw material for later use;
2) ball milling: ball-milling the lignocellulose raw material obtained in the step 1) at 400rpm for 5 hours for later use;
3) enzymolysis: adding the raw material obtained in the step 2) into a sodium acetate buffer solution with the pH value of 5.2, then adding 45FPU cellulase/g substrate, and carrying out enzymolysis for 72h at the temperature of 50 ℃.
4) Separation and washing: and 3) carrying out centrifugal separation on the mixed system obtained in the step 3) to remove carbohydrate, repeatedly washing the precipitate obtained by centrifugation with water, and freeze-drying to obtain the lignin sample.
Comparative example 4
A method for preparing high-yield lignin with high aryl ether bond structure from lignocellulose biomass comprises the following steps:
1) pretreatment: removing impurities from the balsawood raw material, crushing the balsawood raw material to the fineness of 60-100 meshes, and drying the balsawood raw material to obtain a wood fiber biomass raw material for later use;
2) homogenizing: homogenizing the crushed raw materials obtained in the step 1) in a homogenizer, controlling the operation pressure to be 150MPa, the concentration of the homogenized sample injection to be 1%, and the homogenization frequency to be 8 times, wherein the obtained sample is reserved;
3) enzymolysis: adding the raw material obtained in the step 2) into a sodium acetate buffer solution with the pH value of 4.8, then adding 45FPU cellulase/g substrate, and carrying out enzymolysis for 72h at the temperature of 55 ℃.
4) Separation and washing: and 3) carrying out centrifugal separation on the mixed system obtained in the step 3) to remove carbohydrate, repeatedly washing the precipitate obtained by centrifugation with water, and freeze-drying to obtain the lignin sample.
Comparative example 5
A method for preparing high-yield lignin with high aryl ether bond structure from lignocellulose biomass comprises the following steps:
1) pretreatment: removing impurities from the moso bamboo thin-wall cell raw material, crushing to the fineness of 100-;
2) homogenizing: homogenizing the crushed raw materials obtained in the step 1) in a homogenizer, controlling the operation pressure to be 140MPa, the sample injection concentration to be 2 percent and the sample injection homogenization frequency to be 10 times, and obtaining a sample for later use;
3) enzymolysis: adding the raw material obtained in the step 2) into a sodium acetate buffer solution with the pH value of 4.8, then adding 50FPU cellulase/g substrate, and carrying out enzymolysis for 48h at the temperature of 55 ℃.
4) Separation and washing: and 3) carrying out centrifugal separation on the mixed system obtained in the step 3) to remove carbohydrate, repeatedly washing the precipitate obtained by centrifugation with water, and freeze-drying to obtain the lignin sample.
Comparative example 6
A method for preparing high-yield lignin with high aryl ether bond structure from lignocellulose biomass comprises the following steps:
1) pretreatment: removing impurities from a manila hemp raw material, crushing the manila hemp raw material to the fineness of 60-150 meshes, and drying to obtain a wood fiber biomass raw material for later use;
2) homogenizing: homogenizing the crushed raw materials obtained in the step 1) in a homogenizer, controlling the operation pressure to be 130MPa, the concentration of a homogenized sample to be 1 percent, and homogenizing for 8 times to obtain a sample for later use;
3) enzymolysis: adding the raw material obtained in the step 2) into a sodium acetate buffer solution with the pH value of 5.5, then adding 45FPU cellulase/g substrate, and carrying out enzymolysis for 72h at the temperature of 45 ℃.
4) Separation and washing: and 3) carrying out centrifugal separation on the mixed system obtained in the step 3) to remove carbohydrate, repeatedly washing the precipitate obtained by centrifugation with water, and freeze-drying to obtain the lignin sample.
Comparative example 7
A method for preparing high-yield lignin with high aryl ether bond structure from lignocellulose biomass comprises the following steps:
1) pretreatment: removing impurities from the balsawood raw material, crushing the balsawood raw material to the fineness of 60-100 meshes, and drying the balsawood raw material to obtain a wood fiber biomass raw material for later use;
2) ball milling: carrying out ball milling on the lignocellulose raw material obtained in the step 1) at 450rpm for 5 hours for later use;
3) enzymolysis: adding the raw material obtained in the step 2) into a sodium acetate buffer solution with the pH value of 4.8, then adding 50FPU cellulase/g substrate, and carrying out enzymolysis for 72h at the temperature of 50 ℃.
4) And (3) extraction: extracting the residue obtained in the step 3) by using 96% dioxane for 48 hours, and collecting the supernatant for later use.
5) Separation and washing: and (4) carrying out rotary evaporation on the supernatant obtained in the step 4) to remove dioxane, repeatedly washing the precipitate obtained by rotary evaporation with water, and freeze-drying to obtain the lignin sample.
Comparative example 8
A method for preparing high-yield lignin with high aryl ether bond structure from lignocellulose biomass comprises the following steps:
1) pretreatment: removing impurities from the moso bamboo parenchyma cell raw material, crushing to 40-60 meshes, and drying to obtain a wood fiber biomass raw material for later use;
2) ball milling: ball-milling the lignocellulose raw material obtained in the step 1) at 500rpm for 4 hours for later use;
3) enzymolysis: adding the raw material obtained in the step 2) into a sodium acetate buffer solution with the pH value of 5.0, then adding 45FPU cellulase/g substrate, and carrying out enzymolysis for 72h at the temperature of 50 ℃.
4) And (3) extraction: extracting the residue obtained in the step 3) by using 96% dioxane for 36h, and collecting the supernatant for later use.
5) Separation and washing: and (4) carrying out rotary evaporation on the supernatant obtained in the step 4) to remove dioxane, repeatedly washing the precipitate obtained by rotary evaporation with water, and freeze-drying to obtain the lignin sample.
Comparative example 9
A method for preparing high-yield lignin with high aryl ether bond structure from lignocellulose biomass comprises the following steps:
1) pretreatment: removing impurities from a manila hemp raw material, crushing the manila hemp raw material to the fineness of 40-100 meshes, and drying to obtain a wood fiber biomass raw material for later use;
2) ball milling: ball-milling the lignocellulose raw material obtained in the step 1) at 500rpm for 4.5 hours for later use;
3) enzymolysis: adding the raw material obtained in the step 2) into a sodium acetate buffer solution with the pH value of 5.5, then adding 50FPU cellulase/g substrate, and carrying out enzymolysis for 72h at the temperature of 45 ℃.
4) And (3) extraction: extracting the residue obtained in the step 3) by using 96% dioxane for 24 hours, and collecting the supernatant for later use.
5) Separation and washing: and (4) carrying out rotary evaporation on the supernatant obtained in the step 4) to remove dioxane, repeatedly washing the precipitate obtained by rotary evaporation with water, and freeze-drying to obtain the lignin sample.
Comparative example 10
A method for preparing high-yield lignin with high aryl ether bond structure from lignocellulose biomass comprises the following steps:
1) pretreatment: removing impurities from the balsawood raw material, crushing the balsawood raw material to the fineness of 60-100 meshes, and drying the balsawood raw material to obtain a wood fiber biomass raw material for later use;
2) homogenizing: homogenizing the crushed raw materials obtained in the step 1) in a homogenizer, controlling the operation pressure to be 140MPa, the concentration of a homogenized sample to be 1 percent, and the homogenization frequency to be 10 times, wherein the obtained sample is reserved;
3) enzymolysis: adding the raw material obtained in the step 2) into a sodium acetate buffer solution with the pH value of 5.0, then adding 45FPU cellulase/g substrate, and carrying out enzymolysis for 72h at the temperature of 50 ℃.
4) And (3) extraction: extracting the residue obtained in the step 3) by using 96% dioxane for 48 hours, and collecting the supernatant for later use.
5) Separation and washing: and (4) carrying out rotary evaporation on the supernatant obtained in the step 4) to remove dioxane, repeatedly washing the precipitate obtained by rotary evaporation with water, and freeze-drying to obtain the lignin sample.
Comparative example 11
A method for preparing high-yield lignin with high aryl ether bond structure from lignocellulose biomass comprises the following steps:
1) pretreatment: removing impurities from the phyllostachys pubescens parenchyma cell raw material, crushing to 60-100 meshes of fineness, and drying to obtain a wood fiber biomass raw material for later use;
2) homogenizing: homogenizing the crushed raw materials obtained in the step 1) in a homogenizer, controlling the operation pressure to be 150MPa, the concentration of a homogenized sample to be 1%, and the homogenization frequency to be 8 times, wherein the obtained sample is reserved;
3) enzymolysis: adding the raw material obtained in the step 2) into a sodium acetate buffer solution with the pH value of 5.5, then adding 45FPU cellulase/g substrate, and carrying out enzymolysis for 72h at the temperature of 45 ℃.
4) And (3) extraction: extracting the residue obtained in the step 3) by using 96% dioxane for 36h, and collecting the supernatant for later use.
5) Separation and washing: and (4) carrying out rotary evaporation on the supernatant obtained in the step 4) to remove dioxane, repeatedly washing the precipitate obtained by rotary evaporation with water, and freeze-drying to obtain the lignin sample.
Comparative example 12
A method for preparing high-yield lignin with high aryl ether bond structure from lignocellulose biomass comprises the following steps:
1) pretreatment: removing impurities from a manila hemp raw material, crushing the manila hemp raw material to the fineness of 40-100 meshes, and drying to obtain a wood fiber biomass raw material for later use;
2) homogenizing: homogenizing the crushed raw materials obtained in the step 1) in a homogenizer, controlling the operation pressure to be 130MPa, the concentration of a homogenized sample to be 1 percent, and the homogenization frequency to be 10 times, wherein the obtained sample is reserved;
3) enzymolysis: adding the raw material obtained in the step 2) into a sodium acetate buffer solution with the pH value of 4.8, then adding 45FPU cellulase/g substrate, and carrying out enzymolysis for 72h at the temperature of 50 ℃.
4) And (3) extraction: extracting the residue obtained in the step 3) by using 96% dioxane for 48 hours, and collecting the supernatant for later use.
5) Separation and washing: and (4) carrying out rotary evaporation on the supernatant obtained in the step 4) to remove dioxane, repeatedly washing the precipitate obtained by rotary evaporation with water, and freeze-drying to obtain the lignin sample.
The lignin samples of examples 1-3 and comparative examples 1-12 were characterized by two-dimensional single quantum hydrocarbon correlation spectroscopy (2D-HSQC), the linkage signal was integrated and normalized, and the calculated lignin yield, lignin degree, and β -O-4 aryl ether bond content were as shown in table 1.
TABLE 1
| Yield of lignin | Purity of lignin | beta-O-4 aryl ether linkage content | |
| Example 1 | 96.5％ | 97％ | 98.2％ |
| Example 2 | 97.2％ | 97％ | 100％ |
| Example 3 | 95.9％ | 96％ | 100％ |
| Comparative example 1 | 120.5％a | 78％ | Is unable to detectb |
| Comparative example 2 | 123.3％a | 76％ | Is unable to detectb |
| Comparative example 3 | 125.7％a | 77％ | Is unable to detectb |
| Comparative example 4 | 126.6％a | 78％ | Is unable to detectb |
| Comparative example 5 | 118.3％a | 81％ | Is unable to detectb |
| Comparative example 6 | 120.6％a | 79％ | Is unable to detectb |
| Comparative example 7 | 20.1％ | 90％ | 98.9％ |
| Comparative example 8 | 17.9％ | 89％ | 100％ |
| Comparative example 9 | 25.2％ | 92％ | 100％ |
| Comparative example 10 | 18.9％ | 91％ | 98.3％ |
| Comparative example 11 | 20.3％ | 90％ | 100％ |
| Comparative example 12 | 23.1％ | 92％ | 100％ |
Note:
the yield is based on the weight of the final lignin residue/the quality of the lignin in the raw material, so the yield of the lignin sample with low purity is higher than 100% in value.
b, because the lignin residues obtained in the comparative examples 1 to 6 have low purity and low solubility in a deuterated reagent, the detection of nuclear magnetic resonance is caused, and the content of aryl ether bonds cannot be calculated
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (6)
1. A method for preparing high-yield lignin with high aryl ether bond structure from lignocellulose biomass is characterized by comprising the following steps:
1) crushing pretreatment: crushing and sieving the wood fiber biomass to obtain a crushed biomass raw material, and drying for later use;
2) ball milling: performing ball milling treatment on the crushed biomass raw material obtained in the step 1), and controlling the particle size of the material to be 200-300 meshes;
3) homogenizing: homogenizing the raw material obtained in the step 2) in a homogenizer, controlling the operation pressure to be 100-150MPa, the concentration of the homogenized sample injection to be 1-5%, and the homogenization frequency to be 5-10 times, and further homogenizing and dissociating the raw material into fine fibers;
4) enzymolysis: carrying out enzymolysis treatment on the raw material obtained in the step 3);
5) separation and washing: and 4) carrying out centrifugal separation on the mixed system obtained in the step 4), and washing and freeze-drying the precipitate obtained after separation to obtain a residual lignin sample.
2. The method of claim 1, wherein the lignocellulosic biomass comprises: any one of waste bamboo and manila hemp in the processing process of balsawood, moso bamboo parenchyma cells and moso bamboo recombined materials.
3. The method for preparing the high-yield high-aryl ether bond structure lignin from the lignocellulosic biomass according to claim 1, wherein the fineness of the lignocellulosic biomass crushed in the step 1) is 10-100 meshes.
4. The method for preparing high-yield high-aryl ether bond structure lignin from lignocellulosic biomass according to claim 1, wherein the enzymolysis conditions of the step 4) are as follows: enzymolysis is carried out for 24-72 hours, the enzyme activity is 10-50 FPU/g substrate, and the enzymolysis temperature is 40-60 ℃.
5. The method for preparing high-yield high-aryl ether bond structure lignin from lignocellulosic biomass as claimed in claim 4, wherein the cellulase used for enzymolysis is a cellulose complex enzyme, and the cellulose complex enzyme comprises
CTec2、
CTec3 or Celluclast.
6. The method for preparing the lignin with high yield and high aryl ether bond structure from the lignocellulosic biomass as claimed in claim 1, wherein the yield of the lignin is more than or equal to 95%, and the obtained lignin contains aryl ether bonds in a proportion of more than or equal to 90% of the total linkage bonds.
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| CN110055788A (en) * | 2018-01-19 | 2019-07-26 | 山东省圣泉生物质石墨烯研究院 | A kind of micro-nano lignocellulose dispersion liquid and its preparation method and application |
| AU2020102758A4 (en) * | 2020-08-26 | 2020-12-10 | Beijing Forestry University | Method for preparing lignin with high yield and high aryl ether bond structure from lignocellulosic biomass |
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| CN107098803A (en) * | 2017-05-16 | 2017-08-29 | 北京林业大学 | The separating-purifying and biodegrading process of a kind of lignin |
| CN110055788A (en) * | 2018-01-19 | 2019-07-26 | 山东省圣泉生物质石墨烯研究院 | A kind of micro-nano lignocellulose dispersion liquid and its preparation method and application |
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| CN114774494A (en) * | 2022-04-02 | 2022-07-22 | 北京林业大学 | Method for co-producing xylo-oligosaccharide, high aryl ether bond lignin and glucose by catalytic hydrothermal coupling short-time ball milling |
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