CN110205854B - Method for extracting nanocellulose and lignin from wood fiber raw material - Google Patents
Method for extracting nanocellulose and lignin from wood fiber raw material Download PDFInfo
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- CN110205854B CN110205854B CN201910536708.1A CN201910536708A CN110205854B CN 110205854 B CN110205854 B CN 110205854B CN 201910536708 A CN201910536708 A CN 201910536708A CN 110205854 B CN110205854 B CN 110205854B
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- 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
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C3/00—Pulping cellulose-containing materials
- D21C3/20—Pulping cellulose-containing materials with organic solvents or in solvent environment
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/12—Pulp from non-woody plants or crops, e.g. cotton, flax, straw, bagasse
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Abstract
The invention discloses a method for extracting nano-cellulose and lignin from a wood fiber raw material, which takes original wood fibers rich in cellulose, hemicellulose and lignin as raw materials and adopts a one-step acidolysis method to directly extract nano-cellulose and lignin; the method comprises the specific steps of carrying out acidolysis on a wood fiber raw material by oxalic acid and toluenesulfonic acid, filtering and separating filter residue and filtrate after the acidolysis is finished, dialyzing the filter residue, and carrying out centrifugal separation after dialysis to obtain the nano-cellulose. The filtrate is partially added with water to separate out a great amount of high-purity high-added-value lignin.
Description
Technical Field
The invention belongs to the field of nano materials, and particularly relates to a method for extracting nanocellulose and lignin from a wood fiber raw material.
Background
The nano-fiber has the advantages of nano-size, high specific surface area, low density, biodegradability, excellent mechanical strength and optical performance, and natural reproducibility of raw material fiber, so that the nano-fiber becomes a research hotspot in the field of nano-materials at present. At present, the main raw material for extracting the nano-cellulose is microcrystalline cellulose or bleached wood pulp with the main component of cellulose, and then the nano-cellulose is extracted by chemical degradation or mechanical devillicate. Methods for extracting nanocellulose directly from raw lignocellulosic materials rich in cellulose, hemicellulose and lignin have rarely been reported. If the nano-cellulose is directly extracted from the original wood fiber raw material, the technological processes of pulping, bleaching and the like required by separating the cellulose can be saved, the efficiency is improved, and the cost is saved. In addition, the traditional preparation of nano-cellulose by concentrated acid hydrolysis has higher requirements on equipment, and an economic and environment-friendly waste acid recovery method is lacked. Oxalic acid is a compound which can be recrystallized back at room temperatureThe solid acid was recovered, but the acidity was weak (pK)a1.25), the ability to break β -1, 4-glycosidic and hydrogen bonds is poor, and the yield of hydrolyzed nanocellulose is low. The method utilizes strong acidity (pK)aPara-toluenesulfonic acid, a solid acid of-2.8), preferentially dissolves lignin from lignocellulosic raw materials, promotes the degradation of cellulose by oxalic acid, and thus improves the separation efficiency of nanocellulose.
Disclosure of Invention
The invention aims to provide a method for extracting nano-cellulose and lignin from original wood fiber raw materials.
The technical scheme adopted by the invention for solving the technical problems is as follows: the method is characterized in that original wood fibers rich in cellulose, hemicellulose and lignin are used as raw materials, and one-step acidolysis is adopted to directly extract nanocellulose and lignin. Compounding oxalic acid with p-toluenesulfonic acid to hydrolyze an original wood fiber raw material, filtering and separating filter residue and filtrate after the acidolysis is finished, dialyzing the filter residue, and centrifugally separating after dialysis to obtain the nano-cellulose, wherein a large amount of high-purity high-added-value lignin can be separated out by adding water to part of the filtrate. The flow chart is shown in fig. 1.
Preferably, the concentration of oxalic acid is 20-60 wt%, the concentration of p-toluenesulfonic acid is 15-55 wt%, the temperature of oxalic acid composite p-toluenesulfonic acid hydrolysis of the original wood fiber raw material is 90-110 ℃, the solid-liquid ratio is 1:20, and the magnetic stirring time is 30-240 min. After the acidolysis is finished, the filtrate is filtered and separated, water is added into the filtrate part to separate out high-purity high-added-value lignin, and the liquid part is subjected to rotary evaporation to recrystallize and recover oxalic acid and p-toluenesulfonic acid.
Wherein, the oxalic acid and the p-toluenesulfonic acid are purchased from the market.
Wherein, the oxalic acid and the p-toluenesulfonic acid are both solid acids, and the acids can be recovered by recrystallization at room temperature after the acidolysis reaction is finished.
The raw wood fiber raw material applicable to the method comprises softwood, hardwood and gramineous plants.
Advantageous effects
Compared with the prior art, the method adopts oxalic acid compounded with p-toluenesulfonic acid to hydrolyze the original wood fiber raw material to extract the nano cellulose and the lignin, and has the following characteristics:
(1) the original wood fiber rich in cellulose, hemicellulose and lignin is taken as the raw material to extract the nano cellulose, and compared with the traditional bleached wood pulp, the technical processes of pulping, bleaching and the like are reduced;
(2) oxalic acid is compounded with p-toluenesulfonic acid to hydrolyze wood fiber raw materials, the adopted oxalic acid and the p-toluenesulfonic acid are both solid acids, and recrystallization and recycling can be carried out after the acidolysis is finished;
(3) compared with the method for preparing the nano-cellulose by hydrolyzing single oxalic acid, the yield of the nano-cellulose can be effectively improved by adding the p-toluenesulfonic acid;
(4) the p-toluenesulfonic acid can effectively dissolve out lignin, and a large amount of high-purity high-added-value lignin can be separated out by adding water into a filtrate part obtained by filtering and separating after acidolysis.
Drawings
FIG. 1 is a flow diagram of nanocellulose and lignin extraction;
FIG. 2 shows the precipitation (high purity lignin) of the filtrate after acidolysis by adding water;
FIG. 3 is a TEM image of extraction of nanocellulose;
FIG. 4 is a TEM image of precipitated lignin;
fig. 5 is a thermogravimetric analysis and infrared analysis of nanocellulose and lignin, wherein a is a thermogravimetric analysis of nanocellulose, b is an infrared analysis of nanocellulose, c is a thermogravimetric analysis of lignin, and d is an infrared analysis of lignin.
Detailed Description
The present invention will be described in further detail with reference to examples. The reagents or instruments used are not indicated by manufacturers, and are regarded as conventional products which can be purchased in the market.
Oxalic acid and p-toluenesulfonic acid used in the following examples were obtained from national reagents, Inc.
Example 1: oxalic acid is compounded with toluenesulfonic acid to hydrolyze poplar wood powder to extract nano cellulose and lignin.
The concentrations of the P-toluenesulfonic acid compound oxalic acid are O20P55, O30P45, O40P35, O50P25 and O60P15 respectively, wherein O refers to oxalic acid, P refers to P-toluenesulfonic acid, OxPy refers to the mass concentration of oxalic acid as x, and the mass concentration of P-toluenesulfonic acid as y, wherein x is 20 wt%, 30 wt%, 40 wt%, 50 wt% and 60 wt%; y is 55 wt%, 45 wt%, 35 wt%, 25 wt% or 15 wt%;
the acidolysis temperature Ti is i ℃, wherein i is 90, 100 or 110;
and (4) acidolysis time th, wherein th refers to h min, and h is 30, 60, 120 or 240.
Adding oxalic acid, p-toluenesulfonic acid and water into a 100mL blue-covered bottle in proportion, sealing and placing in an oil bath pot for dissolution, adding 20-80 meshes of poplar wood powder after solid acid is completely dissolved, and magnetically stirring at a set temperature at a rotating speed of 500rpm for 30-240 min. And filtering and separating filter residue and filtrate after the acidolysis is finished, washing the filter residue and the filtrate for multiple times by using hot water, transferring the washed filter residue to a dialysis bag, dialyzing the filter residue to be neutral, and performing centrifugal separation to extract the nano-cellulose, wherein the experimental flow is shown in figure 1. The precipitate can be separated out by adding water to the filtrate of acidolysis filtration, as shown in FIG. 2.
Experiments compare the compound concentration of different oxalic acid and p-toluenesulfonic acid, and the yield of extracting nanocellulose and lignin at the acidolysis temperature and time. The yield of nano-cellulose extracted by acidolysis at 100 deg.C for 30min, 60min, 120min and 240min and the yield of lignin precipitated from filtrate by adding water are shown in tables 1, 2, 3 and 4.
TABLE 1 yield of nano-cellulose and lignin from oxalic acid compounded with p-toluenesulfonic acid (100 deg.C, 30min)
TABLE 2 yield of nano-cellulose and lignin from oxalic acid compounded with p-toluenesulfonic acid (100 deg.C, 60min)
TABLE 3 yield of oxalic acid complexed with toluene sulfonic acid for extraction of nanocellulose and lignin (100 ℃, 120min)
TABLE 4 yield of oxalic acid complexed with toluene sulfonic acid for extraction of nanocellulose and lignin (100 deg.C, 240min)
Experimental results show that the increase of the concentration of oxalic acid (20-50%) and the extension of the acidolysis time (30-120 min) can effectively improve the yield of the nano-cellulose. The increase of the concentration of p-toluenesulfonic acid (15% -55%) is beneficial to the dissolution of lignin. Preferably, the acidolysis is carried out for 120min at the conditions that the concentration of oxalic acid is 50%, the concentration of P-toluenesulfonic acid is 25%, the temperature is 100 ℃, namely the yield of the nanocellulose is the highest (30.1%) under the O50P25T100T120 condition, and the dissolution rate of the lignin is 57%; the acid hydrolysis is carried out for 120min at the temperature of 100 ℃ and the concentration of P-toluenesulfonic acid of 55 percent and the concentration of oxalic acid of 20 percent, namely the dissolution rate of lignin is the highest (84.1 percent) under the condition of O20P55T100T 120. FIG. 3 is a TEM image of nanocellulose extracted under O50P25T100T120 condition. The nanocellulose was uniform in length and diameter distribution, with the nanocellulose average length calculated by Image J software being 415nm and the average diameter being 19 nm.
The precipitate obtained after adding water to the acidolysis filtrate was analyzed for its Klason lignin content, and the Klason lignin content in the precipitate was as high as 90% or more, and it was high-purity lignin, and its TEM image is shown in FIG. 4.
The thermogravimetric graph and the infrared spectrogram of the oxalic acid-compounded toluenesulfonic acid for extracting the nanocellulose and the lignin are shown in figure 5. The rapid degradation temperatures of the nano-cellulose and the lignin are 335 ℃ and 345 ℃ respectively, and the nano-cellulose and the lignin have high thermal stability and can be used as green materials under the high-temperature condition.
Example 2: the oxalic acid is compounded with wheat straw powder acidolyzed with toluenesulfonic acid to extract nano-cellulose and lignin.
Adding oxalic acid, P-toluenesulfonic acid and water in a ratio (O50P25) into a 100mL blue-covered bottle, sealing and placing in an oil bath pot for dissolving, adding 20-80 mesh wheat straw wood powder after solid acid is completely dissolved, and magnetically stirring at a set temperature (100 ℃) at a rotating speed of 500rpm for 120 min. Filtering and separating filter residue and filtrate after the acidolysis is finished, washing the filter residue and the filtrate for multiple times by using hot water, transferring the washed filter residue to a dialysis bag, dialyzing the filter residue to be neutral, and centrifugally separating and extracting the nano-cellulose. Adding water into the filtrate of acidolysis filtration to separate out lignin precipitate.
The experimental result shows that the oxalic acid concentration is 50%, the P-toluenesulfonic acid concentration is 25%, the temperature is 100 ℃, and the acidolysis is carried out for 120min, namely the yield of the wheat straw nano-cellulose of O50P25T100T120 is 32.2%, and the dissolution rate of the lignin is 53%. And (3) performing Klason lignin content analysis on the precipitate obtained after the acidolysis filtrate is added with water, wherein the Klason lignin content in the precipitate is up to 90%.
In the experiment, original wood fibers rich in cellulose, hemicellulose and lignin are taken as raw materials, instead of pure cellulose, the nanocellulose is extracted by acidolysis with solid composite acid (oxalic acid compounded with p-toluenesulfonic acid) which can be recycled by recrystallization, and the nanocellulose with the yield up to 30 percent can be extracted by optimizing the concentration of the composite acid and the acidolysis temperature and time. Meanwhile, 50-85% of lignin in the wood fiber raw material is separated, and the purity is as high as more than 90%. The invention provides a simple, high-efficiency, green and environment-friendly method for extracting nano-cellulose, and high-purity lignin is efficiently separated.
The protection of the present invention is not limited to the above embodiments. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept and the scope of the appended claims is intended to be protected.
Claims (2)
1. A method for extracting nano-cellulose and lignin from a wood fiber raw material is characterized in that the method takes original wood fibers rich in cellulose, hemicellulose and lignin as raw materials, adopts one-step acidolysis to directly extract the nano-cellulose and the lignin, and comprises the following specific steps: carrying out acidolysis on an original wood fiber raw material by oxalic acid composite paratoluenesulfonic acid, filtering and separating filter residue and filtrate after the acidolysis is finished, dialyzing the filter residue, carrying out centrifugal separation after dialysis to obtain nano-cellulose, and adding water to part of the acidolysis filtrate for precipitation to separate out lignin; the concentration of the p-toluenesulfonic acid is 15-55 wt%, and the concentration of the oxalic acid is 20-60 wt%; wherein the temperature of oxalic acid composite paratoluenesulfonic acid for acidolysis of the original wood fiber raw material is 90-110 ℃, the solid-to-liquid ratio is 1:20, and the acidolysis time is 30-240 min.
2. The method of claim 1, wherein the filtrate from the acid hydrolysis is used to separate lignin, and the filtrate is recrystallized to recover oxalic acid and p-toluenesulfonic acid for multiple recycling.
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| CN110894696A (en) * | 2019-10-30 | 2020-03-20 | 南京林业大学 | Method for bleaching bamboo pulp |
| CN112480429A (en) * | 2020-12-09 | 2021-03-12 | 国际竹藤中心 | Preparation method and application of bamboo nano lignin sun-screening agent |
| CN113481255B (en) * | 2021-06-17 | 2023-08-15 | 南京师范大学 | Enzymolysis method of cellulose-containing raw material |
| CN113372572B (en) * | 2021-07-26 | 2023-01-10 | 中科南京绿色制造产业创新研究院 | Method for separating lignin by recycling solid organic acid |
| CN114197233B (en) * | 2021-12-17 | 2022-12-02 | 大连理工大学 | Method for separating and extracting cellulose nanofibers from agricultural and forestry solid wastes |
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| CN109208366A (en) * | 2018-09-06 | 2019-01-15 | 刘永红 | A kind of preparation method and application of micro-nano cellulose |
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| CN102295786A (en) * | 2011-06-13 | 2011-12-28 | 青岛科技大学 | Nano cellulose crystal / polyaniline composite material, preparation method and product thereof |
| CN103910805A (en) * | 2012-12-29 | 2014-07-09 | 青岛蔚蓝生物集团有限公司 | Method for preparing nanometer cellulose and recovering acid |
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