CN108014650A - The method and sewage water treatment method of microorganism in smart membrane and preparation method and membrane module and film-bioreactor and trap water - Google Patents

The method and sewage water treatment method of microorganism in smart membrane and preparation method and membrane module and film-bioreactor and trap water Download PDF

Info

Publication number
CN108014650A
CN108014650A CN201610930380.8A CN201610930380A CN108014650A CN 108014650 A CN108014650 A CN 108014650A CN 201610930380 A CN201610930380 A CN 201610930380A CN 108014650 A CN108014650 A CN 108014650A
Authority
CN
China
Prior art keywords
film
iron
membrane
weight
dispersion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201610930380.8A
Other languages
Chinese (zh)
Other versions
CN108014650B (en
Inventor
赵锐
马欣
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Original Assignee
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to CN201610930380.8A priority Critical patent/CN108014650B/en
Publication of CN108014650A publication Critical patent/CN108014650A/en
Application granted granted Critical
Publication of CN108014650B publication Critical patent/CN108014650B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/024—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/028—Molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/34—Polyvinylidene fluoride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/48—Polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/52—Polyethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
    • B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/48—Antimicrobial properties

Abstract

The invention discloses a kind of smart membrane and preparation method thereof and a kind of membrane module and membrane bioreactor and its application, the smart membrane contains film matrix and the dispersion being dispersed in the film matrix, the dispersion contains at least one iron containing compounds of carrier and load on the carrier, and the iron containing compounds are selected from the hydroxide of molysite, the oxide of iron and iron.Method the invention also discloses the microorganism in the trap water using the smart membrane or membrane module and the sewage water treatment method using the membrane bioreactor.Compared with existing antimicrobial membranes, smart membrane of the invention can perceive situation and region of the film by microbial contamination, and targetedly contaminated area is handled, and can pollution alleviate after automatic hold function；The activity and quantity of (such as in biochemical reactor) microorganism will not be killed or suppress in adjacent area, the influence to biochemical reaction is small, can be applied to most of water process environment.

Description

Smart membrane and preparation method and membrane module and film-bioreactor and trap water The method and sewage water treatment method of middle microorganism
Technical field
The present invention relates to a kind of smart membrane and its preparation method and application, and the invention further relates to a kind of membrane module and one kind Film-bioreactor and its application, at a kind of method of microorganism in trap water and a kind of sewage Reason method.
Background technology
With the progress of membrane material and membrane module, membrane separation technique has become the core technology of water purification and sewage treatment field One of, for pollutants such as the microorganism in trap water, suspended particulates.In use, the microbes under film retention are attached In film surface and fenestra, easily grow breeding, cause Pore Blocking, membrane flux is declined rapidly, add Membrane cleaning frequency The service life of film will be also shortened in rate, the irreversible blocking of formation.Therefore, the microbial contamination of film is that application of membrane faces One main problem.
At present, the means for alleviating microbial contamination mainly introduce water wetted material into membrane material, improve the hydrophily of film, Surface energy is improved, so as to reduce fouling membrane；Antiseptic is added in film surface or material internal, such as antibiotic, polycation, nanometer Inorganic material etc., suppresses or kills film surface and surrounding microorganism；The either combination and reinforcing of two methods.Common material Expect for polypyridine salt, polyquaternium, nano silver simple substance or silverbased compound (such as CN104353366A, CN104014256A), carbon Nanotube (such as CN102008908A), titanium dioxide (such as CN104117291A).
But when above-mentioned film is used for film-bioreactor (MBR), bubble-free aeration biochemical reactor and microculture Device is frequently contacted, membrane material when new membrane-bioprocess technology between the film loaded due to the microorganism in reactor with high density The sterilization of material or antibacterial property can also influence the activity and quantity of microorganism, and then reduce the efficiency of bioreactor, or even broken Bad biochemical property.
Therefore, there is an urgent need for a kind of microbial contamination that can judge film, response is targetedly produced, while do not interfere with technique The intelligent solution of required microorganism.
The content of the invention
The sterilization of membrane material or antibacterial property meeting used by it is an object of the invention to overcome existing antimicrobial membranes The activity and quantity of microorganism are influenced, and then reduces the efficiency of bioreactor, or even destroys the technical problem of biochemical property, is carried For a kind of smart membrane, which can not only be reasonably resistant to microbial contamination, and the influence to biochemical process is small.
According to the first aspect of the invention, the present invention provides a kind of smart membrane, the smart membrane contain film matrix and The dispersion being dispersed in the film matrix, the dispersion contain at least one of carrier and load on the carrier and contain Iron compound, the iron containing compounds are selected from the hydroxide of molysite, the oxide of iron and iron.
According to the second aspect of the invention, the present invention provides a kind of preparation method of smart membrane, this method to include：Will Dispersion, pore-foaming agent and film basis material are dispersed in dispersant, obtain casting solution, and the casting solution is formed a film, institute State dispersion and contain at least one iron containing compounds of carrier and load on the carrier, the iron containing compounds are selected from iron The hydroxide of salt, the oxide of iron and iron.
According to the third aspect of the present invention, the present invention provides a kind of method system as described in second aspect of the present invention Standby smart membrane.
According to the fourth aspect of the present invention, the present invention provides a kind of membrane module, the membrane module to contain film and be used for The supporting structure of support membrane, wherein, the film is the smart membrane described in the first aspect of the present invention or the 3rd aspect.
According to the fifth aspect of the present invention, the present invention provides a kind of film-bioreactor, wherein, the film-biology is anti- The film in device is answered as in the smart membrane or the film-bioreactor described in the first aspect of the present invention either the 3rd aspect Membrane module for the present invention the 4th aspect described in membrane module.
According to the sixth aspect of the invention, the present invention provides above-mentioned smart membrane, membrane module or film-bioreactor Application in water process.
According to the seventh aspect of the present invention, the present invention provides a kind of method of microorganism in trap water, this method bag Including makes the water containing microorganism flow through film or membrane module, with the microorganism in trap water, wherein, the film is the present invention first Smart membrane described in a aspect or the 3rd aspect, the membrane module are the membrane module described in the 4th aspect of the present invention.
According to the eighth aspect of the present invention, the present invention provides a kind of sewage water treatment method, this method to be included sewage Biodegradation is carried out in film-bioreactor, while causes the water in bioreactor under the action of film pressure at both sides difference By membrane module, water outlet is obtained, wherein, the film-bioreactor is film-biological respinse described in the 5th aspect of the present invention Device.
Compared with existing antimicrobial membranes, smart membrane according to the present invention has the following advantages that：
(1) according to the present invention smart membrane can perceive situation and region of the film by microbial contamination, targetedly to by Polluted area is handled, and can pollution alleviate after automatic hold function；
(2) (such as in biochemical reactor) microorganism will not be killed or be suppressed in adjacent area to smart membrane according to the present invention Activity and quantity, the influence to biochemical reaction is small；
(3) smart membrane according to the present invention is applied widely, can apply to most of water process environment.
Smart membrane according to the present invention can be prepared by using conventional filming technology, and used raw material is conventional commercial Raw material, beneficial to accomplishing scale production.
Smart membrane according to the present invention can perceive situation and region of the film by microbial contamination, targetedly to contaminated Region is handled, and can may is that after pollution is alleviated the reason for automatic hold function：Iron ion is in aerobic and anaerobic ring Under border, anti-microbial property can change, wherein, Fe2+With broad-spectrum sterilization and bacteriostasis, and Fe3+Without this function； Worked using the biochemical process majority of film under aerobic condition, in the presence of oxygen, in film by the immobilized iron of carrier with Fe3+Form exist, film do not possess sterilization/bacteria resistance function；When film is by microbial contamination, the growth of microorganism, breeding and The extracellular polymeric meeting blocking oxygen of generation is reached in film surface or fenestra, forms local anaerobic zone；Under anaerobic environment, Fe3+The electron acceptor that will be reacted as microbiological oxidation Organic substance in water, receives electronics and is transformed into Fe2+, in the carrier of enriched iron Surrounding locally starting sterilization/bacteria resistance function, alleviates microbial contamination；Carried in addition, the somatic cells killed can also be the process For carbon source and then electron donor is provided, the iron supported until destroying the microbial contamination layer formed to make on film contacts oxygen, oxygen Fe will be substituted3+As electron acceptor, so that again with Fe3+Form stable exist, the sterilization of contaminated area on film/antibacterial Function is automatically switched off.
Also, due to change of the microorganism to iron valence state, can both occur under the ionic state of iron, also can be in the solid shape of iron Occur under formula (oxide of such as iron and the hydroxide of iron), therefore smart membrane can be applied to most of water according to the present invention Processing environment.
Brief description of the drawings
Attached drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.
Fig. 1 shows experimental example 1 and Experimental comparison's example 1-2 in experimentation, and transmembrane pressure changes with time, its In, ordinate TMP is transmembrane pressure (MPa), abscissa t for the time (my god).
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively It can be combined with each other between the endpoint value of a scope and single point value, and individually between point value and obtain one or more New number range, these number ranges should be considered as specific open herein.
According to the first aspect of the invention, the present invention provides a kind of smart membrane, the smart membrane contain film matrix and The dispersion being dispersed in the film matrix, the dispersion contain the iron content chemical combination of carrier and load on the carrier Thing.
Smart membrane according to the present invention, the iron in the iron containing compounds can be ferrous iron, or ferric iron, also Can be ferrous iron and ferric mixing.Usually, the iron in the iron containing compounds is ferric iron.
The iron containing compounds can be the common various compounds that ferro element can be provided for smart membrane, for example, described Iron containing compounds can be more than one or both of hydroxide selected from molysite, the oxide of iron and iron.The iron Salt refer at least part cation be iron ion salt, the iron ion can be ferric ion, or ferrous iron from Son, is preferably ferric ion.
Specifically, the iron containing compounds can be that oxysalt, the cation for containing iron ion selected from cation contain It is more than one or both of hydroxide of the anaerobic hydrochlorate of iron ion, the oxide of iron and iron.It is more specifically, described It selected from inorganic oxysalt that cation is iron ion, cation is the acylate of iron ion, cation that iron containing compounds, which are, It is more than one or both of the oxide of halide, iron for iron ion and the hydroxide of iron.
The preferred embodiment of the iron containing compounds can include but is not limited to iron chloride, ferric nitrate, ferric sulfate, three oxidations two Iron and iron hydroxide.It is highly preferred that the iron containing compounds are one or both of iron chloride, ferric nitrate and ferric sulfate More than.
The iron containing compounds are used to assign smart membrane with anti-microbial property, its content is resisted with that can assign smart membrane with enough Subject to bacterium performance.Usually, on the basis of the total amount of dispersion, the content of iron containing compounds can be 0.5-45 weight %, excellent Elect 1-40 weight % as, more preferably 2-30 weight %, the iron containing compounds are in terms of di-iron trioxide.It is highly preferred that to divide On the basis of the total amount of granular media, the content of the iron containing compounds is 5-25 weight %, can so obtain more stable antibiotic property Energy.
The carrier is used for immobilized iron containing compounds, avoids iron containing compounds from being lost in use, and causes iron content Compound can be uniformly dispersed in film matrix.The carrier can be common porous material, for example, can be porosity without It is more than one or both of machine oxide, clay and molecular sieve.
The porous inorganic oxide can be one or both of aluminium oxide, silica, magnesia and zirconium oxide More than.
The clay can be kaolin, halloysite, montmorillonite, diatomite, galapectite, saponite, rectorite, Hai Pao It is more than one or both of stone, attapulgite, hydrotalcite and bentonite.
The molecular sieve can be one kind in microporous silicon aluminum molecular screen, micropore phosphate aluminium molecular sieve and mesoporous Si-Al molecular sieve Or it is two or more, such as Y type molecular sieve, X-type molecular sieve, A type molecular sieve, L-type molecular sieve, Beta types molecular sieve, FER type molecules In sieve, MOR types molecular sieve, ZSM types molecular sieve, MCM types molecular sieve, SAPO molecular sieve, MCM types molecular sieve and SBA type molecular sieves One or more.The instantiation of the molecular sieve can include but is not limited to Y type molecular sieve, X-type molecular sieve (such as 13X molecular sieves, 10X molecular sieves), A type molecular sieve (such as 3A molecular sieves, 4A molecular sieves, 5A molecular sieves), L-type molecular sieve, Beta types Molecular sieve, FER types molecular sieve, MOR types molecular sieve, type ZSM 5 molecular sieve, ZSM-22 types molecular sieve, ZSM-11 types molecular sieve, ZSM-23 types molecular sieve, ZSM-35 types molecular sieve, MCM-22 types molecular sieve, MCM-49 types molecular sieve, MCM-36 types molecular sieve, MCM-56 types molecular sieve, SAPO-34 types molecular sieve, SAPO-11 types molecular sieve, SAPO-5 types molecular sieve, SAPO-18 type molecules Sieve, APO-5 types molecular sieve, APO-11 types molecular sieve, MeAPO-11 types molecular sieve, MCM-41 types molecular sieve, MCM-48 type molecules Sieve, MCM-50 types molecular sieve, SBA-15 types molecular sieve, SBA-16 types molecular sieve, MSU-1 types molecular sieve and MSU-2 type molecular sieves One or both of more than.
Preferably, the carrier is molecular sieve.
The dispersion is used to introduce iron containing compounds in film matrix, and causes iron containing compounds to can be uniformly dispersed in film In matrix.The content of the dispersion in film matrix so as to introduce subject to enough iron containing compounds.Usually, relative to 100 parts by weight film matrixes, the content of the dispersion can be 5-20 parts by weight, be preferably 8-18 parts by weight, more preferably 10- 15 parts by weight.The content of dispersion can use thermal weight loss method to measure in the smart membrane, (that is, can also be divided by inventory Granular media accounts for the mass percent for the raw material to form film matrix) determine.When measuring dispersion content using thermal weight loss method, test-strips Part is：Measured in air atmosphere, test initial temperature is 25 DEG C, and heating rate is 10 DEG C/min；Sample is before testing 150 DEG C temperature and 1 normal atmosphere depress in argon gas atmosphere it is dry 3 it is small when, quality retention rate during using 600 DEG C is as smart membrane The content of middle dispersion.In embodiment disclosed by the invention, the content of dispersion is determined by inventory in smart membrane.
The particle diameter of the dispersion is the thickness no more than the smart membrane, can be selected according to the thickness of smart membrane Select.Usually, the particle diameter of the dispersion is in the range of 0.5-5 μm, preferably in the range of 0.5-2 μm.In the present invention, " ×-× in the range of " include two endpoint values.
Smart membrane according to the present invention, film matrix are generally polymer film.Polymer in the polymer film can be Common various polymeric film materials, its instantiation can include but is not limited to fluorine-containing polyolefin, polysulfones (including polyether sulfone), It is more than one or both of polyether-ketone, polyamide, polyimides and polyester.The fluorine-containing polyolefin is preferably polyvinylidene fluoride Alkene.Preferably, the polymer in the polymer film is combination more than one or both of fluorine-containing polyolefin, polysulfones.
Smart membrane according to the present invention, can be the film of common various forms, such as can be plate membrane or hollow Tunica fibrosa.
In one embodiment, smart membrane according to the present invention is plate membrane.In this embodiment, the smart membrane It can be self-supported membrane.From film strength is further improved, the smart membrane also contains supporter, the film matrix attachment On at least one surface of the supporter.The supporter can be conventional selection.Specifically, the supporter can be Non-woven cloth or fabric, are preferably non-woven cloth.In this embodiment, the thickness of the film matrix can be according to this The specifically used occasion of smart membrane makes choice.Usually, the thickness of the smart membrane can be 50-150 μm, be preferably 80- 120μm。
In another embodiment, the smart membrane is hollow-fibre membrane.The size of the hollow-fibre membrane can root Made choice according to specifically used occasion.As an example, when for water process, the outside diameter of the hollow-fibre membrane can be 0.5-5mm, is preferably 0.5-3mm, more preferably 0.5-1.5mm；Wall thickness can be 50-500 μm, be preferably 80-300 μm, more Preferably 100-200 μm.
Smart membrane according to the present invention, porosity can be 65-85%, be preferably 70-83%.The porosity is using title Weight method measure, concrete operation method are：At a temperature of 25 DEG C, it is 0.1MPa that the wet film of wetted saturation is positioned over vacuum Vacuum drying oven in drying to constant weight in 60 DEG C, obtain dry film, weigh it is dry before and after film weight change, by the weight change meter The pore volume V of obtained filmHole, the skeleton volume V of the film is determined by the density and dry film weight of membrane materialSkeleton, by following public affairs Formula calculates the porosity of the film：
Porosity=[VHole/(VHole+VSkeleton)] × 100%.
Smart membrane according to the present invention, pure water flux are generally 80-300L/ (m2H), it is preferably 100-250L/ (m2· H), 120-220L/ (m are more preferably2·h).The test method of the pure water flux is specially：Membrane module is made in film：Tablet Diaphragm is positioned over ultrafiltration cup and (is purchased from Millipore, effective membrane area 30cm2) in sealing after directly use；Take 10 hollow fibres Dimension film is put into long 30cm, and in the lucite tube with side water outlet of internal diameter 8cm, both ends are blocked with epoxy resin, and group is made Part, according to epoxy interlamellar spacing and the accurate survey calculation of film wire internal diameter its effective membrane area A.By membrane module room temperature (for 25 DEG C), Under 0.15MPa (gauge pressure) after precompressed 30 minutes, it be 0.1MPa (gauge pressure) to be passed through pure water and keep test pressure, measurement certain time t The interior volume V through pure water.The water passed through by the film of unit area in the following formula unit of account time, i.e. pure water flux J：
J=V/ (At).
According to the second aspect of the invention, the present invention provides a kind of preparation method of smart membrane, this method to include：Will Dispersion, pore-foaming agent and film basis material are dispersed in dispersant, obtain casting solution, and the casting solution is formed a film, institute State dispersion and contain at least one iron containing compounds of carrier and load on the carrier, the iron containing compounds are selected from iron The hydroxide of salt, the oxide of iron and iron.
The dispersion contains the iron containing compounds of carrier and load on the carrier.The iron containing compounds and The species of carrier has been carried out being described in detail above, and details are not described herein again.
Preparation in accordance with the present invention, the content of iron containing compounds can be according to it is contemplated that smart membrane in the dispersion The amount of the iron containing compounds of middle introducing makes choice.Usually, on the basis of the total amount of the dispersion, the iron containing compounds Content can be 0.5-45 weight %, be preferably 1-40 weight %, more preferably 2-30 weight %, the iron containing compounds with Di-iron trioxide meter.It is highly preferred that on the basis of the total amount of dispersion, the content of the iron containing compounds is 5-25 weight %, More stable anti-microbial property can so be obtained.The content of iron containing compounds uses x ray fluorescence spectrometry in the dispersion (XRF) measure, when the method using saturation dipping prepares the dispersion, iron content in dispersion can be measured by inventory The content of compound.
Preparation in accordance with the present invention, the particle diameter of the dispersion can make choice according to the thickness of expected film, So that the particle diameter of resulting dispersion is not more than subject to the thickness of expected film.Specifically, the particle diameter of the dispersion can be in 0.5-5 In the range of μm, preferably in the range of 0.5-2 μm.
Preparation in accordance with the present invention, the dosage of the dispersion can contain according to iron containing compounds in the dispersion Measure and it is contemplated that the amount of the iron containing compounds introduced in smart membrane makes choice.Usually, relative to 100 parts by weight film matrixes Material, the content of the dispersion can be 5-20 parts by weight, be preferably 8-18 parts by weight, more preferably 10-15 parts by weight.
Preparation in accordance with the present invention, the dispersion can be obtained by the way that iron containing compounds are supported on carrier. Iron containing compounds can be supported on carrier using conventional method.
As an example, it can use the method for dipping that iron containing compounds are supported on carrier, so as to obtain described Dispersion.Specifically, the dispersion liquid impregnated carrier for being dispersed with iron containing compounds can be used.The dipping can use saturation to soak Stain, can also use excessive dipping.
In this example, the decentralized medium of the dispersion liquid can be that common energy causes iron containing compounds dissolving or shape Into the medium of stable dispersion, its instantiation can include but is not limited to alcohol and/or water, be preferably water.The dispersion liquid The content of middle iron containing compounds and the number of dipping can according to it is contemplated that the iron containing compounds introduced on carrier content into Row selection, so as to being introduced on carrier subject to enough iron containing compounds.The dipping can carry out at ambient temperature, such as Carried out at a temperature of 10-45 DEG C.The duration of the dipping can be conventional selection, and adsorption equilibrium can be realized by being subject to.
In this example, the solid phase impregnated can be dried under normal conditions, can remove waving on carrier Subject to hair property component.Usually, the drying can carry out at a temperature of 60-180 DEG C, preferably at a temperature of 80-150 DEG C Carry out, carried out more preferably at a temperature of 100-130 DEG C.The drying can carry out under normal pressure (that is, 1 standard atmospheric pressure), It can also carry out at reduced pressure.The duration of the drying can be selected according to dry temperature and pressure Select, be subject to the volatile materials that can be removed to greatest extent on carrier.Usually, the duration of the drying can be 4- 24 it is small when, be preferably 6-20 it is small when, more preferably 10-18 it is small when.
The pore-foaming agent can be the conventional selection of field of membrane preparation, such as can be polyethylene glycol, cellulose ether, poly- ammonia It is more than one or both of ester, polyvinylpyrrolidone.The instantiation of the cellulose ether can include but is not limited to first Base cellulose, hydroxyethylmethylcellulose, carboxymethyl cellulose, ethyl cellulose, benzylcellulose, hydroxyethyl cellulose, hydroxyl Propyl cellulose, hydroxypropyl methyl cellulose, cyanethyl cellulose, benzyl cyanethyl cellulose, carboxymethyl hydroxyethyl cellulose And benzyl cellulose.Preferably, the pore-foaming agent is polyethylene glycol and/or polyvinylpyrrolidone, as polyvinylpyrrolidone, One or both of polyethylene glycol 200, Liquid Macrogol, polyethylene glycol 400, Macrogol 600 and cetomacrogol 1000 with On combination.
The dosage of the pore-foaming agent can be conventional selection, so as to enabling the porosity of the film finally prepared to meet to want Subject to asking.Usually, relative to 100 parts by weight film basis materials, the dosage of the pore-foaming agent can be 5-45 parts by weight, preferably For 10-42 parts by weight.It is highly preferred that relative to 100 parts by weight film basis materials, the dosage of the pore-foaming agent is 15-40 weight Part, the porosity of the film thus prepared can be in 65-85%, preferably in the range of 70-83%.
The dispersant is used to dispersion and pore-foaming agent being uniformly mixed with film basis material, can be used for forming a film to be formed Casting solution.The dispersant can be the various liquid substances that can realize above-mentioned function.Specifically, the dispersant can be It is more than one or both of N, N- dimethylformamide, DMAC N,N' dimethyl acetamide and 1-methyl-2-pyrrolidinone.Relative to 100 weights Part film basis material is measured, the dosage of the dispersant can be 100-900 parts by weight, be preferably 300-850 parts by weight, more preferably For 400-800 parts by weight, more preferably 500-750 parts by weight.
Dispersion, pore-foaming agent and film basis material can be dispersed in dispersant using conventional method, so as to be formed It can be used for the casting solution of film forming.In one embodiment, pore-foaming agent can be dispersed in dispersant, dispersion is added to In the dispersion liquid of formation, film basis material is added after mixing, so as to obtain casting solution.It is scattered uniform from further improving Property and the angle of dispersion efficiency set out, preferably under conditions of with vibration, dispersion is dispersed in the dispersion liquid.Institute It for example can be sonic oscillation to state vibration.The frequency of sonic oscillation can be 25k-130kHz, be preferably 30-100kHz, more excellent Elect 40-60kHz as.The duration of the vibration can be 10 minutes to 2 it is small when, be preferably 0.5-1 it is small when.It is preferred that in 70- Film basis material is mixed with dispersion liquid at a temperature of 90 DEG C.
Preparation in accordance with the present invention, from the angle of the quality for the film for further improving preparation, generally by casting film Liquid carries out deaeration processing, to remove the bubble in casting solution.For example, casting solution can be placed in vacuum environment, so as to remove Bubble in casting solution.
Preparation in accordance with the present invention, can be formed a film casting solution using conventional method.It is for instance possible to use apply Cloth method or solution spinning form a film.
In one embodiment, formed a film using rubbing method.Concrete operations can include：Casting solution is coated on branch At least one surface of support body, solidifies the casting solution of coating, to form the film on the surface for being attached to supporter.The supporter And its species is explained in the smart membrane described in the first aspect of the present invention, is no longer described in detail herein.
It can use conventional method that casting solution is coated on to the surface of supporter, such as：Doctor blade method can be used or squeezed Casting solution is coated on the surface of supporter by pressure rubbing method.Specific coating process is that well known to a person skilled in the art herein No longer it is described in detail.
The coating fluid solidification on the surface of supporter can will be coated under normal conditions, so as to form film.Such as：Can be with The supporter of casting solution is coated with environment temperature (such as 10-45 DEG C), is cooled down with water, so that casting solution solidifies, Form film.Formed after film, conventional method can be used to remove supporter, so as to obtain self-supported membrane.It is preferred that support is not removed Body, and it is so that the film to be formed is attached to the surface of supporter, so as to further improve the film strength of preparation.
In this embodiment, the species of the supporter can make choice according to supporter finally whether is retained. When not removing supporter, the supporter can be non-woven cloth or fabric.
In this embodiment, the dosage of casting solution can make choice according to the thickness of expected film.Usually, it is described The dosage of casting solution make it that the thickness for the film to be formed is 50-150 μm, is preferably 80-120 μm.
Film prepared by the embodiment is used as plate membrane.
In another embodiment, formed a film using solution spinning.What preparation in accordance with the present invention used Casting solution has preferable solution-polymerized SBR performance, under the conditions of conventional solution-polymerized SBR, you can prepare hollow-fibre membrane.Specifically Ground, can carry out spinning, spun doughnut film liquid is by between one section of air using casting solution as spinning solution together with core liquid After gap, hollow-fibre membrane is obtained after being solidified into solidification liquid.
The core liquid and the solidification liquid can be the conventional selection in solution-polymerized SBR field.As an example, the core Liquid and the solidification liquid can be each water.
The flow velocity of the spinning solution and the core liquid can be carried out according to the wall thickness and internal diameter of expected hollow-fibre membrane Selection.Usually, the flow velocity of the spinning solution can be 1.5-8mL/min, be preferably 1.8-5mL/min, more preferably 2- 3mL/min；The flow velocity of the core liquid can be 0.5-8mL/min, be preferably 0.8-5mL/min, more preferably 1-2mL/min. The pressure accommodated in the container of spinning solution generally can be 0.1-0.3MPa (gauge pressure), be preferably 0.15-0.25MPa (gauge pressure). The temperature of spinning solution and core liquid can be each 15-30 DEG C.The temperature of the spinning solution and the core liquid can be identical, also may be used Think difference, it is preferably identical.
The spun filament of spinneret through spinning-drawing machine is by one section of the air gap (that is, spinneret of spinning-drawing machine to solidification The distance of liquid) after, solidified into solidification liquid and form hollow-fibre membrane.The length of the air gap can be conventional selection. Usually, the air gap can be 10-30cm, be preferably 15-25cm, more preferably 20-25cm.
The hollow-fibre membrane of coagulation forming can be collected by reel, and the rotation condition for usually controlling reel at this time is nothing Draw ratio.
Remaining condition of solution-polymerized SBR can be the conventional selection of this area.Usually, the condition of the solution-polymerized SBR makes The outside diameter for the hollow-fibre membrane that must be prepared is 0.5-2mm, is preferably 0.5-3mm, more preferably 0.5-1.5mm；Wall thickness is 50- 500 μm, be preferably 80-300 μm, more preferably 100-200 μm.The specific of solution-polymerized SBR is selected according to expected outside diameter and wall thickness The method of condition is known in those skilled in the art, is repeated no more herein.
Preparation in accordance with the present invention, the film of preparation can be handled using conventional method, that can protect for a long time Deposit.The film of formation is soaked in the mixed liquor formed by G ＆ W for example, preparation in accordance with the present invention preferably further includes It is dry to constant weight in environment temperature (generally 5-45 DEG C) after when bubble 24-48 is small, so as to obtain the film that can be preserved for a long time.Institute State in mixed liquor, the content of glycerine is preferably 30-60 volumes %.
According to the third aspect of the present invention, the present invention provides a kind of method system as described in second aspect of the present invention Standby smart membrane.
According to the fourth aspect of the present invention, the present invention provides a kind of membrane module, the membrane module to contain film and be used for The supporting structure of support membrane, wherein, the film is the film described in the first aspect of the present invention or the 3rd aspect.
The supporting structure is used to film forming a unit, can be made choice according to the specific pattern of film.For example, When the film is plate membrane, the supporting structure can be that the film can be formed as to plate and frame module, takeup type membrane module With the supporting structure of combination more than one or both of cushion cover type membrane module；It is described when the film is hollow-fibre membrane Supporting structure can be the supporting structure that the film can be formed as to tubular membrane component.According to expected membrane module moulder moisture branch The method of support structure is known in those skilled in the art, as space is limited, is no longer described in detail herein.
According to the present invention the first aspect and the 3rd aspect described in film and the 4th aspect described in membrane module tool There are good antimicrobial properties, and region of the film by microbial contamination can be perceived, targetedly contaminated area is carried out Processing, while will not also suppress the activity and quantity of the microorganism in the region adjacent with the film, especially suitable for film-biology work Skill.
Thus, according to the fifth aspect of the present invention, the present invention provides a kind of film-bioreactor, wherein, the film- Film in bioreactor is the film or the film-bioreactor described in the first aspect of the present invention either the 3rd aspect In membrane module for the present invention the 4th aspect described in membrane module.
The film-bioreactor includes film separation unit and biological processing unit, wherein, film separation unit is used for will The fluid handled through biological processing unit is filtered, so as to retain the microorganism in fluid and suspended matter, is obtained purified Fluid.The film-bioreactor has having been widely used in water process.
Film-bioreactor according to the present invention is improved wherein by using film provided by the invention or membrane module The antimicrobial properties of the film used, extend the service life of film, so as to extend the parallel-adder settle-out time of film-microorganism reactor , construction and the method for operation for film-bioreactor are simultaneously not limited.It is referred to existing film-bioreactor Construct to build and run.
According to the sixth aspect of the invention, the present invention provides the first aspect according to the present invention or the 3rd aspect Film-biology described in the 5th aspect of membrane module or the present invention described in the 4th smart membrane, present invention aspect is instead Answer application of the device in water process.
Can during existing water process, the particularly biochemical treatment of water smart membrane incorporated in the present invention, membrane module Or film-bioreactor.
According to the seventh aspect of the present invention, the present invention provides a kind of method of microorganism in trap water, this method bag Including makes the water containing microorganism flow through film or membrane module, with the microorganism in trap water, wherein, the film is the present invention first Smart membrane described in a aspect or the 3rd aspect, the membrane module are the membrane module described in the 4th aspect of the present invention.
The film and membrane module of the present invention can the effectively microorganism in trap water and suspended matter, also, the film and film Component has good antimicrobial properties, can keep the pressure differential of film both sides in the longer time, so as to effectively extend The service life of film and membrane module.
During microorganism in method trap water using the present invention, it can carry out under normal conditions, as long as using this The film or membrane module of invention.Usually, the initial pressure of film both sides poor (that is, transmembrane pressure) can be 0-0.05MPa, Preferably 0.001-0.01MPa.
According to the eighth aspect of the present invention, the present invention provides a kind of sewage water treatment method, this method to be included sewage Biodegradation is being carried out in film-bioreactor, while is causing the water in bioreactor under the action of film pressure at both sides difference By film, water outlet is obtained, wherein, the film-bioreactor described in described the 5th aspect of the film-bioreactor present invention.
Sewage water treatment method according to the present invention by film-bioreactor provided by the invention to sewage at Reason, since the film-bioreactor employs the smart membrane of the present invention, can perceive the region of microbial contamination on film, thus Targetedly contaminated area can be handled, extend the service life of film；And the antimicrobial components in film are consolidated Be loaded on carrier, it is difficult to be lost in from film so that will not or quantity that substantially will not be to the microorganism in bioreactor and work Property has an impact, thus more effectively sewage can be handled.
Sewage water treatment method according to the present invention, is not particularly limited for specific operating condition, can be in conventional strip Carried out under part.For example, the concentration of activated sludge can be 2000-8000mg/L, it is preferably 3000-6000mg/L, is preferably 3500-5000mg/L；Water flux can be 5-40L/ (m2H), it is preferably 10-30L/ (m2·h)。
The present invention will be described in detail with reference to embodiments, but the scope being not intended to limit the present invention.
In following embodiments and comparative example, using the content of iron containing compounds in x-ray fluorescence spectrometry dispersion, The content of iron containing compounds in the film of preparation is determined by inventory.
In following embodiments and comparative example, using the porosity of the film of weight method measure preparation, concrete operation method is： At a temperature of 25 DEG C, the wet film of wetted saturation is positioned in the vacuum drying oven that vacuum is 0.1MPa and is dried to perseverance in 60 DEG C Weight, obtains dry film, weighs the weight change of film before and after drying, the pore volume V for the film being calculated by the weight changeHole, by The density and dry film weight of membrane material determine the skeleton volume V of the filmSkeleton, the porosity of the film is calculated by the following formula：
Porosity=[VHole/(VHole+VSkeleton)] × 100%.
In following embodiments and comparative example, the test method of the water flux of the film of preparation is specially：Membrane module is made in film： Tablet diaphragm is positioned over ultrafiltration cup and (is purchased from Millipore, effective membrane area 30cm2) in sealing after directly use；Take in 10 Empty fiber membrane is put into long 30cm, and in the lucite tube with side water outlet of internal diameter 8cm, both ends are blocked with epoxy resin, system Component, according to epoxy interlamellar spacing and the accurate survey calculation of film wire internal diameter its effective membrane area A.By membrane module in room temperature (for 25 DEG C), under 0.15MPa (gauge pressure) after precompressed 30 minutes, it be 0.1MPa (gauge pressure) to be passed through pure water and keep test pressure, and measurement one is periodically Between in t through the volume V of pure water.The water passed through by the film of unit area in the following formula unit of account time, i.e. pure water lead to Measure J：
J=V/ (At).
Embodiment 1-6 is used to illustrate smart membrane of the present invention and preparation method thereof.
Embodiment 1
(1) using as the molecular sieve of raw material, (for Y type molecular sieve, purchased from sinopec Chang Ling catalyst plant, particle diameter is 0.5-2 μ M) with the iron nitrate aqueous solution that 120mL concentration is 0.5mol/L when room temperature (25 DEG C) saturation dipping 6 is small, will impregnate obtain it is mixed Compound, when 1 normal atmosphere pressure dry 12 is small, obtains dispersion in 120 DEG C.Wherein, on the basis of the total amount of the dispersion, In terms of di-iron trioxide, the content of ferric nitrate is 19 weight %.
(2) PEG 600 (being purchased from Sinopharm Chemical Reagent Co., Ltd.) is dissolved in DMAC N,N' dimethyl acetamide (DMAc) in, dispersion prepared by step (1) is then added, under room temperature (for 25 DEG C) ultrasonic (ultrasonic frequency is 40kHz) 0.5 it is small when.Then, Kynoar (PVDF, purchased from Shanghai Sanaifu New Material Co., Ltd) powder is added, at 90 DEG C At a temperature of stir to being completely dissolved, obtain casting solution.Then, casting solution is placed in vacuum (vacuum 0.1MPa) drying box In, 90 minutes are stood under vacuum in room temperature (for 25 DEG C), carries out deaeration.Wherein, the composition of casting solution：PVDF accounts for 15 weights % is measured, PEG 600 accounts for 5 weight %；DMAc accounts for 79 weight %；Dispersion accounts for the 10% of PVDF weight.
(3) casting solution prepared by step (2) is transferred in the material liquid tank of hollow fiber spinning machine and closed, in 30 DEG C of temperature Degree is lower to stand 60 minutes.Then, nitrogen pressurization is passed through into material liquid tank, pressure maintains 0.2MPa.Metering pump is opened, control is spun The flow velocity of silk liquid (that is, casting solution) is 2.4mL/min, and the flow velocity of core liquid (for deionized water, temperature is 30 DEG C) is 1.1mL/ Min, spun doughnut film liquid enter 30 DEG C of water coagulating bath after 20cm the air gaps expose, are frozen into hollow-fibre membrane Collected afterwards by reel, control no draw ratio.
(4) by hollow-fibre membrane made from step (3) after elution, in Glycerine-Aqueous Solution, (glycerol concentration is 50 bodies Product %) in room temperature (for 25 DEG C) immersion 48 it is small when after take out, under room temperature (for 25 DEG C) dry to constant weight, so as to obtain root According to the smart membrane of the present invention.Wherein, which is (for outside diameter, similarly hereinafter) 1.5mm, and wall thickness is 170 μm, porosity For 77.6%, pure water flux is 157.2L/ (m2·h)。
Comparative example 1
Hollow-fibre membrane is prepared using method same as Example 1, unlike, without step (1), and step (2) casting solution prepared is free of dispersion, so as to prepare hollow-fibre membrane.Wherein, a diameter of 1.5mm of the hollow-fibre membrane, Wall thickness is 170 μm, and porosity 76.2%, pure water flux is 105.4L/ (m2·h)。
Comparative example 2
Hollow-fibre membrane is prepared using method same as Example 1, unlike, without step (1), and step (2) when preparing casting solution, directly using the molecular sieve in 1 step of embodiment (1) as raw material as dispersion (that is, point of use Granular media is the molecular sieve without load ferric nitrate), so as to prepare hollow-fibre membrane.Wherein, the hollow-fibre membrane is a diameter of 1.5mm, wall thickness are 170 μm, and porosity 77.3%, pure water flux is 155.4L/ (m2·h)。
Comparative example 3
Hollow-fibre membrane is prepared using method same as Example 1, unlike, without step (1), and step (2) in, the dispersion in 1 step of embodiment (2) is directly replaced with the ferric nitrate for accounting for PVDF weight 2%, is used to prepare casting solution, So as to prepare hollow-fibre membrane.Wherein, a diameter of 1.5mm of the hollow-fibre membrane, wall thickness are 170 μm, porosity 75.8%, Pure water flux is 98.4L/ (m2·h)。
Comparative example 4
Hollow-fibre membrane is prepared using method same as Example 1, unlike, without step (1), and step (2) in, directly with multi-walled carbon nanotube (the being purchased from Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences) generation for accounting for PVDF weight 2% For the dispersion in 1 step of embodiment (2), casting solution is used to prepare, so as to prepare hollow-fibre membrane.Wherein, the doughnut The a diameter of 1.5mm of film, wall thickness are 170 μm, and porosity 76.5%, pure water flux is 150.2L/ (m2·h)。
Comparative example 5
Hollow-fibre membrane is prepared using method same as Example 1, unlike, in step (1), the weights such as ferric nitrate is used The silver nitrate of amount replaces, so as to prepare hollow-fibre membrane.Wherein, a diameter of 1.5mm of the hollow-fibre membrane, wall thickness are 170 μm, Porosity is 77.2%, and pure water flux is 158.4L/ (m2·h)。
Embodiment 2
(1) by molecular sieve (for type ZSM 5 molecular sieve, purchased from Nan Lian catalyst Co., Ltd, particle diameter is 0.5-2 μm) With the iron nitrate aqueous solution that 120mL concentration is 0.5mol/L when room temperature (for 25 DEG C) saturation dipping 6 is small, will impregnate obtain it is mixed Compound, when 1 normal atmosphere pressure dry 12 is small, obtains dispersion in 120 DEG C.Wherein, on the basis of the total amount of the dispersion, In terms of di-iron trioxide, the content of ferric nitrate is 25 weight %.
(2) PEG 600 (being purchased from Sinopharm Chemical Reagent Co., Ltd.) is dissolved in DMAC N,N' dimethyl acetamide (DMAc) in, dispersion prepared by step (1) is then added, under room temperature (for 25 DEG C) ultrasonic (ultrasonic frequency is 40kHz) 0.5 it is small when.Then, Kynoar (PVDF, purchased from Shanghai Sanaifu New Material Co., Ltd) powder is added, at 90 DEG C At a temperature of stir to being completely dissolved, obtain casting solution.Then, casting solution is placed in vacuum drying chamber (vacuum 0.1MPa) In, 90 minutes are stood in vacuum condition under room temperature (for 25 DEG C), carries out deaeration.Wherein, the composition of casting solution：PVDF accounts for 13 Weight %, PEG 600 accounts for 5 weight %；DMAc accounts for 81 weight %；Dispersion accounts for the 10% of PVDF weight.
(3) casting solution is scratched with scraper and on the surface of non-woven fabrics, forms the film layer that thickness is 100 μm, then by film carrier Nonwoven is arranged in the deionized water that temperature is 25 DEG C, after solidifying 3 minutes, is taken out and is obtained the plate membrane of non-woven fabrics support.
(4) non-woven fabrics support plate membrane eluted with deionized water after, by film be immersed in temperature be 25 DEG C glycerine- In aqueous solution (concentration of glycerine is 50 volume %) 36 it is small when after take out, under room temperature (for 25 DEG C) dry to constant weight so that To the smart membrane according to invention.Wherein, the porosity of film is 80.6%, and pure water flux is 197L/ (m2·h)。
Embodiment 3
Plate membrane is prepared using method same as Example 2, unlike, in step (1), the weight such as molecular sieve is used Aluminium oxide (being purchased from sinopec Chang Ling branch company) replaces, so that the smart membrane according to invention is obtained, wherein, with the dispersion of preparation Total amount on the basis of, in terms of di-iron trioxide, the content of ferric nitrate is 24 weight %.Wherein, the porosity of film is 79.3%, pure Water flux is 190.8L/ (m2·h)。
Embodiment 4
Plate membrane is prepared using method same as Example 2, unlike, in step (1), the concentration of iron nitrate solution Dosage for 1mol/L, and iron nitrate solution remains unchanged, on the basis of the total amount of the dispersion, in terms of di-iron trioxide, and nitre The content of sour iron is 30 weight %, so as to obtain the smart membrane according to invention.Wherein, the porosity of film is 81.5%, and pure water leads to Measure as 174.5L/ (m2·h)。
Embodiment 5
(1) molecular sieve (for MCM-41 type molecular sieves, purchased from Catalyst Factory, Nankai Univ, particle diameter is 0.5-2 μm) is used The ferric chloride in aqueous solution that 100mL concentration is 0.5mol/L will impregnate obtained mixing when room temperature (for 25 DEG C) saturation dipping 6 is small Thing, when 1 normal atmosphere pressure dry 16 is small, obtains dispersion in 110 DEG C.Wherein, on the basis of the total amount of the dispersion, with Di-iron trioxide meter, the content of iron chloride is 10 weight %.
(2) polyvinylpyrrolidone (being purchased from Shanghai Jin Maotai Chemical Co., Ltd.s) is dissolved in 1-methyl-2-pyrrolidinone (NMP) in, dispersion prepared by step (1) is then added, under room temperature (for 25 DEG C) ultrasonic (ultrasonic frequency is 40kHz) 0.5 it is small when.Then, add polysulfones powder (PSF, purchased from Shanghai Plastic industrial association), stirred at a temperature of 80 DEG C to It is completely dissolved, obtains casting solution.Then, casting solution is placed in vacuum drying chamber (vacuum 0.1MPa), in room temperature (for 25 DEG C) 90 minutes are stood under vacuum, carry out deaeration.Wherein, the composition of casting solution：PSF accounts for 12 weight %, polyvinyl pyrrole Alkanone accounts for 2 weight %；NMP accounts for 85 weight %；Dispersion accounts for the 10% of PSF weight.
(3) casting solution prepared by step (2) is transferred in the material liquid tank of hollow fiber spinning machine and closed, in 30 DEG C of temperature Degree is lower to stand 60 minutes.Then, nitrogen pressurization is passed through into material liquid tank, pressure maintains 0.2MPa.Metering pump is opened, control is spun The flow velocity of silk liquid (that is, casting solution) is 2.2mL/min, and the flow velocity of core liquid (for deionized water, temperature is 30 DEG C) is 1.5mL/ Min, spun doughnut film liquid enter 30 DEG C of water coagulating bath after 25cm the air gaps expose, are frozen into hollow-fibre membrane Collected afterwards by reel, control no draw ratio.
(4) by hollow-fibre membrane made from step (3) after elution, in Glycerine-Aqueous Solution, (concentration of glycerine is 30 bodies Product %) in immersion 60 it is small when after take out, under room temperature (for 25 DEG C) dry to constant weight, so as to obtain intelligence according to the present invention Film.Wherein, a diameter of 0.5mm of the hollow-fibre membrane, wall thickness are 120 μm, and the porosity of film is 73.2%, and pure water flux is 141L/(m2·h)。
Embodiment 6
(1) molecular sieve (for Beta type molecular sieves, purchased from Catalyst Factory, Nankai Univ, particle diameter is 0.5-2 μm) is used into 120mL The ferric sulfate aqueous solution (pH=6) that concentration is 0.1mol/L when room temperature (for 25 DEG C) saturation dipping 8 is small, will impregnate obtain it is mixed Compound, when 1 normal atmosphere pressure dry 12 is small, obtains dispersion in 120 DEG C.Wherein, on the basis of the total amount of the dispersion, In terms of di-iron trioxide, the content of ferric sulfate is 5 weight %.
(2) PEG 1000 (being purchased from traditional Chinese medicines chemical reagent) is dissolved in n,N-Dimethylformamide (DMF), then added Dispersion prepared by step (1), when ultrasound (ultrasonic frequency is 60kHz) 1 is small under room temperature (for 25 DEG C).Then, add poly- Ether sulfone powder (PES, purchased from BASF chemistry), stirs to being completely dissolved at a temperature of 70 DEG C, obtains casting solution.Then, will cast Film liquid is placed in vacuum drying chamber (vacuum 0.1MPa), and 90 minutes are stood under vacuum in room temperature (for 25 DEG C), into Row deaeration.Wherein, the composition of casting solution：PES accounts for 14 weight %, PEG 1000 and accounts for 5 weight %；DMF accounts for 80 weight %；Dispersion Account for the 15% of PES weight.
(3) casting solution prepared by step (2) is transferred in the material liquid tank of hollow fiber spinning machine and closed, in 30 DEG C of temperature Degree is lower to stand 60 minutes.Then, nitrogen pressurization is passed through into material liquid tank, pressure maintains 0.25MPa.Open metering pump, control The flow velocity of spinning solution (that is, casting solution) is 3mL/min, and core liquid (for deionized water, temperature is 30 DEG C) revolution speed is 1.6mL/ Min, spun doughnut film liquid enter 30 DEG C of water coagulating bath after 20cm the air gaps expose, are frozen into hollow-fibre membrane Collected afterwards by reel, control no draw ratio.
(4) hollow-fibre membrane made from step (3) is placed in deionized water through elution and soaks 24h, then sweet Take out, dried under room temperature (for 25 DEG C) to constant weight after when immersion 24 is small in oil-aqueous solution (concentration of glycerine is 60 volume %), So as to obtain smart membrane according to the present invention.Wherein, a diameter of 1.5mm of the hollow-fibre membrane, wall thickness are 200 μm, the hole of film Gap rate is 75.7%, and pure water flux is 126.2L/ (m2·h)。
Experimental example 1-6 is used to illustrate the present invention.
Experimental example 1-6
Film prepared by above-described embodiment 1-6 is assembled into membrane module (wherein, hollow-fibre membrane with epoxy resin end socket respectively Curtain type film assembly is made, plate and frame module is made in plate membrane).Establish a set of immersion MBR biochemical reactors (size 0.5 × 0.25 × 0.5 meter), membrane module is immersed in human configuration sewage and (controls COD as 300mg/L or so, NH3- N is 30mg/ L or so, pH are 7 or so), filling film accounts for the 50% of pond body product, and it is 15L/ (m to control water flux2·h).Reactor bottom is set Aeration tube, gas-water ratio 10：1.The water outlet suction pump of reactor intake pump and membrane module is controlled, is maintained at hydraulic detention time 5h.Biochemical sludge is derived from municipal wastewater Treatment stations, starts to test after domestication being inoculated with MBR 4 weeks, the activated sludge in reactor Concentration uses the gravimetric detemination of GB 11901-89, and the results are shown in Table 1.
Experiment is carried out continuously under room temperature (for 25 DEG C), membrane module water outlet side vacuum, i.e. cross-film are monitored in experimentation The concentration of pressure difference (TMP) and activated sludge changes with time, and experimental result is listed in table 1.
Contrast experiment's example 1-5
Membrane module is prepared using the method identical with experimental example 1-6, and is tested, experimental result is listed in table 1.
Reference examples
The service condition of MBR biochemical reactors is identical with experimental example 1-6, unlike, do not load film.
Table 1
Fig. 1 shows experimental example 1 and contrast experiment's example 1-2 in experimentation, and transmembrane pressure changes with time.From figure 1, which can be seen that smart membrane according to the present invention, to be maintained at operation interval by transmembrane pressure within the long period (reaching 50 days), The fluctuation of transmembrane pressure difference is frequent in operational process, shows in continuous operational process, to film under local aerobic and anaerobic environment on film The change of material stable against biological contamination performance.However, in contrast experiment's example 1-2, nominal situation lower film can only stable operation 20 days Left and right, pollution tendencies linearly change substantially, until transmembrane pressure significantly rises, show that Pore Blocking is more serious, it is necessary to right Film is cleaned, or even replaces film.
The result of table 1 can be seen that smart membrane using the present invention, during the experiment, activated sludge concentration in biochemistry pool With experiment preliminary phase than basicly stable, slightly raise.And the film for supporting the excellent silver ion of bactericidal property substantially inhibits reaction The growth of microorganism in device, shows that smart membrane can improve condition of the resistance itself to antimicrobial ability according to the present invention Under, do not have a negative impact to the quantity and activity of microorganism in biochemistry pool.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should equally be considered as content disclosed in this invention.

Claims (42)

1. a kind of smart membrane, which contains film matrix and the dispersion being dispersed in the film matrix, the dispersion Containing carrier and load at least one iron containing compounds on the carrier, the iron containing compounds are selected from molysite, iron The hydroxide of oxide and iron.
2. smart membrane according to claim 1, wherein, on the basis of the total amount of dispersion, the content of iron containing compounds is 0.5-45 weight %, are preferably 1-40 weight %, more preferably 2-30 weight %, more preferably 5-25 weight %, the iron content Compound is in terms of di-iron trioxide.
3. smart membrane according to claim 1 or 2, wherein, relative to 100 parts by weight film matrixes, the dispersion contains Measure as 5-20 parts by weight, preferably 8-18 parts by weight, more preferably 10-15 parts by weight.
4. according to the smart membrane described in any one in claim 1-3, wherein, the iron containing compounds are to contain selected from cation Have in anaerobic hydrochlorate, the oxide of iron and the hydroxide of iron that the oxysalt of iron ion, cation contain iron ion It is one or more kinds of；
Preferably, it selected from inorganic oxysalt that cation is iron ion, cation is iron ion that the iron containing compounds, which are, Acylate, cation are the halide of iron ion, one or both of hydroxide of the oxide of iron and iron with On；
It is highly preferred that the iron containing compounds are in iron chloride, ferric nitrate, ferric sulfate, di-iron trioxide and iron hydroxide It is one or more kinds of.
5. according to the smart membrane described in any one in claim 1-4, wherein, the particle diameter of the dispersion is no more than described The thickness of smart membrane；
Preferably, the particle diameter of the dispersion is in the range of 0.5-5 μm, preferably in the range of 0.5-2 μm.
6. according to the smart membrane described in any one in claim 1-5, wherein, the carrier is to be aoxidized selected from porous inorganic It is more than one or both of thing, clay and molecular sieve；
Preferably, the carrier is molecular sieve.
7. according to the smart membrane described in any one in claim 1-6, wherein, the film matrix is polymer film.
8. smart membrane according to claim 7, wherein, the polymer in the polymer film be selected from fluorine-containing polyolefin, It is more than one or both of polysulfones, polyether-ketone, polyamide, polyimides and polyester；
Preferably, the polymer in the polymer film is combination more than one or both of Kynoar, polysulfones.
9. according to the smart membrane described in any one in claim 1-8, wherein, the smart membrane is hollow-fibre membrane.
10. smart membrane according to claim 9, wherein, the outside diameter of the hollow-fibre membrane is 0.5-2mm, is preferably 0.5-3mm, more preferably 0.5-1.5mm；Wall thickness is 50-500 μm, is preferably 80-300 μm, more preferably 100-200 μm.
11. according to the smart membrane described in any one in claim 1-8, wherein, the smart membrane is plate membrane.
12. smart membrane according to claim 11, wherein, the smart membrane further includes supporter, the film matrix attachment On at least one surface of the supporter.
13. smart membrane according to claim 12, wherein, the supporter is non-woven cloth or fabric.
14. according to the smart membrane described in any one in claim 11-13, wherein, the thickness of the film matrix is 50-150 μ M, is preferably 80-120 μm.
15. according to the smart membrane described in any one in claim 1-14, wherein, the porosity of the smart membrane is 65-85%, Preferably 70-83%.
16. according to the smart membrane described in any one in claim 1-15, wherein, the water flux of the smart membrane is 80-300L/ (m2H), it is preferably 100-250L/ (m2H), 120-220L/ (m are more preferably2·h)。
17. a kind of preparation method of smart membrane, this method include：Dispersion, pore-foaming agent and film basis material are dispersed in point In powder, casting solution is obtained, the casting solution is formed a film, the dispersion contains carrier and load on the carrier At least one iron containing compounds, the iron containing compounds be selected from molysite, the oxide of iron and iron hydroxide.
18. according to the method for claim 17, wherein, this method further includes the step of providing the dispersion, in the step In rapid, with the dispersion liquid impregnated carrier for being dispersed with iron containing compounds, the carrier for being loaded with the dispersion liquid is soaked into 4-8 in water After hour, separation of solid and liquid is carried out, and isolated solid phase is dried.
19. the method according to claim 17 or 18, wherein, the carrier is selected from molecular sieve and porous inorganic oxide One or both of more than；
Preferably, the carrier is molecular sieve.
20. according to the method described in any one in claim 17-19, wherein, on the basis of the total amount of the dispersion, institute The content for stating iron containing compounds is 0.5-45 weight %, is preferably 1-40 weight %, and more preferably 2-30 weight % are further excellent Elect 5-25 weight % as, the iron containing compounds are in terms of di-iron trioxide.
21. according to the method described in any one in claim 17-20, wherein, relative to 100 parts by weight film basis materials, The content of the dispersion is 5-20 parts by weight, is preferably 8-18 parts by weight, more preferably 10-15 parts by weight.
22. according to the method described in any one in claim 17-21, wherein, the iron containing compounds are selected from cation Oxysalt, cation containing iron ion contain in the anaerobic hydrochlorate, the oxide of iron and the hydroxide of iron of iron ion One or more；
Preferably, it selected from inorganic oxysalt that cation is iron ion, cation is iron ion that the iron containing compounds, which are, Acylate, cation are the halide of iron ion, one or both of hydroxide of the oxide of iron and iron with On；
It is highly preferred that the iron containing compounds are in iron chloride, ferric nitrate, ferric sulfate, di-iron trioxide and iron hydroxide It is one or more kinds of.
23. according to the method described in any one in claim 17-22, wherein, the particle diameter of the dispersion is at 0.5-5 μm In the range of, preferably in the range of 0.5-2 μm.
24. according to the method described in any one in claim 17-23, wherein, relative to 100 parts by weight film basis materials, The content of the pore-foaming agent is 5-45 parts by weight, is preferably 10-42 parts by weight, more preferably 15-40 parts by weight.
25. according to the method described in any one in claim 17-24, wherein, the pore-foaming agent is selected from polyethylene glycol, fibre It is more than one or both of the plain ether of dimension, polyurethane, polyvinylpyrrolidone.
26. according to the method described in any one in claim 17-25, wherein, the film basis material is polymer；
Preferably, the film basis material is in fluorine-containing polyolefin, polysulfones, polyether-ketone, polyamide, polyimides and polyester One or more；
It is highly preferred that the film basis material is combination more than one or both of Kynoar, polysulfones.
27. according to the method described in any one in claim 17-26, wherein, the method for the film forming for rubbing method or Solution spinning.
28. according to the method for claim 27, wherein, the method for the film forming includes：Casting solution is coated on supporter At least one surface on, solidify the casting solution of coating, to form film.
29. according to the method for claim 28, wherein, the supporter is non-woven cloth or fabric.
30. the method according to claim 28 or 29, wherein, the dosage of the casting solution make it that the thickness for the film to be formed is 50-150 μm, be preferably 80-120 μm.
31. according to the method for claim 27, wherein, the method for the film forming includes：Using casting solution as spinning solution with Core liquid carries out spinning together, and spun doughnut film liquid obtains behind one section of the air gap after being solidified into solidification liquid Hollow-fibre membrane.
32. according to the method for claim 31, wherein, the core liquid and the solidification liquid are respectively water.
33. according to the method described in claim 31 or 32, wherein, the flow velocity of the spinning solution is 1.5-8mL/min, preferably For 1.8-5mL/min, more preferably 2-3mL/min；The flow velocity of the core liquid is 0.5-8mL/min, is preferably 0.8-5mL/ Min, more preferably 1-2mL/min.
34. according to the method described in any one in claim 31-33, wherein, the air gap is 10-30cm, preferably For 15-25cm, more preferably 20-25cm.
35. according to the method described in any one in claim 31-34, wherein, the dosage of the spinning solution and the core liquid So that the outside diameter of the hollow-fibre membrane formed is 0.5-2mm, and it is preferably 0.5-3mm, more preferably 0.5-1.5mm；Wall thickness is 50- 500 μm, be preferably 80-300 μm, more preferably 100-200 μm.
36. according to the method described in any one in claim 17-35, wherein, this method further include by the film of formation by After when immersion 24-84 is small in the mixed liquor that G ＆ W is formed, it is dried, in the mixed liquor, the content of glycerine is preferably 30-60 volumes %.
37. smart membrane prepared by a kind of method in 17-36 as claim described in any one.
38. a kind of membrane module, which contains film and is used to support the supporting structure of film, it is characterised in that the film is Smart membrane in claim 1-16 and 37 described in any one.
39. a kind of film-bioreactor, it is characterised in that the film in the film-bioreactor is in claim 1-16 and 37 Membrane module in film described in any one, or the film-bioreactor is the membrane module described in claim 38.
40. described in the membrane module described in smart membrane, claim 38 or claim 39 described in claim 1-16 and 37 Application of the film-bioreactor in water process.
41. a kind of method of microorganism in trap water, this method includes making the water containing microorganism flow through film or membrane module, with Microorganism in trap water, it is characterised in that the film is the smart membrane described in any one, institute in claim 1-16 and 37 State the membrane module described in membrane module claim 38.
42. a kind of sewage water treatment method, this method includes carrying out sewage into biodegradation in film-bioreactor, makes at the same time The water in bioreactor is obtained under the action of film pressure at both sides difference by film, obtains water outlet, it is characterised in that the film-life Thing reactor is the film-bioreactor described in claim 39.
CN201610930380.8A 2016-10-31 2016-10-31 Sewage treatment method Active CN108014650B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610930380.8A CN108014650B (en) 2016-10-31 2016-10-31 Sewage treatment method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610930380.8A CN108014650B (en) 2016-10-31 2016-10-31 Sewage treatment method

Publications (2)

Publication Number Publication Date
CN108014650A true CN108014650A (en) 2018-05-11
CN108014650B CN108014650B (en) 2020-01-10

Family

ID=62069618

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610930380.8A Active CN108014650B (en) 2016-10-31 2016-10-31 Sewage treatment method

Country Status (1)

Country Link
CN (1) CN108014650B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108479429A (en) * 2018-05-31 2018-09-04 中国科学院城市环境研究所 It is a kind of to utilize nanometer Fe3O4The preparation method of modified PVDF microfiltration membranes and its utilization
CN109289542A (en) * 2018-09-28 2019-02-01 南方科技大学 Antipollution ultrafiltration membrane preparation method with lightwave CATV catalytic performance

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102489168A (en) * 2011-12-12 2012-06-13 张一琛 Preparation method of inorganic/organic hybridization antibacterial film
CN104107638A (en) * 2013-04-16 2014-10-22 中国科学院宁波材料技术与工程研究所 Forward osmosis membrane and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102489168A (en) * 2011-12-12 2012-06-13 张一琛 Preparation method of inorganic/organic hybridization antibacterial film
CN104107638A (en) * 2013-04-16 2014-10-22 中国科学院宁波材料技术与工程研究所 Forward osmosis membrane and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108479429A (en) * 2018-05-31 2018-09-04 中国科学院城市环境研究所 It is a kind of to utilize nanometer Fe3O4The preparation method of modified PVDF microfiltration membranes and its utilization
CN109289542A (en) * 2018-09-28 2019-02-01 南方科技大学 Antipollution ultrafiltration membrane preparation method with lightwave CATV catalytic performance

Also Published As

Publication number Publication date
CN108014650B (en) 2020-01-10

Similar Documents

Publication Publication Date Title
Xu et al. Antimicrobial polysulfone blended ultrafiltration membranes prepared with Ag/Cu2O hybrid nanowires
KR101090881B1 (en) Membrane bioreactor
Huang et al. Modification of PES membrane with Ag–SiO2: Reduction of biofouling and improvement of filtration performance
Zhang et al. Biogenic silver nanoparticles (bio-Ag0) decrease biofouling of bio-Ag0/PES nanocomposite membranes
Basri et al. Silver-filled polyethersulfone membranes for antibacterial applications—Effect of PVP and TAP addition on silver dispersion
CN102489168B (en) A kind of preparation method of inorganic/organic hybridization antibacterial film
CN109847586A (en) High-flux reverse osmosis membrane and its preparation method and application
KR102143837B1 (en) Enzyme-based membrane with antifouling activity for water treatment and method for manufacturing thereof
Zhang et al. Antibiofouling performance and mechanisms of a modified polyvinylidene fluoride membrane in an MBR for wastewater treatment: Role of silver@ silica nanopollens
Sotto et al. Preparation and characterization of MOF‐PES ultrafiltration membranes
CN106955603B (en) Surface segregation functionalized anti-pollution polymer separation membrane and preparation method thereof
US10016729B2 (en) Antibacterial and antifouling polymeric separation membrane and preparation method thereof
CN106492638A (en) A kind of preparation method of nanometer silver organic frame ultrafilter membrane and the method using its water purification
Shan et al. Flexible, mesoporous, and monodispersed metallic cobalt-embedded inorganic nanofibrous membranes enable ultra-fast and high-efficiency killing of bacteria
García-Ivars et al. Development of mixed matrix membranes: Incorporation of metal nanoparticles in polymeric membranes
CN109316832A (en) A kind of room air sterilization purifying filter element material and preparation method
CN108014650A (en) The method and sewage water treatment method of microorganism in smart membrane and preparation method and membrane module and film-bioreactor and trap water
Ibrahim et al. Development of polyvinylidene fluoride (PVDF)-ZIF-8 membrane for wastewater treatment
He et al. Incorporating metal–organic frameworks into substrates for environmental applications
CN104258738A (en) Forward osmosis organic-inorganic composite membrane and preparation method thereof
CN102553466A (en) Antimicrobial polysulphone flat ultrafiltration membrane and preparation method thereof
Bates et al. Antibacterial electrospun chitosan-PEO/TEMPO-oxidized cellulose composite for water filtration
CN104107641B (en) Forward osmosis organic-inorganic composite membrane and preparation method thereof
Liu et al. Dual‐Functional Coating of Forward Osmosis Membranes for Hydrophilization and Antimicrobial Resistance
CN110280148A (en) A kind of preparation method for the polyvinylidene fluoride (PVDF) ultrafiltration membrane being modified by hydrophilic graphene

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant