CN113600152B - Hydrophilic-hydrophobic asymmetric three-dimensional material and preparation method and application thereof - Google Patents
Hydrophilic-hydrophobic asymmetric three-dimensional material and preparation method and application thereof Download PDFInfo
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- CN113600152B CN113600152B CN202110992624.6A CN202110992624A CN113600152B CN 113600152 B CN113600152 B CN 113600152B CN 202110992624 A CN202110992624 A CN 202110992624A CN 113600152 B CN113600152 B CN 113600152B
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- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 19
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 13
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Classifications
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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
- B01J20/26—Synthetic macromolecular compounds
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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
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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
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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
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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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
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
- B01J20/28035—Membrane, sheet, cloth, pad, lamellar or mat with more than one layer, e.g. laminates, separated sheets
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/44—Materials comprising a mixture of organic materials
- B01J2220/445—Materials comprising a mixture of organic materials comprising a mixture of polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
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- C02F2101/32—Hydrocarbons, e.g. oil
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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)
Abstract
The invention belongs to the technical field of sewage treatment materials, and discloses a hydrophilic-hydrophobic asymmetric three-dimensional material, a preparation method and application thereof. The three-dimensional material sequentially comprises a substrate, a polymer nanoparticle layer and a hydrophobic modification layer; the raw material components for preparing the polymer nanoparticle layer comprise an organic phosphorus compound and a polymer containing-NH-. According to the invention, the polymer nanoparticle layer on the substrate is of a super-hydrophilic structure, the hydrophobic modified layer is of a super-hydrophobic structure, and the prepared three-dimensional material has super-hydrophilicity and super-hydrophobicity at the same time, so that the three-dimensional material has an efficient separation effect on pollutants such as emulsified oil-in-water, emulsified water-in-oil, dye, heavy metal and the like in sewage through direct filtration. Further, the dopamine layer and the polymer layer containing-NH-are sequentially arranged between the substrate and the polymer nanoparticle layer, so that the stability and the load capacity of the polymer nanoparticle layer can be greatly improved, and the sewage treatment capacity of the three-dimensional material is remarkably improved.
Description
Technical Field
The invention belongs to the technical field of sewage treatment materials, and particularly relates to a hydrophilic-hydrophobic asymmetric three-dimensional material, a preparation method and application thereof.
Background
Water is the source of life and is the basis for human survival, but at present, the problem of water pollution is serious. The sewage containing dye, heavy metal and other pollutant and oily sewage discharged by industry have great harm to living environment and ecological balance, and the treatment of sewage containing various pollutants is always an important subject of scientific research. The method can effectively treat a large amount of pollutant sewage containing oil, dye and the like generated by industry so as to achieve the purposes of recycling and standard discharge, and has extremely important significance for environmental protection and water resource conservation. Few or none of the current technologies are capable of simultaneously treating dye, heavy metals and oil contaminants in wastewater. In the prior art, dye and heavy metal pollutants are treated by powder or other materials for adsorption, and the adsorbent is required to be removed by centrifugation, so that the operation is complex and the efficiency is low.
The prior art discloses three-dimensional materials for sewage purification, but mainly adopts an adsorption mode, which is time-consuming and has low efficiency and uncontrollable. Specifically, the prior art discloses a Janus organic porous material, which is prepared by fully contacting and soaking an organic porous material with an acidic treatment solution and a metal ion salt solution in sequence to obtain a first modified organic porous material, then applying an organosilane solution to a selected side of the first modified organic porous material, and then drying the first modified organic porous material to obtain the Janus organic porous material. The Janus organic porous material prepared by the method can only realize the separation of layered oil-water mixtures, and cannot treat sewage containing complex components such as dyes, heavy metals and the like.
Materials that can simultaneously separate contaminants such as emulsified oil-in-water, emulsified water-in-oil, dyes, and heavy metals have not been disclosed in the prior art.
Therefore, it is highly desirable to provide a novel sewage treatment material which can separate oil-in-water emulsion, water-in-oil emulsion, dye, heavy metal and other pollutants in water, and is important for improving sewage treatment efficiency and effect.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides a hydrophilic-hydrophobic asymmetric three-dimensional material, a preparation method and application thereof, wherein the three-dimensional material can separate oil-in-water, water-in-oil-in-water, dye, heavy metal and other pollutants in water, and is very important for improving sewage treatment efficiency and effect.
The invention is characterized in that: according to the invention, the polymer nanoparticle layer formed by reacting the organic phosphorus compound and the polymer containing-NH-is in a super-hydrophilic structure, and the hydrophobic modified layer is in a super-hydrophobic structure, so that the prepared three-dimensional material has super-hydrophilicity and super-hydrophobicity at the same time, and further, the three-dimensional material has an efficient separation effect on pollutants such as emulsified oil-in-water, emulsified water-in-oil, dye, heavy metal and the like in sewage through direct filtration. A dopamine layer and a polymer layer containing-NH-are sequentially arranged between the substrate and the polymer nanoparticle layer; the dopamine layer has good adhesive force to a substrate, the polymer layer containing-NH-is grafted to the surface of the dopamine layer, and the polymer layer containing-NH-is a cationic polymer layer, so that negatively charged polymer nano particles can be loaded on the surface of the polymer layer containing-NH-by utilizing electrostatic adsorption. The stability and the load capacity of the polymer nanoparticle layer are greatly improved, so that the sewage treatment capacity of the three-dimensional material is remarkably improved.
A first aspect of the present invention provides a hydrophilic-hydrophobic asymmetric three-dimensional material.
Specifically, the hydrophilic-hydrophobic asymmetric three-dimensional material sequentially comprises a substrate, a polymer nanoparticle layer and a hydrophobic modification layer; the raw material components for preparing the polymer nanoparticle layer comprise an organic phosphorus compound and a polymer containing-NH-.
Preferably, the substrate comprises an organic porous material; further preferably, the substrate is a sponge; more preferably, the sponge may be composed of wood cellulose, polyether, polyvinyl alcohol, polyester (e.g., polyurethane).
Preferably, the organophosphorus compound includes phytic acid. The phytic acid has wide sources, is biologically nontoxic, is beneficial to reducing the production cost and is beneficial to environmental protection.
Preferably, the-NH-containing polymer comprises at least one of polyethylenimine, polypropylenimine; further preferably, the-NH-containing polymer is a polyethyleneimine. The polymer nanoparticle layer prepared by adopting polyethyleneimine is a super-hydrophilic layer, and the water contact angle is 0 degree.
Preferably, a dopamine layer and a polymer layer containing-NH-are also included between the substrate and the polymer nanoparticle layer. The dopamine layer has good adhesive force to a substrate, and the polymer layer containing-NH-is grafted to the surface of the dopamine layer, so that negatively charged polymer nano particles are loaded on the surface of the polymer layer containing-NH-by utilizing electrostatic adsorption. The stability and the load capacity of the polymer nanoparticle layer are greatly improved, so that the sewage treatment capacity of the three-dimensional material is remarkably improved.
Preferably, the hydrophobically modified layer comprises a hydrophobically modifier; further preferably, the hydrophobic modifier comprises at least one of a siloxane, a silazane, a fluorosilane; more preferably, the hydrophobic modifier (also referred to as a hydrophobic substance or a hydrophobically modified substance) comprises polydimethylsiloxane.
Preferably, the three-dimensional material of the invention takes a substrate as a center, and a dopamine layer, a polymer layer containing-NH-, a polymer nanoparticle layer and a hydrophobic modification layer are sequentially covered on the surface of the substrate; and the hydrophobically modified layer partially covers the polymer nanoparticle layer.
Further preferably, the hydrophobically modified layer covers from one tenth to nine tenth (which may be volume or area) of the polymeric nanoparticle layer. The three-dimensional material contains the super-hydrophilic area and the super-hydrophobic area at the same time, and can directly filter sewage, thus having good separation effect on the sewage.
A second aspect of the invention provides a method of preparing a hydrophilic-hydrophobic asymmetric three-dimensional material.
Specifically, the preparation method of the hydrophilic-hydrophobic asymmetric three-dimensional material comprises the following steps:
(1) Preparation of polymer nanoparticles: mixing and reacting an organic phosphorus compound and a polymer containing-NH-to prepare polymer nano particles;
(2) Soaking the substrate in a mixture containing polymer nano particles for the first time, taking out the substrate, and drying for the first time to obtain a dried substrate (the surface of the dried substrate is provided with a polymer nano particle layer); and mixing the hydrophobic modifier and the solvent to prepare a hydrophobic modifier solution, soaking the dried substrate part in the hydrophobic modifier solution for the second time, taking out the substrate, and drying the substrate for the second time (forming a hydrophobic modified layer on the surface of part of the polymer nano particle layer) to prepare the three-dimensional material.
Preferably, in the step (1), the organophosphorus compound and the polymer containing-NH-are respectively prepared into solutions, then the solution of the polymer containing-NH-is dripped into the solution containing the organophosphorus compound, stirred for 0.5 to 1.5 hours, and then the polymer nano particles are prepared by suction filtration and washing.
Preferably, in step (1), the mass ratio of the organophosphorus compound to the-NH-containing polymer is 2.5: (0.1-1); further preferably, the mass ratio of the organophosphorus compound to the-NH-containing polymer is 2.5: (0.1-0.5); more preferably, the mass ratio of the organophosphorus compound to the-NH-containing polymer is 2.5:0.25.
preferably, in the step (2), the mixture containing the polymer nanoparticles is a mixture formed by mixing the polymer nanoparticles with a solvent; further preferably, the solvent is water.
Preferably, in the step (2), the time of the first soaking is 20-35 minutes; further preferably, the time of the first soaking is 25-30 minutes.
Preferably, in the step (2), the temperature of the first drying is 55-65 ℃; further preferably, the temperature of the first drying is 58-60 ℃.
Preferably, in the step (2), the solvent used in the process of preparing the hydrophobic modifier solution is an organic solvent; further preferably, the organic solvent is n-hexane.
Preferably, in step (2), 0.5-1.5g of the hydrophobic modifier and 5-12mL of the solvent are mixed to prepare a hydrophobic modifier solution.
Preferably, in the step (2), the dried substrate is partially soaked in the hydrophobic modifier solution, and one tenth to nine tenth of the volume of the dried substrate is soaked in the hydrophobic modifier solution.
Preferably, in the step (2), the time of the second soaking is 3-8 minutes; further preferably, the second soaking time is 3-5 minutes.
Preferably, in the step (2), the temperature of the second drying is 75-85 ℃; further preferably, the temperature of the second drying is 78-80 ℃.
Preferably, in the step (2), the time of the second drying is 1.5-2.5 hours; further preferably, the second drying time is 1.8-2 hours.
Preferably, the preparation of the dopamine layer and the polymer layer containing-NH-is also included between the step (1) and the step (2).
Preferably, the preparation process of the dopamine layer and the polymer layer containing-NH-is as follows: mixing an acid-base buffer and water, regulating the pH to 8.0-8.5 by using a pH regulator, adding dopamine to prepare a mixed solution a (the mixed solution a can be called DA/Tris buffer solution), soaking a substrate in the mixed solution a, oscillating for 10-12 hours, taking out, and drying at 50-60 ℃ to prepare the substrate with the dopamine layer on the surface; mixing an acid-base buffer and water, regulating the pH to 8.0-8.5 by using a pH regulator, adding a polymer containing-NH-to prepare a mixed solution b (the mixed solution b can be called PEI/Tris buffer solution), soaking a substrate with a dopamine layer on the surface in the mixed solution b, oscillating for 10-14 hours, taking out, and drying at 50-60 ℃ to prepare the substrate with the polymer layer containing-NH-and the dopamine layer on the surface.
Preferably, the acid-base buffer comprises tris.
Preferably, the pH adjuster is hydrochloric acid.
Preferably, the ratio of the amount of the acid-base buffer, water and dopamine in the mixed solution a is (1-1.5) g:200mL: (0.1-0.8) g; further preferably, the ratio of the amount of the acid-base buffer, water and dopamine is (1.1-1.3) g:200mL: (0.2-0.6) g.
Preferably, the ratio of the amount of acid-base buffer, water, polymer containing-NH-in the mixed solution b is (0.2-1) g:100mL: (0.1-0.5) g; further preferably, the ratio of the amounts of acid-base buffer, water, polymer containing-NH-is (0.4-0.8) g:100mL: (0.1-0.3) g.
Preferably, the water is deionized water.
Preferably, the preparation method aims to prepare a three-dimensional material by using a green and environment-friendly method, prepare negatively charged polymer nano particles by using widely-sourced and biologically non-toxic Phytic Acid (PA) and Polyethyleneimine (PEI), graft the positively charged polyethyleneimine-containing layer onto the dopamine layer by using the excellent adhesiveness of the dopamine layer to the substrate, and finally assemble the negatively charged polymer nano particles onto the three-dimensional substrate by using electrostatic adsorption to prepare the super-hydrophilic/underwater super-oleophobic three-dimensional material. And then the hydrophobic modified solvent is driven and controlled by capillary force to permeate in one side of the super-hydrophilic/underwater super-oleophobic three-dimensional material, so that the modification height of the hydrophobic part can be adjusted, and the three-dimensional material capable of adjusting and controlling the height of the hydrophilic/hydrophobic layer is prepared. The prepared material can realize the efficient treatment and purification of various pollutants such as emulsified oil water, dye, heavy metal and the like.
A third aspect of the invention provides the use of a hydrophilic-hydrophobic asymmetric three-dimensional material.
The application of the hydrophilic-hydrophobic asymmetric three-dimensional material in sewage treatment.
Preferably, the wastewater includes at least one of oil-in-water emulsion, water-in-oil emulsion, dye, and heavy metal contaminants.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the polymer nanoparticle layer formed by reacting the organic phosphorus compound and the polymer containing-NH-is in a super-hydrophilic structure, and the hydrophobic modified layer is in a super-hydrophobic structure, so that the prepared three-dimensional material has super-hydrophilicity and super-hydrophobicity at the same time, and further, the three-dimensional material has an efficient separation effect on pollutants such as emulsified oil-in-water, emulsified water-in-oil, dye, heavy metal and the like in sewage through direct filtration.
(2) A dopamine layer and a polymer layer containing-NH-are sequentially arranged between the substrate and the polymer nanoparticle layer; the dopamine layer has good adhesive force to a substrate, and the polymer layer containing-NH-is grafted to the surface of the dopamine layer, so that negatively charged polymer nano particles are loaded on the surface of the polymer layer containing-NH-by utilizing electrostatic adsorption. The stability and the load capacity of the polymer nanoparticle layer are greatly improved, so that the sewage treatment capacity of the three-dimensional material is remarkably improved.
(3) The raw materials such as phytic acid and dopamine used in the preparation method are biological and nontoxic, the preparation process can be realized by simple soaking without complex equipment, the preparation efficiency is high, and the production cost is low.
Drawings
FIG. 1 is an electron micrograph of an untreated sponge;
FIG. 2 is an electron microscopy image of a sponge with a polymer nanoparticle layer on the surface;
FIG. 3 is an electron microscope image of the three-dimensional material prepared in example 1;
FIG. 4 is an EDS (energy dispersive spectroscopy) diagram of the three-dimensional material prepared in example 1;
FIG. 5 is an XPS (X-ray photoelectron spectroscopy) chart of the three-dimensional material prepared in example 1;
FIG. 6 is a graph showing the phenomenon in which the three-dimensional material prepared in example 1 is contacted with water and oil;
FIG. 7 is a graph showing the separation effect of the three-dimensional material prepared in example 1 on emulsified water-in-oil and emulsified oil-in-water;
FIG. 8 is a graph showing the ultraviolet absorption spectra of the three-dimensional material prepared in example 1 before and after the treatment of dye-containing sewage.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples will be presented. It should be noted that the following examples do not limit the scope of the invention.
The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
Example 1: preparation of hydrophilic-hydrophobic asymmetric three-dimensional materials
The hydrophilic-hydrophobic asymmetric three-dimensional material sequentially comprises a substrate, a dopamine layer, a polymer layer containing-NH-, a polymer nanoparticle layer and a hydrophobic modification layer; the raw material components for preparing the polymer nanoparticle layer comprise phytic acid and polyethyleneimine;
the substrate is sponge; the polymer layer containing-NH-is a polyethyleneimine layer; the hydrophobic modification layer contains a hydrophobic modifier, and the hydrophobic modifier is polydimethylsiloxane hydrophobic modifier.
The three-dimensional material takes a substrate as a center, and a dopamine layer, a polymer layer containing-NH-, a polymer nanoparticle layer and a hydrophobic modification layer are sequentially covered on the surface of the substrate; and the hydrophobically modified layer covers three-tenth of the polymeric nanoparticle layer. Such three-dimensional materials contain both superhydrophilic and superhydrophobic regions.
The preparation method of the hydrophilic-hydrophobic asymmetric three-dimensional material comprises the following steps:
preparation of polymer nanoparticles: respectively dissolving 2.5g of phytic acid in 100mL of water to prepare a phytic acid solution, dissolving 0.25g of polyethyleneimine in 100mL of water to prepare a polyethyleneimine solution, dropwise adding the polyethyleneimine solution into the phytic acid solution, stirring for 1 hour, and carrying out suction filtration and washing to prepare the polymer nano particles;
1.2144g of Tris (hydroxymethyl) aminomethane is dissolved in 200mL of deionized water, the pH value is regulated to 8.5 by hydrochloric acid, then 0.4g of dopamine is added to prepare a mixed solution a (the mixed solution a can be called DA/Tris buffer solution), then a substrate (sponge) is soaked in the mixed solution a, the mixed solution a is vibrated for 12 hours, the substrate is taken out, and the substrate with a dopamine layer on the surface is prepared by drying at 60 ℃;
dissolving 0.6072g of Tris (hydroxymethyl) aminomethane in 100mL of deionized water, regulating the pH value to 8.5 by using hydrochloric acid, adding 0.2g of polyethyleneimine to prepare a mixed solution b (the mixed solution b can be called PEI/Tris buffer solution), soaking a substrate with a dopamine layer on the surface in the mixed solution b, oscillating for 12 hours, taking out the substrate, and drying at 60 ℃ to prepare the substrate with the polymer layer containing-NH-and the dopamine layer on the surface;
soaking a substrate with a polymer layer containing-NH-and a dopamine layer on the surface in a mixture containing polymer nano particles (the mixture contains water and the polymer nano particles), oscillating for 30 minutes, taking out the substrate, and drying for the first time (the drying temperature is 60 ℃) to obtain a dried substrate (the surface of the dried substrate is provided with the dopamine layer, the polymer layer containing-NH-and the polymer nano particle layer); 1g of a hydrophobic modifier (polydimethylsiloxane hydrophobic modifier, available from Dow Corning Co., ltd., product model DC 184) and 9mL of n-hexane were mixed to prepare a hydrophobic modifier solution, and the dried substrate portion (three tenths of volume) was soaked in the hydrophobic modifier solution for a second time of 5 minutes, and then the substrate was taken out, and dried for a second time (drying temperature 80 ℃ C., drying time of 2 hours) to prepare a three-dimensional material.
FIG. 1 is an electron micrograph of an untreated sponge; as can be seen from fig. 1, the original sponge has pores which remain interconnected and has a smooth surface.
FIG. 2 is an electron microscopy image of a sponge with a polymer nanoparticle layer on the surface; as can be seen from fig. 2, the surface of the polymer nanoparticle-loaded sponge has a uniform nanoparticle coarse structure, and still has the characteristic of maintaining a mutually connected pore structure.
FIG. 3 is an electron microscope image of the three-dimensional material prepared in example 1; as can be seen from fig. 3, after the modification by the hydrophobic substance, the polymer nanoparticles are covered by the hydrophobic substance, but the sponge surface still maintains a rich micro-nano coarse structure and has the characteristic of maintaining a mutually communicated pore structure.
FIG. 4 is an EDS (energy dispersive spectroscopy) diagram of the three-dimensional material prepared in example 1; as can be seen from fig. 4, the side modified with the hydrophobic substance has Si element present, and the P and N elements show relative darkness mainly because the hydrophobic modifying substance is polydimethylsiloxane and the regions without hydrophobic modification do not have Si element present.
FIG. 5 is an XPS (X-ray photoelectron spectroscopy) chart of the three-dimensional material prepared in example 1; in fig. 5, the curve "(a 1)" represents an untreated sponge, the curve "(a 2)" represents a sponge having a dopamine layer on the surface, the curve "(a 3)" represents a sponge having a dopamine layer on the surface and a polymer layer containing-NH-, the curve "(a 4)" represents a sponge having a dopamine layer on the surface, a polymer layer containing-NH-, a polymer nanoparticle layer, and the curve "(a 5)" represents a sponge having a dopamine layer on the surface, a polymer layer containing-NH-, a polymer nanoparticle layer, and a hydrophobically modified layer (i.e., the three-dimensional material prepared in example 1). In fig. 5, the abscissa "Binding energy" represents Binding energy, and the ordinate "density" represents Intensity. Peaks of C1s, O1 s and N1s were found on the untreated sponge surface. In XPS spectra of dopamine-modified sponges and-NH-containing polymer (polyethyleneimine) -modified sponges, the N1s peak became stronger, indicating that dopamine and-NH-containing polymer (polyethyleneimine) were deposited on the sponges sequentially. The sponge (curve "(a 4)") with the polymer nanoparticle layer on the surface can find the P element signal generated by phytic acid at the 133.22eV binding energy of P2P, and proves that the polymer nanoparticle is successfully modified on the sponge modified by the polymer layer containing-NH-. The strong Si 2s and Si 2p peaks in the curve "(a 5)" are the result of the hydrophobic modification.
Example 2: preparation of hydrophilic-hydrophobic asymmetric three-dimensional materials
The hydrophilic-hydrophobic asymmetric three-dimensional material sequentially comprises a substrate, a dopamine layer, a polymer layer containing-NH-, a polymer nanoparticle layer and a hydrophobic modification layer; the raw material components for preparing the polymer nanoparticle layer comprise phytic acid and polyethyleneimine;
the substrate is sponge; the polymer layer containing-NH-is a polyethyleneimine layer; the hydrophobic modification layer contains a hydrophobic modifier, and the hydrophobic modifier is polydimethylsiloxane hydrophobic modifier.
The three-dimensional material takes a substrate as a center, and a dopamine layer, a polymer layer containing-NH-, a polymer nanoparticle layer and a hydrophobic modification layer are sequentially covered on the surface of the substrate; and the hydrophobically modified layer covers five tenths of a polymeric nanoparticle layer. Such three-dimensional materials contain both superhydrophilic and superhydrophobic regions.
The preparation method of the hydrophilic-hydrophobic asymmetric three-dimensional material comprises the following steps:
preparation of polymer nanoparticles: respectively dissolving 2.5g of phytic acid in 100mL of water to prepare a phytic acid solution, dissolving 0.5g of polyethyleneimine in 100mL of water to prepare a polyethyleneimine solution, dropwise adding the polyethyleneimine solution into the phytic acid solution, stirring for 1 hour, and carrying out suction filtration and washing to prepare the polymer nano particles;
dissolving 1.4g of tris (hydroxymethyl) aminomethane in 200mL of deionized water, regulating the pH value to 8.5 by using hydrochloric acid, then adding 0.5g of dopamine to prepare a mixed solution a, soaking a substrate in the mixed solution a, oscillating for 12 hours, taking out the substrate, and drying at 60 ℃ to prepare the substrate with a dopamine layer on the surface;
dissolving 0.7g of tris (hydroxymethyl) aminomethane in 100mL of deionized water, regulating the pH value to 8.5 by using hydrochloric acid, then adding 0.3g of polyethyleneimine to prepare a mixed solution b, then soaking a substrate with a dopamine layer on the surface in the mixed solution b, oscillating for 12 hours, taking out the substrate, and drying at 60 ℃ to prepare a substrate with a polymer layer containing-NH-and a dopamine layer on the surface;
soaking a substrate with a polymer layer containing-NH-and a dopamine layer on the surface in a mixture containing polymer nano particles (the mixture contains water and the polymer nano particles), oscillating for 30 minutes, taking out the substrate, and drying for the first time (the drying temperature is 60 ℃) to obtain a dried substrate (the surface of the dried substrate is provided with the dopamine layer, the polymer layer containing-NH-and the polymer nano particle layer); 1.2g of a hydrophobic modifier (polydimethylsiloxane hydrophobic modifier) and 10mL of n-hexane were mixed to prepare a hydrophobic modifier solution, a dried substrate portion (five tenths of a volume) was immersed in the hydrophobic modifier solution for 5 minutes, and then the substrate was taken out and dried for the second time (drying temperature 80 ℃ C., drying time 2 hours) to prepare a three-dimensional material.
Example 3: preparation of hydrophilic-hydrophobic asymmetric three-dimensional materials
The hydrophilic-hydrophobic asymmetric three-dimensional material sequentially comprises a substrate, a dopamine layer, a polymer layer containing-NH-, a polymer nanoparticle layer and a hydrophobic modification layer; the raw material components for preparing the polymer nanoparticle layer comprise phytic acid and polyethyleneimine;
the substrate is sponge; the polymer layer containing-NH-is a polyethyleneimine layer; the hydrophobic modification layer contains a hydrophobic modifier, and the hydrophobic modifier is fluorosilane.
The three-dimensional material takes a substrate as a center, and a dopamine layer, a polymer layer containing-NH-, a polymer nanoparticle layer and a hydrophobic modification layer are sequentially covered on the surface of the substrate; and the hydrophobically modified layer covers eight tenths of a layer of polymeric nanoparticles. Such three-dimensional materials contain both superhydrophilic and superhydrophobic regions.
The preparation method of the hydrophilic-hydrophobic asymmetric three-dimensional material comprises the following steps:
preparation of polymer nanoparticles: respectively dissolving 2.5g of phytic acid in 100mL of water to prepare a phytic acid solution, dissolving 1g of polyethyleneimine in 100mL of water to prepare a polyethyleneimine solution, dropwise adding the polyethyleneimine solution into the phytic acid solution, stirring for 1 hour, and carrying out suction filtration and washing to prepare polymer nano particles;
dissolving 1g of tris (hydroxymethyl) aminomethane in 200mL of deionized water, regulating the pH value to 8.5 by using hydrochloric acid, then adding 0.5g of dopamine to prepare a mixed solution a, soaking a substrate in the mixed solution a, oscillating for 12 hours, taking out the substrate, and drying at 60 ℃ to prepare the substrate with a dopamine layer on the surface;
dissolving 0.5g of tris (hydroxymethyl) aminomethane in 100mL of deionized water, regulating the pH value to 8.5 by using hydrochloric acid, then adding 0.2g of polyethyleneimine to prepare a mixed solution b, then soaking a substrate with a dopamine layer on the surface in the mixed solution b, oscillating for 12 hours, taking out the substrate, and drying at 60 ℃ to prepare a substrate with a polymer layer containing-NH-and a dopamine layer on the surface;
soaking a substrate with a polymer layer containing-NH-and a dopamine layer on the surface in a mixture containing polymer nano particles (the mixture contains water and the polymer nano particles), oscillating for 30 minutes, taking out the substrate, and drying for the first time (the drying temperature is 60 ℃) to obtain a dried substrate (the surface of the dried substrate is provided with the dopamine layer, the polymer layer containing-NH-and the polymer nano particle layer); 1.3g of a hydrophobic modifier (polydimethylsiloxane hydrophobic modifier) and 10mL of n-hexane were mixed to prepare a hydrophobic modifier solution, a dried substrate portion (eight tenths of a volume) was immersed in the hydrophobic modifier solution for 5 minutes, and then the substrate was taken out and dried for the second time (drying temperature 80 ℃ C., drying time 2 hours) to prepare a three-dimensional material.
Product effect test
1. Hydrophobic and hydrophilic Effect test
In examples 1 to 3, the water contact angle of the water drop in the air on the surface of the sponge which is not treated is more than 120 degrees; the water contact angle of the surface of the substrate with the polymer nanoparticle layer on the surface is 0 degrees, which indicates that the sponge is modified by the polymer nanoparticle layer, and the sponge is changed from hydrophobicity to hydrophilicity. On the surface of the sponge with the hydrophobically modified layer, the water contact angle is more than 150 degrees, which indicates that the area after the hydrophobically modification has superhydrophobicity. Namely, the three-dimensional materials prepared in examples 1 to 3 have both superhydrophilic regions and superhydrophobic regions.
The underwater oil drops show the underwater super-oleophobic characteristic in the super-hydrophilic area of the three-dimensional material, and show the super-oleophilic characteristic in the super-hydrophobic area.
The three-dimensional material prepared in example 1 was photographed by a high-speed camera to be contacted with water drops in the air, and the super-hydrophobic region of the three-dimensional material was photographed under water, and the contact phenomenon of the super-hydrophilic region of the three-dimensional material with the oil drops under water was further photographed, and the result is shown in fig. 6. FIG. 6 is a graph showing the phenomenon in which the three-dimensional material prepared in example 1 is contacted with water and oil. "(a)" in fig. 6 represents a phenomenon in which superhydrophobic regions and superhydrophilic regions of a three-dimensional material are respectively contacted with water drops in air; "(b)" in fig. 6 indicates that the superhydrophobic region of the three-dimensional material exhibits a significant "silver mirror phenomenon" under water; "(c)" in fig. 6 shows that the super-hydrophilic region of the three-dimensional material shows excellent underwater super-oleophobic properties after being contacted with underwater oil droplets.
2. Separation effect of emulsified water-in-oil and emulsified oil-in-water
Separation kerosene, diesel oil, gasoline and isooctane are used as oil phases to prepare an emulsified water-in-oil and oil-in-water-in-emulsion to-be-detected object, and then the three-dimensional material prepared in example 1 is used for separating the emulsified water-in-oil and oil-in-water-in-emulsion to-be-detected object, and the result is shown in fig. 7.
FIG. 7 is a graph showing the separation effect of the three-dimensional material prepared in example 1 on emulsified water-in-oil and emulsified oil-in-water; in fig. 7, "(a 1)", "(a 2)", and "(b)", each represent a separation effect diagram of the emulsified oil water; in fig. 7, "(c 1)", "(c 2)", and "(d)" represent a graph of separation effect on emulsified oil-in-water. In fig. 7, "(b)" abscissa "Kerosene" represents Kerosene, "Diesel" represents Diesel, "Gasoline" represents Gasoline, "Isooctane" represents Isooctane, "left ordinate" Separation efficiency "in fig. 7," (b) "Oil flux" represents Oil flux, and the left ordinate "Oil flux" is exemplified by two cylinders corresponding to "Kerosene", the left upper cylinder corresponds to the left ordinate, and the right lower cylinder corresponds to the right ordinate. In fig. 7, "(d)" abscissa "Kerosene" represents Kerosene, "Diesel" represents Diesel, "Gasoline" represents Gasoline, "Isooctane" represents Isooctane, "left ordinate" Separation efficiency "in fig. 7," (d) "represents separation efficiency," Water flux "on the right ordinate represents Water flux, and two cylinders corresponding to" Kerosene "are taken as an example, the upper cylinder on the left side corresponds to the left ordinate, and the lower cylinder on the right side corresponds to the right ordinate.
As can be seen from fig. 7, the three-dimensional material prepared in example 1 was used to separate the emulsified water-in-oil and the emulsified oil-in-water, the emulsion before separation was cloudy, the presence of droplets was observed from a microscopic image (see "(a 1)", "(c 1)") in fig. 7, the emulsion after separation was clear and transparent, and the presence of droplets was not observed (see "(a 2)", "(c 2)") in fig. 7). As can be seen from "(b)" and "(d)" in FIG. 7, the three-dimensional material prepared in example 1 has a separation efficiency of more than 99.8% for kerosene, diesel oil, gasoline, and isooctane. From this, it can be seen that the three-dimensional material prepared in example 1 is excellent in separation effect of emulsified water-in-oil and emulsified oil-in-water.
3. Dye separation effect
The three-dimensional material prepared in example 1 is used for carrying out adsorption separation treatment on the sewage containing the dye (namely, the sewage containing the dye is filtered by the three-dimensional material), and the specific types of the dye are respectively crystal violet, rhodamine B, malachite green and alkaline yellow, and the separation and purification effects are shown in figure 8.
FIG. 8 is a graph showing the ultraviolet absorption spectrum of the three-dimensional material prepared in example 1 before and after treatment of dye-containing sewage; in fig. 8, "(a)" shows the ultraviolet absorption spectrum before and after the crystal violet adsorption treatment, "(B)" shows the ultraviolet absorption spectrum before and after the rhodamine B adsorption treatment, "(c)" shows the ultraviolet absorption spectrum before and after the malachite green adsorption treatment, "(d)" shows the ultraviolet absorption spectrum before and after the alkali Huang Xifu treatment. In fig. 8 (a), a curve "1" represents "Before adsorption of crystal violet", which is an ultraviolet absorption spectrum before crystal violet absorption, and a curve "2" represents "After adsorption of crystal violet", which is an ultraviolet absorption spectrum after crystal violet absorption; (b) The curve "1" in the middle represents "Before adsorption of rhodamine B", which represents the ultraviolet absorption spectrum before rhodamine B is adsorbed, and the curve "2" represents "After adsorption of rhodamine B", which represents the ultraviolet absorption spectrum after rhodamine B is adsorbed; (c) The middle curve "1" represents "Before adsorption of malachite green", which is the ultraviolet absorption spectrum before malachite green adsorption, and the curve "2" represents "After adsorption of malachite green", which is the ultraviolet absorption spectrum after malachite green adsorption; (d) The curve "1" in the middle represents "Before adsorption of alkaline yellow", which represents the ultraviolet absorption spectrum before the adsorption of basic yellow, and the curve "2" represents "After adsorption of alkaline yellow", which represents the ultraviolet absorption spectrum after the adsorption of basic Huang Xi. The abscissa "Wavelength" in fig. 8 represents Wavelength, and the ordinate "absorptance" represents Absorbance.
As can be seen from fig. 8, the three-dimensional material prepared in example 1 can separate multiple dyes, the ultraviolet absorption spectrum before separation can see an obvious peak position, the color of the dye solution is obvious, after the three-dimensional material is filtered, the ultraviolet absorption spectrum can not detect the peak, and the solution becomes clear and transparent, which indicates that the three-dimensional material prepared in example 1 has excellent dye adsorption capability.
4. Heavy metal separation effect
In addition, preparing Co containing heavy metal ions 2+ 、Cu 2+ And Cd 2+ Is filtered by the three-dimensional material prepared in the example 2, co in the water after the filtration 2+ 、Cu 2+ And Cd 2+ The mass content of (2) is reduced by 91%, 92% and 91.5%. Therefore, the three-dimensional material prepared in the embodiment 2 of the invention has a good purifying effect on sewage containing heavy metals.
It should be noted that, in the technical scheme of the invention, various technological parameters are changed, and the prepared three-dimensional material has similar separation effects on the pollutants such as emulsified oil in water, emulsified water in oil, dye, heavy metal and the like in sewage as in the examples 1-2. If the prepared three-dimensional material does not contain a dopamine layer and a polymer layer containing-NH-, the separation efficiency of the three-dimensional material on emulsified water-in-oil and emulsified oil-in-water formed by taking kerosene, diesel oil, gasoline and isooctane as oil phases is about 65-75%.
Claims (5)
1. The three-dimensional material is characterized by comprising a substrate, a polymer nanoparticle layer and a hydrophobic modification layer in sequence, wherein the hydrophobic modification layer partially covers the polymer nanoparticle layer; the raw material components for preparing the polymer nanoparticle layer comprise an organic phosphorus compound and a polymer containing-NH-;
the dopamine-containing polymer nanoparticle comprises a substrate and a polymer nanoparticle layer, wherein the dopamine layer and the polymer nanoparticle layer comprise a dopamine-containing polymer layer and a polymer layer containing-NH-;
the substrate is an organic porous material;
the organic phosphorus compound comprises phytic acid;
the polymer containing-NH-comprises at least one of polyethyleneimine and polypropyleneimine;
the hydrophobic modification layer contains a hydrophobic modifier, and the hydrophobic modifier comprises at least one of siloxane, silazane and fluorosilane.
2. The three-dimensional material of claim 1, wherein the hydrophobically modified layer covers from one tenth to nine tenth of the area or volume of the polymeric nanoparticle layer.
3. A method of producing a three-dimensional material according to any one of claims 1-2, comprising the steps of:
(1) Preparation of polymer nanoparticles: mixing and reacting an organic phosphorus compound and a polymer containing-NH-to prepare polymer nano particles;
(2) Soaking the substrate in a mixture containing polymer nano particles for the first time, taking out the substrate, and drying for the first time to obtain a dried substrate; mixing a hydrophobic modifier with a solvent to prepare a hydrophobic modifier solution, soaking the dried substrate part in the hydrophobic modifier solution for the second time, taking out the substrate, and drying for the second time to prepare the three-dimensional material;
the preparation of the dopamine layer and the polymer layer containing-NH-is also included between the step (1) and the step (2).
4. A method of preparation according to claim 3, wherein the dopamine layer and the-NH-containing polymer layer are prepared by: mixing an acid-base buffer and water, regulating the pH to 8.0-8.5 by using a pH regulator, adding dopamine to prepare a mixed solution a, soaking a substrate in the mixed solution a, oscillating for 10-12 hours, taking out and drying to prepare the substrate with the dopamine layer on the surface; mixing an acid-base buffer and water, regulating the pH to 8.0-8.5 by using a pH regulator, then adding a polymer containing-NH-to prepare a mixed solution b, then soaking a substrate with a dopamine layer on the surface in the mixed solution b, oscillating for 10-14 hours, taking out and drying to prepare the substrate with the polymer layer containing-NH-and the dopamine layer on the surface.
5. Use of the three-dimensional material of any one of claims 1-2 in sewage treatment.
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| 亲水/疏水复合膜强化膜蒸馏深度处理工业废水的研究进展;任静;《化工进展》;第40卷(第11期);全文 * |
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