AU2020103916A4 - Star-shaped lignin-based benzophenone and preparation method and use thereof - Google Patents
Star-shaped lignin-based benzophenone and preparation method and use thereof Download PDFInfo
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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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Abstract
The present invention relates to a star-shaped lignin-based benzophenone and a
preparation method and use thereof. Lignin is suspended in a molten salt hydrate
according to a proportion, and an inorganic acid is added and stirred for a reaction;
5 after the reaction, the solution is cooled, washed and dried to obtain modified lignin;
then the modified lignin is dissolved in an anhydrous organic solvent, an aromatic
acid and a catalyst are added for a reaction, and washing and drying are carried out to
obtain a star-shaped lignin-based benzophenone material. It is shown through
researches on the DPPH oxidation resistance and Cr(VI) adsorption that after
10 depolymerization and acylation modification, the ultraviolet absorption, oxidation
resistance and Cr(VI) adsorption ability of lignin-based benzophenone are
significantly improved, the Cr(VI) adsorption rate of lignin-based benzophenone is 25
times higher than that of unmodified lignin, and the highest Cr(VI) adsorption rate is
as high as 98%. Therefore, the star-shaped lignin-based benzophenone material has a
15 great potential as a metal adsorbent in wastewater treatment.
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Description
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[0001] The present invention belongs to the technical field of lignin treatment and use, and specifically relates to star-shaped lignin-based benzophenone and a preparation method and use thereof in adsorption of Cr(VI) in wastewater.
[0002] As a complex, non-crystalline, three-dimensional network-shaped phenolic polymer, lignin is widely present in higher plant cells and is one of the basic chemical components of conifers, broad-leaved trees and grass plants. Lignin, cellulose, hemicellulose and the like constitute a supramolecular system in plants, and lignin is used to improve the mechanical strength of plants when used as a binder of cellulose. Lignin is the second largest renewable resource in nature after cellulose, and it is estimated that about 6*1014tons of lignin can be produced in the world per year. However, since the molecular structure of lignin is complex and the content of active sites such as hydroxyl groups is low, the reaction activity is low, and thus lignin is difficult to use [Xia Chenglong, Xu Yuzhi, Liu Xiaohuan, Wang Chunpeng. Chemistry and Industry of Forest Products, 2016, 36(2), 57-63.]. At present, most of lignin is burned as fuel, and only a small amount of lignin is used in preparation of phenolic resin, polyurethane, rubber [Kosikova B, Gregorova A. Journal of Applied Polymer Science, 2005, 97(3), 924-929.] and other resins and materials. Therefore, by using renewable lignin as a metal adsorbent of wastewater, not only is the resource utilization of lignin promoted, the environmental pollution is reduced, but also the sustainability of resource utilization can be improved.
[0003] Since lignin contains a large number of functional groups such as benzene rings, hydroxyl groups, carbonyl groups, carboxyl groups, methoxy groups and unsaturated bonds, lignin has ion exchange and adsorption abilities, is more advantageous than other adsorbents such as activated carbon, polymer resins and minerals, and has attracted extensive attention [Qiu Huidong, Duan Chuanren.
Industrial Water Treatment, 2007, 27(1): 5-7.]. However, due to the spherical spatial configuration, the active adsorption sites of lignin are reduced, and the improvement of the adsorption performance of lignin is limited [Tian Biao, Chen Siwei, Song Weiye, et al. Forestry Machinery and Woodworking Equipment, 2019, 47(2): 21-25.]; moreover, since the structure of lignin is complex, the physical and chemical properties are not uniform and the content of reactive functional groups is low, the substitution rate of lignin is low, the reproducibility is low, and therefore, the use and popularization of lignin are limited.
[0004] As a commonly used ultraviolet absorber and antioxidant, polyhydroxy benzophenone is also widely used in microelectronics integrated circuits, industrial photoresists, pharmaceutical intermediates, resin stabilizers, dyes, cosmetics and the like [Xie Bing, Cai Xiaohua, Huang Pengfei. Applied Chemical Industry, 2008, 37(9): 1086-1093.]. However, at present, fossil raw materials are used for synthesis of polyhydroxy benzophenone, and benzophenone ultraviolet absorber products having a low relative molecular mass have the disadvantages of low heat resistance and weather resistance, low compatibility with high molecular polymers and easy volatilization and migration in high molecular materials, resulting in blooming and local crystallization. As a natural polymer with a phenolic hydroxyl structure and a methoxyl structure, lignin can effectively reduce the disadvantages of low-molecular-weight benzophenone and is an ideal natural raw material for preparing polyhydroxy benzophenone. However, due to the disadvantages such as complex structure, polydispersity of macromolecules, nonuniform physical and chemical properties and low reaction sites of lignin, the performance and reproducibility of benzophenone may be affected. Therefore, an effective way of utilizing lignin reorganization to prepare benzophenone includes depolymerization of lignin and structural reorganization to prepare functionalized polyhydroxy benzophenone derivatives, and there is no related report at home and abroad. Thus, a new way for green synthesis and sustainable utilization of benzophenone derivatives is opened up; and at the same time, a new way for high-value utilization of lignin is also provided.
Technical Problem
[0005] The present invention provides a star-shaped lignin-based benzophenone and a preparation method and use thereof. Through depolymerization of a molten salt or demethylation of lignin, the lignin distribution is more uniform, the performance is more stable, and the reaction activity of lignin is improved; in addition, a benzophenone structure is introduced by a Freidel-Crafts reaction, the reaction activity of lignin is further improved, and the ultraviolet absorption performance of lignin can be improved. It is shown through researches that in use of adsorption of Cr(VI) in wastewater, the adsorption performance is significantly improved, and the adsorption rate of lignin-based benzophenone is about 25 times higher than that of unmodified lignin. Therefore, a theoretical basis is provided for high-added-value utilization of lignin.
Technical Solution
[0006] The present invention relates to a preparation method of star-shaped lignin-based benzophenone, comprising the steps: suspending 1g of lignin in 10-50 mL of a molten salt hydrate according to a proportion, adding 50-1500 L of an inorganic acid, and carrying out stirring at 90-150°C for a reaction for 0.5-5 hours; after the reaction solution is cooled, carrying out washing and drying to obtain modified lignin; then dissolving the modified lignin in 5 mL of an anhydrous organic solvent, adding a 50w% aromatic acid and a 10w% catalyst for a reaction for 2 hours, carrying out washing and drying to obtain a star-shaped lignin-based benzophenone material, and applying the material in adsorption of Cr(VI).
[0007] Preferably, the lignin is at least one of Kraft lignin, organic solvent lignin or enzymatic hydrolysis lignin.
[0008] Preferably, the molten salt hydrate is ZnCl 2, ZnBr 2, CuBr 2 , CaBr 2 , LiCl or LiBr.
[0009] Preferably, the inorganic acid is HCl, HBr, HNO 3 or H2 S0 4 .
[0010] Preferably, the anhydrous organic solvent is tetrahydrofuran, DMF or ether.
[0011] Preferably, the aromatic acid is benzoic acid, 2-naphthoic acid, p-hydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,4,5-trihydroxybenzoic acid,
3,4-dimethoxybenzoic acid or 3,4,5-trimethoxybenzoic acid.
[0012] Preferably, the catalyst is anhydrous AlCl 3 , ZnCl2 , H 2 SO4 , SOl 2 , boron trifluoride or polyphosphoric acid.
[0013] Star-shaped lignin-based benzophenone prepared by the preparation method.
[0014] Use of the star-shaped lignin-based benzophenone in adsorption of Cr(VI) in wastewater.
Advantageous Effect
[0015] (1)An acidic molten salt hydrate is used to modify lignin, so that the lignin distribution is more uniform, and the reaction activity is improved; (i benzophenone structure is introduced by a Freidel-Crafts reaction, so that the reaction activity is further improved, the ultraviolet absorption performance of lignin can be improved, and more reaction sites are also provided for lignin to adsorb Cr(VI); (Dhe adsorption performance is significantly improved, and it is shown through researches that the adsorption rate of modified lignin nanomaterials is 25 times higher than that of unmodified lignin.
[0016] Fig. 1 is a comparison diagram showing the antioxidant activity of lignin; LO is unmodified lignin; DL is depolymerized lignin; LB is a sample of Example 12 (lignin-based benzophenone); it can be seen from the figure that the free radical scavenging rate of the unmodified lignin is 41.5%, the free radical scavenging rate of the depolymerized lignin is 48%, and the free radical scavenging rate of lignin-based benzophenone is 61.5%. Therefore, after depolymerization and demethylation of lignin in a molten salt hydrate, the reaction activity is improved; and the activity is
further improved when the benzophenone is introduced into lignin.
[0017] Fig. 2 shows the infrared absorption spectrum of lignin; 3300 is the hydroxyl absorption peak, and 1690 is the carbonyl vibrational absorption peak. It can be seen from the figure that after depolymerization and Friedel-Crafts acylation of lignin, the vibration and absorption of hydroxyl and carbonyl groups are both improved, and the increase of the hydroxyl group is more obvious.
[0018] Fig. 3 is a comparison diagram showing the Cr(VI) adsorption performance of modified nano-lignin; LO is unmodified lignin; DL is depolymerized lignin; LB is a sample of Example 12 (lignin-based benzophenone); it can be seen from the figure that the Cr(VI) scavenging rate of the unmodified lignin is 4.0%, the Cr(VI) scavenging rate of the depolymerized lignin is 12%, and the Cr(VI) scavenging rate of lignin-based benzophenone is as high as 99%. After depolymerization and demethylation of a molten salt hydrate, the hydroxyl group is increased, and therefore, the Cr(VI) scavenging activity is improved; after the introduction of a polyhydroxy benzophenone structure, the content of the hydroxyl group is significantly increased, so that the Cr(VI) scavenging ability is also significantly improved, and almost all Cr (VI) in water can be scavenged.
[0019] Fig. 4 shows the ultraviolet absorption spectrum of lignin; as shown in the figure, the ultraviolet absorption of unmodified lignin is 280 nm (LO), and there is no ultraviolet absorption at 300 nm or above; when a benzophenone structure is introduced, two ultraviolet absorption peaks (LB) appear at 302 nm and 328 nm because of two reasons including a red shift phenomenon (--itelectron transition between a benzene ring and a carbonyl group) and appearance of the absorption peak of benzophenone (n--+ electron transition of a carbonyl group).
[0020] The specific steps for preparing molten salt hydrate modified lignin and star-shaped lignin-based benzophenone thereof include:
[0021] step one: suspending 1g of lignin in 10-50 mL of a molten salt hydrate according to a proportion, adding 50-1500 L of an inorganic acid, and carrying out stirring at 90-150°C for a reaction for 0.5-5 hours; after the reaction solution is cooled, carrying out washing and drying to obtain modified lignin;
[0022] step two: dissolving the modified lignin in 5 mL of an anhydrous organic solvent, adding an aromatic acid and a catalyst for a reaction for 2 hours, and carrying out washing and drying to obtain a star-shaped lignin-based benzophenone material; and
[0023] step three: determining the Cr(VI) adsorption performance of nano-lignin according to the national standard GB/C17593.3-2006.
[0024] The lignin is one or more of Kraft lignin, organic solvent lignin or enzymatic hydrolysis lignin; the molten salt hydrate is ZnC 2 , ZnBr 2 , CuBr2 , CaBr 2, LiCl, LiBr and the like; the inorganic acid is any one of HCl, HBr, HNO 3 or H 2 SO 4 ; the anhydrous organic solvent is tetrahydrofuran, DMF or ether; the catalyst is anhydrous AlCl3 , ZnC 2 , H2 SO 4 , SOCl 2 , boron trifluoride or polyphosphoric acid; the Cr(VI) adsorption performance is determined according to the national standard GB/C17593.3-2006.
Example 1
[0025] 1 g of Kraft lignin is suspended in 10 mL of a ZnCl 2 molten salt hydrate and stirred uniformly, and 50 L of HCl is added and stirred at 90°C for a reaction for 0.5 hours; after the reaction solution is cooled, washing and drying are carried out to obtain modified lignin; and then the modified lignin is dissolved in 5 mL of anhydrous THF, 50% benzoic acid and 10% anhydrous AlCl 3 are added for a reaction for 2 hours, and washing and drying are carried out to obtain a star-shaped lignin-based benzophenone material.
Example 2
[0026] 1 g of Kraft lignin is suspended in 10 mL of a CaBr 2 molten salt hydrate and stirred uniformly, and 100 L of HBr is added and stirred at 100°C for a reaction for 2 hours; after the reaction solution is cooled, washing and drying are carried out to obtain modified lignin; and then the modified lignin is dissolved in 5 mL of anhydrous DMF, 2-naphthoic acid and anhydrous ZnCl2 are added for a reaction for 2 hours, and washing and drying are carried out to obtain a star-shaped lignin-based benzophenone material.
Example 3
[0027] 1 g of Kraft lignin is suspended in 10 mL of a CuBr 2 molten salt hydrate and stirred uniformly, and 150 L of HN03 is added and stirred at 120°C for a reaction for 1 hour; after the reaction solution is cooled, washing and drying are carried out to obtain modified lignin; and then the modified lignin is dissolved in 5 mL of anhydrous ether, p-hydroxybenzoic acid and concentrated sulfuric acid are added for a reaction for 2 hours, and washing and drying are carried out to obtain a star-shaped lignin-based benzophenone material.
Example 4
[0028] 1 g of organic solvent lignin is suspended in 10 mL of a LiC1 molten salt hydrate and stirred uniformly, and 100 L of H2 SO4 is added and stirred at 130°C for a reaction for 3 hours; after the reaction solution is cooled, washing and drying are carried out to obtain modified lignin; and then the modified lignin is dissolved in 5 mL of anhydrous DMF, 3,4-dihydroxybenzoic acid and SOCl2 are added for a reaction for 2 hours, and washing and drying are carried out to obtain a star-shaped lignin-based benzophenone material.
Example 5
[0029] 1 g of enzymatic hydrolysis lignin is suspended in 10 mL of a LiBr molten salt hydrate and stirred uniformly, and 250 L of H2 SO4 is added and stirred at 110°C for a reaction for 1 hour; after the reaction solution is cooled, washing and drying are carried out to obtain modified lignin; and then the modified lignin is dissolved in 5 mL of anhydrous THF, 3,4,5-trihydroxybenzoic acid and polyphosphoric acid are added for a reaction for 2 hours, and washing and drying are carried out to obtain a star-shaped lignin-based benzophenone material.
Example 6
[0030] 1 g of enzymatic hydrolysis lignin is suspended in 10 mL of a LiCl molten salt hydrate and stirred uniformly, and 500 L of H2 SO4 is added and stirred at 150°C for a reaction for 4 hours; after the reaction solution is cooled, washing and drying are carried out to obtain modified lignin; and then the modified lignin is dissolved in 5 mL of anhydrous THF, 3,4-dimethoxybenzoic acid and boron trifluoride diethyl etherate are added for a reaction for 2 hours, and washing and drying are carried out to obtain a star-shaped lignin-based benzophenone material.
Example 7
[0031] 1 g of organic solvent lignin is suspended in 10 mL of a CuBr 2 molten salt hydrate and stirred uniformly, and 1500 L of HN03 is added and stirred at 140°C for a reaction for 5 hours; after the reaction solution is cooled, washing and drying are carried out to obtain modified lignin; and then the modified lignin is dissolved in 5 mL of anhydrous DMF, 3,4,5-trimethoxybenzoic acid and boron trifluoride diethyl etherate are added for a reaction for 2 hours, and washing and drying are carried out to obtain a star-shaped lignin-based benzophenone material.
Example 8
[0032] 1 g of Kraft lignin is suspended in 30 mL of a ZnBr 2 molten salt hydrate and stirred uniformly, and 500 L of HN03 is added and stirred at 130°C for a reaction for 2 hours; after the reaction solution is cooled, washing and drying are carried out to obtain modified lignin; and then the modified lignin is dissolved in 5 mL of anhydrous ether, benzoic acid and anhydrous ZnCl2 are added for a reaction for 2 hours, and washing and drying are carried out to obtain a star-shaped lignin-based benzophenone material.
Example 9
[0033] 1 g of Kraft lignin is suspended in 50 mL of a ZnCl 2 molten salt hydrate and stirred uniformly, and 1000 L of HCl is added and stirred at 110°C for a reaction for 1 hour; after the reaction solution is cooled, washing and drying are carried out to obtain modified lignin; and then the modified lignin is dissolved in 5 mL of anhydrous THF, 2-naphthoic acid and concentrated sulfuric acid are added for a reaction for 2 hours, and washing and drying are carried out to obtain a star-shaped lignin-based benzophenone material.
Example 10
[0034] 1 g of organic solvent lignin is suspended in 40 mL of a LiBr molten salt hydrate and stirred uniformly, and 1500 L of HBr is added and stirred at 100°C for a reaction for 2 hours; after the reaction solution is cooled, washing and drying are carried out to obtain modified lignin; and then the modified lignin is dissolved in 5 mL of anhydrous THF, p-hydroxybenzoic acid and polyphosphoric acid are added for a reaction for 2 hours, and washing and drying are carried out to obtain a star-shaped lignin-based benzophenone material.
Example 11
[0035] 1 g of enzymatic hydrolysis lignin is suspended in 20 mL of a ZnBr 2 molten salt hydrate and stirred uniformly, and 500 L of HCl is added and stirred at 90°C for a reaction for 0.5 hours; after the reaction solution is cooled, washing and drying are carried out to obtain modified lignin; and then the modified lignin is dissolved in 5 mL of anhydrous DMF, 3,4-dihydroxybenzoic acid and anhydrous AlCl 3 are added for a reaction for 2 hours, and washing and drying are carried out to obtain a star-shaped lignin-based benzophenone material.
Example 12
[0036] 1 g of Kraft lignin is suspended in 10 mL of a LiBr2 molten salt hydrate and stirred uniformly, and 1000 L of HCl is added and stirred at 100°C for a reaction for 1 hour; after the reaction solution is cooled, washing and drying are carried out to obtain modified lignin; and then the modified lignin is dissolved in 5 mL of anhydrous DMF, 3,4,5-trihydroxybenzoic acid and polyphosphoric acid are added for a reaction for 2 hours, and washing and drying are carried out to obtain a star-shaped lignin-based benzophenone material.
[0037] It is shown through researches (as shown in the table below) that, after depolymerization or demethylation of lignin, the content of element carbon is reduced, and the content of element oxygen is increased. Therefore, it can be inferred that an acidic molten salt hydrate promotes depolymerization and demethylation of lignin, so that the content of hydroxyl groups is increased, and the reaction activity of lignin is improved; after the introduction of benzophenone by a Friedel-Crafts reaction, the content of oxygen is further increased, so that the reaction activity is further improved.
[0038] Elemental analysis of modified nano-lignin
Sample C H 0 Raw material lignin 60.92 5.75 25.24 Depolymerized and demethylated lignin 58.52 5.15 27.01 Sample of Example 12 56.31 5.04 29.06
Example 13
[0039] 1 g of Kraft lignin is suspended in 30 mL of a LiBr2 molten salt hydrate and stirred uniformly, and 250 L of H 2 SO4 is added and stirred at 100°C for a reaction for 1 hour; after the reaction solution is cooled, washing and drying are carried out to obtain modified lignin; and then the modified lignin is dissolved in 5 mL of anhydrous DMF, 3,4-dimethoxybenzoic acid and anhydrous AlCl3 are added for a reaction for 2 hours, and washing and drying are carried out to obtain a star-shaped lignin-based benzophenone material.
Example 14
[0040] 1 g of Kraft lignin is suspended in 10 mL of a LiBr2 molten salt hydrate and stirred uniformly, and 300 L of HCl is added and stirred at 100°C for a reaction for 1 hour; after the reaction solution is cooled, washing and drying are carried out to obtain modified lignin; and then the modified lignin is dissolved in 5 mL of anhydrous DMF, 3,4,5-trimethoxybenzoic acid and anhydrous concentrated sulfuric acid are added for a reaction for 2 hours, and washing and drying are carried out to obtain a star-shaped lignin-based benzophenone material.
Example 15
[0041] An antioxidant activity (DPPH) determination method of lignin: The antioxidant ability of various lignins is determined according to the DPPH free radical scavenging ability. An experimental method: 0.025 g of lignin is dissolved in a dioxane solution with a 1,4-dioxane to water volume ratio of 9:1; 0.96 mL of a lignin dioxane solution with a concentration of 0.05 mg/L is taken and added into 3.54 mL of a DPPH ethanol solution with a concentration of 0.024 g/L; at the same time, as a blank experiment, a reaction is carried out in the dark at room temperature for 16 minutes; after the reaction is completed, the absorbance value is measured at 517 nm by using an electronic ultraviolet spectrophotometer; and the antioxidant ability of tested lignin is calculated according to the following formula:
[0042] DPPH (scavenging rate)=(Ao-A1)/Ao*100%
[0043] In the formula: Ao is the absorbance of a blank sample measured at 517 nm, and A 1 is the absorbance of a lignin sample measured at 517 nm.
Example 16
[0044] The adsorption performance of Cr(VI) in a solution is determined according to the national standard GB/C17593.3-2006, and then the concentration of Cr(VI) in the solution before and after adsorption is determined by using a spectrophotometer at an absorption wavelength of 540 nm.
[0045] A calculation formula for calculating the adsorption rate of Cr(VI) by prepared nanoparticles is:
[0046] E=(Co-Cp)/Co*100%
[0047] In the formula: Co and Cp refer to the concentration (mg/L) of Cr(VI) before and after adsorption.
[0048] The embodiments described above are only used for explaining the technical ideas and characteristics of the present invention to enable a person skilled in the art to understand and implement the content of the present invention, and are not intended to limit the protection scope of the present invention. That is, any equivalent change or modification made according to the spirit disclosed in the present invention shall still fall within the protection scope of the present invention.
Claims (9)
1. A preparation method of star-shaped lignin-based benzophenone, comprising the
steps: suspending 1 g of lignin in 10-50 mL of a molten salt hydrate according to a
proportion, adding 50-1500 pL of an inorganic acid, and carrying out stirring at
-150°C for a reaction for 0.5-5 hours; after the reaction solution is cooled, carrying
out washing and drying to obtain modified lignin; then dissolving the modified lignin
in 5 mL of an anhydrous organic solvent, adding a 50w% aromatic acid and a 10w%
catalyst for a reaction for 2 hours, carrying out washing and drying to obtain a
star-shaped lignin-based benzophenone material, and applying the material in
adsorption of Cr(VI).
2. The preparation method of star-shaped lignin-based benzophenone according to
claim 1, wherein the lignin is at least one of Kraft lignin, organic solvent lignin or
enzymatic hydrolysis lignin.
3. The preparation method of star-shaped lignin-based benzophenone according to
claim 1, wherein the molten salt hydrate is ZnC 2 , ZnBr 2, CuBr 2, CaBr2, LiCl or LiBr.
4. The preparation method of star-shaped lignin-based benzophenone according to
claim 1, wherein the inorganic acid is HCl, HBr, HN03 or H 2 SO4 .
5. The preparation method of star-shaped lignin-based benzophenone according to
claim 1, wherein the anhydrous organic solvent is tetrahydrofuran, DMF or ether.
6. The preparation method of star-shaped lignin-based benzophenone according to
claim 1, wherein the aromatic acid is benzoic acid, 2-naphthoic acid, p-hydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,4,5-trihydroxybenzoic acid,
3,4-dimethoxybenzoic acid or 3,4,5-trimethoxybenzoic acid.
7. The preparation method of star-shaped lignin-based benzophenone according to
claim 1, wherein the catalyst is anhydrous AlCl 3 , ZnCl 2 , H 2 SO 4 , SOCl 2 , boron
trifluoride or polyphosphoric acid.
8. Star-shaped lignin-based benzophenone prepared by any one of the preparation methods according to claim 1 to 7.
9. Use of the star-shaped lignin-based benzophenone according to claim 8 in adsorption of Cr(VI) in wastewater.
DPPH scavenging rate (%) ro oj -t* ai 05 o o o o o o o o i i i i
o
|-rj O 05 1/4
fa 3 ?r o
ro
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