CN111408278A - MABR (moving average biofilm reactor) supported composite oxygen-containing membrane, preparation method and application - Google Patents
MABR (moving average biofilm reactor) supported composite oxygen-containing membrane, preparation method and application Download PDFInfo
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Abstract
The invention relates to the technical field of MABR sewage treatment, in particular to an MABR supported composite oxygen-containing membrane, a preparation method and application thereof. The preparation method of the MABR supported composite oxygen-containing membrane is characterized by mainly comprising the following steps: cleaning the surface of the substrate and removing burrs through heat treatment to obtain a mesoporous support substrate; preparing a filler with high-efficiency oxygen permeation and transmission performance; coating the filler on the surface of the mesoporous support matrix, and performing crosslinking or curing treatment to obtain a high-efficiency oxygen-permeable support composite oxygen-containing membrane; and soaking the high-efficiency oxygen-permeable supported composite oxygen-containing membrane in a hydrophilic bionic modifier solution, and carrying out fixation treatment to obtain the biological supported composite oxygen-containing membrane with the high-efficiency oxygen-permeable parent substance. The preparation method in the embodiment has the advantages of simple process, low material price and no toxic reagent involved in the experimental process, and the obtained MABR supported composite oxygen-containing membrane has stable performance in the MABR sewage treatment process, excellent sewage treatment effect and wide application value.
Description
Technical Field
The invention relates to the technical field of MABR sewage treatment, in particular to an MABR supporting composite oxygen-containing membrane, a preparation method and application thereof.
Background
With the progress of urban population, a large amount of domestic sewage is concentrated in the industry and a large amount of industrial wastewater is generated in the rapid development process of the industries such as steel, paper making, textile, oil refining and the like, the domestic sewage and the industrial wastewater cause great damage to the ecological environment such as rivers, lakes, oceans and the like, and seriously threaten the stable development of the society and the health of people.
As is well known, microorganisms have strong absorption and degradation functions on pollutants in water and can effectively purify the pollutants in the water. By creating favorable conditions suitable for the growth and reproduction of microorganisms, the microorganisms in the polluted water body are rapidly proliferated, and a large amount of microorganisms with purifying capacity are domesticated to degrade organic pollutants in the water body, so that the water environment pollution can be obviously reduced or finally eliminated. An aeration membrane biofilm reactor (MABR) is a novel sewage treatment process combining a gas separation membrane technology and a biofilm sewage treatment technology, and is mainly divided into three types: a dense membrane, a hydrophobic microporous membrane, and a supported complex oxygen-containing membrane. However, in the process of implementing the invention, the inventor finds that: the comprehensive performance of the MABR membrane developed at the present stage also has the following problems: 1) under the given membrane aeration pressure condition, the compact membrane has large gas mass transfer resistance, high pressure requirement and low gas flux, can not provide sufficient oxygen for the microorganisms on the surface of the biological membrane, and is applied less at present; 2) the microporous membrane has low bubble point pressure, so that the biomembrane layer on the surface of the membrane is easily damaged by the transmission of gas through the membrane pores; 3) the conventional support composite oxygen-containing membrane directly coats the hydrophilic material on the hydrophobic substrate, the hydrophilic material and the hydrophobic material have great difference in properties, the surface wettability is poor, the biocompatibility is low, the biological membrane is easy to fall off, and the hydrophilic layer can face the risk of falling off in the application process, so that the conventional support composite oxygen-containing membrane is not beneficial to long-term practical application.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the main object of the present invention is to provide a preparation method, which mainly comprises the following steps:
cleaning the surface of the substrate and removing burrs through heat treatment to obtain a mesoporous support substrate;
preparing a filler with high-efficiency oxygen permeation and transmission performance;
coating the filler on the surface of the mesoporous support matrix, and performing crosslinking or curing treatment to obtain the efficient oxygen-permeable support composite oxygen-containing membrane;
and soaking the high-efficiency oxygen-permeable support composite oxygen-containing membrane in a hydrophilic bionic modifier solution, and carrying out fixation treatment to obtain the biological support composite oxygen-containing membrane with the high-efficiency oxygen-permeable parent biomass.
Further, the preparation of the filler is as follows: mixing a silicone resin or a liquid silicone rubber: organosilicon curing agent: organosilicon catalyst: the inorganic filler comprises the following components in percentage by mass: 10-80:0.01-10:0-10:0-10, and dispersing and dissolving in organic solvent to prepare filling solution.
Further, the filling solution is a uniform solution with the solid content controlled between 0.5 and 50 weight percent.
Further, the filler is coated on the surface of the mesoporous support matrix and then is subjected to crosslinking or curing treatment;
wherein the crosslinking or curing treatment comprises a high temperature heat treatment or a light irradiation treatment.
Further, the fixing treatment comprises surface adsorption fixing, deposition fixing, high-temperature heat treatment, light irradiation or crosslinking curing treatment by adding glutaraldehyde.
Furthermore, the mesoporous support matrix is prepared from at least one of polypropylene, polyethylene, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyester, polyamide, nylon and glass fiber;
the mesoporous support matrix comprises at least one of a flat microporous membrane, a hollow fiber microporous membrane, a fine fiber non-woven fabric or a hollow woven fiber tube.
Furthermore, the mesoporous size of the mesoporous support matrix is controlled to be 0.01-1000 μm.
Further, the structural formula of the silicone resin or the liquid silicone rubber is shown as follows:
wherein m and n are any one integer of 1,00 to 100,000. R1-R10Respectively is hydrogen, hydroxyl, fatty alkyl (such as: -C)xH2x+1Where x is any integer from 1 to 100), vinyl (e.g.: -CH ═ CxH2xWherein x is any integer of 1-100), phenyl, chlorphenyl, and fluoroalkyl.
Further, the organosilicon curing agent is at least one of hydrogen-containing silicone oil (methyl hydrogen-containing silicone oil, ethyl hydrogen-containing silicone oil, phenyl hydrogen-containing silicone oil, hydrogen-containing cyclotetrasiloxane), alkoxysilane (tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, trimethoxyphenylsilane, trimethoxyoctylsilane, aminopropyltriethoxysilane), peroxide (diacyl peroxide, tertiary alkyl peroxyester, alkyl hydroperoxide, dialkyl peroxide or dialkyl peroxyketal) curing agent.
Further, the inorganic filler comprises at least one of silicon dioxide, titanium dioxide, zinc oxide, aluminum oxide, ferroferric oxide, MOF, copper oxide, silver, gold, graphene or carbon nanotubes or carbon black.
Further, the organic solvent includes at least one of methanol, ethanol, ethylene glycol, glycerol, isopropanol, acetone, n-hexane, n-heptane, toluene, xylene, or dimethyl sulfoxide.
Further, the hydrophilic biomimetic modifier comprises at least one of polyether modified silicone, hydrophilic silicone coupling agent, glycolipid, Polydopamine (PDA), Tannic Acid (TA), acrylic acid, gelatin, collagen, heparin, polyvinyl alcohol, polyethyleneimine, or 3-Aminopropyltriethoxysilane (APTES).
Furthermore, the concentration of the hydrophilic bionic modifier is 0.1-20%.
The embodiment also discloses an MABR supported complex oxygen-containing membrane prepared by the preparation method, which comprises the following steps:
a mesoporous support matrix prepared from a high-strength hydrophobic mesoporous material is used as a support base material layer;
the surface of the supporting substrate layer is filled and coated with fillers to form a compact oxygen permeable permeation transmission layer;
a bionic bioaffinity surface layer fixed on the surface of the permeation and transmission layer.
Further, the thickness of the compact oxygen permeable permeation transmission layer is controlled to be 10-500 nm; the thickness of the bionic bioaffinity surface layer is controlled to be 0-100 nm.
The embodiment also discloses application of the MABR supporting composite oxygen-containing membrane in MABR sewage treatment, in particular application in the field of realizing the synergistic implementation of oxygen consumption and anaerobic microorganism degradation processes in the MABR sewage treatment.
In the embodiment, a mesoporous material with high strength and hydrophobicity is used as a supporting substrate, and then the filler made of a high-efficiency oxygen permeation and transmission polymer material is used for filling and coating on the surface of the supporting substrate, so that part of the filler enters a membrane hole, and therefore, the permeation of oxygen can be effectively increased, the gas mass transfer resistance can be reduced, and the surface roughness of the membrane can be improved. Meanwhile, the bionic biocompatible surface layer with excellent hydrophilicity and microbial affinity is fixed on the surface of the support substrate coated with the filler, so that the rough surface of the substrate coated with the filler has biological affinity, the bionic biocompatible surface layer is ensured to be not easy to fall off, the problem that the surface layer can face to fall off in the actual application process is solved, and the long-term actual application is facilitated.
Meanwhile, the preparation method in the embodiment is simple in process, low in material price and free of toxic reagents in the experimental process, and the obtained MABR supported composite oxygen-containing membrane is stable in performance in the MABR sewage treatment process, excellent in sewage treatment effect and wide in application value.
Drawings
In order to more clearly illustrate the detailed description of the invention or the technical solutions in the prior art, the drawings that are needed in the detailed description of the invention or the prior art will be briefly described below. Throughout the drawings, like elements or portions are generally identified by like reference numerals. In the drawings, elements or portions are not necessarily drawn to scale.
Fig. 1 is a schematic structural view of an MABR-supported complex-oxygen-containing membrane according to an embodiment of the present invention;
fig. 2 is another schematic view of fig. 1 according to an embodiment of the invention.
A-a support substrate layer, B-a permeation and transmission layer and C-a bionic bioaffinity surface layer.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are only for illustrating the technical solutions of the present invention more clearly, and therefore are only examples, and the protection scope of the present invention is not limited thereby.
It should be noted that, in the embodiments of the present invention, the terms referred to are:
a membrane aeration bioreactor (generally abbreviated as MABR) is a type of membrane bioreactor, and is a sewage treatment technology in which oxygen and pollutants form a concentration difference near a biological membrane by oxygenating a hydrophobic and air-permeable hollow fiber membrane cavity 100, the oxygen and the pollutants diffuse in different directions from inside to outside and from outside to inside with the membrane cavity as a center, and dissolved oxygen is consumed by metabolism of microorganisms in the biological membrane to degrade organic pollutants in sewage.
The mesoporous support base is a support base material prepared from mesoporous materials, and the mesoporous materials are porous materials with the pore diameter of 2-50 nm. The mesoporous material has the characteristics of extremely high specific surface area, regular and ordered pore channel structure, narrow pore size distribution, continuously adjustable pore size and the like, so that the mesoporous material plays a role in the adsorption and separation of macromolecules, particularly catalytic reaction, which are difficult to complete by a plurality of microporous zeolite molecular sieves.
The types of the organic silicon resin or the liquid silicon rubber mainly comprise three types of hydroxyl-terminated type, vinyl-terminated type and methyl-terminated type; the curing and crosslinking modes of different types of silicone resins or silicone rubbers are as follows:
condensation reaction crosslinking type, wherein the structural formula of a curing agent is RSiX3, X comprises chloro, methoxy, ethoxy and acetoxyl, such as tetraethoxysilane, trimethoxyphenylsilane, trimethoxyoctylsilane, gamma-aminopropyltriethoxysilane and other alkoxy silanes, a catalyst is dibutyltin dilaurate (DBTO L), a group X in the curing agent is hydrolyzed to generate silanol Si (OH)3, and hydroxyl in the silanol and hydroxyl in hydroxyl-terminated silicon resin or silicon rubber can generate dehydration condensation reaction to generate an Si-O-Si crosslinking structure;
addition reaction crosslinking type, the curing agent structure contains multiple Si-H bonds, such as methyl hydrogen silicone oil, ethyl hydrogen silicone oil, phenyl hydrogen silicone oil, hydrogen cyclotetrasiloxane, and the catalyst is metal Pt or chloroplatinic acid (H2PtCl6 & 6H 2O). Si-H bonds in the curing agent and double bonds in the vinyl-terminated silicon resin or silicon rubber are added to generate a Si-CH2-CH2-Si structure;
peroxide crosslinking type, wherein the curing agent structure comprises a peroxy bond (-O-O-), such as diacyl peroxide, tertiary alkyl peroxyester, alkyl hydroperoxide, dialkyl peroxide, dialkyl peroxyketal. The peroxy bond generates RO and oxygen-containing radical under heating, and the radical abstracts H in terminal methyl silicone resin or silicone rubber to generate-CH 2-structure, -CH 2-cross-links to each other to generate-CH 2-CH 2-structure.
In the following, the skin care of the smart mirror device provided by the embodiments of the invention will be described and explained in detail through several specific embodiments.
The preparation method mainly comprises the following steps:
cleaning the surface of the substrate and removing burrs through heat treatment to obtain a mesoporous support substrate;
preparing a filler with high-efficiency oxygen permeation and transmission performance;
coating the filler on the surface of the mesoporous support matrix, and performing crosslinking or curing treatment to obtain the efficient oxygen-permeable support composite oxygen-containing membrane;
and soaking the high-efficiency oxygen-permeable support composite oxygen-containing membrane in a hydrophilic bionic modifier solution, and carrying out fixation treatment to obtain the biological support composite oxygen-containing membrane with the high-efficiency oxygen-permeable parent biomass.
Further, the preparation of the filler is as follows: mixing a silicone resin or a liquid silicone rubber: organosilicon curing agent: organosilicon catalyst: the inorganic filler comprises the following components in percentage by mass: 10-80:0.01-10:0-10:0-10, and dispersing and dissolving in organic solvent to prepare filling solution.
Further, the filling solution is a uniform solution with the solid content controlled between 0.5 and 50 weight percent.
Further, the filler is coated on the surface of the mesoporous support matrix and then is subjected to crosslinking or curing treatment;
wherein the crosslinking or curing treatment comprises a high temperature heat treatment or a light irradiation treatment.
Further, the fixing treatment comprises surface adsorption fixing, deposition fixing, high-temperature heat treatment, light irradiation or crosslinking curing treatment by adding glutaraldehyde.
Furthermore, the mesoporous support matrix is prepared from at least one of polypropylene, polyethylene, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyester, polyamide, nylon and glass fiber;
the mesoporous support matrix comprises at least one of a flat microporous membrane, a hollow fiber microporous membrane, a fine fiber non-woven fabric or a hollow woven fiber tube.
Furthermore, the mesoporous size of the mesoporous support matrix is controlled to be 0.01-1000 μm.
Further, the structural formula of the silicone resin or the liquid silicone rubber is shown as follows:
wherein m and n are any one integer of 1,00 to 100,000. R1-R10Respectively is hydrogen, hydroxyl, fatty alkyl (such as: -C)xH2x+1Where x is any integer from 1 to 100), vinyl (e.g.: -CH ═ CxH2xWherein x is any integer of 1-100), phenyl, chlorphenyl, and fluoroalkyl.
Further, the organosilicon curing agent is at least one of hydrogen-containing silicone oil (methyl hydrogen-containing silicone oil, ethyl hydrogen-containing silicone oil, phenyl hydrogen-containing silicone oil, hydrogen-containing cyclotetrasiloxane), alkoxysilane (tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, trimethoxyphenylsilane, trimethoxyoctylsilane, aminopropyltriethoxysilane), peroxide (diacyl peroxide, tertiary alkyl peroxyester, alkyl hydroperoxide, dialkyl peroxide or dialkyl peroxyketal) curing agent.
Further, the inorganic filler comprises at least one of silicon dioxide, titanium dioxide, zinc oxide, aluminum oxide, ferroferric oxide, MOF, copper oxide, silver, gold, graphene or carbon nanotubes or carbon black.
Further, the organic solvent includes at least one of methanol, ethanol, ethylene glycol, glycerol, isopropanol, acetone, n-hexane, n-heptane, toluene, xylene, or dimethyl sulfoxide.
Further, the hydrophilic biomimetic modifier comprises at least one of polyether modified silicone, hydrophilic silicone coupling agent, glycolipid, Polydopamine (PDA), Tannic Acid (TA), acrylic acid, gelatin, collagen, heparin, polyvinyl alcohol, polyethyleneimine, or 3-Aminopropyltriethoxysilane (APTES).
Furthermore, the concentration of the hydrophilic bionic modifier is 0.1-20%.
The embodiment also discloses an MABR supported complex oxygen-containing membrane prepared by the preparation method, which comprises the following steps:
a mesoporous support matrix prepared from a high-strength hydrophobic mesoporous material is used as a support base material layer;
the surface of the supporting substrate layer is filled and coated with fillers to form a compact oxygen permeable permeation transmission layer;
a bionic bioaffinity surface layer fixed on the surface of the permeation and transmission layer.
Further, the thickness of the compact oxygen permeable permeation transmission layer is controlled to be 10-500 nm; the thickness of the bionic bioaffinity surface layer is controlled to be 0-100 nm.
The embodiment also discloses application of the MABR supporting composite oxygen-containing membrane in MABR sewage treatment, in particular application in the field of realizing the synergistic implementation of oxygen consumption and anaerobic microorganism degradation processes in the MABR sewage treatment.
In the embodiment, a mesoporous material with high strength and hydrophobicity is used as a base material, and then the filler made of a high-efficiency oxygen permeation and transmission polymer material is used for filling and coating on the surface of the base material, so that part of the filler enters a membrane hole, and therefore, the permeation of oxygen can be effectively increased, the gas mass transfer resistance can be reduced, and the surface roughness of the membrane can be improved. Meanwhile, the bionic bioaffinity surface layer with excellent hydrophilicity and microbial affinity is fixed on the surface of the base material coated with the filler, so that the rough surface of the base material coated with the filler has the bioaffinity, the MABR supporting composite oxygen-containing membrane is ensured not to fall off easily, the problem that the surface layer can fall off in the practical application process is solved, and the method is more beneficial to long-term practical application
Meanwhile, the preparation method in the embodiment is simple in process, low in material price and free of toxic reagents in the experimental process, and the obtained MABR supported composite oxygen-containing membrane is stable in performance in the MABR sewage treatment process, excellent in sewage treatment effect and wide in application value.
The following is illustrated by several specific examples of actual MABR support composite oxygenation membrane preparation:
example 1:
(1) cleaning the surface of a section of polyvinylidene fluoride hollow fiber porous membrane with the average pore diameter of about 0.15 mu m for 3 times by using ethanol, and drying for later use;
(2) dispersing and dissolving hydroxyl-terminated Polydimethylsiloxane (PDMS), tetraethoxysilane, DBTO L and titanium dioxide in dimethylbenzene to prepare a uniform solution with the solid content of 25 wt%, namely a filler, wherein the ratio of PDMS to tetraethoxysilane to DBTO L to titanium dioxide is 10:1:0.5: 0;
(3) and (3) soaking the mesoporous polyvinylidene fluoride matrix filling and coating high-efficiency oxygen permeation supporting composite oxygen-containing membrane obtained in the step (2) in 10% of PDA and polyethyleneimine solution, and fixing the membrane through surface chemical codeposition treatment to obtain the mesoporous polyvinylidene fluoride filling and coating high-efficiency oxygen permeation supporting composite oxygen-containing membrane.
Example 2:
(1) cleaning the surface of a section of polytetrafluoroethylene hollow fiber porous membrane with the average pore diameter of about 0.02 mu m for 5 times by using ethanol, and drying for later use;
(2) dispersing and dissolving hydroxyl-terminated polydimethylsiloxane, trimethoxyoctylsilane, DBTO L and silicon dioxide in normal hexane to prepare a uniform solution with the solid content of 0.5 wt%, namely a filler, wherein the ratio of PDMS to trimethoxyoctylsilane to DBTO L to silicon dioxide is 10:0.1:0.075: 0.1;
(3) and (3) soaking the mesoporous polytetrafluoroethylene substrate filling and coating high-efficiency oxygen permeation supporting composite oxygen-containing membrane obtained in the step (2) in a 20% TA solution, and performing surface coating and fixing through normal-temperature curing treatment to obtain the mesoporous polytetrafluoroethylene filling and coating high-efficiency oxygen permeation supporting MABR supporting composite oxygen-containing membrane.
Example 3:
(1) cleaning a section of polyethylene fine fiber non-woven fabric with the average pore diameter of about 0.1 mu m for 2 times by using ethanol, and drying for later use;
(2) vinyl-terminated Polydimethylsiloxane (PDMS) and a cross-linking agent 2,4,6, 8-tetramethylcyclotetrasiloxane
H2PtCl6·6H2O, MOF is dispersed and dissolved in a mixed solution of n-hexane/toluene (1:1) to prepare a uniform solution with a solid content of 50 wt%, namely the filler, wherein the weight ratio of PDMS:
H2PtCl6·6H2o: the ratio of MOFs was: 50:10:10: 9; the solution is filled and coated on the surface of a polyvinylidene fluoride hollow fiber membrane, and high-efficiency oxygen is obtained through high-temperature thermosetting treatmentThe mesoporous polyethylene substrate with the permeation and transmission performance is filled and coated with a high-efficiency oxygen-permeable support composite oxygen-containing membrane, namely the high-efficiency oxygen-permeable support composite oxygen-containing membrane;
(3) and (3) soaking the mesoporous polyethylene substrate filled and coated high-efficiency oxygen permeable support composite oxygen-containing membrane obtained in the step (2) in 5% of polyvinyl alcohol solution, and performing surface fixation through glutaraldehyde crosslinking treatment to obtain the mesoporous polyvinylidene fluoride filled and coated high-efficiency oxygen permeable MABR support composite oxygen-containing membrane.
Example 4:
(1) cleaning a polyester fine fiber non-woven fabric with an average pore diameter of about 50 mu m for 5 times by using ethanol, and drying for later use;
(2) dispersing and dissolving methyl-terminated Polydimethylsiloxane (PDMS), dibenzoyl peroxide (BPO) and gold in a mixed solution of ethanol/glycerol (1:1) to prepare a uniform solution with the solid content of 20 wt%, namely the filler, wherein the weight ratio of PDMS: BPO: the proportion of gold is: 10:1: 3; the solution is filled and coated on the surface of the polyester fine fiber non-woven fabric, and the mesoporous polyester fine fiber non-woven fabric substrate with high-efficiency oxygen permeation and transmission performance is obtained through high-temperature thermosetting treatment, and is filled and coated with high-efficiency oxygen permeation composite non-woven fabric, namely the high-efficiency oxygen permeation support composite oxygen-containing membrane;
(3) and (3) filling and coating the mesoporous polyester fine fiber non-woven fabric substrate obtained in the step (2) with a high-efficiency oxygen-permeable composite non-woven fabric, soaking the substrate in 0.1% of PDA solution, and carrying out surface fixation through the bionic adhesion effect of the PDA to obtain the mesoporous polyester fine fiber non-woven fabric filled and coated with the high-efficiency oxygen-permeable parent substance composite non-woven fabric, namely the MABR supported composite oxygen-containing membrane.
Example 5:
(1) cleaning a polyurethane hollow fiber braided tube with the average pore diameter of about 0.45 mu m for 4 times by using ethanol, and drying for later use;
(2) dispersing and dissolving fluorine-containing polysiloxane, di-tert-butyl peroxide and zinc oxide in a xylene solution to prepare a uniform solution with a solid content of 20 wt%, namely the filler, wherein the fluorine-containing polysiloxane: di-tert-butyl peroxide: the proportion of zinc oxide is as follows: 80:10: 3; filling and coating the solution on the surface of a polyurethane hollow fiber braided tube, and performing high-temperature thermosetting treatment to obtain a mesoporous polyurethane hollow fiber braided tube with high-efficiency oxygen permeation and transmission performance, wherein the mesoporous polyurethane hollow fiber braided tube is filled and coated with a high-efficiency oxygen permeation and support composite oxygen-containing membrane, namely the high-efficiency oxygen permeation and support composite oxygen-containing membrane;
(3) and (3) filling and coating the high-efficiency oxygen-permeable supporting composite oxygen-containing membrane on the mesoporous polyurethane hollow fiber braided tube obtained in the step (2), performing surface plasma treatment to generate activated carboxyl on the surface, then soaking the surface in a 2% heparin and APTES solution, and performing surface grafting APTES and heparin electrostatic adsorption to fix the surface, thus obtaining the high-efficiency oxygen-permeable supporting composite oxygen-containing membrane on the mesoporous polyurethane hollow fiber braided tube.
Example 6:
(1) washing a section of polyamide hollow fiber braided tube with the average pore diameter of about 1000 mu m for 3 times by using ethanol, and drying for later use;
(2) dispersing and dissolving phenyl silicone oil, tert-butyl hydroperoxide and ferroferric oxide in an n-heptane solution to prepare a uniform solution with the solid content of 8 wt%, namely the filler, wherein the weight ratio of the phenyl silicone oil: t-butyl hydroperoxide: the proportion of ferroferric oxide is as follows: 10:0.01: 0.1; filling and coating the solution on the surface of a polyamide hollow fiber braided tube, and performing high-temperature thermosetting treatment to obtain a mesoporous polyamide hollow fiber braided tube with high-efficiency oxygen permeation and transmission performance, wherein the mesoporous polyamide hollow fiber braided tube is filled and coated with a high-efficiency oxygen permeation and support composite oxygen-containing membrane, namely the high-efficiency oxygen permeation and support composite oxygen-containing membrane;
(3) and (3) filling and coating the high-efficiency oxygen-permeable supporting composite oxygen-containing membrane on the mesoporous polyamide hollow fiber braided tube obtained in the step (2), performing surface plasma treatment to generate activated hydroxyl on the surface, fixing APTES through electrostatic adsorption, soaking the APTES in 1% polyethyleneimine solution, and performing crosslinking and fixing through glutaraldehyde to obtain the high-efficiency oxygen-permeable supporting composite oxygen-containing membrane filled and coated on the mesoporous polyamide hollow fiber braided tube.
Example 7:
(1) cleaning a polypropylene hollow fiber membrane with the average pore diameter of about 0.25 mu m for 5 times by using ethanol, and drying for later use;
(2) mixing vinyl-terminated PDMS and polymethyl methacrylateRadical hydrogen siloxane, H2PtCl6·6H2Dispersing and dissolving O and titanium dioxide in isopropanol solution to prepare uniform solution with solid content of 15 wt%, namely the filler, wherein the mass ratio of PDMS: polymethylhydrosiloxane: h2PtCl6·6H2O: the proportion of the copper oxide is as follows: 10:1:1: 10; filling and coating the solution on the surface of a polypropylene hollow fiber membrane, and performing high-temperature thermosetting treatment after the solvent is evaporated to obtain a mesoporous polypropylene hollow fiber membrane with high-efficiency oxygen permeation and transmission performance, wherein the mesoporous polypropylene hollow fiber membrane is filled and coated with a high-efficiency oxygen permeation and support composite oxygen-containing membrane, namely the high-efficiency oxygen permeation and support composite oxygen-containing membrane;
(3) and (3) soaking the mesoporous nylon hollow fiber braided tube obtained in the step (2) filled and coated with the high-efficiency oxygen permeation supporting composite oxygen-containing membrane in 1% of mixed solution of PDA and polyethyleneimine (the ratio is 1:1), and carrying out surface fixation by a surface chemical codeposition method to obtain the mesoporous polypropylene hollow fiber membrane filled and coated with the high-efficiency oxygen permeation supporting composite oxygen-containing membrane.
Example 8:
(1) cleaning a glass fiber hollow fiber braided tube with the average pore diameter of about 0.01 mu m for 5 times by using ethanol, and drying for later use;
(2) the preparation method comprises the steps of dispersing and dissolving side methoxy Polysiloxane (PMOS), hydroxyl-terminated Polydimethylsiloxane (PDMS) and dibutyltin dilaurate (DBTO L) in an ethanol solution to prepare a uniform solution with the solid content of 20 wt%, namely a filler, wherein the ratio of the PMOS to the PDMS to the DBTO L is 30:9: 10;
(3) and (3) soaking the mesoporous hollow fiber braided tube filling and coating high-efficiency oxygen permeation supporting composite oxygen-containing membrane obtained in the step (2) in 5% of mixed solution of PDA and polyether modified organic silicon, and fixing by a surface chemical deposition method to obtain the high-efficiency oxygen permeation supporting composite oxygen-containing membrane filling and coating the mesoporous glass fiber hollow fiber braided tube.
The above examples were tested to obtain table 1:
from table 1, it is understood that the contact angles of the terminal vinyl groups and the terminal methyl PDMS in examples 3, 4 and 7 are increased compared to the hydroxyl-terminated PDMS used in examples 1 and 2, and the contact angle after modification is further increased due to the strong hydrophobicity of F atoms in the fluorine-containing polysiloxane of example 5. After different hydrophilic layers are treated, the contact angles of the supported composite oxygen-containing membrane are all reduced to be below 70 degrees, and the successful coating of the oxygen high-efficiency permeation and transmission polymer layer and the bionic biological affinity surface layer is proved.
After the surface of the base material is coated with the silicone resin with the efficient oxygen permeation and transmission effect, the surface contact angle is increased, and the hydrophobicity is slightly improved. Meanwhile, after different types of silicone resin are coated, the gas transmission flux of the membrane material developed in the embodiments 1 to 8 is improved by 25.5 to 47.3 percent compared with that before modification, which shows that the permeation and transmission efficiency of the substrate material to oxygen is obviously improved by utilizing the coating modification of the silicone resin, mainly because the Si-O-Si bond in the dense silicone resin polymer has high flexibility and is beneficial to the permeation and transmission of oxygen molecules.
After the surface of the high-efficiency oxygen-permeable support composite oxygen-containing membrane is subjected to hydrophilization treatment, the contact angles of the materials are all reduced to be below 70 degrees. Tests show that the microbial load of the materials in examples 1-8 is improved by 30.4% -55.3% and the microbial film thickness is increased by 28.3% -49.7% in the same time before and after hydrophilization treatment. Compared with the supported complex oxygen-containing membrane which is not filled and coated with the silicon resin and is directly coated with the hydrophilic layer, the surface roughness of the hydrophobic layer is increased, so that the substance of the parent substance layer is fixed, and the sewage treatment efficiency is improved by 33.3-57.8% (calculated by the reduction value of COD and N content in water in unit time).
According to the embodiments, the technical solution of the present embodiment teaches the following advantages:
1) the support base material layer can effectively ensure the mechanical strength of the support composite oxygen-containing membrane, and simultaneously can reduce the effective thickness of the gas efficient transmission and permeation high polymer material, improve the gas permeation transmission efficiency and effectively reduce the mass transfer resistance;
2) the oxygen high-efficiency permeation and transmission high polymer material has excellent oxygen permeation and transmission performance and super-hydrophobic performance, can ensure oxygen high-efficiency permeation and transmission, and can prevent water from wetting and leaking;
3) the oxygen high-efficiency permeation and transmission polymer material can improve the gas transmission performance after the surface of the membrane is filled and coated, can improve the surface roughness of the base material, is beneficial to the firm fixation of the bionic affinity surface layer, further promotes the adhesion and the growth of microorganisms on the bionic affinity surface layer carrier of the high-efficiency permeation and affinity biomass membrane in the application process, and can obviously improve the activity of the microorganisms and the sewage treatment efficiency;
4) when in aeration and oxygen supply, oxygen can be directly utilized by microorganisms growing on the surface layer of the supporting composite oxygen-containing membrane with excellent hydrophilicity and microbial affinity through the transmission of the hydrophobic mesoporous substrate, and does not need to pass through a liquid phase boundary layer, thereby being beneficial to the improvement of oxygen supply speed and the utilization rate of the surface microorganisms to the oxygen, and the oxygen utilization rate can reach 100 percent theoretically;
5) the MABR supporting composite oxygen-containing membrane with the composite structure can realize gas micro-bubbling, can be used for treating wastewater containing volatile components, cannot blow off volatile organic compounds, and avoids secondary pollution caused by the fact that volatile substances in the wastewater enter the atmosphere along with bubbles in the conventional aeration process; the foaming problem due to surfactant or microbial secretion can be avoided during aeration.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the present invention, and they should be construed as being included in the following claims and description. In particular, the technical features mentioned in the embodiments can be combined in any way as long as there is no structural conflict. It is intended that the invention not be limited to the particular embodiments disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (10)
1. A preparation method of an MABR supported composite oxygen-containing membrane is characterized by mainly comprising the following steps:
cleaning the surface of the substrate and removing burrs through heat treatment to obtain a mesoporous support substrate;
preparing a filler with high-efficiency oxygen permeation and transmission performance;
coating the filler on the surface of the mesoporous support matrix, and performing crosslinking or curing treatment to obtain a high-efficiency oxygen-permeable support composite oxygen-containing membrane;
and soaking the high-efficiency oxygen-permeable supported composite oxygen-containing membrane in a hydrophilic bionic modifier solution, and carrying out fixation treatment to obtain the biological supported composite oxygen-containing membrane with the high-efficiency oxygen-permeable parent substance.
2. The method for preparing according to claim 1, wherein the filler is prepared by: mixing a silicone resin or a liquid silicone rubber: organosilicon curing agent: organosilicon catalyst: the inorganic filler comprises the following components in percentage by mass: 10-80:0.01-10:0-10:0-10, and dispersing and dissolving in organic solvent to prepare filling solution.
3. The method of claim 2, wherein the filling solution is a homogeneous solution having a controlled solid content of 0.5 wt% to 50 wt%.
4. The preparation method according to claim 1 or 2, characterized in that the filler is coated on the surface of the mesoporous support matrix and then is subjected to crosslinking or curing treatment;
wherein the crosslinking or curing treatment comprises a high temperature heat treatment or a light irradiation treatment.
5. The method according to claim 1, wherein the fixing treatment comprises surface adsorption fixing, deposition fixing, high-temperature heat treatment, light irradiation, or crosslinking curing treatment with glutaraldehyde.
6. The preparation method according to claim 1, wherein the mesoporous supporting matrix is prepared from at least one of polypropylene, polyethylene, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyester, polyamide, nylon and glass fiber;
the mesoporous support matrix comprises at least one of a flat microporous membrane, a hollow fiber microporous membrane, a fine fiber non-woven fabric or a hollow woven fiber tube.
7. The method according to claim 1 or 6, wherein the mesoporous size of the mesoporous support matrix is controlled to be 0.01 to 1000 μm.
8. The method according to claim 1, wherein the structural formula of the silicone resin or the liquid silicone rubber is as follows:
wherein m and n are any one integer of 1,00 to 100,000. R1-R10Respectively is hydrogen, hydroxyl, fatty alkyl (such as: -C)xH2x+1Where x is any integer from 1 to 100), vinyl (e.g.: -CH ═ CxH2xWherein x is any integer of 1-100), phenyl, chlorphenyl, and fluoroalkyl.
9. An MABR-supported complex oxygen-containing film produced by the production method according to any one of claims 1 to 8, comprising:
a mesoporous support matrix prepared from a high-strength hydrophobic mesoporous material is used as a support base material layer;
the surface of the supporting substrate layer is filled and coated with fillers to form a compact oxygen permeable permeation transmission layer;
a bionic bioaffinity surface layer fixed on the surface of the permeation and transmission layer.
10. An application of an MABR supported composite oxygen-containing membrane in MABR sewage treatment is characterized by realizing the application in the field of the synergistic implementation of oxygen consumption and anaerobic microorganism degradation processes in the MABR sewage treatment.
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