CN113292747B - Preparation method and application of biomass lignin nanoshell - Google Patents
Preparation method and application of biomass lignin nanoshell Download PDFInfo
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- 239000002078 nanoshell Substances 0.000 title claims abstract description 70
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- 239000003814 drug Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2397/00—Characterised by the use of lignin-containing materials
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- Engineering & Computer Science (AREA)
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Abstract
The invention relates to a preparation method and application of a biomass lignin nanoshell. The preparation method comprises the following steps: (1) Mixing a lignocellulose raw material with an acidic lithium bromide solution, and then heating for reaction; after the reaction is finished, carrying out solid-liquid separation to obtain a pretreatment solution and a solid precipitate, and cleaning and drying the solid precipitate to obtain a lignin raw material; (2) Dispersing the lignin raw material obtained in the step (1) in tetrahydrofuran to obtain dispersion liquid, dissolving lignin by ultrasonic waves, filtering and collecting the solution, diluting the solution by adopting tetrahydrofuran, and performing dialysis treatment to remove an organic solvent and polymerize the lignin into spheres to obtain the biomass lignin nanoshell. The invention adopts a two-stage treatment mode to realize the grading utilization of the lignocellulose raw material, the obtained high-value lignin raw material is used for preparing the lignin nanoshell, and the separated pretreatment solution contains the reaction solvent, cellulose and hemicellulose hydrolysis sugar and can be subjected to the next reaction and conversion.
Description
Technical Field
The invention relates to a preparation method and application of a biomass lignin nanosheet, and belongs to the technical field of biomass refining.
Background
Among biomass resources, lignin is a natural polymer widely existing in plant cell walls, and is the second most renewable resource with the second best reserve in nature than cellulose. At present, the utilization rate of lignin is low, most of the lignin is combusted, and not only is the natural ecological environment polluted, but also the waste of natural wood resources is caused. The reasonable and efficient utilization of the lignin has important significance for the environment and the economy. Usually, lignin cannot be dissolved in water or acidic aqueous solution, and has better solubility property in common organic solvents such as tetrahydrofuran, ethylene glycol, dimethylformamide and the like. The lignin is a biopolymer with a three-dimensional network structure formed by connecting three phenylpropane units through ether bonds and carbon-carbon bonds, and active groups such as aromatic groups, phenolic hydroxyl groups, alcoholic hydroxyl groups, carbon-based conjugated double bonds and the like exist in the molecular structure, so that various chemical reactions can be carried out. Despite its good chemical structure potential and reactivity, lignin is still an underdeveloped natural biomass material, and its application is limited by various functional groups and macromolecular structures.
The lignin is a natural high molecular compound, has rich surface functional groups, and can be processed to form a high-value-added lignin product. The lignin nanoparticles have high specific surface area and excellent permeability, and the hollow nanosphere shells have great application potential as a carrier. Meanwhile, the lignin has good biocompatibility due to the antibacterial and non-cytotoxic properties, and can be applied to the medical pharmacy.
The preparation of the lignin nanoshell is mostly prepared by an organic solvent method, but the lignin has the requirement on hydrophilicity and hydrophobicity, acetylation is often adopted to enable the lignin as a raw material to have strong hydrophobicity, and the requirement on the source of the lignin raw material is high. For example, chinese patent document CN109012608A (application No. 201810752879.3) discloses a method for preparing lignin nanoparticles, which comprises the steps of modifying lignin by hydrophobicity through a microwave acetylation method, dissolving acetylated lignin in tetrahydrofuran solvent, and finally preparing lignin nanoparticles through solvent exchange and ultrasonic assisted methods.
Lignocellulosic feedstock is one of the most abundant renewable resources in the world, with a complex structure, mainly composed of cellulose, hemicellulose and lignin, which can be used by hydrolysis in sugar-platform biorefineries. However, cellulose is tightly wrapped by a network structure formed by covalent bonds of hemicellulose and lignin, thereby forming a stubborn compact structure. The lignocellulosic feedstock must then be pretreated prior to bioconversion to break the network structure of hemicellulose and lignin. Thus, the pretreatment process plays a crucial role in the development of the biorefinery industry for lignocellulosic feedstocks.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method and application of a biomass lignin nanoshell. The invention provides a preparation method of lignin nanoshells, which takes lignocellulose raw materials as raw materials, has wide raw material sources, low cost and strong operability, and can realize the adjustment of the particle size of the nanoshells by changing the reaction preparation conditions.
The technical scheme of the invention is as follows:
a preparation method of biomass lignin nanoshells comprises the following steps:
(1) Mixing a lignocellulose raw material with an acidic lithium bromide solution, and then heating for reaction; after the reaction is finished, carrying out solid-liquid separation to obtain a pretreatment solution and a solid precipitate, and cleaning and drying the solid precipitate to obtain a lignin raw material;
(2) Dispersing the lignin raw material obtained in the step (1) in tetrahydrofuran to obtain dispersion liquid, dissolving lignin by ultrasonic waves, filtering and collecting the solution, diluting the solution by adopting tetrahydrofuran, and performing dialysis treatment to remove an organic solvent and polymerize the lignin into spheres to obtain the biomass lignin nanoshell.
Preferably according to the invention, the lignocellulosic feedstock in step (1) comprises agricultural waste, forestry waste, and sugar processing residues; the agricultural waste includes, but is not limited to, corn stover, wheat straw, barley straw, canola straw, rice straw, and soybean stover; the forestry waste includes, but is not limited to, poplar, willow, locust, cedar and wood chips thereof; the sugar processing residues include, but are not limited to, bagasse and beet pulp.
Preferably according to the invention, the particle size of the lignocellulosic feedstock in step (1) is in the range of 20 to 40 mesh.
According to the invention, the mass-to-volume ratio of the lignocellulose raw material to the acidic lithium bromide solution in the step (1) is 1 (10-20), g/mL; preferably 1.
According to the invention, the acidic lithium bromide solution in the step (1) is prepared by adding HCl into a lithium bromide aqueous solution, wherein the concentration of the lithium bromide is 60wt%, and the addition amount of the HCl is 50-60 mg/15mL of the acidic lithium bromide solution.
According to the invention, the heating reaction in the step (1) is carried out at the temperature of 100-150 ℃ for 20-50min; preferably, the reaction is carried out at 110 ℃ for 20min.
According to the invention, in the step (1), the solid-liquid separation is preferably carried out by using a sand core funnel.
In the invention, after the lignocellulose raw material and the acidic lithium bromide solution in the step (1) are heated and reacted, the cellulose and the hemicellulose are converted into monosaccharide, and the lignin is stored in a solid form; the obtained pretreatment solution contains various monosaccharides, a small amount of polysaccharides, an acidic lithium bromide solvent and a small amount of dissolved lignin, and can be used for further conversion and utilization; and cleaning, drying and collecting the obtained solid precipitate to obtain a high-value lignin raw material for preparing the lignin nano spherical shell. The invention adopts a two-stage treatment mode, and realizes the graded utilization of biomass.
According to the invention, the mass volume ratio of the lignin raw material to the tetrahydrofuran in the dispersion liquid in the step (2) is 1 (1-5), g/L; further preferably 1 (1-2), g/L.
Preferably, according to the invention, the filtration in step (2) is carried out with a 0.22 μm organic filter membrane.
Preferably according to the invention, the dilution in step (2) is between 2 and 10 fold; preferably 2.5 to 5 times.
According to the invention, the dialysis treatment in the step (2) has a molecular weight cut-off of 7000D, a dialysis time of 24-60h, and a dialysis solvent of water; further preferably, the dialysis time is 36h.
According to the invention, the biomass lignin nanoshells in step (2) preferably have a particle size of 50-400nm and a hollow or solid nanoshell shape.
The biomass lignin nanoshell prepared according to the preparation method has a particle size of 50-400nm and is hollow or solid nanoshell-shaped.
The application of the biomass lignin nanoshell in the preparation of a drug carrier.
Has the beneficial effects that:
1. compared with the prior art, the method utilizes the lignocellulose raw material with wide raw material sources to obtain the lignin, and the lignocellulose raw material comprises agricultural waste, forestry waste and sugar treatment residues; wherein the agricultural waste includes, but is not limited to, corn stover, wheat straw, barley straw, canola straw, rice straw, and soybean stover; forestry wastes including, but not limited to, poplar, willow, locust, cedar and wood chips thereof; sugar processing residues include, but are not limited to, bagasse and beet pulp. The lignocellulose raw material adopted by the invention has wide sources, and the high-value lignin raw material which does not need to be modified can be directly obtained from the lignocellulose raw material to prepare the nano spherical shell, so that the preparation process of the lignin spherical shell is greatly simplified.
2. According to the invention, firstly, lignin components are efficiently separated, intramolecular and intermolecular links of cellulose and hemicellulose are effectively destroyed by high-concentration lithium bromide under an acidic condition, so that the cellulose and the hemicellulose are dissolved in a reaction solution, and lignin serving as a connecting substance is released along with the dissolution of the cellulose and the hemicellulose. Meanwhile, the structure of the lignin is relatively stable in the reaction process and exists in a solid form, and the hydrophobicity of the obtained lignin is favorable for the generation of a spherical shell shape. The prepared nano spherical shell is a hollow opening, the size and the particle size of the opening can be adjusted according to dialysis concentration and time, and whether the nano spherical shell is hollow or not and whether the nano spherical shell is open or not can also be adjusted. In addition, the lignin nanoshell prepared by the method disclosed by the invention does not contain toxic elements, has good biocompatibility and can be used for medical drug loading.
3. The invention adopts a two-stage treatment mode to realize the fractional utilization of the lignocellulose raw material, the obtained high-value lignin raw material is used for preparing the lignin nanoshell, and the separated pretreatment solution contains the reaction solvent, cellulose and hemicellulose hydrolysis sugar and can be subjected to the next reaction and conversion.
Drawings
FIG. 1 is an SEM topography of lignin nanoparticles obtained in example 2.
FIG. 2 is an SEM topography of lignin nanoparticles obtained in example 3.
FIG. 3 is an SEM topography of lignin nanoparticles obtained in example 4.
FIG. 4 is an SEM topography of lignin nanoparticles obtained in example 5.
FIG. 5 is an SEM topography of lignin nanoparticles obtained in example 6.
FIG. 6 is an SEM topography of lignin nanoparticles obtained in example 7.
FIG. 7 is an SEM topography of lignin nanoparticles obtained in example 8.
FIG. 8 is an SEM topography of lignin nanoparticles obtained in example 9.
FIG. 9 is an SEM topography of the lignin nanoparticles obtained in comparative example 1.
FIG. 10 is an SEM topography of lignin nanoparticles obtained in comparative example 4.
Detailed Description
The technical solution of the present invention is further described below with reference to the following examples and drawings, but the scope of the present invention is not limited thereto. The raw materials and reagents used in the examples are all common commercial products unless otherwise specified.
The preparation method of the acidic lithium bromide solution comprises the following steps: 75g of dried lithium bromide powder was slowly added to 50g of deionized water and completely dissolved by magnetic stirring. After the solution was cooled to room temperature, HCl0.5g (37% by mass) was slowly added thereto and stirred to mix it uniformly, and after the solution was cooled to room temperature, it was transferred to a 250mL volumetric flask for further use.
Example 1:
preparing a lignin raw material:
selecting a lignocellulose raw material as poplar, and crushing the poplar into 20-40 meshes for later use;
adding 1g of 20-40-mesh poplar and 15mL of acidic lithium bromide solution (the concentration of lithium bromide is 60 wt%) into a pressure-resistant bottle, placing the pressure-resistant bottle in a magnetic heating stirrer, heating to 110 ℃, and reacting at constant temperature for 20min, so as to convert cellulose and hemicellulose and remove lignin; after the reaction is finished, taking out the pressure-resistant bottle and rapidly cooling to room temperature; then carrying out solid-liquid separation by using a sand core funnel to obtain a pretreatment solution and a solid precipitate; and washing the solid precipitate to neutrality, and drying to obtain the solid high-value lignin raw material. The obtained pretreatment solution contains various monosaccharides, a small amount of polysaccharides, an acidic lithium bromide solvent and a small amount of dissolved lignin, and can be used for further conversion and utilization.
Example 2:
taking 0.1g of the lignin raw material prepared in the example 1, dispersing the lignin raw material in 100mL of tetrahydrofuran, then dissolving the lignin raw material by microwave ultrasonic, and collecting the lignin raw material by an organic filter membrane (0.22 mu m) after the lignin raw material is completely dissolved; diluting the solution after membrane filtration by adopting tetrahydrofuran, wherein the volume ratio of the solution to the tetrahydrofuran is 1:9, the dilution multiple is 10 times; and dialyzing in distilled water for 36h by using a 7000D dialysis bag after dilution to remove the organic solvent and polymerize lignin into spheres to obtain the biomass lignin nanoshells.
The scanning electron microscope photo of the biomass lignin nanoshell prepared as described above is shown in fig. 1, and the particle size of the lignin nanoshell is mostly concentrated between 50-200nm as judged by particle size measurement, and the morphology of the lignin nanoshell observed under the scanning electron microscope is found to be nanoshell, but a small amount of irregular blocks exist.
Example 3:
0.1g of the lignin raw material prepared in example 1 is taken and dispersed in 100mL of tetrahydrofuran, and then dissolved by microwave ultrasonic, and collected by an organic filter membrane (0.22 μm) after being completely dissolved; diluting the solution after membrane filtration by adopting tetrahydrofuran, wherein the volume ratio of the solution to the tetrahydrofuran is 2:8, the dilution multiple is 5 times; and dialyzing in distilled water for 36h by using a 7000D dialysis bag after dilution to remove the organic solvent and polymerize lignin into spheres to obtain the biomass lignin nanoshells.
The scanning electron microscope photo of the biomass lignin nanoshell prepared as shown in fig. 2 shows that the particle size of the lignin nanoshell is mostly concentrated between 100 nm and 300nm according to particle size determination, and the morphology of the lignin nanoshell observed under the scanning electron microscope is all in a nanosphere shell shape, so that irregular blocks are almost not existed.
Example 4:
0.1g of the lignin raw material prepared in example 1 is taken and dispersed in 100mL of tetrahydrofuran, and then dissolved by microwave ultrasonic, and collected by an organic filter membrane (0.22 μm) after being completely dissolved; diluting the solution after membrane filtration by adopting tetrahydrofuran, wherein the volume ratio of the solution to the tetrahydrofuran is 3:7, the dilution multiple is 3.33 times; and dialyzing the solution for 36 hours in distilled water by using a 7000D dialysis bag after dilution to remove the organic solvent and polymerize the lignin into spheres, thereby obtaining the biomass lignin nanoshell.
The scanning electron microscope photo of the biomass lignin nanoshell prepared as shown in fig. 3 shows that the particle size of the lignin nanoshell is mostly concentrated between 100 nm and 300nm according to particle size determination, and the morphology of the lignin nanoshell is observed under the scanning electron microscope to be nanoshell-shaped without irregular blocks, so that the morphology of the lignin nanoshell is most uniform and is hollow nanoshell-shaped under the condition.
Example 5:
the preparation method is basically the same as the preparation method of the example 4, except that the dialysis time is 24h, and the specific steps are as follows:
0.1g of the lignin raw material prepared in example 1 is taken and dispersed in 100mL of tetrahydrofuran, and then dissolved by microwave ultrasonic, and collected by an organic filter membrane (0.22 μm) after being completely dissolved; diluting the solution after the membrane is passed by adopting tetrahydrofuran, wherein the volume ratio of the solution to the tetrahydrofuran is 3:7, the dilution multiple is 3.33 times; and dialyzing the solution in distilled water for 24 hours by using a 7000D dialysis bag after dilution to remove the organic solvent and polymerize the lignin into spheres, thereby obtaining the biomass lignin nanoshell.
The scanning electron microscope photo of the biomass lignin nanoshell prepared as shown in fig. 4 shows that the particle size of the lignin nanoshell is mostly concentrated between 100 nm and 300nm according to particle size determination, and the morphology of the lignin nanoshell is observed under the scanning electron microscope to be nanoshell-shaped without irregular blockiness, but the morphology of the lignin nanoshell is not uniform under the condition.
Example 6:
the preparation method is basically the same as the preparation method of the example 4, except that the dialysis time is 48h, and the specific steps are as follows:
0.1g of the lignin raw material prepared in example 1 is taken and dispersed in 100mL of tetrahydrofuran, and then dissolved by microwave ultrasonic, and collected by an organic filter membrane (0.22 μm) after being completely dissolved; diluting the solution after the membrane is passed by adopting tetrahydrofuran, wherein the volume ratio of the solution to the tetrahydrofuran is 3:7, the dilution multiple is 3.33 times; and dialyzing in distilled water for 48h by using a 7000D dialysis bag after dilution to remove the organic solvent and polymerize lignin into spheres to obtain the biomass lignin nanoshells.
The scanning electron microscope photo of the biomass lignin nanoshell prepared as shown in fig. 5 shows that the particle size of the lignin nanoshell is mostly concentrated between 100 nm and 300nm according to particle size determination, and the morphology of the lignin nanoshell is observed under a scanning electron microscope to be nanoshell-shaped without irregular blocks, so that the lignin nanoshell is uniform in morphology under the condition, but is partially solid and spherical due to overlong time.
Example 7:
the preparation method is basically the same as the preparation method of the embodiment 4, except that the dialysis time is 60h, and the specific steps are as follows:
0.1g of the lignin raw material prepared in example 1 is taken and dispersed in 100mL of tetrahydrofuran, and then dissolved by microwave ultrasonic, and collected by an organic filter membrane (0.22 μm) after being completely dissolved; diluting the solution after the membrane is passed by adopting tetrahydrofuran, wherein the volume ratio of the solution to the tetrahydrofuran is 3:7, the dilution multiple is 3.33 times; and dialyzing in distilled water for 60h by using a 7000D dialysis bag after dilution to remove the organic solvent and polymerize the lignin into spheres to obtain the biomass lignin nanoshells.
The scanning electron microscope photo of the biomass lignin nanoshell prepared as described above is shown in fig. 6, and the particle size of the lignin nanoshell is mostly concentrated between 100 nm and 300nm through particle size determination and judgment, and observation of the morphology under the scanning electron microscope shows that the lignin nanoshell is nanoshell-shaped and does not have irregular blocks, and under the condition, the morphology of the lignin nanoshell is uniform, but the nanoshell is mostly solid due to the overlong dialysis time.
Example 8:
taking 0.1g of the lignin raw material prepared in the example 1, dispersing the lignin raw material in 100mL of tetrahydrofuran, then dissolving the lignin raw material by microwave ultrasonic, and collecting the lignin raw material by an organic filter membrane (0.22 mu m) after the lignin raw material is completely dissolved; diluting the solution after the membrane is passed by adopting tetrahydrofuran, wherein the volume ratio of the solution to the tetrahydrofuran is 4:6, the dilution multiple is 2.5 times; and dialyzing the solution for 36 hours in distilled water by using a 7000D dialysis bag after dilution to remove the organic solvent and polymerize the lignin into spheres, thereby obtaining the biomass lignin nanoshell.
The scanning electron micrograph of the biomass lignin nanoshell prepared as described above is shown in fig. 7, and the particle size of the lignin nanoshell is mostly concentrated between 200nm and 300nm according to particle size determination.
Example 9:
taking 0.1g of the lignin raw material prepared in the example 1, dispersing the lignin raw material in 100mL of tetrahydrofuran, then dissolving the lignin raw material by microwave ultrasonic, and collecting the lignin raw material by an organic filter membrane (0.22 mu m) after the lignin raw material is completely dissolved; diluting the solution after membrane filtration by adopting tetrahydrofuran, wherein the volume ratio of the solution to the tetrahydrofuran is 5:5, the dilution multiple is 2 times; and dialyzing the solution for 36 hours in distilled water by using a 7000D dialysis bag after dilution to remove the organic solvent and polymerize the lignin into spheres, thereby obtaining the biomass lignin nanoshell.
The scanning electron microscope photo of the biomass lignin nanoshell prepared as shown in fig. 8 shows that the particle size of the lignin nanoshell is mostly concentrated between 200-400nm according to particle size determination, and the morphology of the lignin nanoshell observed under the scanning electron microscope is all in a nanosphere shell shape, but a large number of solid nanospheres exist.
Comparative example 1:
taking 0.1g of the lignin raw material prepared in the example 1, dispersing the lignin raw material in 100mL of tetrahydrofuran, then dissolving the lignin raw material by microwave ultrasonic, and collecting the lignin raw material by an organic filter membrane (0.22 mu m) after the lignin raw material is completely dissolved; diluting the solution after membrane filtration by adopting tetrahydrofuran, wherein the volume ratio of the solution to the tetrahydrofuran is 0.5:9.5, the dilution multiple is 20 times; and dialyzing in distilled water for 36h by using a 7000D dialysis bag after dilution to remove the organic solvent and polymerize lignin into spheres to obtain the biomass lignin nanoshells.
The scanning electron micrograph of the biomass lignin nanoshells prepared above is shown in fig. 9, and the particle sizes of the lignin nanoshells are mostly concentrated between 100 nm and 200nm as judged by particle size measurement, and the morphology of the lignin nanoshells observed under the scanning electron micrograph is found to be nanoshells, but the lignin nanoshells have a large number of irregular blocks compared to example 2.
Comparative example 2
The preparation of the lignin raw material is different from the preparation of the lignin raw material in example 1 in that the used solvent is an acidic calcium chloride solution, and the steps are as follows:
selecting a lignocellulose raw material as poplar, and crushing the poplar into 20-40 meshes for later use;
adding 1g of 20-40-mesh poplar and 15mL of acidic calcium chloride solution (the concentration of calcium chloride is 60wt%, and the using amount of HCl is the same as that of the acidic lithium bromide solution) into a pressure bottle, placing the pressure bottle in a magnetic heating stirrer, heating to 110 ℃, and reacting at constant temperature for 20min, so as to convert cellulose and hemicellulose and remove lignin; after the reaction is finished, taking out the pressure-resistant bottle and rapidly cooling to room temperature; then, performing solid-liquid separation by using a sand core funnel to obtain a pretreatment solution and a solid precipitate; and washing the solid precipitate to neutrality, and drying to obtain the solid raw material.
Biomass lignin nanoshells were prepared as described in example 4.
Since a large amount of cellulose and hemicellulose remained in the solid raw material, most of the solid was insoluble when dissolved in THF, and no nanoshells could be prepared, and thus the acidic calcium chloride solution was not suitable for preparing lignin nanoshells under this experimental condition.
Comparative example 3
The preparation of the lignin raw material is different from the preparation of the lignin raw material in example 1 in that the used solvent is an acidic calcium bromide solution, and the steps are as follows:
selecting a lignocellulose raw material as poplar, and crushing the poplar into 20-40 meshes for later use;
adding 1g of 20-40-mesh poplar and 15mL of acidic calcium bromide solution (the concentration of calcium bromide is 60wt%, the dosage of HCl is the same as that of the acidic lithium bromide solution) into a pressure bottle, placing the pressure bottle in a magnetic heating stirrer, heating to 110 ℃, and reacting at constant temperature for 20min, so as to convert cellulose and hemicellulose and remove lignin; after the reaction is finished, taking out the pressure-resistant bottle and rapidly cooling to room temperature; then, performing solid-liquid separation by using a sand core funnel to obtain a pretreatment solution and a solid precipitate; washing the solid precipitate to neutrality, and drying to obtain solid material.
Biomass lignin nanoshells were prepared as described in example 4.
Since a large amount of cellulose and hemicellulose remain in the solid raw material, most of the solid is insoluble when dissolved by THF, and the nanoshells cannot be prepared, so the acidic calcium bromide solution is not suitable for preparing the lignin nanoshells under this experimental condition.
Comparative example 4
Lignin nanoshells were prepared as described in example 4 using a commercial lignin source (Shandong Longli Biotech, inc.).
The scanning electron micrograph of the biomass lignin nanoshells prepared above is shown in fig. 10. When the method is adopted to prepare the lignin nanoshell, the lignin nanoparticle can be prepared due to the fact that the commercial lignin is high in hydrophilicity and molecular weight and low in THF (tetrahydrofuran) dissolving capacity, but the spherical morphology is poor.
Claims (8)
1. The preparation method of the biomass lignin nanoshell is characterized by comprising the following steps:
(1) Mixing a lignocellulose raw material with an acidic lithium bromide solution, and heating for reaction; after the reaction is finished, carrying out solid-liquid separation to obtain a pretreatment solution and a solid precipitate, and cleaning and drying the solid precipitate to obtain a lignin raw material;
(2) Dispersing the lignin raw material obtained in the step (1) in tetrahydrofuran to obtain a dispersion liquid, wherein the mass volume ratio of the lignin raw material to the tetrahydrofuran in the dispersion liquid is 1,g/L; dissolving lignin by ultrasonic, filtering and collecting a dissolved solution, diluting by adopting tetrahydrofuran, wherein the dilution multiple is 3.33 times, removing an organic solvent and polymerizing the lignin into a spherical biomass lignin through dialysis treatment, wherein the dialysis time is 36 hours, the dialysis solvent is water, and the spherical biomass lignin shell is obtained, has the particle size of 100-300nm and is hollow.
2. The method of claim 1, wherein the lignocellulosic feedstock in step (1) comprises agricultural waste, forestry waste, and sugar processing residues; the agricultural wastes comprise corn stalks, wheat stalks, barley stalks, rape stalks, rice stalks and soybean stalks; the forestry wastes comprise poplar, willow, locust, cedar and sawdust; the sugar processing residue includes bagasse and beet pulp.
3. The method of claim 1, wherein the lignocellulosic feedstock in step (1) has a particle size of 20 to 40 mesh.
4. The preparation method according to claim 1, wherein the mass-to-volume ratio of the lignocellulose raw material to the acidic lithium bromide solution in the step (1) is 1 (10-20), g/mL.
5. The preparation method according to claim 1, wherein the acidic lithium bromide solution in the step (1) is prepared by adding HCl into an aqueous lithium bromide solution, wherein the concentration of the lithium bromide is 60wt%, and the addition amount of the HCl is 50 to 60mg/15mL of the acidic lithium bromide solution.
6. The method according to claim 1, wherein the heating reaction in the step (1) is carried out at 100 to 150 ℃ for 20 to 50min.
7. The method according to claim 1, wherein the solid-liquid separation in step (1) is carried out using a sand core funnel.
8. The method of claim 1, wherein step (2) satisfies one or more of the following conditions:
i. the filtration is carried out by adopting a 0.22 mu m organic filter membrane;
the dialysis treatment has a molecular weight cut-off of 7000D.
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