CN114733493A - Heavy metal ion adsorption material and application thereof in water body cleaning field - Google Patents

Heavy metal ion adsorption material and application thereof in water body cleaning field Download PDF

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Publication number
CN114733493A
CN114733493A CN202210447056.6A CN202210447056A CN114733493A CN 114733493 A CN114733493 A CN 114733493A CN 202210447056 A CN202210447056 A CN 202210447056A CN 114733493 A CN114733493 A CN 114733493A
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lignin
phenolization
heavy metal
metal ion
modification
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刘钦泽
张宗英
姚金水
乔从德
李仲伟
张长斌
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Qilu University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—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
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Water Treatment By Sorption (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention relates to a heavy metal ion adsorption material and application thereof in the field of water body cleaning. The invention firstly provides a lignin phenolization modification method: pyrogallic acid is adopted as a phenolization reagent to react under an acidic condition to obtain phenolized lignin. The phenolization modification method provided by the invention can effectively reduce the dosage of toxic reagents and can obtain products with more abundant phenolic hydroxyl sites. And after phenolization modification, the lignin is further subjected to Michael addition reaction with a polyamine substance to prepare the polyphenylamine modified lignin, and meanwhile, the polyphenylamine modified lignin is rich in phenolic hydroxyl groups and amino active groups, so that the adsorption of heavy metal ions is facilitated. The heavy metal ion adsorption material prepared based on the polyphenol amine lignin is simple to prepare, stable in performance and low in cost, the reaction activity of the lignin is increased through phenolization modification, the utilization of the lignin is increased, and the application of the heavy metal ion adsorption material in the field of water pollution treatment is promoted through improving the activity of phenolic hydroxyl.

Description

Heavy metal ion adsorption material and application thereof in water body cleaning field
Technical Field
The invention belongs to the technical field of lignin modification, and particularly relates to a method for modifying lignin by using polyphenylamine, polyphenylamine-modified lignin prepared by the method, a heavy metal ion adsorption material and application of the adsorption material in the field of water body cleaning.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The lignin is used as a natural polymer with abundant reserves in nature, has wide sources, and is a renewable chemical raw material which is inexhaustible and has good renewability. For example, lignin extracted from byproducts of the pulping and papermaking industry generally exists in the form of lignin, has a molecular weight of hundreds to millions, has remarkable dispersibility and good physicochemical properties, and can be used for removing heavy metal ions, dyes and organic pollutants.
Because the active sites of the lignin are few, the value of the lignin directly used as an adsorbent is not high. However, the phenolic hydroxyl group of lignin and the active hydrogen atom adjacent to the phenolic hydroxyl group are easy to generate chemical reaction, and a functional group with adsorption performance can be introduced through the chemical reaction, so that the lignin is endowed with excellent performance. Therefore, chemical modification (such as oxidation, sulfomethylation, alkylation, etc.) of lignin to obtain lignin-based adsorption material with high performance has become a research focus in recent years. In one improvement direction, alkali lignin is used as a raw material and reacts with amine substances (such as triethylene tetramine, diethanol amine and L-asparagine) respectively to generate the amine lignin, so that the adsorption capacity can be effectively improved. In the modification process, the phenolization of the lignin is beneficial to increasing the content of phenolic hydroxyl in the lignin, reducing the molecular weight of the lignin, improving the water solubility of the lignin and providing more abundant reaction sites for the modification of a subsequent structure. After phenolization modification, the lignin is further subjected to Michael addition reaction with a polyamine substance to prepare polyphenylamine-modified lignin, and the polyphenylamine-modified lignin is rich in phenolic hydroxyl groups and amino active groups, so that adsorption of heavy metal ions is facilitated.
The inventors believe that the current phenolization modification of lignin also has the following problems:
1. in the existing lignin modification method, phenol is mainly used for phenolization modification of lignin, and the introduced radical active groups are relatively less.
2. In the existing lignin modification methods, the amount of lignin used is relatively small and usually requires reaction under heating conditions.
Disclosure of Invention
In view of the above problems in the prior art, the present invention provides a method for phenolizing lignin, which comprises using pyrogallic acid as a phenolizing reagent. Pyrogallic acid is a multi-substituted aryl compound, contains a large amount of phenolic hydroxyl, and is used for phenolization modification of lignin, so that the content of the phenolic hydroxyl of the lignin is increased, and the active sites of the lignin are increased. And after phenolization modification, the lignin is further subjected to Michael addition reaction with a polyamine substance to prepare the polyphenylamine modified lignin, and meanwhile, the polyphenylamine modified lignin is rich in phenolic hydroxyl groups and amino active groups, so that the adsorption of heavy metal ions is facilitated.
Based on the research results, the invention firstly provides a phenolic lignin-based method for modifying lignin by using polyphenylamine, and the polyphenylamine modified lignin prepared by the modification method. The modification method provided by the invention is simple and easy to implement, the preparation process can be carried out at room temperature, and industrial scale-up production is easy to realize.
The method increases the number of phenolic hydroxyl active sites in the polyphenylamine modified lignin, and is beneficial to improving the dissolving effect of the lignin in a water environment, thereby improving the adsorption effect. Furthermore, the invention also introduces amino through further reaction on the basis of the lignin phenolate to prepare a novel adsorbing material containing a large number of active groups, and the adsorbing material shows good adsorption performance on heavy metal ions. Not only improves the application performance of the lignin, but also has wide application performance in the field of sewage treatment. Therefore, the invention also provides the heavy metal ion adsorption material and a preparation method thereof.
Compared with unmodified lignin, the heavy metal ion adsorption material has a good adsorption effect, has a good adsorption effect on various metal ions, and is particularly suitable for treatment of industrial dye sewage. The heavy metal ion adsorption material also has the characteristic of good stability, and can be conveniently recycled and reused from water. In addition, the heavy metal adsorption material has a more sensitive adsorption effect under an acidic condition (pH 1-4), and is more convenient to apply when being applied to treatment of acidic heavy metal ion industrial wastewater, such as treatment of chromium electroplating industrial wastewater and mining wastewater.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 shows the results of the adsorption test of the heavy metal ion adsorption material for chromium electroplating actual wastewater in example 1.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As introduced in the background art, lignin phenolization modification in the prior art also has the defect of low phenolic hydroxyl linking efficiency, and in order to solve the technical problems, the invention provides a lignin phenolization modification method, pyrogallic acid is used as a phenolization reagent, and phenolization preparation of lignin can be realized by a simple and convenient mode.
In a first aspect of the present invention, there is provided a lignin phenolization modification method, comprising the steps of: mixing lignin and pyrogallic acid, and adding acid solution for phenolization reaction.
Preferably, the lignin is an alkali lignin or lignosulfonate.
Preferably, the mass ratio of the lignin to the pyrogallic acid is 1: 0.05-20.
Preferably, the lignin and pyrogallic acid are mixed with an organic solvent, and the organic solvent is an organic solvent which can satisfy the dissolution of the above components and has a lower boiling point, including but not limited to acetone.
Further, the organic solvent is acetone, and the specific mixing mode is as follows: adding lignin and pyrogallic acid into acetone, mixing, and removing solvent; the solvent is removed by means including but not limited to evaporation, evaporation to dryness or rotary evaporation.
Preferably, the acid solution is a sulfuric acid solution, the concentration of the sulfuric acid solution is 50-95% (wt%), and further the concentration of the sulfuric acid solution is 68-75% (wt%); the addition amount of the sulfuric acid solution is 50-1000% of the mass of the lignin.
In one embodiment of the above preferred embodiment, the lignin phenolization modification method specifically comprises the steps of:
adding a certain amount of lignin and pyrogallic acid into acetone, stirring at room temperature to uniformly mix, removing the acetone by rotary evaporation to obtain a mixture of the lignin and the pyrogallic acid, slowly dropwise adding a sulfuric acid solution into the mixture to react at room temperature for 5-7 h, and removing sulfuric acid in a reaction system by dialysis after the reaction is finished to obtain the phenolated lignin.
In a second aspect of the present invention, there is provided phenolized lignin modified by the lignin phenolization process of the first aspect.
In a third aspect of the present invention, there is provided a method for producing a heavy metal ion adsorbing material, comprising adding a diamine or polyamine to the phenolated lignin of the second aspect to perform amination.
Preferably, the diamine contains-NH2-(CH2)n-NH2-, where n is 2 to 12; further, the diamine is one of ethylenediamine or hexamethylenediamine.
Furthermore, the molar ratio of the pyrogallic acid to the diamine is 1: 0.01-5.
Preferably, the polyamine is one or a combination of diethylenetriamine, triethylene tetramine and tetraethylene pentamine; the molar ratio of the pyrogallic acid to the polyamine is 1: 0.05-10.
In an embodiment of the above preferred technical solution, the preparation method of the heavy metal ion adsorption material is as follows: and (3) adding polyamine or diamine dropwise into the phenolated lignin solution, and stirring and reacting for 40-50 h at room temperature.
The invention provides a heavy metal ion adsorbing material prepared by the preparation method of the third party.
In a fifth aspect of the invention, an application of the heavy metal ion adsorbing material in the fourth aspect in the field of water body cleaning is provided.
The application of the field of water body cleaning is mainly applied to the adsorption of heavy metal ions in water bodies, wherein the heavy metal ions include but are not limited to Cr (VI), Fe (III), Cu (II) and Pb (II), and the adsorption material has a more remarkable adsorption effect on Cr (VI).
Preferably, the industrial wastewater is acidic industrial wastewater, and the pH value is 1-4.
The application form of the heavy metal adsorption material comprises the preparation of a sewage treatment agent, and the heavy metal adsorption material can also be combined with other active ingredients with sewage treatment effects to prepare the sewage treatment agent.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1
4.15g of lignin and 0.83g of pyrogallic acid were weighed into a single-neck flask, 20ml of acetone was added and stirred magnetically for 10min to mix well. Acetone was then removed by rotary evaporation, after which 10ml of 72% H was slowly added dropwise to the flask2SO4After reacting for 6H at room temperature, removing H by dialysis2SO4To obtain phenolated lignin. And finally, 0.83g of tetraethylenepentamine is dripped into the phenolated lignin liquid, stirred for 48 hours at room temperature, washed by deionized water, and freeze-dried.
The adsorption amount of the heavy metal ion adsorption material prepared by the method on Cr (VI) is 355 mg/g. The amount of adsorption of other metal ions such as Fe (III) was 26 mg/g.
In this example, the heavy metal ion adsorbing material was used in the adsorption test of real wastewater from chromium electroplating, in which 0.025g of the adsorbing material was put into 100mL of wastewater for adsorption for 6 hours. The test results are shown in fig. 1, and it can be seen that under the acidic pH condition, the chromium ions in the wastewater have more sufficient adsorption effect.
Example 2
3.33g of lignin and 1.66g of pyrogallic acid were weighed into a single-neck flask, 20ml of acetone was added and stirred magnetically for 10min to mix well. Acetone was then removed by rotary evaporation, after which 10ml of 72% H was slowly added dropwise to the flask2SO4After reacting for 6H at room temperature, removing H by dialysis2SO4To obtain phenolated lignin. And finally, 0.83g of tetraethylenepentamine is dripped into the phenolated lignin liquid, stirred for 48 hours at room temperature, washed by deionized water, and freeze-dried.
The adsorption quantity of the heavy metal ion adsorption material prepared by the method on Cr (VI) is 426 mg/g. The adsorption capacity to other metal ions such as Cu (II) is about 23 mg/g. Compared with the lignin subjected to modification treatment (Cr (VI) adsorption amount is 241mg/g), the adsorption amount is greatly improved.
Example 3
2.5g of lignin and 2.5g of pyrogallic acid were weighed into a single-neck flask, 20ml of acetone was added and stirred magnetically for 10min to mix well. Acetone was then removed by rotary evaporation, and 10ml of 72% H was slowly added dropwise to the flask2SO4After reacting for 6H at room temperature, removing H by dialysis2SO4To obtain phenolated lignin. Finally, 2g of tetraethylenepentamine is dripped into the phenolated lignin liquid, stirred for 48 hours at room temperature, washed by deionized water and freeze-dried.
The adsorption amount of the heavy metal ion adsorption material prepared by the method on Cr (VI) is 445 mg/g. The amount of adsorption of other metal ions such as Fe (III) was 28 mg/g. Compared with the lignin subjected to modification treatment (Cr (VI) adsorption amount is 241mg/g), the adsorption amount is greatly improved.
Example 4
2.5g of lignin and 2.5g of pyrogallic acid were weighed into a single-neck flask, 20ml of acetone was added and stirred magnetically for 10min to mix well. Acetone was then removed by rotary evaporation, after which 10ml of 72% H was slowly added dropwise to the flask2SO4After reacting for 6H at room temperature, removing H by dialysis2SO4To obtain phenolated lignin. Finally, 1.5g of tetraethylenepentamine is dripped into the phenolated lignin liquid, mechanically stirred for 48 hours at room temperature, washed by deionized water and freeze-dried.
The adsorption amount of the heavy metal ion adsorption material prepared by the method on Cr (VI) is 436 mg/g. The amount adsorbed on other metal ions such as Pb (II) was 16 mg/g.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A lignin phenolization modification method, characterized in that the modification method comprises the following steps: mixing lignin and pyrogallic acid, and adding acid solution for phenolization reaction.
2. The method for phenolization modification of lignin according to claim 1, wherein said lignin is an alkali lignin or a lignosulfonate.
3. The method for phenolization modification of lignin according to claim 1, wherein the mass ratio of lignin to pyrogallic acid is 1:0.05 to 20.
4. The method for modifying lignin phenolization according to claim 1, wherein the lignin and pyrogallic acid are mixed with the aid of an organic solvent, the organic solvent is acetone, and the mixing method is as follows: adding lignin and pyrogallic acid into acetone, mixing, and removing solvent; the solvent is removed by evaporation, evaporation or rotary evaporation.
5. The method for modifying lignin phenolization according to claim 1, wherein the acid solution is a sulfuric acid solution, and the concentration of the sulfuric acid solution is 50% to 95%; the addition amount of the sulfuric acid solution is 50-1000% of the mass of the lignin.
6. The method for phenolization modification of lignin according to claim 4 or 5, wherein the specific steps of the method for phenolization of lignin are as follows:
adding a certain amount of lignin and pyrogallic acid into acetone, stirring at room temperature to uniformly mix, removing the acetone by rotary evaporation to obtain a mixture of the lignin and the pyrogallic acid, slowly dropwise adding a sulfuric acid solution into the mixture to react at room temperature for 5-7 h, and removing sulfuric acid in a reaction system by dialysis after the reaction is finished to obtain the phenolated lignin.
7. Phenolized lignin modified by the lignin phenolization process according to any one of claims 1 to 6.
8. A method for producing a heavy metal ion-adsorbing material, which comprises adding a diamine or polyamine to the phenolated lignin of claim 7 to conduct amination; the diamine contains-NH2-(CH2)n-NH2-, where n is 2 to 12; the molar ratio of the pyrogallic acid to the diamine is 1: 0.01-5.
The polyamine is one or the combination of diethylenetriamine, triethylene tetramine and tetraethylene pentamine; the molar ratio of the pyrogallic acid to the polyamine is 1: 0.05-10.
9. The heavy metal ion adsorption material prepared by the preparation method of claim 8.
10. The application of the heavy metal ion adsorption material of claim 9 in the field of water body cleaning.
CN202210447056.6A 2022-04-26 2022-04-26 Heavy metal ion adsorption material and application thereof in water body cleaning field Pending CN114733493A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006077152A (en) * 2004-09-10 2006-03-23 Kinousei Mokushitsu Shinsozai Gijutsu Kenkyu Kumiai Manufacturing method for phenol derivative of lignin
CN104974355A (en) * 2015-07-27 2015-10-14 华南理工大学 pH-responsive amino sodium lignosulphonate as well as preparation method and application thereof
CN109453747A (en) * 2018-11-27 2019-03-12 华南理工大学 A method of cellulase adsorbent is used for based on lignin preparation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006077152A (en) * 2004-09-10 2006-03-23 Kinousei Mokushitsu Shinsozai Gijutsu Kenkyu Kumiai Manufacturing method for phenol derivative of lignin
CN104974355A (en) * 2015-07-27 2015-10-14 华南理工大学 pH-responsive amino sodium lignosulphonate as well as preparation method and application thereof
CN109453747A (en) * 2018-11-27 2019-03-12 华南理工大学 A method of cellulase adsorbent is used for based on lignin preparation

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
刘妮: "蔗渣碱木质素酚化-胺化改性及其重金属离子吸附机制研究" *
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