CN110652971A - Modified nano lignin and preparation method and application thereof - Google Patents
Modified nano lignin and preparation method and application thereof Download PDFInfo
- Publication number
- CN110652971A CN110652971A CN201911058383.7A CN201911058383A CN110652971A CN 110652971 A CN110652971 A CN 110652971A CN 201911058383 A CN201911058383 A CN 201911058383A CN 110652971 A CN110652971 A CN 110652971A
- Authority
- CN
- China
- Prior art keywords
- lignin
- modified nano
- ultrapure water
- repeating
- molten salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- B01J20/22—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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Compounds Of Unknown Constitution (AREA)
Abstract
A modified nano lignin and its preparation method and application, according to the proportion, suspend 1g lignin in 10-50mL molten salt hydrate, add 50-500 μ L inorganic acid, at 90-150 duC, stir and react for 0.5-5 h; cooling the reaction liquid to obtain modified lignin; and adding ultrapure water into the modified lignin, cleaning, repeating for more than 3 times, centrifuging, dissolving in 100mL of organic solvent, dialyzing in 1L of ultrapure water, repeating for 3 times, and freeze-drying to obtain the target nano material adsorbent. Antioxidant and Cr (VI) adsorption studies on DPPH show that: with the increase of the content of the inorganic acid added into the sample, the antioxidant activity and the Cr (VI) adsorption capacity of the sample are increased, the adsorption rate of the modified lignin nano material is improved by 2.5 times compared with that of unmodified lignin, and the highest adsorption rate of Cr (VI) is up to 48%. Therefore, the nano lignin material has great potential as a metal adsorbent in the aspect of wastewater treatment.
Description
Technical Field
The invention belongs to the field of lignin treatment, and particularly relates to nano lignin as well as a preparation method and application thereof.
Background
Lignin is a complex, noncrystalline, three-dimensional network phenolic high molecular polymer, widely exists in higher plant cells, and is one of the basic chemical compositions of coniferous trees, broad-leaved trees and grasses. Lignin, together with cellulose, hemicellulose and the like, forms a supramolecular system in plants, and lignin serves as a binder for cellulose to enhance the mechanical strength of the plants. Lignin is the second most renewable resource in nature after cellulose, and is estimated to produce about 6X 10 per year worldwide14Ton. However, lignin has a complex molecular structure and low content of active sites such as hydroxyl, resulting in low reactivity and difficulty in utilization [ Xia Cheng Long, xu Yu Zhi, Liu Xiao Hua, Wang Chun Peng, Ling Cheng chemical and industry, 2016,36(2),57-63]. At present, lignin is mostly burned off as a fuel, and only a small amount is used for phenolic resins, polyurethanes and rubbers [ Kosikova B, Gregorova A. journal of Applied Polymer Science,2005,97(3),924-]And the like in the preparation of resins and materials. Therefore, the renewable lignin is used as the metal adsorbent of the wastewater, so that the resource utilization of the lignin is promoted, the environmental pollution is reduced, and the sustainability of the resource utilization can be improved.
Because lignin contains a large number of functional groups such as benzene rings, hydroxyl groups, carbonyl groups, carboxyl groups, methoxyl groups, unsaturated bonds and the like, the lignin has ion exchange and adsorption capacities, is more advantageous than other adsorbents such as active carbon, high polymer resin, mineral substances and the like, and is widely concerned [ Qiuedong, Chunduo, Industrial Water treatment, 2007, 27(1):5-7 ]. However, the spherical spatial configuration reduces the active adsorption sites of lignin, limiting its improvement in adsorption performance [ canvases, chenyixian, song excellence, et al, forestry machines and woodworking equipment, 2019, 47(2):21-25 ]; and the lignin has complex structure, inhomogeneous physical and chemical properties and low content of reactive functional groups, so that the defects of low lignin substitution rate, poor reproducibility and the like are caused, thereby limiting the popularization and application of the lignin.
Recently, we reported studies of molten salt hydrates to depolymerize and demethylate lignin, which can effectively break the β -O-4, α -O-4 and Ar-O-CH of lignin3The structure of the catalyst enables the molecular weight of the catalyst to be obviously reduced, the distribution of the catalyst is more uniform, and the reaction activity is greatly improved [ Yang X ]; li N.; lin X.; pan X.; zhou Y.J.Agric.food chem.2016,64, 8379-8387; method for demethoxylation of lignin from Yangxiao, Zhouyonghong, Hulihong and thin-adopted glume 201710886266.4]. Therefore, the acidic molten salt hydrate modified lignin nano material and the metal adsorption thereof are researched.
Disclosure of Invention
The technical problem to be solved is as follows: the invention provides a modified nano lignin and a preparation method and application thereof, and the method improves the reaction activity and increases the total specific surface area of the lignin by modifying the nano lignin; therefore, in the application of adsorbing Cr (VI) in wastewater, the adsorption performance is obviously improved, namely the adsorption rate of the modified lignin nano material is improved by 2.5 times compared with that of unmodified lignin. Thereby providing a theoretical basis for the high value-added utilization of the lignin.
The technical scheme is as follows: a preparation method of modified nano lignin comprises the following steps: suspending 1g of lignin in 10-50mL of molten salt hydrate according to a proportion, adding 50-1500 mu L of inorganic acid, stirring and reacting for 0.5-5 h at 90-150 ℃, and cooling the reaction liquid to obtain a target solution; transferring the target solution into an ultrafiltration tube for centrifugal treatment, collecting a bottom product, and adding ultrapure water for cleaning; dissolving the centrifugal product in 100mL of organic solvent, dialyzing in 1L of ultrapure water, repeating for 3 times, and freeze-drying to obtain the modified nano lignin.
Preferably, the lignin is Kraft lignin, organic solvent lignin or enzymatic lignin.
Preferably, the molten salt hydrate is ZnCl2、ZnBr2、CuBr2、CaBr2LiCl or LiBr.
Preferably, the inorganic acid is HCl, HBr, HNO3Or H2SO4。
Preferably, the organic solvent is at least one of tetrahydrofuran, ethanol, ethyl acetate and DMF.
The modified nano lignin prepared by the preparation method.
The modified nano lignin is applied to the preparation of products for adsorbing Cr (VI).
Has the advantages that: firstly, acid molten salt hydrate is utilized to modify lignin, so that the activity of the lignin is increased; the total specific surface area of the nano lignin is increased, so that more contact sites are provided for adsorbing Cr (VI) by the lignin; ③ the adsorption performance is obviously improved, and the research shows that: the adsorption rate of the modified lignin nano material is improved by 2.5 times compared with that of unmodified lignin.
Drawings
FIG. 1 is a schematic diagram of the study of antioxidant activity of lignin;
l1 is a lignin raw material, and L2-7 are examples 2-7, respectively. It is shown that the increased DPPH radical clearance of lignin, i.e. the increased antioxidant activity of lignin, is due to the increased acidity, which leads to a higher degree of depolymerization and demethylation of lignin, and that the relatively high temperature and long reaction time also favour the depolymerization and demethylation of lignin. Thus, there are more free hydroxyl groups and lignin activity is enhanced.
FIG. 2 is a SEM image of nanoparticles;
as can be seen from the figure, the average particle size of the modified nano lignin was 0.23. mu.m.
FIG. 3 is a schematic diagram of Cr (VI) adsorption performance of modified nano-lignin;
in the figure, L1 is unmodified lignin; l2 is the sample of example 2; l3 is the sample from example 12; the graph shows that the Cr (VI) adsorption performance of the nano lignin is obviously improved compared with that of unmodified lignin, and the main reason is that the acidic molten salt hydrate promotes depolymerization and demethylation of the lignin, so that the hydroxyl content is increased, and the reaction activity of the lignin is improved; in addition, the specific surface area of the nano lignin is increased compared with that of the lignin, so that the contact sites of the nano lignin are improved, and the adsorption performance of the nano lignin can also be improved.
Detailed Description
The preparation method of the molten salt hydrate modified lignin and the nano material thereof comprises the following specific steps:
the method comprises the following steps: suspending 1g of lignin in 10-50mL of molten salt hydrate according to the proportion, adding 50-1500 mu L of inorganic acid, and stirring and reacting for 0.5-5 h at 90-150 ℃; cooling the reaction solution to obtain a target solution;
step two: transferring the target solution into an ultrafiltration tube for centrifugal treatment, collecting a bottom product, adding ultrapure water for cleaning, and repeating for more than 3 times;
step three: dissolving the final centrifugation product in 100mL of organic solvent, dialyzing in 1L of ultrapure water, repeating for 3 times, and freeze-drying to obtain the target nano material adsorbent;
step four: the Cr (VI) adsorption performance of the nano lignin is measured according to the national standard GB/C17593.3-2006
The lignin is any one or more of Kraft lignin, organic solvent type lignin or enzymatic hydrolysis lignin; the molten salt hydrate is ZnCl2、ZnBr2、CuBr2、CaBr2LiCl, LiBr, etc.; the catalyst is HCl, HBr and HNO3Or H2SO4Any one of (a); the organic solvent is one or a mixed solvent of tetrahydrofuran, ethanol, ethyl acetate and DMF; the Cr (VI) adsorption property is measured according to the national standard GB/C17593.3-2006.
Example 1.
1g of Kraft lignin suspended in 10mL ZnCl2Uniformly stirring the molten salt hydrate, adding 50 mu L of HCl, and stirring and reacting for 0.5h at 90 ℃; cooling the reaction solution to obtain a target solution; transferring the target solution into an ultrafiltration tube for centrifugal treatment, collecting a bottom product, adding ultrapure water for cleaning, and repeating for more than 3 times; and dissolving the final centrifugation product in 100ml of THF, dialyzing in 1L of ultrapure water, repeating for 3 times, and freeze-drying to obtain the target nano material adsorbent.
Example 2.
1g of Kraft lignin was suspended in 10mL CaBr2Uniformly stirring the molten salt hydrate, adding 100 mu L HBr, and stirring and reacting for 2h at 100 ℃; cooling the reaction solution to obtain a target solution; transferring the target solution into an ultrafiltration tube for centrifugal treatment, collecting a bottom product, adding ultrapure water for cleaning, and repeating for more than 3 times; and dissolving the final centrifugation product in 100mL of ethanol, dialyzing in 1L of ultrapure water, repeating for 3 times, and freeze-drying to obtain the target nano material adsorbent.
Example 3.
1g of Kraft lignin was suspended in 10mL of CuBr2Stirring the mixture evenly in the molten salt hydrate, and adding 150 mu L of HNO3Stirring and reacting for 1h at 120 ℃; cooling the reaction solution to obtain a target solution; transferring the target solution into an ultrafiltration tube for centrifugal treatment, collecting a bottom product, adding ultrapure water for cleaning, and repeating for more than 3 times; and (3) dissolving the centrifugation product of the last time in 100mL of DMF, dialyzing in 1L of ultrapure water, repeating for 3 times, and freeze-drying to obtain the target nano-material adsorbent.
Example 4.
Suspending 1g organic solvent type lignin in 10mL LiCl molten salt hydrate, stirring well, adding 100 μ L H2SO4Stirring and reacting for 3 hours at the temperature of 130 ℃; cooling the reaction solution to obtain a target solution; transferring the target solution into an ultrafiltration tube for centrifugal treatment, collecting a bottom product, adding ultrapure water for cleaning, and repeating for more than 3 times; the final centrifugation product was dissolved in 100mL THF/ethyl acetate (95:5, v/v), dialyzed against 1L ultrapure water, repeated 3 times, and freeze-dried to obtain the target nanomaterial adsorbent.
Example 5.
Suspending 1g of enzymatic hydrolysis lignin in 10mL of LiBr molten salt hydrate, stirring uniformly, adding 250 mu L of H2SO4Stirring and reacting for 1h at 110 ℃; cooling the reaction solution to obtain a target solution; transferring the target solution into an ultrafiltration tube for centrifugal treatment, collecting a bottom product, adding ultrapure water for cleaning, and repeating for more than 3 times; dissolving the final centrifugation product in 100ml of THF/ethanol (95:5, v/v), dialyzing in 1L of ultrapure water, repeating for 3 times, and freeze-drying to obtain the target nanomaterial adsorbent.
Example 6.
Suspending 1g of enzymatic hydrolysis lignin in 10mL of LiCl molten salt hydrate, stirring uniformly, adding 500 μ L of H2SO4Stirring and reacting for 4 hours at 150 ℃; cooling the reaction solution to obtain a target solution; transferring the target solution into an ultrafiltration tube for centrifugal treatment, collecting a bottom product, adding ultrapure water for cleaning, and repeating for more than 3 times; dissolving the final centrifugation product in 100ml of THF/ethyl acetate (90:10, v/v), dialyzing in 1L of ultrapure water, repeating for 3 times, and freeze-drying to obtain the target nanomaterial adsorbent.
Example 7.
1g of organosolv lignin suspended in 10mL of CuBr2Stirring the molten salt hydrate evenly, and adding 1500 mu L of HNO3Stirring and reacting for 5 hours at the temperature of 140 ℃; cooling the reaction solution to obtain a target solution; transferring the target solution into an ultrafiltration tube for centrifugal treatment, collecting a bottom product, adding ultrapure water for cleaning, and repeating for more than 3 times; the final centrifugation product was dissolved in 100mL THF/ethyl acetate (85:15, v/v), dialyzed against 1L ultrapure water, repeated 3 times, and freeze-dried to obtain the target nanomaterial adsorbent.
Example 8.
1g of Kraft lignin suspended in 30mL of ZnBr2Stirring the mixture evenly in the molten salt hydrate, and adding 500 mu L of HNO3Stirring and reacting for 2 hours at the temperature of 130 ℃; cooling the reaction solution to obtain a target solution; transferring the target solution into an ultrafiltration tube for centrifugal treatment, collecting a bottom product, adding ultrapure water for cleaning, and repeating for more than 3 times; dissolving the final centrifugation product in 100mL THF/ethanol (90:10, v/v), dialyzing in 1L ultrapure water, repeating for 3 times, and freeze-drying to obtain the target nanomaterial adsorbent.
Example 9.
1g of Kraft lignin suspended in 50mL ZnCl2Uniformly stirring the molten salt hydrate, adding 1000 mu L of HCl, and stirring and reacting for 1h at 110 ℃; cooling the reaction solution to obtain a target solution; transferring the target solution into an ultrafiltration tube for centrifugal treatment, collecting bottom products, adding ultrapure water for cleaning, and repeating for 3 timesThe above; dissolving the final centrifugation product in 100mL of DMF/ethyl acetate (95:5, v/v), dialyzing in 1L of ultrapure water, repeating for 3 times, and freeze-drying to obtain the target nanomaterial adsorbent.
Example 10.
Suspending 1g of organic solvent type lignin in 40mL of LiBr molten salt hydrate, uniformly stirring, adding 1500 mu L of HBr, and stirring and reacting for 2h at 100 ℃; cooling the reaction solution to obtain a target solution; transferring the target solution into an ultrafiltration tube for centrifugal treatment, collecting a bottom product, adding ultrapure water for cleaning, and repeating for more than 3 times; dissolving the final centrifugation product in 100mL of DMF/ethyl acetate (90:10, v/v), dialyzing in 1L of ultrapure water, repeating for 3 times, and freeze-drying to obtain the target nanomaterial adsorbent.
Example 11.
1g of enzymatically hydrolyzed lignin was suspended in 20mL of ZnBr2Uniformly stirring the molten salt hydrate, adding 500 mu L of HCl, and stirring and reacting for 0.5h at 90 ℃; cooling the reaction solution to obtain a target solution; transferring the target solution into an ultrafiltration tube for centrifugal treatment, collecting a bottom product, adding ultrapure water for cleaning, and repeating for more than 3 times; dissolving the final centrifugation product in 100ml of THF/DMF/ethyl acetate (90:5:5, v/v), dialyzing in 1L of ultrapure water, repeating for 3 times, and freeze-drying to obtain the target nanomaterial adsorbent.
Example 12.
1g of Kraft lignin was suspended in 10mL LiBr2Uniformly stirring the molten salt hydrate, adding 1000 mu L of HCl, and stirring and reacting for 1h at 100 ℃; after the reaction liquid is cooled, transferring the target solution into an ultrafiltration tube for centrifugal treatment, collecting a bottom product, adding ultrapure water for cleaning, and repeating for more than 3 times; the final centrifugation product was dissolved in 100mL THF/DMF/ethyl acetate (70:25:5, v/v), dialyzed against 1L ultrapure water, repeated 3 times, and freeze-dried to obtain the target nanomaterial adsorbent.
The study showed (as shown in the following table) that lignin has a reduced carbon content and an increased oxygen content with an increase in acidity, and therefore, it is inferred that acidic molten salt hydrate promotes depolymerization and demethylation of lignin, so that the hydroxyl content is increased and the reactivity of lignin is improved.
Elemental analysis of modified nano-lignin
Example 13.
1g of Kraft lignin was suspended in 30mL LiBr2The molten salt hydrate is stirred evenly and added with 250 mu L of H2SO4Stirring and reacting for 1h at 100 ℃; after the reaction liquid is cooled, transferring the target solution into an ultrafiltration tube for centrifugal treatment, collecting a bottom product, adding ultrapure water for cleaning, and repeating for more than 3 times; the final centrifugation product was dissolved in 100mL THF/DMF/ethyl acetate (80:15:5, v/v), dialyzed against 1L ultrapure water, repeated 3 times, and freeze-dried to obtain the target nanomaterial adsorbent.
Example 14.
1g of Kraft lignin was suspended in 10mL LiBr2Uniformly stirring the molten salt hydrate, adding 300 mu L of HCl, and stirring and reacting for 1h at 100 ℃; after the reaction liquid is cooled, transferring the target solution into an ultrafiltration tube for centrifugal treatment, collecting a bottom product, adding ultrapure water for cleaning, and repeating for more than 3 times; the final centrifugation product was dissolved in 100mL THF/DMF/ethyl acetate (70:25:5, v/v), dialyzed against 1L ultrapure water, repeated 3 times, and freeze-dried to obtain the target nanomaterial adsorbent.
Example 15.
Determination method of wood antioxidant activity (DPPH): DPPH free radical scavenging capacity was used to test the antioxidant capacity of various lignins. Experimental method 0.025g of lignin was dissolved in a 1, 4-dioxane to water volume ratio of 9: 1 in dioxane solution; adding 0.96mL of 0.05mg/L lignin dioxane solution into 3.54mL of 0.024g/L DPPH ethanol solution; meanwhile, a blank experiment is carried out, and the reaction is carried out for 16min at room temperature in a dark place; after the reaction is finished, measuring a light absorption value at 517nm by using an electronic ultraviolet spectrophotometer; the antioxidant capacity of the lignin to be tested is calculated according to the following formula:
DPPH (clear)Division ratio of (A)0-A1)/A0×100％
In the formula: a. the0Is the absorbance of the blank sample measured at 517nm, A1Is the absorbance at 517nm of the lignin sample measured.
Example 16.
The measurement of the Cr (VI) adsorption performance in the solution needs to measure the Cr (VI) concentration in the solution before and after adsorption by adopting a spectrophotometer under the condition that the absorption wavelength is 540nm according to the national standard GB/C17593.3-2006. Wherein, the calculation formula of the adsorption rate of the prepared nano particles to Cr (VI) is as follows:
E＝(C0-CP)/C0×100％
in the formula: c0、CPThe concentrations (mg/L) of Cr (VI) before and after adsorption, respectively.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (7)
1. A preparation method of modified nano lignin is characterized by comprising the following steps: suspending 1g of lignin in 10-50mL of molten salt hydrate according to a proportion, adding 50-1500 mu L of inorganic acid, stirring and reacting for 0.5-5 h at 90-150 ℃, and cooling the reaction liquid to obtain a target solution; transferring the target solution into an ultrafiltration tube for centrifugal treatment, collecting a bottom product, and adding ultrapure water for cleaning; dissolving the centrifugal product in 100mL of organic solvent, dialyzing in 1L of ultrapure water, repeating for 3 times, and freeze-drying to obtain the modified nano lignin.
2. The method for preparing modified nano lignin according to claim 1, wherein the lignin is Kraft lignin, organic solvent type lignin or enzymatic hydrolysis lignin.
3. Root of herbaceous plantThe method for preparing the modified nano lignin according to claim 1, wherein the molten salt hydrate is ZnCl2、ZnBr2、CuBr2、CaBr2LiCl or LiBr.
4. The method for preparing the modified nano lignin according to claim 1, wherein the inorganic acid is HCl, HBr, HNO3Or H2SO4。
5. The method for preparing modified nano lignin according to claim 1, wherein the organic solvent is at least one of tetrahydrofuran, ethanol, ethyl acetate and DMF.
6. The modified nano lignin prepared by the preparation method of any one of claims 1 to 5.
7. The use of the modified nano lignin of claim 6 in the preparation of adsorbed Cr (VI) products.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911058383.7A CN110652971A (en) | 2019-11-01 | 2019-11-01 | Modified nano lignin and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911058383.7A CN110652971A (en) | 2019-11-01 | 2019-11-01 | Modified nano lignin and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110652971A true CN110652971A (en) | 2020-01-07 |
Family
ID=69042560
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911058383.7A Pending CN110652971A (en) | 2019-11-01 | 2019-11-01 | Modified nano lignin and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110652971A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112646196A (en) * | 2020-12-18 | 2021-04-13 | 安徽工业大学 | Method for preparing nano lignin from lignin extracting solution by utilizing acid sedimentation and dialysis |
| CN112724544A (en) * | 2020-12-09 | 2021-04-30 | 永一橡胶有限公司 | Heat-conducting vulcanized capsule and preparation method thereof |
| CN113861244A (en) * | 2021-09-14 | 2021-12-31 | 中国林业科学研究院林产化学工业研究所 | Lignin bacteriostatic agent and preparation method and application thereof |
| CN114749156A (en) * | 2022-04-21 | 2022-07-15 | 齐鲁工业大学 | Method for preparing demethylated lignin adsorption material by ball milling |
| CN115521345A (en) * | 2022-09-23 | 2022-12-27 | 大连工业大学 | Method for depolymerizing industrial alkali lignin by inorganic molten salt hydrate system |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080277351A1 (en) * | 2005-03-04 | 2008-11-13 | Cornell Research Foundation, Inc. | Remediation and Reclamation of Heavy Metals From Aqueous Liquid |
| US20130252302A1 (en) * | 2012-03-25 | 2013-09-26 | Wisconsin Alumni Reserarch Foundation | Saccharification of lignocellulosic biomass |
| CN107722295A (en) * | 2017-09-27 | 2018-02-23 | 中国林业科学研究院林产化学工业研究所 | The method of lignin demethoxylation |
-
2019
- 2019-11-01 CN CN201911058383.7A patent/CN110652971A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080277351A1 (en) * | 2005-03-04 | 2008-11-13 | Cornell Research Foundation, Inc. | Remediation and Reclamation of Heavy Metals From Aqueous Liquid |
| US20130252302A1 (en) * | 2012-03-25 | 2013-09-26 | Wisconsin Alumni Reserarch Foundation | Saccharification of lignocellulosic biomass |
| CN107722295A (en) * | 2017-09-27 | 2018-02-23 | 中国林业科学研究院林产化学工业研究所 | The method of lignin demethoxylation |
Non-Patent Citations (2)
| Title |
|---|
| P. MIRETZKY AND A. FERNANDEZ CIRELLI: ""Cr(VI) and Cr(III) removal from aqueous solution by raw and modified lignocellulosic materials: A review"", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
| 田彪，陈思危，宋玮晔， 刘静宜，林剑: ""木质素纤维对水溶液中Cr6+的吸附"", 《林业机械与木工设备》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112724544A (en) * | 2020-12-09 | 2021-04-30 | 永一橡胶有限公司 | Heat-conducting vulcanized capsule and preparation method thereof |
| CN112724544B (en) * | 2020-12-09 | 2022-07-05 | 永一橡胶有限公司 | Heat-conducting vulcanized capsule and preparation method thereof |
| CN112646196A (en) * | 2020-12-18 | 2021-04-13 | 安徽工业大学 | Method for preparing nano lignin from lignin extracting solution by utilizing acid sedimentation and dialysis |
| CN113861244A (en) * | 2021-09-14 | 2021-12-31 | 中国林业科学研究院林产化学工业研究所 | Lignin bacteriostatic agent and preparation method and application thereof |
| CN114749156A (en) * | 2022-04-21 | 2022-07-15 | 齐鲁工业大学 | Method for preparing demethylated lignin adsorption material by ball milling |
| CN114749156B (en) * | 2022-04-21 | 2023-09-29 | 齐鲁工业大学 | Method for preparing demethylated lignin adsorption material by ball milling |
| CN115521345A (en) * | 2022-09-23 | 2022-12-27 | 大连工业大学 | Method for depolymerizing industrial alkali lignin by inorganic molten salt hydrate system |
| CN115521345B (en) * | 2022-09-23 | 2024-03-01 | 大连工业大学 | Method for depolymerizing industrial alkali lignin by inorganic molten salt hydrate system |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110652971A (en) | Modified nano lignin and preparation method and application thereof | |
| Jin et al. | Clickable synthesis of 1, 2, 4-triazole modified lignin-based adsorbent for the selective removal of Cd (II) | |
| CN101824118B (en) | Porous polymer nanoparticles and preparation method thereof | |
| CN105642233B (en) | A kind of method that continuity method prepares CMC/GO composite hydrogel microballoons | |
| Wang et al. | Barium alginate as a skeleton coating graphene oxide and bentonite-derived composites: Excellent adsorbent based on predictive design for the enhanced adsorption of methylene blue | |
| CN107298765B (en) | Black phosphorus alkene/corn stalk stalks of rice, wheat, etc. holocellulose ether blended gel preparation method and application | |
| CN107893062B (en) | Method for immobilizing cellulase and hydrolyzing cellulose | |
| Wang et al. | Carbon microspheres prepared from the hemicelluloses-rich pre-hydrolysis liquor for contaminant removal | |
| CN108262072A (en) | It is a kind of for catalyzed by ruthenium complexes agent of acetylene hydrochlorination and its preparation method and application | |
| CN110681361A (en) | Preparation method and application of magnetic cellulose microspheres with core-shell structure | |
| CN110964211A (en) | Star-shaped lignin-based benzophenone and preparation method and application thereof | |
| CN103588886A (en) | Easily-water dispersible nanocrystalline cellulose and preparation method thereof | |
| CN107722295A (en) | The method of lignin demethoxylation | |
| Zhang et al. | Novel dual modified alkali lignin based adsorbent for the removal of Pb2+ in water | |
| Lin et al. | Immobilization of ferric tannate on wood fibers to functionalize wood fibers/diphenylmethane di-isocyanate composites | |
| CN113816373A (en) | Preparation method of biomass modified phenolic resin carbon spheres with controllable particle size | |
| CN115124757A (en) | Cellulose-based aerogel small ball capable of efficiently removing chromium, and preparation method and application thereof | |
| CN105854936B (en) | A kind of lignin electrostatic nanoparticle copper-loading catalyst and preparation and application | |
| Li et al. | Acetone fractionation: a simple and efficient method to improve the performance of lignin for dye pollutant removal | |
| Yi et al. | Preparation and adsorption performance of cellulose nanofibrils/polyvinyl alcohol composite gel spheres with millimeter size | |
| CN102337026B (en) | Preparation method of natural plant cellulose-modified PA6 composite material | |
| Li et al. | Preparation of biomass film from waste biomass energy corn stalk under carbon neutralization strategy | |
| Sun et al. | Adsorption efficiency of ordered mesoporous carboxyl-functionalized tube bundles in functional wood toward heavy metal ions: Optimization, performance and chemiluminescence reuse after adsorption | |
| CN105032349A (en) | Asphaltic resin composite spherical activated carbon with expanded graphite enhanced oil absorption property and preparation method therefor | |
| CN102775525A (en) | Preparation method and application of cross-linking type hemicellulose |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200107 |
|
| RJ01 | Rejection of invention patent application after publication |