CN113042008B - Alkali lignin micro/nanosphere/paper-based adsorption material, preparation method thereof and application thereof in treatment of dye wastewater - Google Patents
Alkali lignin micro/nanosphere/paper-based adsorption material, preparation method thereof and application thereof in treatment of dye wastewater Download PDFInfo
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- 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
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- C—CHEMISTRY; METALLURGY
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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
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Abstract
The invention discloses an alkali lignin micro/nanosphere/paper-based adsorption material, a preparation method thereof and application thereof in treating dye wastewater. Firstly, potassium persulfate and ferrous ammonium sulfate are used as initiators to improve the radical activity of alkali lignin; then, stearoyl chloride is used as an esterification reagent, N, N-dimethylformamide is used as a solvent, triethylamine is used as an acid-binding agent and a catalyst, and the acetylation degree of the alkali lignin is controlled by controlling the proportion of the stearoyl chloride to the alkali lignin; then tetrahydrofuran is used as a solvent, cyclohexane is used as an anti-solvent, and the alkali lignin micro/nanospheres are prepared on the filter paper in situ by a self-assembly method. The alkali lignin micro-nanospheres prepared by the invention are micro-nano spherical reverse micelles with hydrophobic surfaces and hydrophilic interiors, can be well dispersed on water or a load material, and are not easy to agglomerate. In addition, the adsorbing material can be made into various shapes, is convenient to use, has high adsorption efficiency, can be recycled and reused, can be used for multiple times and has low cost.
Description
Technical Field
The invention belongs to the technical field of adsorption materials and dye wastewater treatment, and particularly relates to an alkali lignin micro-nanosphere/paper-based adsorption material, a preparation method thereof and application thereof in treating dye wastewater.
Background
The paper making and printing industry emits waste water with high organic pollutant content, deep color and high alkalinity, and how to effectively treat the waste water becomes a great problem and challenge of global attention. Rhodamine B is a heteroaromatic compound which is commonly used for coloring hemp, silk fabrics, cotton cloth, paper, bamboo and wood, and has wide application. The dye wastewater containing rhodamine B has high concentration, deep chromaticity, high toxicity, and great influence on environmental sanitation and human safety, and the pollution caused by the dye wastewater containing rhodamine B becomes a serious environmental problem. The current methods for removing color from dye wastewater mainly comprise the following steps: flocculation sedimentation, ion exchange, membrane separation, chemical oxidation, biodegradation, electrolysis, but these techniques have limited applications due to high cost, low efficiency, or high cost for regeneration after use. Therefore, the invention discloses a simple, economic and environment-friendly adsorbing material, and has very important practical significance in removing rhodamine B in wastewater.
The technical problems to be solved by the invention are as follows:
1. solves the problem of alkali lignin hydrophobic modification
The alkali lignin has a large amount of hydroxyl and phenolic hydroxyl which have strong interaction force and are easy to agglomerate. At present, the hydrophobic modification of alkali lignin is mainly carried out through acetylation modification, pyridine is required to be used as a lignin solvent and an acid applying agent in the method, acetyl chloride or acetyl bromide is used as an acetylation reagent to carry out acetylation on the alkali lignin, but the pyridine is high in toxicity and price and difficult to biodegrade, and the acetyl bromide and the acetyl chloride are strong in corrosivity and harmful to the environment.
2. Solves the problems of uniform shape and dispersibility of the alkali lignin micro-nanospheres.
As is known, lignin is widely present in plant cell walls, is the second natural high molecular compound with the content inferior to that of cellulose in terrestrial plants, is a byproduct of alkaline pulping, contains a hydrophobic skeleton mainly comprising a phenylpropane structural unit and hydrophilic hydroxyl and phenolic hydroxyl in the molecule, is a natural amphiphilic polymer, and can be used for preparing lignin micro/nanospheres by a self-assembly method. However, the alkali lignin has more hydrophilic groups and strong hydrogen bonding capability, so that the prepared micro-nanospheres are not uniform in shape and are not easy to disperse.
At present, the preparation method of the self-assembly of the lignin micro-nanospheres is to dissolve lignin by using solvents such as tetrahydrofuran, dioxane and the like, and then dropwise add an anti-solvent to obtain the lignin micro-nanospheres. However, the solubility of the alkali lignin in tetrahydrofuran is low, the prepared lignin micro-nanospheres are poor in stability and difficult to store, and the shapes are not uniform and the dispersibility is poor, so that the industrial production is not facilitated.
3. Solves the problems of the load of the alkali lignin micro/nanospheres and the repeated use of the adsorption material.
In the prior art, most lignin-based adsorbing materials are prepared by preparing lignin at high temperatureActivated carbon with pores, but in this process, oxygen-containing functional groups originally present in lignin molecules are converted into CO at high temperatures2The content of the functional group playing a role in adsorption on the lignin carbon is reduced, so that the adsorption performance of the lignin porous carbon is limited, and the energy consumption in the preparation process of the lignin porous carbon is high, so that the practical application is hindered.
Most alkali lignin adsorption materials are in a highly aggregated state in an aqueous solution at present, the specific surface area is small, and a large number of adsorbable sites are embedded in lignin and cannot play an adsorption role, so that the adsorption performance is limited, and wastewater cannot be efficiently treated. In addition, the alkali lignin adsorption material prepared in the prior art is difficult to reuse, high in use cost, poor in adsorption effect, short in service life, difficult to recover and the like.
For the above reasons, the present application has been made.
Disclosure of Invention
In view of the problems or defects of the prior art, the invention aims to provide an alkali lignin micro/nanosphere/paper-based adsorption material, a preparation method thereof and application thereof in treating dye wastewater. According to the invention, alkali lignin micro-nanospheres are prepared on filter paper in situ by using stearic acid chloride modified alkali lignin through a self-assembly method, so that the efficient, green and environment-friendly alkali lignin micro-nanosphere/paper-based adsorption material is obtained.
In order to achieve one of the above objects of the present invention, the present invention adopts the following technical solutions:
a preparation method of an alkali lignin micro/nanosphere/paper-based adsorption material comprises the following steps:
(1) and (3) purification: dissolving industrial alkali lignin in an alkaline aqueous solution, fully stirring, carrying out suction filtration, and removing insoluble impurities to obtain a filtrate; then adjusting the pH value of the obtained filtrate to 2-3 to fully separate out alkali lignin; performing suction filtration, washing the obtained filter residue to be neutral, drying to constant weight, and grinding to obtain purified alkali lignin;
(2) and (3) activation: dissolving potassium persulfate and ammonium ferrous sulfate in a proper amount of deionized water to obtain an initiator solution; adding the initiator solution into the purified alkali lignin obtained in the step (1) according to the ratio, heating the obtained mixed solution to 60-80 ℃, stirring at constant temperature, and reacting for 0.5-1.5 h; after the reaction is finished, repeatedly cleaning the product until the obtained cleaning solution is neutral to obtain activated alkali lignin;
(3) modification of stearoyl chloride: sequentially adding N, N-dimethylformamide, triethylamine and stearoyl chloride into the activated alkali lignin obtained in the step (2) according to the proportion to obtain a mixed reaction solution; then heating the mixed reaction liquid to 70-90 ℃ and reacting for 5-20 h at constant temperature; after the reaction is finished, carrying out suction filtration, cleaning and vacuum drying on the obtained product to obtain stearoyl chloride modified alkali lignin; wherein: the cleaning solution for cleaning is n-hexane;
(4) preparing the alkali lignin micro-nanosphere/paper-based adsorption material by solvent-antisolvent self-assembly: dissolving the alkali lignin modified by stearoyl chloride obtained in the step (3) by using tetrahydrofuran, and diluting to obtain an alkali lignin tetrahydrofuran solution modified by stearoyl chloride; then pouring the stearoyl chloride modified alkali lignin tetrahydrofuran solution into a container with filter paper, after the filter paper is completely immersed, dropwise adding cyclohexane into the container, and enabling the alkali lignin micro-nanospheres to generate in-situ in the pores and the surface of the loaded filter paper; and after the dropwise addition of cyclohexane is finished, performing ultrasonic oscillation on the container for 0.5-2 hours at normal temperature and normal pressure, and finally taking out the filter paper and performing vacuum drying to obtain the alkali lignin micro-nanosphere/paper-based adsorbing material.
Further, in the above technical solution, in the step (1), the alkaline aqueous solution is an aqueous sodium hydroxide solution, and the pH of the aqueous sodium hydroxide solution is preferably 11 to 12.
Further, in the technical scheme, in the step (1), the stirring time is preferably 2-3 h.
Further, in the above technical solution, in the step (1), the pH regulator used for regulating the filtrate is preferably a dilute hydrochloric acid aqueous solution, and the concentration of the dilute hydrochloric acid aqueous solution may be 0.5 to 2mol/L, and more preferably 1 mol/L.
Further, in the above technical scheme, in the step (1), the solvent used for washing the filter residue is preferably deionized water.
Further, in the above technical scheme, in the step (2), the mass ratio of the purified alkali lignin to potassium persulfate and ammonium ferrous sulfate is 1: 0.005-0.03: 0.001 to 0.004.
Further, in the above technical scheme, in the step (2), the reaction temperature is preferably 70 ℃, and the reaction time is preferably 1 h.
Further, in the above technical scheme, in the step (2), the cleaning agent for washing the product is deionized water.
Further, in the above technical scheme, in the step (3), the mass ratio of the activated alkali lignin to the stearoyl chloride is 1: 1.5 to 4.5, preferably 1: 3.
further, in the technical scheme, in the step (3), the molar ratio of stearoyl chloride to triethylamine is 2-4: 1, more preferably 3: 1.
further, in the above technical scheme, in the step (3), the usage ratio of the activated alkali lignin to the N, N-dimethylformamide is 1 part by mass: 30 parts by volume, wherein: the mass part and the volume part are as follows: mL was used as a reference.
Further, in the above technical solution, in the step (3), the vacuum drying process is preferably as follows: drying in a vacuum drying oven at 80 ℃ for 24 h.
Further, in the above technical scheme, in the step (4), the concentration of the alkali lignin tetrahydrofuran solution modified by stearoyl chloride is 0.5-2 mg/mL, and more preferably 1 mg/mL.
Further, in the above technical solution, in the step (4), the filter paper may be any one or more of a plant fiber filter paper, a nonwoven filter material, a composite filter material, and the like; the filter paper may be a filter paper with different numbers of layers, such as a single layer filter paper, a double layer filter paper, or a multi-layer filter paper. The filter paper mainly plays a role of loading the lignin micro-nanospheres.
Further, in the above technical scheme, in the step (4), the addition amount of the cyclohexane is 70-90%, and more preferably 80% of the total volume of the alkali lignin tetrahydrofuran solution modified by stearoyl chloride.
Further, in the above technical scheme, in the step (4), the ultrasonic oscillation time is preferably 1h, and the purpose of the ultrasonic oscillation in the step is to make the distribution of the alkali lignin micro/nanospheres more uniform, and at the same time, make the alkali lignin micro/nanospheres and the loaded filter paper become an integrated adsorbing material.
Further, in the above technical solution, in the step (4), the vacuum drying is preferably performed for 12 hours at 80 ℃.
Specifically, in the above technical scheme, in the step (4), the alkali lignin micro/nanosphere/paper-based adsorption material can be processed into various forms, and a single layer, a double layer or a plurality of layers are adopted, that is, different layers are used for different shapes of filtration devices.
The second purpose of the invention is to provide the alkali lignin micro/nanosphere/paper-based adsorption material prepared by the method.
The third purpose of the invention is to provide the application of the alkali lignin micro/nanosphere/paper-based adsorption material prepared by the method in treating dye wastewater, and the alkali lignin micro/nanosphere/paper-based adsorption material can be used for removing dyes in the dye wastewater.
Further, in the above technical solution, the dye is preferably an organic dye, for example, rhodamine B.
The fourth purpose of the invention is to provide an application method of the alkali lignin micro/nanosphere/paper-based adsorption material prepared by the method in treating dye wastewater, which specifically comprises the following steps:
and (2) fixing the dye wastewater in a funnel at the temperature of 25-40 ℃, placing a beaker below the funnel for receiving the filtrate through the alkali lignin micro-nanosphere/paper-based adsorption material prepared by the method, adsorbing the filtrate in the beaker for 1 time, then circularly adsorbing the filtrate for 3-5 times through the adsorption material again, and finally measuring the concentration of the residual dye in the filtrate by using an ultraviolet spectrophotometer.
Further, according to the technical scheme, the dosage ratio of the dye wastewater to the adsorbing material is 1L: 2-5 g.
Further, according to the technical scheme, the concentration of the dye in the dye wastewater is preferably 50-200 mg/L.
Further, according to the technical scheme, the pH value of the dye wastewater is preferably 2-9.
The fifth purpose of the invention is to provide a recycling method of the alkali lignin micro/nanosphere/paper-based adsorption material after adsorbing the dye in the dye wastewater, which comprises the following specific steps:
soaking the alkali lignin micro-nanosphere/paper base adsorbing material adsorbed with the dye in a dilute hydrochloric acid aqueous solution for 1-5 hours, taking out the adsorbing material with a pair of tweezers, repeatedly soaking the adsorbing material in the dilute hydrochloric acid aqueous solution until the dilute hydrochloric acid aqueous solution soaked in the adsorbing material is not red, washing the adsorbing material with deionized water until the filtrate is neutral, and drying to obtain the recyclable alkali lignin micro-nanosphere/paper base adsorbing material.
Further, according to the technical scheme, the concentration of the dilute hydrochloric acid aqueous solution is 0.1-0.5 mol/L.
Further, according to the technical scheme, the soaking times of the adsorbing material are generally 2-5 times.
Further, according to the technical scheme, the baking temperature for drying is 50-80 ℃, and the baking time is 10-40 hours.
The reaction principle and innovation points of the invention are as follows:
according to the invention, alkali lignin micro-nanospheres are prepared on filter paper in situ by using stearic acid chloride modified alkali lignin through a self-assembly method, and the efficient, green and environment-friendly alkali lignin micro-nanosphere/paper-based adsorption material is obtained.
One of the innovation points of the invention is as follows: firstly, potassium persulfate and ferrous ammonium sulfate are used as initiators to improve the radical activity of the alkali lignin, stearoyl chloride is used as an esterification reagent, N, N-dimethylformamide is used as a solvent, triethylamine is used as an acid-binding agent and a catalyst, and the acetylation degree of the alkali lignin is controlled by controlling the proportion of the stearoyl chloride and the alkali lignin. And then, preparing the alkali lignin micro-nanospheres by a self-assembly method by taking tetrahydrofuran as a solvent and cyclohexane as an anti-solvent. In which stearoyl chloride is used as an acetylation reagent instead of acetyl bromide, and triethylamine is used as an acid-binding agent and a catalyst instead of toxic pyridine. According to the solvent-anti-solvent self-assembly method, cyclohexane is adopted to replace water to serve as an anti-solvent, and the prepared alkali lignin micro-nano sphere is a micro-nano spherical anti-micelle with a hydrophobic surface and a hydrophilic interior, can be well dispersed on water or a load material, and is not easy to agglomerate.
The adsorption mechanism of the alkali lignin on the rhodamine B is that a pi-pi hydrophobic bond is formed between hydrophobic groups such as benzene rings, carbonyl groups, ether bonds and the like on the alkali lignin and the rhodamine B, so that the adsorption effect is achieved. Tetrahydrofuran is used as a solvent, cyclohexane is used as an anti-solvent, the alkali lignin micro-nanospheres are prepared by a self-assembly method, the prepared alkali lignin micro-nanospheres are hydrophobic on the surface, and the internal hydrophilic micro-nano spherical micelles can well expose hydrophobic groups on the surface, so that the adsorption effect is improved.
The second innovation point of the invention is that: in the process of self-assembly of the solvent and the anti-solvent, a special loading material is designed, so that the alkali lignin micro-nanospheres are generated in situ in the pores and the surface of the loading material and the filter paper and are uniformly distributed, and the alkali lignin micro-nanospheres and the loading filter paper are integrated into an efficient adsorption material.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method reduces hydroxyl and phenolic hydroxyl on the alkali lignin by chemically modifying the stearoyl chloride. The modified alkali lignin amphiphilic polymer micelle is a micro-nano spherical micelle with hydrophobic surface and hydrophilic interior, can be well dispersed in water or a hydrophilic solution, and is not easy to agglomerate.
(2) According to the method, stearoyl chloride is used as an esterification reagent, N, N-dimethylformamide is used as a solvent, triethylamine is used as an acid-binding agent and a catalyst, and the esterification degree of alkali lignin is controlled by controlling the proportion of stearoyl chloride and alkali lignin. According to the method, stearoyl chloride is used for replacing acetyl bromide to serve as an esterification reagent, triethylamine is used for replacing toxic pyridine to serve as an acid-binding agent and a catalyst, and the contents of hydroxyl and phenolic hydroxyl on alkali lignin can be reduced.
(3) According to the invention, hydroxyl and phenolic hydroxyl on the alkali lignin are reduced by chemical modification of stearoyl chloride, tetrahydrofuran is used as a solvent, cyclohexane is used as an anti-solvent, and the alkali lignin micro-nanospheres are prepared by a self-assembly method.
(4) The invention adopts stearic acyl chloride modified alkali lignin, and the alkali lignin micro-nanospheres are generated in situ in the pores and the surface of the loading material, namely filter paper, by a solvent-anti-solvent self-assembly method.
(5) After the alkali lignin micro/nanosphere/paper-based adsorption material obtained by the invention can be regenerated and utilized for desorbing for 1 time, the adsorption capacity is hardly reduced; after 2 times of desorption, the removal efficiency of rhodamine B can still reach 98 percent; the removal efficiency of rhodamine B can still reach 96% after 3 times of desorption; the removal rate of 3 times of desorption to rhodamine B is up to more than 96 percent.
Drawings
FIG. 1 is a flow chart of the preparation process of the alkali lignin micro-nanosphere/paper-based adsorption material of the invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image of alkali lignin micro-nanospheres in the alkali lignin micro-nanospheres/paper-based adsorbing material prepared in example 1 of the present invention;
FIG. 3 is a Scanning Electron Microscope (SEM) image of the alkali lignin micro/nanosphere/paper-based adsorption material prepared in example 1 of the present invention;
FIG. 4 is an ultraviolet spectrophotometric chart of residual rhodamine B in the filtrate after 20min and 60min of single-layer adsorption material adsorption in application example 1 of the present invention.
Detailed Description
The present invention will be described in further detail below with reference to examples. The present invention is implemented on the premise of the technology of the present invention, and the detailed embodiments and specific procedures are given to illustrate the inventive aspects of the present invention, but the scope of the present invention is not limited to the following embodiments.
Various modifications to the precise description of the invention will be readily apparent to those skilled in the art from the information contained herein without departing from the spirit and scope of the appended claims. It is to be understood that the scope of the invention is not limited to the procedures, properties, or components defined, as these embodiments, as well as others described, are intended to be merely illustrative of particular aspects of the invention. Indeed, various modifications of the embodiments of the invention which are obvious to those skilled in the art or related fields are intended to be covered by the scope of the appended claims.
For a better understanding of the invention, and not as a limitation on the scope thereof, all numbers expressing quantities, percentages, and other numerical values used in this application are to be understood as being modified in all instances by the term "about". At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
The test methods used in the following examples are all conventional methods unless otherwise specified; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from ordinary commercial sources and the like.
Example 1
The preparation method of the alkali lignin micro/nanosphere/paper-based adsorption material of the embodiment specifically comprises the following steps:
(1) and (3) purification: fully dissolving industrial alkali lignin in a sodium hydroxide aqueous solution with the pH value of 12, stirring for 2 hours, performing suction filtration, and removing insoluble impurities; adjusting the pH value of the obtained filtrate to 2 by using a dilute hydrochloric acid aqueous solution with the concentration of 1mol/L to fully separate out alkali lignin; and (3) carrying out suction filtration, washing the obtained filter residue to be neutral by using deionized water, drying the filter residue for 12 hours at the temperature of minus 40 ℃ by using a freeze dryer to constant weight, and grinding to obtain purified alkali lignin of 40-60 mu m.
(2) And (3) activation: dissolving potassium persulfate and ferrous ammonium sulfate in deionized water according to a ratio to obtain an initiator solution; then adding a proper amount of purified alkali lignin obtained in the step (1) into a three-neck flask; adding all the initiator solution into the three-neck flask, heating the obtained mixed solution to 70 ℃, stirring at constant temperature and reacting for 1 h; after the reaction is finished, repeatedly cleaning the product by using deionized water until the obtained cleaning solution is neutral to obtain activated alkali lignin; wherein: the using amount ratio of the purified alkali lignin to the potassium persulfate, the ammonium ferrous sulfate and the deionized water is 1 part by mass: 0.01 parts by mass: 0.001 parts by mass: 40 parts by volume; wherein: the mass part and the volume part are as follows: mL was used as a reference.
(3) Modification of stearoyl chloride: putting the activated alkali lignin obtained in the step (2) into a three-neck flask according to the proportion, and then sequentially adding N, N-dimethylformamide as a solvent, a certain amount of triethylamine as a catalyst, an acid-binding agent and stearoyl chloride to obtain a mixed reaction solution; heating the mixed reaction solution to 90 ℃ for constant-temperature reaction for 7 hours, after the reaction is finished, carrying out suction filtration on the obtained product, cleaning the product with n-hexane, and then placing the product into a vacuum drying oven for constant-temperature drying for 24 hours at the temperature of 80 ℃; obtaining alkali lignin modified by stearoyl chloride; wherein: the mass ratio of the activated alkali lignin to the stearoyl chloride is 1: 3; the molar ratio of stearoyl chloride to triethylamine is 3: 1; the dosage ratio of the activated alkali lignin to the N, N-dimethylformamide is 1 part by mass: 30 parts by volume, wherein: the mass part and the volume part are as follows: mL is taken as a reference;
(4) preparing the alkali lignin micro-nanosphere/paper-based adsorption material by solvent-antisolvent self-assembly: dissolving the stearoyl chloride modified alkali lignin obtained in the step (3) by using tetrahydrofuran, and diluting to obtain a stearoyl chloride modified alkali lignin tetrahydrofuran solution with the concentration of 1 mg/mL; then pouring the alkali lignin tetrahydrofuran solution modified by stearoyl chloride into a container with filter paper, after the filter paper is completely immersed, dropwise adding cyclohexane into the container, and enabling the alkali lignin micro-nanospheres to generate in-situ in pores and surfaces of the loaded filter paper; after the dropwise addition of cyclohexane is finished, performing ultrasonic oscillation on the container for 1h at normal temperature and normal pressure to enable the alkali lignin micro-nanospheres to be distributed more uniformly, enabling the alkali lignin micro-nanospheres and loaded filter paper to be an integrated adsorption material, finally taking out the filter paper, and performing vacuum drying for 12h at the temperature of 80 ℃ to obtain the alkali lignin micro-nanospheres/paper-based adsorption material; wherein: the adding amount of the cyclohexane is 80% of the total volume of the alkali lignin tetrahydrofuran solution modified by the stearoyl chloride; the filter paper is single-layer plant fiber filter paper.
FIG. 2 is a Scanning Electron Microscope (SEM) image of alkali lignin micro-nanospheres in the alkali lignin micro-nanospheres/paper-based adsorbing material prepared in example 1 of the present invention; fig. 3 is a Scanning Electron Microscope (SEM) image of the alkali lignin micro/nanosphere/paper-based adsorption material prepared in example 1 of the present invention. As can be seen from FIG. 2, alkali lignin micro-nanospheres with uniform shapes can be prepared after modification by stearoyl chloride; as can be seen from FIG. 3, the modified alkali lignin can form alkali lignin micro-nanospheres in situ on the plant fiber microporous filter membrane.
Example 2
The preparation method of the alkali lignin micro/nanosphere/paper-based adsorption material of the embodiment specifically comprises the following steps:
(1) and (3) purification: fully dissolving industrial alkali lignin in a sodium hydroxide aqueous solution with the pH value of 12, stirring for 2 hours, performing suction filtration, and removing insoluble impurities; adjusting the pH value of the obtained filtrate to 2 by using a dilute hydrochloric acid aqueous solution with the concentration of 1mol/L to fully separate out alkali lignin; and (3) carrying out suction filtration, washing the obtained filter residue to be neutral by using deionized water, drying the filter residue for 12 hours at the temperature of minus 40 ℃ by using a freeze dryer to constant weight, and grinding to obtain purified alkali lignin of 40-60 mu m.
(2) And (3) activation: dissolving potassium persulfate and ferrous ammonium sulfate in deionized water according to a ratio to obtain an initiator solution; then adding a proper amount of purified alkali lignin obtained in the step (1) into a three-neck flask; adding all the initiator solution into the three-neck flask, heating the obtained mixed solution to 70 ℃, stirring at constant temperature and reacting for 1 h; after the reaction is finished, repeatedly cleaning the product by using deionized water until the obtained cleaning solution is neutral to obtain activated alkali lignin; wherein: the using amount ratio of the purified alkali lignin to the potassium persulfate, the ammonium ferrous sulfate and the deionized water is 1 part by mass: 0.03 parts by mass: 0.003 parts by mass: 40 parts by volume; wherein: the mass portion and the volume portion are as follows: mL was used as a reference.
(3) Modification of stearoyl chloride: putting the activated alkali lignin obtained in the step (2) into a three-neck flask according to the proportion, and then sequentially adding N, N-dimethylformamide serving as a solvent, a certain amount of triethylamine serving as a catalyst, an acid binding agent and stearoyl chloride to obtain a mixed reaction solution; heating the mixed reaction solution to 80 ℃ for constant-temperature reaction for 10 hours, after the reaction is finished, carrying out suction filtration on the obtained product, cleaning the product with n-hexane, and then putting the product into a vacuum drying oven for constant-temperature drying for 24 hours at the temperature of 80 ℃; obtaining alkali lignin modified by stearoyl chloride; wherein: the mass ratio of the activated alkali lignin to the stearoyl chloride is 1: 2; the molar ratio of the stearoyl chloride to the triethylamine is 4: 1; the dosage ratio of the activated alkali lignin to the N, N-dimethylformamide is 1 part by mass: 30 parts by volume, wherein: the mass part and the volume part are as follows: mL is taken as a benchmark;
(4) preparing the alkali lignin micro-nanosphere/paper-based adsorption material by solvent-antisolvent self-assembly: dissolving the alkali lignin modified by stearoyl chloride obtained in the step (3) by using tetrahydrofuran, and diluting to obtain an alkali lignin tetrahydrofuran solution modified by stearoyl chloride with the concentration of 1 mg/mL; then pouring the stearoyl chloride modified alkali lignin tetrahydrofuran solution into a container with filter paper, after the filter paper is completely immersed, dropwise adding cyclohexane into the container, and enabling the alkali lignin micro-nanospheres to generate in-situ in the pores and the surface of the loaded filter paper; after the dropwise addition of cyclohexane is finished, performing ultrasonic oscillation on the container for 1h at normal temperature and normal pressure to enable the alkali lignin micro-nanospheres to be distributed more uniformly, enabling the alkali lignin micro-nanospheres and loaded filter paper to be an integrated adsorption material, finally taking out the filter paper, and performing vacuum drying for 12h at the temperature of 80 ℃ to obtain the alkali lignin micro-nanospheres/paper-based adsorption material; wherein: the addition amount of the cyclohexane is 80 percent of the total volume of the alkali lignin tetrahydrofuran solution modified by the stearoyl chloride; the filter paper is three layers of plant fiber filter paper.
Example 3
The preparation method of the alkali lignin micro/nanosphere/paper-based adsorption material of the embodiment specifically comprises the following steps:
(1) and (3) purification: fully dissolving industrial alkali lignin in a sodium hydroxide aqueous solution with the pH value of 11, stirring for 3 hours, performing suction filtration, and removing insoluble impurities; adjusting the pH value of the obtained filtrate to 2.5 by using a dilute hydrochloric acid aqueous solution with the concentration of 2mol/L to fully separate out alkali lignin; and (3) carrying out suction filtration, washing the obtained filter residue to be neutral by using deionized water, drying the filter residue for 12 hours at the temperature of minus 40 ℃ by using a freeze dryer to constant weight, and grinding to obtain purified alkali lignin of 40-60 mu m.
(2) And (3) activation: dissolving potassium persulfate and ferrous ammonium sulfate in deionized water according to a ratio to obtain an initiator solution; then adding a proper amount of purified alkali lignin obtained in the step (1) into a three-neck flask; then adding all the initiator solution into the three-neck flask, heating the obtained mixed solution to 60 ℃, stirring at constant temperature and reacting for 1.5 h; after the reaction is finished, repeatedly cleaning the product by using deionized water until the obtained cleaning solution is neutral to obtain activated alkali lignin; wherein: the using amount ratio of the purified alkali lignin to the potassium persulfate, the ammonium ferrous sulfate and the deionized water is 1 part by mass: 0.01 parts by mass: 0.004 parts by mass: 40 parts by volume; wherein: the mass part and the volume part are as follows: mL was used as a reference.
(3) Modification of stearoyl chloride: putting the activated alkali lignin obtained in the step (2) into a three-neck flask according to the proportion, and then sequentially adding N, N-dimethylformamide as a solvent, a certain amount of triethylamine as a catalyst, an acid-binding agent and stearoyl chloride to obtain a mixed reaction solution; heating the mixed reaction solution to 70 ℃ for constant-temperature reaction for 20 hours, after the reaction is finished, carrying out suction filtration on the obtained product, cleaning the product with n-hexane, and then putting the product into a vacuum drying oven for constant-temperature drying for 24 hours at the temperature of 80 ℃; obtaining alkali lignin modified by stearoyl chloride; wherein: the mass ratio of the activated alkali lignin to the stearoyl chloride is 1: 1.5; the molar ratio of the stearoyl chloride to the triethylamine is 2: 1; the dosage ratio of the activated alkali lignin to the N, N-dimethylformamide is 1 part by mass: 30 parts by volume, wherein: the mass part and the volume part are as follows: mL is taken as a benchmark;
(4) preparing the alkali lignin micro-nanosphere/paper-based adsorption material by solvent-antisolvent self-assembly: dissolving the stearoyl chloride modified alkali lignin obtained in the step (3) by using tetrahydrofuran, and diluting to obtain a stearoyl chloride modified alkali lignin tetrahydrofuran solution with the concentration of 0.5 mg/mL; then pouring the stearoyl chloride modified alkali lignin tetrahydrofuran solution into a container with filter paper, after the filter paper is completely immersed, dropwise adding cyclohexane into the container, and enabling the alkali lignin micro-nanospheres to generate in-situ in the pores and the surface of the loaded filter paper; after the dropwise addition of cyclohexane is finished, performing ultrasonic oscillation on the container for 0.5h at normal temperature and normal pressure to enable the alkali lignin micro-nanospheres to be distributed more uniformly, enabling the alkali lignin micro-nanospheres and the loaded filter paper to form an integrated adsorption material, finally taking out the filter paper, and performing vacuum drying for 12h at 80 ℃ to obtain the alkali lignin micro-nanospheres/paper-based adsorption material; wherein: the addition amount of the cyclohexane is 70% of the total volume of the alkali lignin tetrahydrofuran solution modified by the stearoyl chloride; the filter paper is double-layer plant fiber filter paper.
Example 4
The preparation method of the alkali lignin micro/nanosphere/paper-based adsorption material of the embodiment specifically comprises the following steps:
(1) and (3) purification: fully dissolving industrial alkali lignin in a sodium hydroxide aqueous solution with the pH value of 12, stirring for 2 hours, performing suction filtration, and removing insoluble impurities; adjusting the pH value of the obtained filtrate to 3 by using a dilute hydrochloric acid aqueous solution with the concentration of 0.5mol/L to fully separate out alkali lignin; and (3) carrying out suction filtration, washing the obtained filter residue to be neutral by using deionized water, drying the filter residue for 12 hours at the temperature of minus 40 ℃ by using a freeze dryer to constant weight, and grinding to obtain purified alkali lignin of 40-60 mu m.
(2) And (3) activation: dissolving potassium persulfate and ferrous ammonium sulfate in deionized water according to a ratio to obtain an initiator solution; then adding a proper amount of purified alkali lignin obtained in the step (1) into a three-neck flask; then adding all the initiator solution into the three-neck flask, heating the obtained mixed solution to 80 ℃, stirring at constant temperature and reacting for 0.5 h; after the reaction is finished, repeatedly cleaning the product by using deionized water until the obtained cleaning solution is neutral to obtain activated alkali lignin; wherein: the using amount ratio of the purified alkali lignin to the potassium persulfate, the ammonium ferrous sulfate and the deionized water is 1 part by mass: 0.005 parts by mass: 0.001 parts by mass: 40 parts by volume; wherein: the mass part and the volume part are as follows: mL was used as a reference.
(3) Modification of stearoyl chloride: putting the activated alkali lignin obtained in the step (2) into a three-neck flask according to the proportion, and then sequentially adding N, N-dimethylformamide as a solvent, a certain amount of triethylamine as a catalyst, an acid-binding agent and stearoyl chloride to obtain a mixed reaction solution; heating the mixed reaction solution to 90 ℃ for constant-temperature reaction for 7 hours, after the reaction is finished, carrying out suction filtration on the obtained product, cleaning the product with n-hexane, and then putting the product into a vacuum drying oven for constant-temperature drying for 24 hours at the temperature of 80 ℃; obtaining alkali lignin modified by stearoyl chloride; wherein: the mass ratio of the activated alkali lignin to the stearoyl chloride is 1: 4.5; the molar ratio of stearoyl chloride to triethylamine is 4: 1; the dosage ratio of the activated alkali lignin to the N, N-dimethylformamide is 1 part by mass: 30 parts by volume, wherein: the mass part and the volume part are as follows: mL is taken as a benchmark;
(4) preparing the alkali lignin micro-nanosphere/paper-based adsorption material by solvent-antisolvent self-assembly: dissolving the stearoyl chloride modified alkali lignin obtained in the step (3) by using tetrahydrofuran, and diluting to obtain a stearoyl chloride modified alkali lignin tetrahydrofuran solution with the concentration of 2 mg/mL; then pouring the stearoyl chloride modified alkali lignin tetrahydrofuran solution into a container with filter paper, after the filter paper is completely immersed, dropwise adding cyclohexane into the container, and enabling the alkali lignin micro-nanospheres to generate in-situ in the pores and the surface of the loaded filter paper; after the dropwise addition of cyclohexane is finished, performing ultrasonic oscillation on the container for 2 hours at normal temperature and normal pressure to enable the alkali lignin micro-nanospheres to be distributed more uniformly, enabling the alkali lignin micro-nanospheres and loaded filter paper to be an integrated adsorption material, finally taking out the filter paper, and performing vacuum drying for 12 hours at the temperature of 80 ℃ to obtain the alkali lignin micro-nanospheres/paper-based adsorption material; wherein: the adding amount of the cyclohexane is 90% of the total volume of the alkali lignin tetrahydrofuran solution modified by the stearoyl chloride; the filter paper is double-layer plant fiber filter paper.
Example 5
The preparation method of the alkali lignin micro/nanosphere/paper-based adsorption material of the present embodiment is substantially the same as that of example 1, except that: the mass ratio of the activated alkali lignin to the stearoyl chloride in the step (3) is 1: 1.5.
example 6
The preparation method of the alkali lignin micro/nanosphere/paper-based adsorption material of the present embodiment is substantially the same as that of example 1, except that: the mass ratio of the activated alkali lignin to the stearoyl chloride in the step (3) is 1: 4.5.
example 7
The preparation method of the alkali lignin micro/nanosphere/paper-based adsorption material of the present embodiment is substantially the same as that of embodiment 2, except that: the mass ratio of the activated alkali lignin to the stearoyl chloride in the step (3) is 1: 1.5.
example 8
The preparation method of the alkali lignin micro/nanosphere/paper-based adsorption material of the present embodiment is substantially the same as that of embodiment 2, except that: the mass ratio of the activated alkali lignin to the stearoyl chloride in the step (3) is 1: 3.
example 9
The preparation method of the alkali lignin micro/nanosphere/paper-based adsorption material of the present embodiment is substantially the same as that of embodiment 2, except that: the mass ratio of the activated alkali lignin to the stearoyl chloride in the step (3) is 1: 4.5.
application example 1
The application method of the alkali lignin micro/nanosphere/paper-based adsorption material in the application embodiment in treating the rhodamine B-containing wastewater specifically comprises the following steps:
dissolving 100mg of rhodamine B in 1L of deionized water to prepare 100mg/L rhodamine B aqueous solution; taking 50mL of the rhodamine B aqueous solution, adjusting the pH value to be 6, heating to 40 ℃, then fixing 0.1g of the alkali lignin micro-nanosphere/paper-based adsorption material prepared by the method in the embodiment 1 in a funnel, placing a beaker below the funnel for receiving filtrate, after 1-time adsorption, enabling the filtrate in the beaker to pass through the adsorption material again, circularly adsorbing for 3 times, and finally measuring the concentration of the residual rhodamine B dye in the filtrate by using an ultraviolet spectrophotometer.
Tests show that the rhodamine B water solution can adsorb more than 65 percent of rhodamine B within 20min of circulating through the adsorbing material, and the adsorption rate is very quick within 60 min. The decolouring rate of rhodamine B can reach 96.46 mg/g.
Application example 2
The application method of the alkali lignin micro/nanosphere/paper-based adsorption material in the application embodiment in treating the rhodamine B-containing wastewater specifically comprises the following steps:
dissolving 100mg of rhodamine B in 1L of deionized water to prepare 100mg/L rhodamine B aqueous solution; taking 50mL of the rhodamine B aqueous solution, adjusting the pH value to 6, heating to 40 ℃, then fixing 0.15g of the alkali lignin micro-nanosphere/paper-based adsorption material prepared by the method in the embodiment 2 in a funnel, placing a beaker below the funnel for receiving the filtrate, after 1-time adsorption, enabling the filtrate in the beaker to pass through the adsorption material again, circularly adsorbing for 3 times, and finally measuring the concentration of the residual dye in the filtrate by using an ultraviolet spectrophotometer.
Tests prove that the rhodamine B water solution can adsorb more than 76.2 percent of rhodamine B within 20min after circulating through the adsorbing material, the adsorption rate is very quick within 60min, and the decoloring rate of the rhodamine B can reach 98.37 mg/g.
Application example 3
The recycling method of the alkali lignin micro/nanosphere/paper-based adsorption material in the application example 1 comprises the following steps:
soaking the alkali lignin micro-nanosphere/paper-based adsorption material saturated and adsorbing rhodamine B in the application example 1 in a 0.2mol/L diluted hydrochloric acid aqueous solution for 1h, and taking out the adsorption material by using tweezers; soaking the substrate for 1 hour by using dilute hydrochloric acid aqueous solution with the same concentration, repeatedly soaking for 3 times until the dilute hydrochloric acid aqueous solution soaked with the adsorption material does not turn red, washing the adsorption material by using deionized water until filtrate is neutral, and drying to obtain the recyclable alkali lignin micro/nano sphere/paper-based adsorption material; wherein: the baking temperature for drying is 80 ℃, and the baking time is 10 hours.
Tests show that the adsorption capacity of the adsorption material desorbed for 1 time in the application example is hardly reduced; the adsorbing material after desorbing for 2 times still has the rhodamine B removing efficiency of 98 percent; the removal efficiency of the adsorbing material after desorbing for 3 times on rhodamine B can still reach 96%. The removal rate of 3 times of desorption of rhodamine B is up to more than 96 percent.
Application example 4
The recycling method of the alkali lignin micro/nanosphere/paper-based adsorption material in the application example 2 comprises the following steps:
soaking the alkali lignin micro/nanosphere/paper-based adsorption material saturated and adsorbed with rhodamine B in the application example 1 for 1h by using a dilute hydrochloric acid aqueous solution with the concentration of 0.2mol/L, and taking out the adsorption material by using tweezers; soaking the substrate for 1 hour by using dilute hydrochloric acid aqueous solution with the same concentration, repeatedly soaking for 3 times until the dilute hydrochloric acid aqueous solution soaked with the adsorption material does not turn red, washing the adsorption material by using deionized water until filtrate is neutral, and drying to obtain the recyclable alkali lignin micro/nano sphere/paper-based adsorption material; wherein: the baking temperature for drying is 80 ℃, and the baking time is 15 h.
Tests show that the adsorption capacity of the adsorption material desorbed for 1 time in the application example is hardly reduced; the adsorbing material after desorbing for 2 times still has the rhodamine B removing efficiency of 98.6 percent; the removal efficiency of the adsorbing material after desorbing for 3 times on rhodamine B can still reach 97 percent. The removal rate of 3 times of desorption of rhodamine B is as high as more than 97 percent.
Claims (8)
1. A preparation method of an alkali lignin micro/nanosphere/paper-based adsorption material is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) and (3) purification: dissolving industrial alkali lignin in an alkaline aqueous solution, fully stirring, carrying out suction filtration, and removing insoluble impurities to obtain a filtrate; then adjusting the pH value of the obtained filtrate to 2-3 to fully separate out alkali lignin; performing suction filtration, washing the obtained filter residue to be neutral, drying to constant weight, and grinding to obtain purified alkali lignin;
(2) and (3) activation: dissolving potassium persulfate and ammonium ferrous sulfate in a proper amount of deionized water to obtain an initiator solution; adding the initiator solution into the purified alkali lignin obtained in the step (1) according to the ratio, heating the obtained mixed solution to 60-80 ℃, stirring at constant temperature, and reacting for 0.5-1.5 h; after the reaction is finished, repeatedly cleaning the product until the obtained cleaning solution is neutral to obtain activated alkali lignin; the mass ratio of the purified alkali lignin to the potassium persulfate and the ammonium ferrous sulfate is 1: 0.005-0.03: 0.001 to 0.004;
(3) modification of stearoyl chloride: sequentially adding N, N-dimethylformamide, triethylamine and stearoyl chloride into the activated alkali lignin obtained in the step (2) according to the proportion to obtain a mixed reaction solution; then heating the mixed reaction liquid to 70-90 ℃ and reacting for 5-20 h at constant temperature; after the reaction is finished, carrying out suction filtration, cleaning and vacuum drying on the obtained product to obtain stearoyl chloride modified alkali lignin; wherein: the cleaning solution for cleaning is n-hexane; the mass ratio of the activated alkali lignin to the stearoyl chloride is 1: 1.5 to 4.5; the molar ratio of stearoyl chloride to triethylamine is 2-4: 1;
(4) preparing the alkali lignin micro-nanosphere/paper-based adsorption material by solvent-antisolvent self-assembly: dissolving the alkali lignin modified by stearoyl chloride obtained in the step (3) by using tetrahydrofuran, and diluting to obtain an alkali lignin tetrahydrofuran solution modified by stearoyl chloride; then pouring the stearoyl chloride modified alkali lignin tetrahydrofuran solution into a container with filter paper, after the filter paper is completely immersed, dropwise adding cyclohexane into the container, and enabling the alkali lignin micro-nanospheres to generate in-situ in the pores and the surface of the loaded filter paper; and after the dropwise addition of cyclohexane is finished, ultrasonically oscillating the container at normal temperature and normal pressure for 0.5-2 h, finally taking out the filter paper, and drying in vacuum to obtain the alkali lignin micro/nanosphere/paper-based adsorbing material.
2. The preparation method of the alkali lignin micro/nanosphere/paper-based adsorption material according to claim 1, characterized in that: the filter paper is any one or more of plant fiber filter paper, non-woven filter material and composite filter material.
3. The preparation method of the alkali lignin micro/nanosphere/paper-based adsorption material according to claim 1, characterized in that: in the step (4), the addition amount of the cyclohexane is 70-90% of the total volume of the alkali lignin tetrahydrofuran solution modified by stearoyl chloride.
4. The alkali lignin micro-nanosphere/paper-based adsorption material prepared by the preparation method of the alkali lignin micro-nanosphere/paper-based adsorption material according to any one of claims 1 to 3.
5. The application of the alkali lignin micro/nanosphere/paper-based adsorption material prepared by the method of any one of claims 1 to 3 in treatment of dye wastewater.
6. The application method of the alkali lignin micro/nanosphere/paper-based adsorption material prepared by the method of any one of claims 1-3 in dye wastewater treatment is characterized in that: the method specifically comprises the following steps:
and (2) fixing the dye wastewater in a funnel at the temperature of 25-40 ℃, placing a beaker below the funnel for receiving the filtrate through the alkali lignin micro-nanosphere/paper-based adsorption material prepared by the method, adsorbing the filtrate in the beaker for 1 time, then circularly adsorbing the filtrate for 3-5 times through the adsorption material again, and finally measuring the concentration of the residual dye in the filtrate by using an ultraviolet spectrophotometer.
7. The application method of the alkali lignin micro/nanosphere/paper-based adsorption material in the treatment of dye wastewater according to claim 6, wherein the method comprises the following steps: the concentration of the dye in the dye wastewater is 50-200 mg/L; the pH value of the dye wastewater is 2-9.
8. The recycling method of the alkali lignin micro/nanosphere/paper-based adsorption material prepared by any one of claims 1 to 3 after adsorbing the dye in the dye wastewater is characterized in that: the method specifically comprises the following steps:
soaking the alkali lignin micro-nanosphere/paper base adsorbing material adsorbed with the dye in a dilute hydrochloric acid aqueous solution for 1-5 hours, taking out the adsorbing material with a pair of tweezers, repeatedly soaking the adsorbing material in the dilute hydrochloric acid aqueous solution until the dilute hydrochloric acid aqueous solution soaked in the adsorbing material is not red, washing the adsorbing material with deionized water until the filtrate is neutral, and drying to obtain the recyclable alkali lignin micro-nanosphere/paper base adsorbing material.
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