CN111617748A - Multifunctional sewage treatment pH response composite membrane and preparation method and application thereof - Google Patents

Multifunctional sewage treatment pH response composite membrane and preparation method and application thereof Download PDF

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CN111617748A
CN111617748A CN202010490703.2A CN202010490703A CN111617748A CN 111617748 A CN111617748 A CN 111617748A CN 202010490703 A CN202010490703 A CN 202010490703A CN 111617748 A CN111617748 A CN 111617748A
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palygorskite
composite membrane
sewage treatment
multifunctional
fiber
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CN111617748B (en
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李欣欣
金玲
王亦景
薛涛
徐业晟
施航
朱丁思
曲紫倩
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East China University of Science and Technology
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Abstract

The invention belongs to the field of sewage treatment materials, and particularly relates to a multifunctional sewage treatment pH response composite membrane, and a preparation method and application thereof, wherein the preparation method comprises the steps of firstly carrying out acid activation and silane coupling agent modification on palygorskite; then, the polymer grafted palygorskite is prepared by carrying out graft polymerization modification on the palygorskite by adopting a pH response monomer, and the polymer grafted palygorskite and the plant fiber are uniformly dispersed and mixed to prepare the pH response type plant fiber/grafted palygorskite composite membrane. The composite membrane has excellent pH response wettability, shows super-hydrophilic and super-oleophobic property under an acidic condition, shows super-hydrophobic and super-oleophilic property under a neutral or alkaline condition, and can flexibly change the wettability according to actual requirements. The preparation method is simple and quick, the used raw materials are economical and easy to obtain, and the composite membrane has good oil-water separation capacity, strong adsorption capacity on water-soluble dyes and heavy metal ion pollutants and good stability. Has wide application prospect in the field of sewage treatment.

Description

Multifunctional sewage treatment pH response composite membrane and preparation method and application thereof
Technical Field
The invention belongs to the field of sewage treatment materials, and particularly relates to a multifunctional sewage treatment pH response composite membrane, and a preparation method and application thereof.
Background
In recent years, with the continuous development of global industry, various kinds of oily sewage, dye sewage and heavy metal sewage, which constitute great harm to the ecological environment and human health, are polluted. Therefore, the design and development of a low-cost, environment-friendly and multifunctional sewage treatment material for removing the oil stain in the oily wastewater, the water-soluble dye and the heavy metal ions have important practical significance.
CN110479226A reports that a composite adsorbent prepared from clay minerals and agricultural and forestry waste biomass has the capability of simultaneously adsorbing and removing organic dyes, heavy metal ions, fluorine ions and the like by adopting methods of ball milling and pulping, mixing by an open mill and tabletting and forming. Wang et al reported coating of loess on PVDF in Green Chemistry 2019,21,3190-The PVDF film has super oleophobic property under water, can effectively separate oil-water emulsion, and can effectively adsorb dyes such as methylene blue and crystal violet and Cu due to loess having good adsorption property2+、Pd2+And (3) heavy metal ions.
Currently developed sewage treatment materials have single functions, most of the materials are only suitable for separating immiscible oil-water mixtures or oil-water emulsions, the wettability of the materials cannot be changed according to the environment, or the materials are only suitable for removing water-soluble pollutants in water, and the practical application is limited. The invention provides a multifunctional novel pH response composite membrane for sewage treatment, which has controllable wettability and can realize oil-water separation and removal of water-soluble pollutants.
Disclosure of Invention
The invention aims to prepare a multifunctional sewage treatment pH response composite membrane and a preparation method and application thereof, and on one hand, the multifunctional sewage treatment pH response composite membrane can be used for oil-water separation; on the other hand, the organic dye and heavy metal ions can be effectively adsorbed.
The technical scheme of the invention is as follows:
a preparation method of a pH response composite membrane for multifunctional sewage treatment comprises the following steps:
step 1: preparation of functional polymer graft modified palygorskite
(1) Mixing palygorskite with acid liquor, filtering, washing to be neutral, and drying to obtain acid-activated palygorskite;
(2) reacting a silane coupling agent with double bonds with the acid activated palygorskite mentioned in the step (1), heating for 1-2 hours, filtering, washing to be neutral, and drying to obtain silane modified palygorskite;
the silane coupling agent is a silane coupling agent with double bonds, and can be selected from commercially available silane coupling agents, including but not limited to: vinyltrimethoxysilane, vinyltriethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane and the like.
The dosage of the acid activated palygorskite is 0.5 to 1.5 times of the mass part of the silane coupling agent;
(3) selecting a monomer and the silane modified palygorskite in the step (2) to prepare polymer grafted modified palygorskite;
the monomer has pH responsiveness, and particularly refers to a basic monomer with an amino structure, including but not limited to: one or more of dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminomethyl methacrylate and diethylaminomethyl acrylate; the monomers can also be copolymerized with other common vinyl monomers to adjust cost and performance;
the mass of the monomer grafted to the palygorskite is 3-25% of the mass of the palygorskite;
step 2: graft modified palygorskite and fiber composite
Fully stirring and dispersing the polymer grafted modified palygorskite in the step 1 and natural plant fibers, and filtering to obtain a pH response composite membrane; the using amount of the plant fiber is 0.1-1 times of that of the polymer grafted modified palygorskite by mass.
Further, in the step 1 (1), the acid solution is 0.15M-0.2M diluted hydrochloric acid, the acidification temperature is from room temperature to reflux, and the reaction is carried out for 3-6 hours.
According to the preparation method of the pH response composite membrane for multifunctional sewage treatment, the acidification treatment effect can be further enhanced by heating and ultrasonic reflux in the step 1 (1).
Further, in step 1 (3), polymer graft modified palygorskite is prepared, reacted at 60-80 ℃ for 3-6 hours, and N is carried out as required2And (4) protecting.
According to the preparation method of the pH response composite membrane for multifunctional sewage treatment, further, in the step 1 (3), the mass of the monomer grafted to the palygorskite is 5-15% of the mass of the palygorskite.
According to the preparation method of the pH response composite membrane for multifunctional sewage treatment, further, the method implemented in step 1 (3) is a conventional radical polymerization method.
According to the preparation method of the pH-responsive composite membrane for multifunctional sewage treatment, further, in step 2, the natural plant fiber may be one or more of kapok fiber, bamboo fiber, cotton fiber, poplar catkin fiber and sisal fiber.
According to the preparation method of the pH response composite membrane for multifunctional sewage treatment, disclosed by the invention, further, in the step 2, the natural plant fiber is used in an amount which is 0.3-0.6 times of the mass of the polymer grafted and modified palygorskite.
According to the preparation method of the pH response composite membrane for multifunctional sewage treatment, the natural plant fiber is pretreated by sodium chlorite in step 2.
The invention also provides a pH response composite membrane for multifunctional sewage treatment, which is prepared by the preparation method of the pH response composite membrane for multifunctional sewage treatment.
The invention also provides application of the pH response composite membrane for multifunctional sewage treatment in sewage treatment, and the wettability of the pH response composite membrane is changed by adjusting pH, so that the oil-water separation performance of the composite membrane under different environments is controlled.
Detailed description of the invention:
the invention provides a preparation method of a pH response composite membrane for multifunctional sewage treatment, which comprises the following steps:
step 1: preparation of functional polymer graft modified palygorskite
(1) The palygorskite is mixed with acid liquor, and if necessary, the mixture can be further heated and ultrasonically refluxed to enhance the acidification treatment effect. Filtering, washing to neutrality, and drying to obtain acid activated palygorskite.
(2) Reacting a silane coupling agent having a double bond with the acid-activated palygorskite mentioned in the above (1). Filtering, washing to neutrality, and drying to obtain silane modified palygorskite.
The silane coupling agent is a silane coupling agent with double bonds, and can be selected from commercially available silane coupling agents, including but not limited to: vinyltrimethoxysilane, vinyltriethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane and the like.
The dosage of the acid activated palygorskite is 0.5 to 1.5 times of the mass part of the silane coupling agent.
(3) And (3) selecting a monomer and the silane modified palygorskite in the step (2) to prepare the polymer grafted modified palygorskite.
The monomer has pH responsiveness, and particularly refers to a basic monomer with an amino structure, including but not limited to: dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminomethyl methacrylate, diethylaminomethyl acrylate, and the like. The monomer is one or more of the above-mentioned monomers, and can be copolymerized with other common vinyl monomers to adjust the cost and performance. The mass of the monomer grafted to the palygorskite is 3% -25% of the mass of the palygorskite, and preferably 5% -15%.
The method of implementation is a conventional free radical polymerization process.
Step 2: graft modified palygorskite and fiber composite
And (2) fully stirring and dispersing the polymer grafted modified palygorskite in the step (1) and natural plant fibers, and filtering to obtain the pH response composite membrane. The composite membrane can be used for a filtering layer for sewage treatment.
The plant fiber can be any one of kapok fiber, bamboo fiber, cotton fiber, salix chinensis fiber, sisal fiber and the like, and can also be a plurality of mixed fibers. From the viewpoint of performance, it is preferable that the dispersion performance is excellent and the fiber strength is high, and the cost performance is preferable in consideration of the fiber cost. The amount of the plant fiber is 0.1 to 1 time of that of the polymer grafted and modified palygorskite, and preferably 0.3 to 0.6 time of that of the polymer grafted and modified palygorskite.
Within the scope of the present invention, the above-mentioned technical features of the present invention and those specifically described below (e.g., examples) can be combined with each other to constitute a new or preferred technical solution.
The invention has the beneficial effects that:
(1) the invention designs polymer modified palygorskite, so that the palygorskite is loaded with a polymer with pH responsiveness, the modified palygorskite and plant fiber are physically mixed to prepare the pH responsive composite membrane for sewage treatment, and the preparation method is simple and quick.
(2) The pH response composite membrane for sewage treatment prepared by the invention can effectively separate oil from water, and the wettability of the composite membrane is changed by adjusting pH. The pH response composite membrane for sewage treatment shows super-hydrophilicity under an acidic condition, and the contact angle is less than 10 degrees; exhibits superhydrophobicity under neutral or alkaline conditions with contact angles greater than 150 deg. The oil-water separation performance under different environments is controlled by adjusting the hydrophilicity or lipophilicity.
(3) The pH response composite membrane for sewage treatment prepared by the invention can effectively adsorb organic dye and heavy metal ions at the same time, and has great application prospect in the field of removing water-soluble pollutants.
Drawings
Fig. 1 is a contact angle image of a pH-responsive composite membrane for sewage treatment according to example 1 of the present invention at different pH.
Detailed Description
For a better understanding of the present invention, the following examples are provided to illustrate specific embodiments of the present invention and to enable those skilled in the art to understand the invention.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1: preparation of composite membranes
Step 1: preparation of polymer grafted modified palygorskite
(1) Palygorskite is mixed with 0.15M dilute hydrochloric acid and stirred and dispersed at normal temperature. Filtering, washing to neutrality, and drying to obtain acid-activated palygorskite;
(2) 20g of gamma- (methacryloyloxy) propyltrimethoxysilane was dispersed in 200mL of a 0.001mol/L acetic acid solution, and 20g of acid-activated palygorskite was added and heated under reflux for 1 hour. Filtering, washing to neutrality, and drying the product to obtain silane modified palygorskite;
(3) weighing 10g of silane modified palygorskite, and adding 5mL of dimethylaminoethyl methacrylate; then, 0.5g of potassium persulfate was added, mixed and dispersed in 100ml of N, N-dimethylformamide, and reacted at 80 ℃ for 5 hours. Filtering, washing to neutrality, and drying the product to obtain the polymer grafted and modified palygorskite.
Step 2: composition of graft modified palygorskite and natural plant fiber
Weighing 1g of the polymer graft modified palygorskite in the step 1 to prepare a suspension with the mass fraction of 5%, adding 0.2g of kapok fiber pretreated by sodium chlorite, and stirring to fully disperse the kapok fiber. And carrying out suction filtration and drying to obtain the pH response composite membrane.
The contact angle of the composite membrane prepared in this example at pH 1 was 0, showing super-hydrophilicity; when the pH value reaches 7, the contact angle is 153.5 degrees, and the composite material is super-hydrophobic; as the pH continued to increase to 13, the contact angle was 155.5 °, super-hydrophobic.
FIG. 1 is a photograph of the contact angle of the composite membrane at different pH values.
Example 2: preparation of composite membranes
Step 1: preparation of polymer grafted modified palygorskite
(1) Palygorskite is mixed with 0.2M dilute hydrochloric acid and stirred and dispersed at 80 ℃. Filtering, washing to neutrality, and drying to obtain acid-activated palygorskite;
(2) 15g of vinyltrimethoxysilane was dispersed in 100mL of a 0.001mol/L acetic acid solution, and 8g of acid-activated palygorskite was added and heated under reflux for 1 hour. Filtering, washing to neutrality, and drying the product to obtain silane modified palygorskite;
(3) weighing 4g of silane modified palygorskite, and adding 3mL of diethylaminomethyl methacrylate; then, 0.02g of potassium persulfate was added, mixed and dispersed in 50ml of N-dimethylformamide, and reacted at 70 ℃ for 5 hours. Filtering, washing to neutrality, and drying the product to obtain the polymer grafted and modified palygorskite.
Step 2: composition of graft modified palygorskite and natural plant fiber
Weighing 1g of the polymer graft modified palygorskite in the step 1 to prepare a suspension with the mass fraction of 5%, adding 0.2g of cotton fiber pretreated by sodium chlorite, and stirring to fully disperse the cotton fiber. And carrying out suction filtration and drying to obtain the pH response composite membrane.
The contact angle of the composite membrane prepared in this example at pH 1 was 0, showing super-hydrophilicity; when the pH value reaches 7, the contact angle is 151.4 degrees, and the film is super-hydrophobic; as the pH continued to increase to 13, the contact angle was 155.8 °, super-hydrophobic.
Example 3: preparation of composite membranes
Step 1: preparation of polymer grafted modified palygorskite
(1) The palygorskite is mixed with 0.15M dilute hydrochloric acid, heated, refluxed, stirred and dispersed. Filtering, washing to neutrality, and drying to obtain acid-activated palygorskite;
(2) 20g of vinyltriethoxysilane was dispersed in 250mL of 0.001mol/L acetic acid solution, and 20g of acid-activated palygorskite was added and heated under reflux for 1 hour. Filtering, washing to neutrality, and drying the product to obtain silane modified palygorskite;
(3) weighing 10g of silane modified palygorskite, and adding 20mL of dimethylaminoethyl acrylate; then, 0.25g of potassium persulfate was added, mixed and dispersed in 200ml of N, N-dimethylformamide2The reaction was carried out at 80 ℃ for 5 hours under an atmosphere. Filtering, washing to neutrality, and drying the product to obtain the polymer grafted and modified palygorskite.
Step 2: composition of graft modified palygorskite and natural plant fiber
Weighing 1g of the polymer graft modified palygorskite in the step 1 to prepare a suspension with the mass fraction of 5%, adding 0.2g of salix populi catkin fibers pretreated by sodium chlorite, and stirring to fully disperse the salix populi catkin fibers. And carrying out suction filtration and drying to obtain the pH response composite membrane.
The contact angle of the composite membrane prepared in this example at pH 1 was 0, showing super-hydrophilicity; when the pH value reaches 7, the contact angle is 154.3 degrees, and the composite material is super-hydrophobic; as the pH continued to increase to 13, the contact angle was 156.4 °, super-hydrophobic.
Example 4: preparation of composite membranes
Step 1: preparation of polymer grafted modified palygorskite
(1) Palygorskite is mixed with 0.15M dilute hydrochloric acid and stirred and dispersed at normal temperature. Filtering, washing to neutrality, and drying to obtain acid-activated palygorskite;
(2) 20g of gamma- (methacryloyloxy) propyltrimethoxysilane was dispersed in 300mL of a 0.001mol/L acetic acid solution, and acid-activated palygorskite equivalent to the silane coupling agent was added and heated under reflux for 1 hour. Filtering, washing to neutrality, and drying the product to obtain silane modified palygorskite;
(3) weighing 10g of silane modified palygorskite, and adding 5mL of a mixture of diethylaminomethyl acrylate and dimethylaminoethyl methacrylate (the volume ratio of the two monomers is 1: 1); then, 0.04g of potassium persulfate was added, mixed and dispersed in 200ml of N, N-dimethylformamide2The reaction was carried out at 80 ℃ for 5 hours under an atmosphere. Filtering, washing to neutrality, and drying the product to obtain the polymer grafted and modified palygorskite.
Step 2: composition of graft modified palygorskite and natural plant fiber
Weighing 1g of the polymer graft modified palygorskite in the step 1 to prepare a suspension with the mass fraction of 5%, adding 0.2g of sisal fibers pretreated by sodium chlorite, and stirring to fully disperse the sisal fibers. And carrying out suction filtration and drying to obtain the pH response composite membrane.
The contact angle of the composite membrane prepared in this example at pH 1 was 0, showing super-hydrophilicity; when the pH value reaches 7, the contact angle is 152.8 degrees, and the composite material is super-hydrophobic; as the pH continued to increase to 13, the contact angle was 153.1 °, super-hydrophobic.
Application example 1:
the separation efficiency of the pH responsive composite membrane for sewage treatment prepared in examples 1 to 4 for different oil and water mixtures is shown in Table 1:
TABLE 1 separation efficiency (%)% of pH-responsive composite membrane for sewage treatment for different oil-water mixtures
Figure BDA0002520976730000061
Figure BDA0002520976730000071
Application example 2:
the adsorption efficiency of the pH-responsive composite membranes for sewage treatment prepared in examples 1 to 4 to different concentrations of methylene blue is shown in table 2:
TABLE 2 adsorption efficiency (%)
Figure BDA0002520976730000072
Application example 3:
examples 1 to 4 pH responsive composite membranes for wastewater treatment prepared for different concentrations of Pb2+The adsorption efficiency of (b) is shown in table 3:
TABLE 3 pH-responsive composite membranes for sewage treatment for different concentrations of Pb2+Adsorption efficiency (%)
Figure BDA0002520976730000073
The above examples are further illustrative of the present invention and are not intended to limit the scope of the present invention. It will be understood by those skilled in the art that various changes and modifications may be made, and equivalents may be substituted, without departing from the spirit and scope of the invention, which is intended to be covered by the claims.

Claims (9)

1. A preparation method of a pH response composite membrane for multifunctional sewage treatment is characterized by comprising the following steps:
step 1: preparation of functional polymer graft modified palygorskite
(1) Mixing palygorskite with acid liquor, filtering, washing to be neutral, and drying to obtain acid-activated palygorskite;
(2) reacting a silane coupling agent having a double bond with the acid-activated palygorskite mentioned in the above (1); filtering, washing to neutrality, and drying to obtain silane modified palygorskite;
the silane coupling agent is a silane coupling agent with double bonds, and can be selected from commercially available silane coupling agents, including but not limited to: vinyltrimethoxysilane, vinyltriethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane and the like.
The dosage of the acid activated palygorskite is 0.5 to 1.5 times of the mass part of the silane coupling agent;
(3) selecting a monomer and the silane modified palygorskite in the step (2) to prepare polymer grafted modified palygorskite;
the monomer has pH responsiveness, and particularly refers to a basic monomer with an amino structure, including but not limited to: one or more of dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminomethyl methacrylate and diethylaminomethyl acrylate; the monomers can also be copolymerized with other common vinyl monomers to adjust cost and performance;
the mass of the monomer grafted to the palygorskite is 3-25% of the mass of the palygorskite;
step 2: graft modified palygorskite and fiber composite
Fully stirring and dispersing the polymer grafted modified palygorskite in the step 1 and natural plant fibers, and filtering to obtain a pH response composite membrane; the using amount of the plant fiber is 0.1-1 times of that of the polymer grafted modified palygorskite by mass.
2. The method for preparing the multifunctional pH-responsive composite membrane for sewage treatment according to claim 1, wherein the acidification treatment effect can be enhanced by further heating and ultrasonic reflux in step 1 (1).
3. The method for preparing a multifunctional pH response composite membrane for sewage treatment as claimed in claim 1, wherein the mass of the monomer grafted to the palygorskite in step 1 (3) is 5% -15% of the mass of the palygorskite.
4. The method for preparing a multifunctional pH-responsive composite membrane for sewage treatment according to claim 1, wherein the method performed in step 1 (3) is a conventional radical polymerization method.
5. The method as claimed in claim 1, wherein the natural plant fiber in step 2 is one or more of kapok fiber, bamboo fiber, cotton fiber, salix mongolica fiber and sisal fiber.
6. The method for preparing a multifunctional pH-responsive composite membrane for sewage treatment as claimed in claim 1, wherein the amount of the natural plant fiber used in step 2 is 0.3-0.6 times by mass of the polymer graft-modified palygorskite.
7. The method for preparing a multifunctional pH-responsive composite membrane for sewage treatment as claimed in claim 1, wherein said natural plant fiber is pretreated with sodium chlorite in step 2.
8. A multifunctional pH-responsive composite membrane for sewage treatment, which is prepared by the method for preparing the multifunctional pH-responsive composite membrane for sewage treatment according to any one of claims 1 to 7.
9. The multifunctional pH-responsive composite membrane for sewage treatment as set forth in claim 8, wherein the wettability of the pH-responsive composite membrane is changed by adjusting pH, so as to control the oil-water separation performance under different environments.
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