CN109012608A - The preparation method and application of lignin nanosphere - Google Patents
The preparation method and application of lignin nanosphere Download PDFInfo
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- CN109012608A CN109012608A CN201810752879.3A CN201810752879A CN109012608A CN 109012608 A CN109012608 A CN 109012608A CN 201810752879 A CN201810752879 A CN 201810752879A CN 109012608 A CN109012608 A CN 109012608A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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Abstract
The present invention provides a kind of preparation method and applications of lignin nanosphere.It is first hydrophobic modified to lignin progress by the method for microwave acetylation, then the lignin after acetylation is dissolved in tetrahydrofuran solvent, finally by exchange of solvent and the method for ultrasonic wave added, prepares lignin nanosphere.By adjusting lignin/tetrahydrofuran solution concentration and ultrasound intensity, prepare the nanosphere for having many advantages, such as that appearance is uniform, shape is regular, the distribution of good dispersion, single hole and yield are higher, the lignin nanosphere UVResistant effect is excellent, can be used for the fields such as suncream.Traditional method of modifying using a large amount of solvents and catalyst is avoided during lignin modification, the method of ultrasonic wave added is used in nanosphere preparation process simultaneously, it avoids using the method that dialysis etc. is time-consuming and separation is difficult, effectively reduces preparation cost and simplify preparation flow.
Description
Technical field
The present invention relates to the preparation methods of a kind of nanometer of carbosphere, and in particular to a kind of biorefinery lignin nanosphere
Preparation method and application.
Background technique
Lignin mainly passes through carbon-carbon bond by guaiacyl (G), lilac base (S) and p-hydroxyphenyl (H) structural unit
The amorphous aromatic polymer being formed by connecting with ehter bond.Wherein, the functional functional group of lignin mainly includes methoxyl group, phenol
Hydroxyl, aliphatic hydroxyl and carboxyl.5,000 ten thousand tons of lignin is totalled over every year in slurrying and biorefinery industry as useless
Material generates, however the only lignin of 2-5% is utilized, other to be primarily used to burn and fill, and not only causes serious
The wasting of resources and also give environment band heavy pressure.Therefore, the high value added utilization approach of industrial lignin how is expanded
Become the difficult point studied now.
In recent years, the preparation of nano lignin causes the highest attention of numerous scholars.Due to nano lignin have compared with
Big specific surface area and excellent dispersibility and compatibility, and its modified surface, therefore with potential in various fields
Application value.CN105819426 discloses a kind of alkali lignin carbon nanometer micro ball and its preparation method and application, first will be wooden
Quality is dissolved in n,N-Dimethylformamide or glacial acetic acid solution, is obtained lignin microballoon by electrostatic spray, is then existed
Oxidation processes are carried out at a temperature of 250-280 DEG C, finally carbonization obtains alkali lignin microballoon at a temperature of 400-900 DEG C.
CN105293488 discloses a kind of preparation method of Lignin-Based Activated Carbon microballoon, is mixed by wood powder with phenol
It liquefies under the conditions of acidic catalyst afterwards, then prepares microballoon by the way that stabilizer and surfactant is added, then will preparation
Microballoon be cured at high temperature and be carbonized, prepare activated carbon microballon.
CN106582549 discloses a kind of preparation method of monodisperse lignin microballoon, by adding into lignin liquor
Enter crosslinking agent and regulator prepares dispersed phase solution, then a certain amount of surfactant is added in organic solution and is prepared continuously
Phase solution, the shearing finally by capillary through continuous phase form the lignin monodisperse drop of Water-In-Oil, then again certain
At a temperature of reaction given time formed lignin microballoon.
The above method needs to solidify at high temperature and be carbonized or need a large amount ofization with the preparation method of lignin microballoon
Reagent is learned, not only preparation process is cumbersome, energy consumption is high but also needs a large amount of chemical reagent, and preparation cost is higher and environmental pollution
Seriously.In addition, the lignin Microsphere Size homogeneity of preparation is poor, generally between 10nm-10 μm
Summary of the invention
Based on the above prior art there are complex process, energy consumption is larger and lignin Microsphere Size homogeneity obtained and point
The deficiencies of property is poor place is dissipated, the purpose of the present invention is to provide the preparations of a kind of green and simple biorefinery lignin microballoon
Method.
Purpose proposed by the present invention is achieved through the following technical solutions:
1) lignin and acetic anhydride are uniformly mixed in reactor tank, acetylation process is carried out in Microwave system, reacted
It is instilled in the pH=2 sour water of 5-10 times of volume after the completion, is filtered, washed, is freeze-dried and obtains acetylation lignin.
2) prepared by microballoon: the acetylation lignin that step 1) obtains being dissolved in tetrahydrofuran solution, is then dropped evenly
Water is into the solution and handles to obtain lignin microballoon dispersion liquid using ultrasonic wave added.
3) 2) freeze-drying after the lignin microballoon dispersion liquid ultralow temperature supercentrifuge centrifugation of preparation is obtained wooden
Plain microballoon.
4) 3) the lignin microballoon of preparation is mixed with commercial face cream to enhance its uvioresistant ability.
The mass ratio of method above-mentioned, step 1) lignin and acetic anhydride is 1:5.
Method above-mentioned, microwave power is 400W time 2min when step 1) heats up, and keeps the temperature power 200W, time 10min.
Method above-mentioned, lignin/tetrahydrofuran solution concentration of step 2) preparation are 1-4mg/mL.
Method above-mentioned, the 0-200W of step 2) ultrasonic power.
Method above-mentioned, step 3) lignin additive amount are 1-5%.
Preparation method of the invention and resulting product have the advantages that compared with prior art
Lignin used in the present invention is biorefinery lignin, but is not limited only to industrial lignin, and preparation method used is green
Colour circle guarantor, easy to operate, low energy consumption, chemicals dosage is less, and the lignin microballoon prepared has yield higher, point
Dissipate the advantages that property is preferable, dimensional homogeneity and uvioresistant performance are excellent.
Detailed description of the invention
Fig. 1 is lignin microballoon scanning electron microscope (SEM) photograph prepared by the embodiment of the present invention 1.
Fig. 2 is lignin microballoon transmission electron microscope picture prepared by the embodiment of the present invention 1.
Specific embodiment:
Below with reference to examples and drawings, present invention is further described in detail, but protection scope of the present invention not by
The limitation of specific embodiment.
Embodiment 1
The preparation method of lignin nanosphere, comprising the following steps:
1) 10g lignin and 50g acetic anhydride are put into microwave after mixing in reactor tank, then with 400W power
Heating 2min is warming up to 110 DEG C, and 10min is then kept the temperature under 200W power, and lignin mixed liquor is instilled 10 after reaction
It in the sour water of the pH=2 of times volume, is finally filtered, washed, is freeze-dried and obtains acetylation lignin.
2) the acetylation lignin that step 1) obtains is dissolved in the wood for being configured to that concentration is 1mg/mL in tetrahydrofuran solvent
Then quality solution is dropped evenly 70mL water in prepared lignin/tetrahydrofuran solution with the speed of 0.2mL/min
And the ultrasonic treatment that adjoint power is 200W, obtain lignin nanosphere dispersion liquid.
3) the lignin microballoon dispersion liquid ultralow temperature supercentrifuge for obtaining step 2) is with the revolving speed of 10000r/min
It is centrifuged 10min, finally freeze-drying obtains lignin nanosphere.
The scanning electron microscope and transmission electron microscope picture of lignin nanosphere manufactured in the present embodiment respectively as Fig. 1 (a x 5000,
E x 20000) and Fig. 2 (a) shown in.As seen from the figure: lignin nanospheres show good appearance form: real
The heart, size are smaller and homogeneity is good, while having good dispersion performance.
Embodiment 2
The preparation method of lignin nanosphere, comprising the following steps:
1) 10g lignin and 50g acetic anhydride are put into microwave after mixing in reactor tank, then with 400W power
Heating 2min is warming up to 110 DEG C, and 10min is then kept the temperature under 200W power, and lignin mixed liquor is instilled 10 after reaction
It in the sour water of the pH=2 of times volume, is finally filtered, washed, is freeze-dried and obtains acetylation lignin.
2) the acetylation lignin that step 1) obtains is dissolved in the wood for being configured to that concentration is 2mg/mL in tetrahydrofuran solvent
Then quality solution is dropped evenly 70mL water in prepared lignin/tetrahydrofuran solution with the speed of 0.2mL/min
And the ultrasonic treatment that adjoint power is 200W, obtain lignin nanosphere dispersion liquid.
3) the lignin microballoon dispersion liquid ultralow temperature supercentrifuge for obtaining step 2) is with the revolving speed of 10000r/min
It is centrifuged 10min, finally freeze-drying obtains lignin nanosphere.
The scanning electron microscope and transmission electron microscope picture of lignin nanosphere manufactured in the present embodiment respectively as Fig. 1 (b) x 5000,
(f) shown in x 20000 and Fig. 2 (b).As seen from the figure: lignin nanospheres show good appearance form, out
Existing single pore structure, size increases compared with embodiment 1 and homogeneity is preferable, while having good dispersion performance.
Embodiment 3
The preparation method of lignin nanosphere, comprising the following steps:
1) 10g lignin and 50g acetic anhydride are put into microwave after mixing in reactor tank, then with 400W power
Heating 2min is warming up to 110 DEG C, and 10min is then kept the temperature under 200W power, and lignin mixed liquor is instilled 10 after reaction
It in the sour water of the pH=2 of times volume, is finally filtered, washed, is freeze-dried and obtains acetylation lignin.
2) the acetylation lignin that step 1) obtains is dissolved in the wood for being configured to that concentration is 3mg/mL in tetrahydrofuran solvent
Then quality solution is dropped evenly 70mL water in prepared lignin/tetrahydrofuran solution with the speed of 0.2mL/min
And the ultrasonic treatment that adjoint power is 200W, obtain lignin nanosphere dispersion liquid.
3) the lignin microballoon dispersion liquid ultralow temperature supercentrifuge for obtaining step 2) is with the revolving speed of 10000r/min
It is centrifuged 10min, finally freeze-drying obtains lignin nanosphere.
The scanning electron microscope and transmission electron microscope picture of lignin nanosphere manufactured in the present embodiment respectively as Fig. 1 (c) x 5000,
(g) shown in x 20000 and Fig. 2 (c).As seen from the figure: lignin nanospheres show good appearance form, open
Begin the pore structure for occurring single, and size is further increased compared with embodiment 2 and homogeneity is preferable, while having good dispersibility
Energy.
Embodiment 4
The preparation method of lignin nanosphere, comprising the following steps:
1) 10g lignin and 50g acetic anhydride are put into microwave after mixing in reactor tank, then with 400W power
Heating 2min is warming up to 110 DEG C, and 10min is kept the temperature under 200W power, and lignin mixed liquor is instilled 10 times of volumes after reaction
PH=2 sour water in, be finally filtered, washed, be freeze-dried and obtain acetylation lignin.
2) the acetylation lignin that step 1) obtains is dissolved in the wood for being configured to that concentration is 4mg/mL in tetrahydrofuran solvent
Then quality solution is dropped evenly 70mL water in prepared lignin/tetrahydrofuran solution with the speed of 0.2mL/min
And the ultrasonic treatment that adjoint power is 200W, obtain lignin nanosphere dispersion liquid.
3) the lignin microballoon dispersion liquid ultralow temperature supercentrifuge for obtaining step 2) is with the revolving speed of 10000r/min
It is centrifuged 10min, finally freeze-drying obtains lignin nanosphere.
The scanning electron microscope and transmission electron microscope picture of lignin nanosphere manufactured in the present embodiment respectively as Fig. 1 (d) x 5000,
(f) shown in x 20000 and Fig. 2 (d).As seen from the figure: lignin nanospheres show good appearance form, tool
Have that single pore structure, size reach maximum and homogeneity is preferable, while there is good dispersion performance.
Embodiment 5
The preparation method of lignin nanosphere, comprising the following steps:
1) by embodiment 4) in prepare lignin nanosphere and be added in commercial face cream with the ratio of mass fraction 5%,
It is configured to lignin nanosphere-face cream mixture.
2) by the lignin nanosphere-face cream mixture prepared in step 1) under the conditions of being protected from light with magnetic agitation with
The revolving speed of 400r/min, which is stirred overnight, is uniformly mixed it.
3) mixture prepared in step 2) is uniformly applied on ultraviolet testboard, makes it with a thickness of 1 millimeter or so, then
It is tested in the ultraviolet spectra with integrating sphere.
The more not commercial face cream uvioresistant ability of lignin nanosphere-face cream mixture manufactured in the present embodiment improves 4 times
As many as.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation.Therefore, it is other it is any without departing from the spirit and principles of the present invention made by modification, substitution and simplify, belong to
Within protection scope of the present invention.
Claims (8)
1. the method for preparing lignin microballoon.It is characterized in that, mainly comprising the steps that
1) lignin is mixed with acetic anhydride, acetylization reaction is carried out in microwave, to which mixture is instilled 5- after the reaction was completed
In the sour water (pH=2) of 10 times of volumes, it is filtered, washed, is freeze-dried to obtain acetylation lignin；
2) 1) acetylation lignin obtained in is dissolved in tetrahydrofuran solvent, is dropped evenly until completely dissolved into 7-10 times
Water, and with ultrasonic treatment；
3) 2) the microballoon aqueous solution obtained be centrifuged at 8000-10000r/min, filtered, be freeze-dried and obtain lignin
Nanosphere；
4) 3) the lignin microballoon obtained is mixed with commercial face cream, is measured for uvioresistant ability.
2. method according to claim 1, which is characterized in that microwave acetylation process used in step 1), wood
Quality and acetic anhydride ratio are 1:5-1:10, time 10min.
3. method according to claim 1, which is characterized in that the speed that water is added dropwise in step 2) is 0.2mL/min, wood
Quality concentration is 1mg/mL, 2mg/mL, 3mg/mL and 4mg/mL, ultrasound intensity 0,100W and 200W.
4. method according to claim 1, which is characterized in that using centrifuge separation in step 3).
5. method according to claim 1, which is characterized in that lignin additive amount is 1-5% in step 4).
6. according to the lignin nanosphere of the described in any item method preparations of claims 1-3.
7. the lignin nanosphere prepared according to 6 the method for claims, which is characterized in that the lignin nanometer is micro-
The yield of ball is high, uniform sphere diameter distribution, and partial size has single pore structure and good dispersion in 100-800nm.
8. the lignin nanosphere according to claims 6 or 7 is preparing the application in anti-ultraviolet material.
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Cited By (3)
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| CN113042008A (en) * | 2021-03-31 | 2021-06-29 | 浙江科技学院 | Alkali lignin micro/nanosphere/paper-based adsorption material, preparation method thereof and application thereof in treatment of dye wastewater |
| CN113292747A (en) * | 2021-05-21 | 2021-08-24 | 齐鲁工业大学 | Preparation method and application of biomass lignin nanoshell |
| CN118638445A (en) * | 2024-08-14 | 2024-09-13 | 安徽大学 | Bio-based unsaturated polyester resin-based atomic ash for rail transit |
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| CN105199119A (en) * | 2015-09-18 | 2015-12-30 | 华南理工大学 | Method for making industrial lignin light-colored |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113042008A (en) * | 2021-03-31 | 2021-06-29 | 浙江科技学院 | Alkali lignin micro/nanosphere/paper-based adsorption material, preparation method thereof and application thereof in treatment of dye wastewater |
| CN113292747A (en) * | 2021-05-21 | 2021-08-24 | 齐鲁工业大学 | Preparation method and application of biomass lignin nanoshell |
| CN113292747B (en) * | 2021-05-21 | 2022-10-28 | 齐鲁工业大学 | Preparation method and application of biomass lignin nanoshell |
| CN118638445A (en) * | 2024-08-14 | 2024-09-13 | 安徽大学 | Bio-based unsaturated polyester resin-based atomic ash for rail transit |
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