CN113461978B - Preparation method for preparing high-yield lignin nanoparticles with assistance of ball milling pretreatment - Google Patents
Preparation method for preparing high-yield lignin nanoparticles with assistance of ball milling pretreatment Download PDFInfo
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- CN113461978B CN113461978B CN202110774888.4A CN202110774888A CN113461978B CN 113461978 B CN113461978 B CN 113461978B CN 202110774888 A CN202110774888 A CN 202110774888A CN 113461978 B CN113461978 B CN 113461978B
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Abstract
The invention belongs to a preparation method for preparing high-yield lignin nanoparticles by ball milling pretreatment assistance, which comprises the following components: the concentration of the ethanol solution is 0 to 100 percent, the concentration of the lignin suspension is 0.5 to 10 weight percent, and the preparation method comprises the following steps: 1) Weighing 1.5-30 g of lignin, dispersing in 0-100% ethanol solution to prepare 0.5-10 wt% lignin/ethanol suspension, and ball-milling at 500-3000rpm for 0-48h; 2) Centrifuging the ball-milled lignin at 1000-10000 rpm for 5-60min; 3) Dissolving the separated solid in gamma-valerolactone, dripping 1-10 times volume of deionized water into the solution at the speed of 0.1-10 mL/min, and stirring for 1-10h under the magnetic stirring condition of 100-1000rpm to form a lignin nanoparticle colloidal solution; 4) Simultaneously, dropwise adding distilled water into the supernatant under the same conditions to form a lignin nanoparticle colloidal solution; 5) Centrifuging the prepared colloidal solution at 4000-15000rpm for 5-60min, washing with deionized water, and freeze drying to obtain lignin nanoparticles with high yield and uniform size.
Description
Technical Field
The invention belongs to the field of nano materials, and mainly relates to a preparation method for preparing high-yield lignin nanoparticles by ball milling pretreatment assistance, which can be applied to the application fields of organic pollutant treatment, drug carriers, ultraviolet shielding, catalytic carriers, antioxidant materials and the like.
Technical Field
Lignin is the most abundant natural aromatic high polymer in nature, widely found in the woody portion of trees and other vascular plants. Lignin is a polyphenol biomolecule that has many unique properties, such as corrosion resistance, resistance to biological attack, uv shielding, high hardness, and resistance to oxidation. Thus, lignin as a large reserve raw material has the potential to produce high value products. However, most of lignin can be dissolved in an aqueous system only under an alkaline environment, which greatly limits the wide application of the lignin, and the preparation of the lignin water-dispersible nano system provides a new approach for the wide application of the lignin. The nano-structured lignin, especially the lignin nanoparticles with the size distribution in the range of 1-100nm, has the advantages of large specific surface area and the like, thereby endowing the lignin with unique performance. The lignin nanoparticles are widely applied to replace toxic nanoparticles,Drug loading system, hydrophobic material, ultraviolet barrier, antibiosis, antioxidation and electrode material. At present, the preparation method of lignin nanoparticles is various, and mainly comprises a solvent exchange method, an acid precipitation method, a reverse micelle forming method and CO 2 Precipitation methods, and the like. The Chinese patent CN110452396B authorizes a preparation method of lignin micro/nanospheres, lignin is added into an organic solvent, water is added for emulsification to form emulsion, then the organic solvent in the mixed emulsion is volatilized to obtain lignin micro/nanosphere-water mixed solution, finally solid-liquid separation, washing and cold drying are carried out to obtain a product, the organic solvent is one or more of ethyl acetate, dichloromethane and trichloromethane, and the added water contains a certain amount of surfactant. However, the used organic solvent has certain toxicity, the complexity of the preparation process is increased by the use of the surfactant, and the prepared lignin spheres have large and uneven sizes. Chinese patent CN109012609A discloses a green preparation method of lignin nano-microspheres, which adopts ethylene glycol to dissolve lignin, adds acid and water with different concentrations into the lignin at constant speed, and finally carries out solid-liquid separation through one-step centrifugal operation to obtain the lignin nano-microspheres. The preparation method of the lignin-based nano-microsphere is easy to operate, the chemical structure change of lignin and the use of toxic reagents are effectively avoided, but the use of acid can corrode equipment, the equipment requirement is improved, and the prepared lignin particle is irregular in shape and is not a microsphere in the true sense. The mechanical treatment is a method for preparing the lignin nanoparticles, which has a good application prospect and has the advantages of high yield, convenient operation, environmental protection and the like. Iulian Andrei Gilca et al (Gilca I A, popa V I, crestini C. Obtating lignin nanoparticles by Sound [ J ]]Ultrasonics Sonochemistry,2015, 23: 369-375.) proposes a physical method for preparing lignin nanoparticles by ultrasonic modification of lignin, which comprises dispersing lignin in water, and treating the suspension by ultrasonic horn oscillation to obtain uniform and stable nano dispersion. But the prepared lignin nanoparticles have irregular shapes. The dry-wet ball milling treatment is widely applied to the nano-material process such as CNC, nano electro-catalyst and nano carbon material preparation. The US patent 9102801B1 discloses a synthesis method of lignin nanoparticles, lignin sulfonate is dried at 105 ℃ to remove residual moisture, and then transferred to a ball mill for ball milling to prepare lignin nanoparticles. The lignin nanoparticles prepared by the method have an average size of less than 40nm, but the morphology of the nanoparticles is irregular. Therefore, it is very necessary to prepare lignin nanoparticles with stable and uniform size and regular morphology by using organic solvent assisted by mechanical activation.
Disclosure of Invention
The invention aims to develop a preparation method for preparing high-yield lignin nanoparticles by ball milling pretreatment, which adopts a mechanical method-ball milling method for pretreatment, improves the yield of the lignin nanoparticles and obtains a nanostructure with uniform and stable size and regular shape.
The invention is realized by the following steps of the technical scheme:
step 1: weighing 1.5-30 g of lignin, dispersing in 0-100% ethanol solution to prepare 0.5-10 wt% lignin/ethanol suspension, and ball-milling at 500-3000rpm for 0-48h;
step 2: centrifuging the ball-milled lignin at 1000-10000 rpm for 5-60min;
and step 3: dissolving the solid separated in the step 2 in gamma-valerolactone, dripping deionized water with the volume of 1-10 times of that of the solution at the speed of 0.1-10 mL/min, and stirring for 1-10h under the magnetic stirring condition of 100-1000rpm to form a lignin nanoparticle colloidal solution;
and 4, step 4: simultaneously, dropwise adding 1-10 times of volume of deionized water into the supernatant in the step 2 at the speed of 0.1-10 mL/min, and stirring for 1-10h under the condition of magnetic stirring at 100-1000rpm to form a lignin nanoparticle colloidal solution;
and 5: and (4) centrifuging the colloidal solution prepared in the steps (3) and (4) at 4000-15000rpm for 5-60min, washing with deionized water, removing the upper liquid, and freeze-drying to obtain lignin nanoparticles with yield of more than 80% and uniform size.
The mechanical pretreatment method is ball milling pretreatment.
The concentration of the ethanol solution is 0-100%.
The concentration of the lignin-ethanol suspension is 0.5wt% -10wt%.
The rotation speed of the ball milling pretreatment is 500rpm-3000rpm.
The time of ball milling treatment is 0-48h.
The yield of the obtained lignin nano-particles is more than 80 percent.
The method adopts ball milling as a mechanical pretreatment means, the structure of lignin is destroyed by the ball milling pretreatment means, the size and the molecular weight of the lignin are reduced, and the dissolution of the lignin by an organic solvent is promoted, so that lignin nanoparticles with higher yield are obtained; meanwhile, the appearance of the formed lignin nanoparticles is modified by dissolving lignin by using an organic solvent, so that the size uniformity of the lignin nanoparticles is improved. Therefore, the invention provides a preparation method of the high-yield lignin nanoparticles through ball milling pretreatment, so that the industrial production and application of the lignin nanoparticles have important significance.
Drawings
FIG. 1 is a transmission electron micrograph of lignin nanoparticles from the supernatant obtained at 3h ball milling; FIG. 2 is a transmission electron micrograph of lignin nanoparticles obtained by redissolving insoluble materials at 3h of ball milling treatment.
Detailed Description
The invention will be more fully and more readily understood by reference to the following examples, which are given to illustrate the invention more clearly, and are not intended to limit the invention in any way.
The ball mill of each embodiment was a CSN type 0.3 laboratory nanomiller. And are not intended to limit the invention.
Example 1
Weighing 3g of lignin, adding 100% ethanol solution of a certain mass to enable the concentration of the lignin to be 1wt%, carrying out ball milling treatment at 2000rpm for 3h, and then centrifuging at 10000rpm for 20min for solid-liquid separation. The isolated solid was dissolved in 10mL of gamma valerolactone. And (3) dropwise adding 4.5 times volume of deionized water into the wood/gamma-valerolactone solution and the separated supernatant at the speed of 2.5mL/min, and stirring for 1h under the magnetic stirring condition of 600rpm to form a lignin nanoparticle colloidal solution. And centrifuging the prepared lignin nanoparticle colloidal solution at 10000rpm for 20min, washing with deionized water, removing upper-layer liquid, and freeze-drying to obtain the lignin nanoparticles.
Example 2
Weighing 6g of lignin, adding 100% ethanol solution of a certain mass to enable the concentration of the lignin to be 2wt%, carrying out ball milling treatment at 2000rpm for 3h, and then centrifuging at 10000rpm for 20min for solid-liquid separation. The isolated solid was dissolved in 10mL of gamma valerolactone. And (3) dropwise adding 4.5 times volume of deionized water into the lignin/gamma-valerolactone solution and the separated supernatant at the speed of 2.5mL/min, and stirring for 1h under the magnetic stirring condition of 600rpm to form a lignin nanoparticle colloidal solution. And centrifuging the prepared lignin nanoparticle colloidal solution at 10000rpm for 20min, washing with deionized water, removing upper-layer liquid, and freeze-drying to obtain the lignin nanoparticles.
Example 3
Weighing 3g of lignin, adding 70% ethanol solution with a certain mass to enable the concentration of the lignin to be 1wt%, carrying out ball milling treatment at 2000rpm for 3h, and then centrifuging at 10000rpm for 20min for solid-liquid separation. The isolated solid was dissolved in 10mL of gamma valerolactone. And (3) dropwise adding 4.5 times volume of deionized water into the lignin/gamma-valerolactone solution and the separated supernatant at the speed of 2.5mL/min, and stirring for 1h under the magnetic stirring condition of 600rpm to form a lignin nanoparticle colloidal solution. And centrifuging the prepared lignin nanoparticle colloidal solution at 10000rpm for 20min, washing with deionized water, removing the upper liquid, and freeze-drying to obtain the lignin nanoparticles.
Example 4
Weighing 3g of lignin, adding 100% ethanol solution of a certain mass to enable the concentration of the lignin to be 1wt%, carrying out ball milling treatment at the rotating speed of 1000rpm for 3h, and then centrifuging at the rotating speed of 10000rpm for 20min for solid-liquid separation. The isolated solid was dissolved in 10mL of gamma valerolactone. And (3) dropwise adding 4.5 times volume of deionized water into the lignin/gamma-valerolactone solution and the separated supernatant at the speed of 2.5mL/min, and stirring for 1h under the magnetic stirring condition of 600rpm to form a lignin nanoparticle colloidal solution. And centrifuging the prepared lignin nanoparticle colloidal solution at 10000rpm for 20min, washing with deionized water, removing upper-layer liquid, and freeze-drying to obtain the lignin nanoparticles.
Example 5
Weighing 3g of lignin, adding 100% ethanol solution of a certain mass to enable the concentration of the lignin to be 1wt%, carrying out ball milling treatment at 2000rpm for 12h, and then centrifuging at 10000rpm for 20min for solid-liquid separation. The isolated solid was dissolved in 10mL of gamma valerolactone. And (3) respectively dripping deionized water with the volume of 4.5 times of that of the lignin-gamma-valerolactone solution and the supernatant obtained by separation at the speed of 2.5mL/min, and stirring for 1h under the magnetic stirring condition of 600rpm to form a lignin nanoparticle colloidal solution. And centrifuging the prepared lignin nanoparticle colloidal solution at 10000rpm for 20min, washing with deionized water, removing the upper liquid, and freeze-drying to obtain the lignin nanoparticles.
Example 5
Weighing 3g of lignin, adding 100% ethanol solution of a certain mass to enable the concentration of the lignin to be 1wt%, carrying out ball milling treatment at 2000rpm for 3h, and then centrifuging at 5000rpm for 40min for solid-liquid separation. The isolated solid was dissolved in 10mL of gamma valerolactone. And (3) respectively dripping 8 times of deionized water into the lignin/gamma-valerolactone solution and the separated supernatant at the speed of 4mL/min, and stirring for 5 hours at the magnetic stirring condition of 800rpm to form a lignin nanoparticle colloidal solution. And centrifuging the prepared lignin nanoparticle colloidal solution at 10000rpm for 20min, washing with deionized water, removing upper-layer liquid, and freeze-drying to obtain the lignin nanoparticles.
Example 6
Weighing 3g of lignin, adding deionized water with a certain mass to enable the concentration of the lignin to be 1wt%, carrying out ball milling treatment at the rotating speed of 2000rpm for 3h, diluting by a certain multiple, and carrying out freeze drying to obtain the lignin nanoparticles.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, and equivalents thereof are intended to be included in the scope of the present invention.
Claims (2)
1. A preparation method for preparing high-yield lignin nanoparticles with the assistance of ball milling pretreatment is characterized by comprising the following steps:
step 1: weighing 1.5g-30g of lignin, dispersing in 70-100% ethanol solution to prepare 0.5wt% -10wt% lignin/ethanol suspension, and ball-milling at 500-3000rpm for 0-48h;
step 2: centrifugally separating the ball-milled lignin at 1000-10000 rpm for 5-60min;
and step 3: dissolving the separated solid in gamma-valerolactone to obtain a lignin-gamma-valerolactone solution, respectively dripping deionized water with the volume of 1-10 times of that of the lignin-gamma-valerolactone solution and the supernatant obtained by separation in the step 2 at the speed of 0.1-10 mL/min, and stirring for 1-10 hours under the magnetic stirring condition of 100-1000rpm to form a lignin nanoparticle colloidal solution;
and 4, step 4: centrifuging the prepared lignin nanoparticle colloidal solution at 4000-15000rpm for 5-60min, washing with deionized water, removing the upper layer liquid, and freeze drying to obtain lignin nanoparticles with high yield and uniform size.
2. The method of claim 1, wherein: the yield of the lignin nano-particles is more than 80 percent.
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| US9102801B1 (en) * | 2012-08-29 | 2015-08-11 | Sandia Corporation | Lignin nanoparticle synthesis |
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| CN113026405A (en) * | 2021-03-03 | 2021-06-25 | 西南交通大学 | Method for synchronously preparing nano lignin particles and nano cellulose fibers from agriculture and forestry biomass raw materials |
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| WO2019183350A1 (en) * | 2018-03-21 | 2019-09-26 | Simo Sarkanen | Compositions including lignin and methods for making the same |
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Patent Citations (7)
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| US9102801B1 (en) * | 2012-08-29 | 2015-08-11 | Sandia Corporation | Lignin nanoparticle synthesis |
| CN103113596A (en) * | 2013-02-21 | 2013-05-22 | 中国科学院过程工程研究所 | Method for improving lignin quality by dry ball milling |
| CN103131021A (en) * | 2013-02-21 | 2013-06-05 | 中国科学院过程工程研究所 | Method for improving lignin activity by wet ball milling |
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| CN109621851A (en) * | 2018-12-12 | 2019-04-16 | 天津科技大学 | A kind of preparation method of gamma-valerolactone/glycerol system high yield pulp1 lignin micro-nano ball |
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