CN104548959B - Anti-pollution modification method of polypropylene hollow fiber membrane module - Google Patents
Anti-pollution modification method of polypropylene hollow fiber membrane module Download PDFInfo
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- CN104548959B CN104548959B CN201310473160.3A CN201310473160A CN104548959B CN 104548959 B CN104548959 B CN 104548959B CN 201310473160 A CN201310473160 A CN 201310473160A CN 104548959 B CN104548959 B CN 104548959B
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Abstract
The invention relates to the field of a membrane technology and membrane surface modification and concretely relates to an anti-pollution modification method of a polypropylene hollow fiber membrane module. The method comprises the following steps of selecting a compound with strong hydrophily and multiple active groups as a modifier, adsorbing the modifier by the surface of the polypropylene hollow fiber membrane module in a dynamic cycle way, and under coordination complexation of the active groups in the modifier molecule and an inorganic bacteriostatic agent, fixing the modifier to the polypropylene hollow fiber membrane module so that the polypropylene hollow fiber membrane module with hydrophily and antibacterial properties is prepared. Through control of a flowing direction of a cross-linking agent solution, a modification compound solution and a metal ion soluble salt solution, the method realizes hydrophilic and antibacterial modification of an inner surface, an outer surface and membrane apertures of the polypropylene hollow fiber membrane module, greatly improves work efficiency and treatment effects, needs simple requirement and is suitable for industrial application.
Description
Technical field
The present invention relates to membrane technology and membrane surface modification field, a kind of hollow polypropylene
The method that fiber film component antipollution is modified.Espespecially polypropylene hollow fiber membrane assembly is entered by one
The method that row hydrophilic antimicrobial is modified.
Background technology
Fouling membrane refer to the microgranule in the material being processed, colloidal particle or solute transportation due to
There is physics, chemistry or biological interaction with film, cause film surface or fenestra internal adsorption, sink
Long-pending microgranule, colloidal particle or solute transportation, cause membrane aperture to diminish the most directly and block fenestra,
Make film produce the phenomenon of flux and the reversible or irreversible change of stalling characteristic, currently affect film skill
One of Main Bottleneck of art application is exactly fouling membrane.
Polypropylene with its good mechanical property and chemical stability, has concurrently cheap excellent
Gesture, receives the attention of membrane science worker.At present, such material is successfully used for preparing micro-
The porous membranes (i.e. polypropylene separation membrane) such as filter, ultrafiltration, be widely used in water process,
The fields such as Membrane Materials, infiltration evaporation, enzyme immobilization, biological agent separation.Although polypropylene divides
There is certain advantage from film and obtain certain application, but polypropylene material surface can be low,
Contact angle is at about 100 °, and hydrophobicity is relatively strong, during water treatment applications, due to its table
Face free energy resists attachment and parent's profit of hydrone, causes transmembrane pressure big, and water flux is low；With
Time polyacrylic hydrophobicity make its easily absorption Organic substance and microorganism, thus cause fouling membrane and not
Easy cleaning, service efficiency reduces, and cost increases, and the existence of these defects limits polypropylene and divides
Process at water from film, application in the water separation system such as biological, medical, therefore, prepare poly-third
Alkene antipollution perforated membrane has become the development trend in water treatment applications.
The effective way solving polypropylene screen pollution problem is to carry out hydrophilic to polypropylene separation membrane
Change modified and improve its bacteriostasis property.The hydrophilic modification method of polypropylene separation membrane is currently mainly
Have material to be blended, the oxidation of surface-coated, surface chemistry, surface plasma process etc., not
On the premise of changing polypropylene bulk properties, it is contemplated that the Cost Problems of masking, poly-third
It is a kind of easy to be easy that existing membrane material carries out during alkene separation film preparation surface hydrophilic modification
The film-forming method of row, is also current membrane material and the focus of masking technique research；Inorganic antibacterial
Have has a broad antifungal spectrum, heat-resist, safety is high, does not produce the advantages such as drug resistance for a long time, as
The tens of kinds of pathogenic microorganism such as escherichia coli, gonococcus, chlamydia trachomatis are all had strongly by silver
Suppression and killing action, and the antibacterial of drug resistance, silver ion and compound thereof will not be produced
Mechanism is to cause microorganism have component damage or produce dysfunction by haptoreaction, the most micro-
When amount silver ion contacts with microbial cell, silver ion can penetrate microorganism wall and enter cell
In, and react with sulfydryl and make protein coagulating, the activity of destruction microbial cell synzyme, make
Microbial cell lose division growth ability and dead, silver ion can also destroy microorganism electronics biography
Communication system, respiratory system and substance delivery system, copper ion also has the antibacterial machine similar to silver
Reason and bacteriostasis, therefore, if introducing metal cation components such as inorganic antibacterial such as silver, copper
In the preparation process of polypropylene separation membrane, the microporous membrane of preparation will obtain antibacterial functions, make film
Antifouling property be improved.
Membrane module is the elementary cell in film engineer applied, and in prior art, pollution-resistant membrane is modified
Often it is only limited to film individuality be individual Flat Membrane or single hollow-fibre membrane is modified, modified
Efficiency is low, treatment effect is wayward.And membrane module entirety is carried out scale antifouling property
Improve and former have no report.
Summary of the invention
For defect present in prior art, it is an object of the invention to provide a kind of polypropylene
The method that hollow fiber film assembly antipollution is modified, the method is gathered with the elementary cell in membrane process
Propylene hollow fiber film assembly carries out antifouling property improvement as entirety, and selects hydrophilic strong
Compound as the modifying agent of polypropylene hollow fiber membrane assembly, by cross-linking reaction by modification
Agent is adsorbed in the surface of polypropylene hollow fiber membrane assembly, a large amount of in recycling modifier molecules
Amino, with Ag+、Cu2+There is ligand complex reaction, by Ag+、Cu2+Inorganic antibacterial passes through network
Cooperation with immobilized in the surface of polypropylene hollow fiber membrane assembly, and by controlling in reforming apparatus
The flow direction of various solution makes the inner surface of polypropylene hollow fiber membrane assembly, outer surface and fenestra same
Time or be respectively provided with hydrophilic and excellent bacteriostasis, make polypropylene hollow fiber membrane assembly
Antifouling property obtains raising by a relatively large margin.
For reaching object above, the present invention adopts the technical scheme that:
A kind of method that polypropylene hollow fiber membrane assembly antipollution is modified, it is characterised in that right
Polypropylene hollow fiber membrane assembly entirety carries out scale antifouling property improvement, is closed by selection
Suitable modified compound and the soluble salt solutions of metal ion, utilize antipollution reforming apparatus to depend on
Secondary control cross-linking agent solution, modified compound solution, the soluble salt solutions of metal ion, second
Flow velocity in polypropylene hollow fiber membrane assembly of alcohol-water solution and deionized water and flow direction,
Modified compound is coupled at the surface of polypropylene hollow fiber membrane assembly, and metal ion is by changing
Active group in property compound is immobilized on the surface of polypropylene hollow fiber membrane assembly, makes poly-third
Alkene hollow fiber film assembly has hydrophilic and excellent bacteriostasis simultaneously, thus prepares anti-
The polypropylene hollow fiber membrane assembly that pollution capacity is strong.
On the basis of such scheme, described polypropylene hollow fiber membrane assembly is in the following ways
Preparation: take polypropylene hollow fiber membrane first with soak with ethanol 4～12 hours, then use deionized water
Clean 2～5 times, remove the absorption impurity on polypropylene hollow fiber membrane surface, be subsequently placed in
In 50～80 DEG C of baking ovens, it is packaged into polypropylene hollow fiber membrane assembly after drying.
On the basis of such scheme, described antipollution modification specifically includes following steps:
Step 1, the pretreatment of polypropylene hollow fiber membrane assembly: cross-linking agent solution is transported to
In polypropylene hollow fiber membrane assembly, control the flow velocity of cross-linking agent solution and at hollow polypropylene fibre
Flow direction in dimension membrane module, dynamic circulation certain time, carries out polypropylene hollow fiber membrane
The pretreatment of assembly；
Step 2, the crosslinking of modified compound, absorption: modified compound solution is transported to pre-
In polypropylene hollow fiber membrane assembly after process, control modified compound solution flow velocity and
Flow direction in polypropylene hollow fiber membrane assembly, makes modified compound fine at hollow polypropylene
Surface-crosslinked, absorption a period of time of dimension membrane module；
Step 3, the coordination of metal ion, complexation: by defeated for the soluble salt solutions of metal ion
Deliver to through step 2 process after polypropylene hollow fiber membrane assembly in, control metal ion can
The flow velocity of soluble solution and the flow direction in polypropylene hollow fiber membrane assembly, carry out one
Coordination, the complex reaction fixed time form chelate, make metal ion immobilized in through step 2 place
The surface of the polypropylene hollow fiber membrane assembly after reason；
Step 4, washing: ethanol water is transported to the hollow polypropylene after step 3 processes
In fiber film component, control ethanol water flowing side in polypropylene hollow fiber membrane assembly
To, circulation washing 6～12 hours, then be transported to deionized water wash through ethanol water circulation
In polypropylene hollow fiber membrane assembly after washing, wash 6～10 hours with deionized water recirculation；
Step 5, be dried: the polypropylene hollow fiber membrane assembly after step 4 is cleaned, 50～
At a temperature of 80 DEG C after drying, i.e. can get the polypropylene hollow fiber membrane group that antipollution is modified
Part.
On the basis of such scheme, described polypropylene hollow fiber membrane assembly need to be installed to anti-soil
In dye reforming apparatus, carry out step 1,2,3 and 4 by antipollution reforming apparatus.
On the basis of such scheme, described antipollution reforming apparatus includes:
It is provided with the fluid reservoir 1 of agitating device, flow control mechanism, liquid delivery pump 4, pressure
Power controlling organization, flow direction control mechanism；
Described flow direction control mechanism includes:
It is located at the flow divider 7 of the liquid feeding side of polypropylene hollow fiber membrane assembly,
It is located at the converging valve 9 of the tapping side of polypropylene hollow fiber membrane assembly,
Between inlet and the fluid reservoir 1 of flow divider 7, set gradually stream by liquid flow direction
Speed control mechanism, liquid delivery pump 4, pressure control mechanism,
Between liquid outlet and the fluid reservoir 1 of converging valve 9, by being provided with the pipe of the 3rd valve 10
Road connects.
On the basis of such scheme, described flow control mechanism, by liquid flow direction successively
Including: effusion meter the 2, first valve 3.
On the basis of such scheme, described pressure control mechanism, by liquid flow direction successively
Including: Pressure gauge 5 and the second valve 6.
On the basis of such scheme, described polypropylene hollow fiber membrane assembly is installed to antipollution
The concrete connected mode of reforming apparatus is:
The liquid feeding side of polypropylene hollow fiber membrane assembly 8 is provided with shaft orientation liquid feeding hole 8-1 and laterally enters
Fluid apertures 8-2,
The tapping side of polypropylene hollow fiber membrane assembly 8 is provided with Axial-running Out fluid apertures 8-4 and laterally goes out
Fluid apertures 8-3,
First outlet of flow divider 7 is connected with shaft orientation liquid feeding hole 8-1,
Second outlet of flow divider 7 is connected with lateral inlet opening 8-2；
First import of converging valve 9 is connected with Axial-running Out fluid apertures 8-4,
Second import of converging valve 9 is connected with lateral liquid outlet 8-3.
On the basis of such scheme, described fluid reservoir 1 according to the carrying out of antipollution modification procedure,
Be respectively used to store cross-linking agent solution, modified compound solution, metal ion soluble-salt molten
Liquid, ethanol water and deionized water, or it is respectively provided with some special containers, store friendship respectively
Connection agent solution, modified compound solution, the soluble salt solutions of metal ion, ethanol water
And deionized water, according to the carrying out of antipollution modification procedure, different special containers is connected into anti-
Pollute reforming apparatus.
On the basis of such scheme, described modified compound solution, the solubility of metal ion
The flowing in polypropylene hollow fiber membrane assembly 8 of saline solution, ethanol water and deionized water
Direction is all consistent with the flow direction of cross-linking agent solution in pretreatment.
On the basis of such scheme, realize polypropylene hollow fiber by controlling flow direction
The process of membrane module inner surface, or realize the place to polypropylene hollow fiber membrane module outer surface
Reason, or realize polypropylene hollow fiber membrane assembly is carried out simultaneously inner surface, outer surface and fenestra
Process.
On the basis of such scheme, realize polypropylene hollow fiber by controlling flow direction
Membrane module carries out inner surface, outer surface and fenestra simultaneously and processes.
On the basis of such scheme, described realization is to polypropylene hollow fiber membrane module inner
The concretely comprising the following steps of process:
Make inlet and first outlet of flow divider 7, make the first import of converging valve 9 and go out
Liquid mouth connects, and keeping other valves in antipollution reforming apparatus is open mode.
On the basis of such scheme, described realization is to polypropylene hollow fiber membrane module outer surface
The concretely comprising the following steps of process:
Make inlet and second outlet of flow divider 7, make the second import of converging valve 9 and go out
Liquid mouth connects, and keeping other valves in antipollution reforming apparatus is open mode.
On the basis of such scheme, polypropylene hollow fiber membrane assembly is entered by described realization simultaneously
Concretely comprising the following steps of the process of row inner surface, outer surface and fenestra:
Make inlet and first outlet of flow divider 7, make the second import of converging valve 9 and go out
Liquid mouth connects, and keeping other valves in antipollution reforming apparatus is open mode.
On the basis of such scheme, the cross-linking agent in step 2 is formaldehyde, glutaraldehyde, fourth two
Aldehyde, Biformyl or ethylene glycol bis glycidyl ether.
On the basis of such scheme, in step 2 mass concentration of cross-linking agent solution be 10～
50%。
On the basis of such scheme, in step 2 flow velocity of cross-linking agent solution be 1～
50ml/min, the time of dynamic circulation is 2～6 hours.
On the basis of such scheme, in step 3, modified compound is polymine, poly-relies
One or both in propylhomoserin, poly arginine, histidine, ethanolamine, lysine or arginine
The mixture of any of the above proportioning.
On the basis of such scheme, in step 3, the mass concentration of modified compound solution is
1%～15%.
On the basis of such scheme, in step 3 flow velocity of modified compound solution be 1～
50ml/min, the time cross-link, adsorbed is 1～4 hour.
On the basis of such scheme, in step 4, the soluble salt solutions of metal ion is following
Any one in solution: Cu2+Acetic acid, nitric acid, hydrochloric acid or sulfuric acid solution, or Ag+Nitre
Acid solution.
On the basis of such scheme, the quality of the soluble salt solutions of metal ion in step 4
Concentration is 1%～15%.
On the basis of such scheme, the flow velocity of the soluble salt solutions of metal ion in step 4
It is 1～50ml/min, carries out being coordinated, the time of complex reaction is 1～4 hour.
On the basis of such scheme, in step 5 mass concentration of ethanol water be 40～
90%。
The method that polypropylene hollow fiber membrane assembly antipollution of the present invention is modified, it is useful
Effect is:
1, the present invention with polypropylene hollow fiber membrane assembly for entirety to polypropylene hollow fiber membrane
It is modified that inner surface, outer surface and fenestra wall carry out antipollution simultaneously, it is possible to by regulation threeway control
Valve processed and valve, control the concrete side that modified solution flows in polypropylene hollow fiber membrane assembly
To, targetedly inner surface, outer surface and the fenestra of polypropylene hollow fiber membrane assembly is entered
Row modification, simple process, treatment effect is reliable, efficiency improves, and required device is built easily,
Without complicated equipment, easily amplify, it is adaptable to industrially scalable is applied；
2, the present invention by crosslinking absorption, ligand complex method by hydrophilic compound and tool
The metal ion having bacteriostasis is immobilized on the surface of polypropylene hollow fiber membrane assembly, makes poly-third
Alkene hollow fiber film assembly has hydrophilic and antibacterial dual anti-pollution simultaneously, increases substantially
The antifouling property of polypropylene hollow fiber membrane assembly, chemical crosslinking and the crane span structure of metal ion
Effect makes polypropylene hollow fiber membrane assembly modified layer stable, hydrophilic antimicrobial consistency of performance, and
Improve polypropylene hollow fiber membrane assembly antifouling property to decay the most in time rapid defect.
Accompanying drawing explanation
The present invention has a drawings described below:
The process schematic of Fig. 1 present invention.
In figure: 1, fluid reservoir；2, effusion meter；3, the first valve；4, liquid delivery pump；
5, Pressure gauge；6, the second valve；7, flow divider；8, polypropylene hollow fiber membrane assembly；
8-1, assembly shaft orientation liquid feeding hole；The lateral inlet opening of 8-2, assembly；8-3, assembly laterally go out liquid
Hole；8-4, assembly Axial-running Out fluid apertures；9, converging valve；10, the 3rd valve.
Detailed description of the invention
Below in conjunction with accompanying drawing, the present invention is described in further detail.
As it is shown in figure 1, polypropylene hollow fiber membrane assembly antipollution of the present invention modification
Method, carries out scale antifouling property improvement to polypropylene hollow fiber membrane assembly entirety, logical
Cross and select suitable modifying agent (modified compound) and inorganic antibacterial (containing Cu2+、Ag+Metal
Ion), utilize antipollution reforming apparatus control successively cross-linking agent solution, modified compound solution,
The soluble salt solutions of metal ion, ethanol water and deionized water are at polypropylene hollow fiber
Flow velocity in membrane module and flow direction, be coupled at polypropylene hollow fiber membrane assembly by modifying agent
Surface, inorganic antibacterial is immobilized on polypropylene hollow fiber by the active group in modifying agent
The surface of membrane module, makes polypropylene hollow fiber membrane assembly have hydrophilic and excellent pressing down simultaneously
Bacterium ability, thus prepare the polypropylene hollow fiber membrane assembly that contamination resistance is strong.
Polypropylene hollow fiber membrane assembly of the present invention, it is preferred to use prepared by the following manner:
Take polypropylene hollow fiber membrane (for commercially available prod) first with soak with ethanol 4～12 hours, then use
Deionized water cleans 2～5 times, removes the absorption impurity on polypropylene hollow fiber membrane surface,
It is subsequently placed in 50～80 DEG C of baking ovens, is packaged into polypropylene hollow fiber membrane assembly after drying (poly-
Propylene hollow fiber film assembly be encapsulated as prior art).
On the basis of technique scheme, antipollution modification specifically includes following steps:
1) pretreatment of polypropylene hollow fiber membrane assembly: cross-linking agent solution is transported to poly-third
In alkene hollow fiber film assembly, control the flow velocity of cross-linking agent solution and at polypropylene hollow fiber membrane
Flow direction in assembly, dynamic circulation certain time, carries out polypropylene hollow fiber membrane assembly
Pretreatment；
2) crosslinking of modified compound, absorption: modified compound solution is transported to pretreatment
After polypropylene hollow fiber membrane assembly in, control modified compound solution flow velocity and poly-third
Flow direction in alkene hollow fiber film assembly, makes modified compound at polypropylene hollow fiber membrane
Surface-crosslinked, absorption a period of time of assembly；
3) coordination of metal ion, complexation: the soluble salt solutions of metal ion is transported to
Through step 2) process after polypropylene hollow fiber membrane assembly in, control metal ion solvable
Property the flow velocity of saline solution and flow direction in polypropylene hollow fiber membrane assembly, carry out certain
The coordination of time, complex reaction form chelate, make the metal ion immobilized in through step 2) place
The surface of the polypropylene hollow fiber membrane assembly after reason；
4) washing: ethanol water is transported to the hollow polypropylene after step 3) processes fine
In dimension membrane module, control ethanol water flowing side in polypropylene hollow fiber membrane assembly
To, circulation washing 6～12 hours, then be transported to deionized water wash through ethanol water circulation
In polypropylene hollow fiber membrane assembly after washing, wash 6～10 hours with deionized water recirculation；
5) it is dried: the polypropylene hollow fiber membrane assembly after step 4) is cleaned, at 50～80 DEG C
At a temperature of dried, i.e. can get the polypropylene hollow fiber membrane assembly that antipollution is modified.
On the basis of such scheme, polypropylene hollow fiber membrane assembly is installed to antipollution and changes
In property device, by antipollution reforming apparatus carry out step 1), 2), 3) and 4).
On the basis of such scheme, described antipollution reforming apparatus includes:
It is provided with the fluid reservoir 1 of agitating device, flow control mechanism, liquid delivery pump 4, pressure
Power controlling organization, flow direction control mechanism；
Described flow direction control mechanism includes:
It is located at the flow divider of the liquid feeding side of polypropylene hollow fiber membrane assembly,
It is located at the converging valve of the tapping side of polypropylene hollow fiber membrane assembly,
Between inlet and the fluid reservoir 1 of flow divider, set gradually flow velocity by liquid flow direction
Controlling organization, liquid delivery pump 4, pressure control mechanism,
Between liquid outlet and the fluid reservoir 1 of converging valve, by being provided with the pipeline of the 3rd valve 10
Connect.
This kind of connected mode forms loop so that the solution in fluid reservoir 1 can be at whole device
Middle dynamic circulation.
On the basis of such scheme, described flow control mechanism includes: effusion meter 2, first
Valve 3.Set gradually by liquid flow direction.
On the basis of such scheme, described pressure control mechanism includes: Pressure gauge 5 and second
Valve 6, is set gradually by liquid flow direction.Arranging pressure control mechanism is to adjust for convenience
Throttling speed.
On the basis of such scheme, it is modified that polypropylene hollow fiber membrane assembly is installed to antipollution
The concrete connected mode of device is:
The liquid feeding side of polypropylene hollow fiber membrane assembly 8 is provided with shaft orientation liquid feeding hole 8-1 and laterally enters
Fluid apertures 8-2,
The tapping side of polypropylene hollow fiber membrane assembly 8 is provided with Axial-running Out fluid apertures 8-4 and laterally goes out
Fluid apertures 8-3,
Flow divider 7 first outlet with shaft orientation liquid feeding hole 8-1 be connected,
Second outlet of flow divider 7 is connected with lateral inlet opening 8-2；
First import of converging valve 9 is connected with Axial-running Out fluid apertures 8-4,
Second import of converging valve 9 is connected with lateral liquid outlet 8-3.
On the basis of such scheme, fluid reservoir 1, according to the carrying out of antipollution modification procedure, divides
Yong Yu not store cross-linking agent solution, modified compound solution, the soluble salt solutions of metal ion,
Ethanol water and deionized water.During this kind of mode, before changing storage liquid, need to use every time
Deionized water cleans fluid reservoir 1.
Also some special containers be can be respectively provided with, cross-linking agent solution, modified compound stored respectively
Solution, the soluble salt solutions of metal ion, ethanol water and deionized water, according to anti-soil
The carrying out of dye modification procedure, is connected into antipollution reforming apparatus by different special containers.
On the basis of such scheme, modified compound solution, metal ion soluble-salt molten
Liquid, ethanol water and the deionized water flow direction in polypropylene hollow fiber membrane assembly 8
All consistent with the flow direction of cross-linking agent solution in pretreatment.
On the basis of such scheme, realize polypropylene hollow fiber by controlling flow direction
The process of membrane module inner surface, or realize the place to polypropylene hollow fiber membrane module outer surface
Reason, or realize polypropylene hollow fiber membrane assembly is carried out simultaneously inner surface, outer surface and fenestra
Process.Be preferably polypropylene hollow fiber membrane assembly carried out simultaneously inner surface, outer surface and
Fenestra processes.
On the basis of such scheme, described realization is to polypropylene hollow fiber membrane module inner
The concretely comprising the following steps of process:
Make inlet and first outlet of flow divider 7, make the first import of converging valve 9 and go out
Liquid mouth connects, and keeping other valves in antipollution reforming apparatus is open mode.
Liquid in fluid reservoir 1 is from the shaft orientation liquid feeding hole 8-1 of polypropylene hollow fiber membrane assembly 8
(i.e. tube-side inlet) enters, from Axial-running Out fluid apertures 8-4 after polypropylene hollow fiber membrane assembly 8
(i.e. tube side outlet) out.
On the basis of such scheme, described realization is to polypropylene hollow fiber membrane module outer surface
The concretely comprising the following steps of process:
Make inlet and second outlet of flow divider 7, make the second import of converging valve 9 and go out
Liquid mouth connects, and keeping other valves in antipollution reforming apparatus is open mode.
Liquid in fluid reservoir 1 is from the lateral inlet opening 8-2 of polypropylene hollow fiber membrane assembly 8
(i.e. shell side inlet) enters, from lateral liquid outlet 8-3 after polypropylene hollow fiber membrane assembly 8
(i.e. shell-side outlet) out.
On the basis of such scheme, polypropylene hollow fiber membrane assembly is entered by described realization simultaneously
Concretely comprising the following steps of the process of row inner surface, outer surface and fenestra:
Make inlet and first outlet of flow divider 7, make the second import of converging valve 9 and go out
Liquid mouth connects, and keeping other valves in antipollution reforming apparatus is open mode.
Liquid in fluid reservoir 1 is from the shaft orientation liquid feeding hole 8-1(of polypropylene hollow fiber membrane assembly i.e.
Tube-side inlet) enter, after polypropylene hollow fiber membrane assembly from lateral liquid outlet 8-3(i.e.
Shell-side outlet) out.
On the basis of such scheme, the cross-linking agent in step 1) is formaldehyde, glutaraldehyde, fourth
Dialdehyde, Biformyl or ethylene glycol bis glycidyl ether.
On the basis of such scheme, in step 1) the mass concentration of cross-linking agent solution be 10～
50%。
On the basis of such scheme, in step 1) the flow velocity of cross-linking agent solution be 1～
50ml/min, the time of dynamic circulation is 2～6 hours.
On the basis of such scheme, step 2) in modified compound be polymine, poly-
One in lysine, poly arginine, histidine, ethanolamine, lysine or arginine or two
Plant the mixture of any of the above proportioning.
On the basis of such scheme, step 2) in the mass concentration of modified compound solution be
1%～15%.
On the basis of such scheme, step 2) in the flow velocity of modified compound solution be 1～
50ml/min, the time cross-link, adsorbed is 1～4 hour.
On the basis of such scheme, in step 3) the soluble salt solutions of metal ion be with
Any one in lower solution: Cu2+Acetic acid, nitric acid, hydrochloric acid or sulfuric acid solution, or Ag+
Salpeter solution.
On the basis of such scheme, the matter of the soluble salt solutions of metal ion in step 3)
Amount concentration is 1%～15%.
On the basis of such scheme, the stream of the soluble salt solutions of metal ion in step 3)
Speed is 1～50ml/min, carries out being coordinated, the time of complex reaction is 1～4 hour.
On the basis of such scheme, in step 4) the mass concentration of ethanol water be 40～
90%。
It it is below specific embodiment.
The performance measurement of polypropylene hollow fiber membrane assembly includes that strainability measures and antipollution
Performance measurement:
1, strainability measures
The strainability of polypropylene hollow fiber membrane assembly is characterized by pure water flux.Respectively
By first for polypropylene hollow fiber membrane assembly forward and backward for modification precompressed 30min under 0.15Mpa,
Until water flux is basicly stable, under 0.1MPa, measure polypropylene hollow fiber membrane group the most again
The pure water flux of part.
2, antifouling property measures
The antifouling property of polypropylene hollow fiber membrane assembly is by measuring modified forward and backward polypropylene
Hollow fiber film assembly (is specifically designed to the bacterium colony that water treatmenting performance measures, for commercially available to indicator bacteria
Product) bacteriostasis rate characterize, concrete mensuration process is: by pending polluted raw and
The water sample after the process of polypropylene hollow fiber membrane assembly after modified, is added drop-wise to bacterium colony total respectively
On number test sheet, coating uniformly, is cultivated 24 hours at 37 DEG C, and counting viable count also calculates
Bacteriostasis rate (R, %), R=1-X/A,
Wherein, X and A is respectively sample after polypropylene hollow fiber membrane assembly after modified processes
Clump count in product and the clump count in pending polluted raw sample.
Embodiment 1
1) choose film silk mean inside diameter be 1.2mm, external diameter 1.8mm, membrane aperture be 0.1 μm
Polypropylene hollow fiber membrane, first uses soak with ethanol 12 hours, then cleans 3 times with deionized water,
Remove the absorption impurity on polypropylene hollow fiber membrane surface, be subsequently placed in 60 DEG C of baking ovens, dry
Dry post package becomes polypropylene hollow fiber membrane assembly, and length component is 22cm, loads film silk radical
It it is 16；
2) packaged polypropylene hollow fiber membrane assembly 8 is connected to antipollution modification used
Device in, open the first valve 3 and the second valve 6, by mass percent in fluid reservoir 1 be
The glutaraldehyde cross-linking agent solution of 50%, is transported to polypropylene with liquid delivery pump 4 under continuous stirring
In hollow fiber film assembly 8, regulation effusion meter 2 and Pressure gauge 5, control the stream of cross-linking agent solution
Speed is 30ml/min, by regulation flow divider 7 and converging valve 9, controls cross-linking agent solution from film group
The shaft orientation liquid feeding hole 8-1 of part enters, from lateral liquid outlet after polypropylene hollow fiber membrane assembly
8-3 goes out, and opens the 3rd valve 10, dynamic circulation 4 hours, carries out polypropylene hollow fiber simultaneously
The pretreatment of membrane module inner surface, outer surface and fenestra；
3), after fluid reservoir 1 is washed with deionized water only, adding mass percent is 10% polyethyleneimine
Amine modified compound solution, under continuous stirring with liquid delivery pump 4 by modified compound solution
It is transported in pretreated polypropylene hollow fiber membrane assembly, by effusion meter 2 and Pressure gauge
5, the flow velocity controlling modified compound solution is 20ml/min, by regulation flow divider 7 and interflow
Valve 9, makes the modified compound solution shaft orientation liquid feeding hole 8-1 from polypropylene hollow fiber membrane assembly 8
Enter, go out from lateral liquid outlet 8-3 after polypropylene hollow fiber membrane assembly 8, make polyethyleneimine
Amine crosslinking absorption in inner surface, outer surface and the fenestra of polypropylene hollow fiber membrane assembly simultaneously
2 hours；
4) prepare the Schweinfurt green soluble salt solutions that mass percent is 12% and add the liquid storage cleaned
In tank 1, with liquid delivery pump 4, soluble salt solutions is transported to crosslinked suction under continuous stirring
In the polypropylene hollow fiber membrane assembly of agglomeration aziridine, by effusion meter 2 and Pressure gauge 5,
The flow velocity controlling soluble salt solutions is 20ml/min, by regulation flow divider 7 and converging valve 9,
Control the soluble salt solutions concrete flow direction in polypropylene hollow fiber membrane assembly 8, make
Soluble salt solutions enters from the shaft orientation liquid feeding hole 8-1 of polypropylene hollow fiber membrane assembly 8, Jing Guoju
Going out from lateral liquid outlet 8-3 after propylene hollow fiber film assembly 8, carrying out ligand complex, to react 4 little
Time, form chelate and make metal ion immobilized in the surface of polypropylene hollow fiber membrane assembly 8；
5) the polypropylene hollow fiber membrane assembly being modified by the mass concentration in fluid reservoir 1 is first
40～the ethanol water circulation washing 12 hours of 90%, then 6 little through deionized water circulation washing
Time, close the first valve the 3, second valve 6 and the 3rd valve 10, take out the polypropylene after cleaning
Hollow fiber film assembly, finally dried at a temperature of 60 DEG C, i.e. can get antipollution modified
Polypropylene hollow fiber membrane assembly.
Its pure water under the conditions of 0.1MPa of polypropylene hollow fiber membrane assembly the most before modified
Flux stabilized is at 215.8L/h.m2, modified for 303.6L/h.m2；Modified the gathering of antipollution
After propylene hollow fiber film assembly runs 4 weeks, its bacteriostasis rate is than improving 81.2% before modified.
Embodiment 2
1) choose film silk mean inside diameter be 1.4mm, external diameter 2.1.mm, membrane aperture be 0.1 μm
Polypropylene hollow fiber microporous membrane, first by soak with ethanol 4 hours, then clean 2 with deionized water
Secondary, remove the absorption impurity on film surface, be subsequently placed in 50 DEG C of baking ovens, be packaged into after drying
Polypropylene hollow fiber membrane assembly, length component is 20cm, and filling film silk radical is 15；
2) packaged propylene hollow fiber film assembly 8 is connected to what antipollution modification was used
In device, open the first valve 3 and the second valve 6, be 10% by mass percent in fluid reservoir 1
Glutaraldehyde cross-linking agent solution, be transported in polypropylene with liquid delivery pump 4 under continuous stirring
In hollow fiber membrane module 8, regulation effusion meter 2 and Pressure gauge 5, control the flow velocity of cross-linking agent solution
For 1ml/min, by regulation flow divider 7 and converging valve 9, control cross-linking agent solution from membrane module
Shaft orientation liquid feeding hole 8-1 enter, from lateral liquid outlet 8-3 after polypropylene hollow fiber membrane assembly
Go out, open the 3rd valve 10, dynamic circulation 6 hours, carry out polypropylene hollow fiber membrane simultaneously
The pretreatment of module inner, outer surface and fenestra；
3) fluid reservoir 1 is washed with deionized water the clean rear mass percent that adds is that 12% polylysine changes
Property compound solution, is transported to pre-place with liquid delivery pump 4 by modified compound solution under stirring
In polypropylene hollow fiber membrane assembly after reason, by effusion meter 2 and Pressure gauge 5, control modification
The flow velocity of compound solution is 10ml/min, by regulation flow divider 7 and converging valve 9, makes modification
Solution enters from the shaft orientation liquid feeding hole 8-1 of polypropylene hollow fiber membrane assembly 8, after membrane module from
Lateral liquid outlet 8-3 goes out, and makes polylysine simultaneously at polypropylene hollow fiber membrane inner surface, outer
Crosslinking absorption 2 hours in surface and fenestra；
4) prepare the silver nitrate soluble salt solutions that mass percent is 15% and add the liquid storage cleaned
In tank 1, it is transported to liquid delivery pump 4 under stirring in the polypropylene of crosslinked absorption polylysine
In hollow fiber membrane module 8, by effusion meter 2 and Pressure gauge 5, control the stream of soluble salt solutions
Speed is 50ml/min, by regulation flow divider 7 and converging valve 9, controls soluble salt solutions poly-
Concrete flow direction in propylene hollow fiber film assembly 8, makes soluble salt solutions from polypropylene
The shaft orientation liquid feeding hole 8-1 of hollow fiber film assembly 8 enters, from lateral liquid outlet after membrane module
8-3 goes out, and carries out ligand complex and reacts 4 hours, forms chelate and makes metal ion immobilized in poly-third
The surface of alkene hollow fiber film assembly 8；
5) the polypropylene hollow fiber membrane assembly being modified by the mass concentration in fluid reservoir 1 is first
40～90% ethanol water circulation washing 6 hours, then through deionized water circulation washing 6 hours,
Close the first valve the 3, second valve 6 and the 3rd valve 10, take out the hollow polypropylene after cleaning
Fiber film component, finally dried at a temperature of 50 DEG C, i.e. can get modified the gathering of antipollution
Propylene hollow fiber film assembly.
Its pure water under the conditions of 0.1MPa of polypropylene hollow fiber membrane assembly the most before modified
Flux stabilized is at 128.3L/h.m2, modified for 117.9L/h.m2；Modified the gathering of antipollution
After propylene hollow fiber film assembly runs 4 weeks, its bacteriostasis rate is than improving 89.1% before modified.
Embodiment 3
1) choose film silk mean inside diameter be 1.5mm, external diameter 2.3mm, membrane aperture be 0.2 μm
Polypropylene hollow fiber membrane, first uses soak with ethanol 8 hours, then cleans 4 times with deionized water, goes
Except the absorption impurity on film surface, it is subsequently placed in 80 DEG C of baking ovens, is packaged into polypropylene after drying
Hollow fiber film assembly, length component is 23cm, and filling film silk radical is 17；
2) packaged polypropylene hollow fiber membrane assembly 8 is connected to antipollution modification used
Device in, open the first valve 3 and the second valve 6, by mass percent in fluid reservoir 1 be
The Biformyl cross-linking agent solution of 40%, is transported to polypropylene with liquid delivery pump 4 under continuous stirring
In hollow fiber film assembly 8, regulation effusion meter 2 and Pressure gauge 5, control the stream of cross-linking agent solution
Speed is 50ml/min, by regulation flow divider 7 and converging valve 9, controls the solution axle from membrane module
Enter to inlet opening 8-1, go out from lateral liquid outlet 8-3 after membrane module, open the 3rd valve 10,
Dynamic circulation 2 hours, carry out simultaneously polypropylene hollow fiber membrane module inner, outer surface and
The pretreatment of fenestra；
3) fluid reservoir 1 is washed with deionized water the clean rear mass percent that adds is 1% ethanolamine modification
Polymer solution, modified compound solution is transported to pre-place by continuously stirred lower liquid delivery pump 4
In polypropylene hollow fiber membrane assembly after reason, regulation effusion meter 2 and Pressure gauge 5, control modification
The flow velocity of compound solution is 1ml/min, by regulation flow divider 7 and converging valve 9, makes modification
Solution enters from the shaft orientation liquid feeding hole 8-1 of polypropylene hollow fiber membrane assembly 8, after membrane module from
Lateral liquid outlet 8-3 goes out, make ethanolamine simultaneously polypropylene hollow fiber membrane assembly inner surface,
Crosslinking absorption 4 hours in outer surface and fenestra；
4) prepare the copper sulfate soluble salt solutions that mass percent is 1% and add the liquid storage cleaned
In tank 1, under stirring, it is transported to the hollow polypropylene of crosslinked absorption ethanolamine with liquid delivery pump 4
In fiber film component 8, by regulation effusion meter 2 and Pressure gauge 5, control soluble salt solutions
Flow velocity is 1ml/min, regulation flow divider 7 and converging valve 9, controls soluble salt solutions poly-third
Concrete flow direction in alkene hollow fiber film assembly 8, makes soluble salt solutions from polypropylene
The shaft orientation liquid feeding hole 8-1 of hollow fiber membrane module 8 enters, from lateral liquid outlet 8-3 after membrane module
Go out, carry out ligand complex and react 4 hours, form chelate and make metal ion immobilized in polypropylene
The surface of hollow fiber film assembly 8；
5) the polypropylene hollow fiber membrane assembly being modified by the mass concentration in fluid reservoir 1 is first
40～the ethanol water circulation washing 10 hours of 90%, then 10 little through deionized water circulation washing
Time, close the first valve the 3, second valve 6 and the 3rd valve 10, take out the polypropylene after cleaning
Hollow fiber film assembly, finally dried at a temperature of 80 DEG C, i.e. can get antipollution modified
Polypropylene hollow fiber membrane assembly.
Its pure water under the conditions of 0.1MPa of polypropylene hollow fiber membrane assembly the most before modified
Flux stabilized is at 731.6L/h.m2, modified for 789.4L/h.m2；Modified the gathering of antipollution
After propylene hollow fiber film assembly runs 4 weeks, its bacteriostasis rate is than improving 73.2% before modified.
Embodiment 4
1) choose film silk mean inside diameter be 1.2mm, external diameter 1.8mm, membrane aperture be 0.1 μm
Polypropylene hollow fiber membrane, first uses soak with ethanol 10 hours, then cleans 5 times with deionized water,
Remove the absorption impurity on film surface, be subsequently placed in 60 DEG C of baking ovens, be packaged into poly-third after drying
Alkene hollow fiber film assembly, length component is 22cm, and filling film silk radical is 16；
2) packaged polypropylene hollow fiber membrane assembly 8 is connected to antipollution modification used
Device in, open the first valve 3 and the second valve 6, by mass percent in fluid reservoir 1 be
It is fine that the butanedial solution of 30% is transported to hollow polypropylene with liquid delivery pump 4 under continuous stirring
In dimension membrane module 8, regulation effusion meter 2 and Pressure gauge 5, the flow velocity controlling cross-linking agent solution is
20ml/min, by regulation flow divider 7 and converging valve 9, controls cross-linking agent solution from membrane module
Shaft orientation liquid feeding hole 8-1 enters, from lateral liquid outlet 8-3 after polypropylene hollow fiber membrane assembly
Go out, open the 3rd valve 10, dynamic circulation 5 hours, carry out polypropylene hollow fiber membrane simultaneously
The pretreatment of module inner, outer surface and fenestra；
3) fluid reservoir 1 is washed with deionized water the clean rear mass percent that adds is the poly arginine of 15%
Modified compound solution, stirring is lower uses liquid delivery pump 4 by modified compound solution from fluid reservoir 1
It is transported in pretreated polypropylene hollow fiber membrane assembly, by effusion meter 2 and Pressure gauge
5, the flow velocity controlling modified compound solution is 50ml/min, regulation flow divider 7 and converging valve 9,
Modified compound solution is made to enter from the shaft orientation liquid feeding hole 8-1 of polypropylene hollow fiber membrane assembly 8, warp
Go out from lateral liquid outlet 8-3 after crossing polypropylene hollow fiber membrane assembly, make poly arginine exist simultaneously
Crosslinking absorption 1 hour in the inner surface of polypropylene hollow fiber membrane assembly, outer surface and fenestra；
4) prepare the copper chloride soluble salt solutions that mass percent is 12% and add the liquid storage cleaned
In tank 1, with liquid delivery pump 4, soluble salt solutions is transported to crosslinked absorption under stirring and gathers essence
In the polypropylene hollow fiber membrane assembly of propylhomoserin, regulation effusion meter 2 and Pressure gauge 5, control solvable
Property saline solution flow velocity be 30ml/min, by regulation flow divider 7 and converging valve 9, control solvable
Property saline solution enters from the shaft orientation liquid feeding hole 8-1 of polypropylene screen assembly, from laterally after membrane module
Liquid outlet 8-3 goes out, and carries out ligand complex and reacts 2 hours, forms chelate and makes metal ion immobilized
Surface in polypropylene hollow fiber membrane assembly 8；
5) the polypropylene hollow fiber membrane assembly being modified by the mass concentration in fluid reservoir 1 is first
40～the ethanol water circulation washing 12 hours of 90%, then 8 little through deionized water circulation washing
Time, close the first valve the 3, second valve 6 and the 3rd valve 10, take out the polypropylene after cleaning
Hollow fiber film assembly, finally dried at a temperature of 70 DEG C, i.e. can get antipollution modified
Polypropylene hollow fiber membrane assembly.
Its pure water under the conditions of 0.1MPa of polypropylene hollow fiber membrane assembly the most before modified
Flux stabilized is at 215.8L/h.m2, modified for 201.6L/h.m2；Modified the gathering of antipollution
After propylene hollow fiber film assembly runs 4 weeks, its bacteriostasis rate is than improving 76.2% before modified.
Embodiment 5
1) choose film silk mean inside diameter be 0.9mm, external diameter 1.4mm, membrane aperture be 0.1 μm
Polypropylene hollow fiber membrane, first uses soak with ethanol 8 hours, then cleans 4 times with deionized water, goes
Except the absorption impurity on film surface, it is subsequently placed in 60 DEG C of baking ovens, is packaged into polypropylene after drying
Hollow fiber film assembly, length component is 20cm, and filling film silk radical is 15；
2) packaged polypropylene hollow fiber membrane assembly 8 is connected to antipollution modification used
Device in, open the first valve 3 and the second valve 6, by mass percent in fluid reservoir 1 be
The formalin of 20% is transported to polypropylene hollow fiber with liquid delivery pump 4 under continuous stirring
In membrane module 8, regulation effusion meter 2 and Pressure gauge 5, the flow velocity controlling cross-linking agent solution is
10ml/min, by regulation flow divider 7 and converging valve 9, controls cross-linking agent solution from membrane module
Lateral inlet opening 8-2 enters, from lateral liquid outlet 8-3 after polypropylene hollow fiber membrane assembly
Go out, open the 3rd valve 10, dynamic circulation 3 hours, carry out polypropylene hollow fiber membrane assembly
The pretreatment of outer surface；
3) fluid reservoir 1 be washed with deionized water clean after add by the histidine that mass percent is 2%,
The lysine of 2% and the modified compound solution of the arginine composition of 2%, carry with liquid under stirring
Modified compound solution is transported to pretreated polypropylene hollow fiber from fluid reservoir 1 by pump 4
In membrane module 8, by effusion meter 2 and Pressure gauge 5, the flow velocity controlling modified compound solution is
30ml/min, by regulation flow divider 7 and converging valve 9, makes modified compound solution from polypropylene
The shaft orientation liquid feeding hole 8-2 of hollow fiber film assembly 8 enters, after polypropylene hollow fiber membrane assembly
Go out from lateral liquid outlet 8-3, make modified compound in the appearance of polypropylene hollow fiber membrane assembly
Face crosslinking absorption 3 hours；
4) prepare the copper nitrate soluble salt solutions that mass percent is 8% and add the liquid storage cleaned
In tank 1, it is transported to poly-the third of crosslinked adsorbent modifier under continuous stirring with liquid delivery pump 4
In alkene hollow fiber film assembly 8, regulation effusion meter 2 and Pressure gauge 5, control soluble salt solutions
Flow velocity be 20ml/min, by regulation flow divider 7 and converging valve 9, control soluble salt solutions
Concrete flow direction in polypropylene hollow fiber membrane assembly 8, makes the solution axle from membrane module
Enter to inlet opening 8-2, go out from lateral liquid outlet 8-3 after polypropylene hollow fiber membrane assembly 8,
Carry out ligand complex to react 1 hour, form chelate and make metal ion immobilized in hollow polypropylene
The outer surface of fiber film component 8；
5) the polypropylene hollow fiber membrane assembly being modified by the mass concentration in fluid reservoir 1 is first
40～the ethanol water circulation washing 12 hours of 90%, then 10 little through deionized water circulation washing
Time, close the first valve the 3, second valve 6 and the 3rd valve 10, take out the polypropylene after cleaning
Hollow fiber film assembly, finally dried at a temperature of 60 DEG C, i.e. can get antipollution modified
Polypropylene hollow fiber membrane assembly.
Its pure water under the conditions of 0.1MPa of polypropylene hollow fiber membrane assembly the most before modified
Flux stabilized is at 128.6L/h.m2, modified for 152.3L/h.m2；Modified the gathering of antipollution
After propylene hollow fiber film assembly runs 4 weeks, its modified polypropylene hollow fiber membrane assembly
Bacteriostasis rate is than improving 51.6% before modified.
Embodiment 6
1) choose film silk mean inside diameter be 1.5mm, external diameter 2.2mm, membrane aperture be 0.2 μm
Polypropylene hollow fiber membrane, first uses soak with ethanol 12 hours, then cleans 3 times with deionized water,
Remove the absorption impurity on film surface, be subsequently placed in 70 DEG C of baking ovens, be packaged into poly-third after drying
Alkene hollow fiber film assembly, length component is 22cm, and filling film silk radical is 16；
2) packaged polypropylene hollow fiber membrane assembly 8 is connected to antipollution modification used
Device in, open the first valve 3 and the second valve 6, by mass percent in fluid reservoir 1 be
The ethylene glycol bis (+)-2,3-Epoxy-1-propanol ethereal solution of 30% is transported to liquid delivery pump 4 under continuous stirring
In polypropylene hollow fiber membrane assembly 8, regulation effusion meter 2 and Pressure gauge 5, control cross-linking agent molten
The flow velocity of liquid is 10ml/min, by regulation flow divider 7 and converging valve 9, controls cross-linking agent solution
Enter, from axially after polypropylene hollow fiber membrane assembly 8 from the shaft orientation liquid feeding hole 8-1 of membrane module
Liquid outlet 8-4 goes out, and opens the 3rd valve 10, dynamic circulation 3 hours, carries out hollow polypropylene fine
The pretreatment of dimension membrane module inner surface；
3) fluid reservoir 1 be washed with deionized water clean after add by the lysine that mass percent is 2% and
The modified compound solution of the arginine composition of 3%, stirring is lower uses liquid delivery pump 4 by modification
Polymer solution is transported in pretreated polypropylene hollow fiber membrane assembly, by effusion meter 2
With Pressure gauge 5, the flow velocity controlling modified compound solution is 30ml/min, is shunted by regulation
Valve 7 and converging valve 9, make axial from polypropylene hollow fiber membrane assembly 8 of modified compound solution
Inlet opening 8-1 enters, and goes out from Axial-running Out fluid apertures 8-4 after membrane module, makes modifier compound exist
The inner surface crosslinking absorption of polypropylene hollow fiber membrane assembly 1 hour；
4) prepare the silver nitrate soluble salt solutions that mass percent is 10% and add the liquid storage cleaned
In tank 1, under stirring, with liquid delivery pump 4, soluble salt solutions is transported to crosslinked adsorption of modification
In the polypropylene hollow fiber membrane assembly 8 of compound, by effusion meter 2 and Pressure gauge 5, control
The flow velocity of soluble salt solutions is 30ml/min, by regulation flow divider 7 and converging valve 9, controls
The soluble salt solutions concrete flow direction in polypropylene hollow fiber membrane assembly 8, makes solvable
Property saline solution enters from membrane module shaft orientation liquid feeding hole 8-1, after polypropylene hollow fiber membrane assembly
Go out from lateral liquid outlet 8-4, carry out ligand complex react 2 hours, formed chelate make metal from
Son is immobilized in the inner surface of polypropylene hollow fiber membrane assembly 8；
5) the polypropylene hollow fiber membrane assembly being modified by the mass concentration in fluid reservoir 1 is first
40～the ethanol water circulation washing 12 hours of 90%, then 6 little through deionized water circulation washing
Time, close the first valve the 3, second valve 6 and the 3rd valve 10, take out the polypropylene after cleaning
Hollow fiber film assembly, finally dried at a temperature of 60 DEG C, i.e. can get antipollution modified
Polypropylene hollow fiber membrane assembly.
Its pure water under the conditions of 0.1MPa of polypropylene hollow fiber membrane assembly the most before modified
Flux stabilized is at 653.8L/h.m2, modified for 683.1L/h.m2；Modified the gathering of antipollution
After propylene hollow fiber film assembly runs 4 weeks, its bacteriostasis rate is than improving 63.2% before modified.
The content not being described in detail in this specification belongs to known in professional and technical personnel in the field
Prior art.
Claims (19)
1. the method that a polypropylene hollow fiber membrane assembly antipollution is modified, it is characterised in that
Polypropylene hollow fiber membrane assembly entirety is carried out scale antifouling property improvement, by selecting
Suitably modified compound and the soluble salt solutions of metal ion, utilize antipollution reforming apparatus
Control successively cross-linking agent solution, modified compound solution, the soluble salt solutions of metal ion,
Flow velocity in polypropylene hollow fiber membrane assembly of ethanol water and deionized water and flowing side
To, modified compound is coupled at the surface of polypropylene hollow fiber membrane assembly, metal ion leads to
Cross the active group in modified compound and be immobilized on the surface of polypropylene hollow fiber membrane assembly, make
Polypropylene hollow fiber membrane assembly has hydrophilic and excellent bacteriostasis simultaneously, thus prepares
Go out the polypropylene hollow fiber membrane assembly that contamination resistance is strong；
Described antipollution modification specifically includes following steps:
Step 1, the pretreatment of polypropylene hollow fiber membrane assembly: cross-linking agent solution is transported to
In polypropylene hollow fiber membrane assembly, control the flow velocity of cross-linking agent solution and at hollow polypropylene fibre
Flow direction in dimension membrane module, dynamic circulation certain time, carries out polypropylene hollow fiber membrane
The pretreatment of assembly；
Step 2, the crosslinking of modified compound, absorption: modified compound solution is transported to pre-
In polypropylene hollow fiber membrane assembly after process, control modified compound solution flow velocity and
Flow direction in polypropylene hollow fiber membrane assembly, makes modified compound fine at hollow polypropylene
Surface-crosslinked, absorption a period of time of dimension membrane module；
Step 3, the coordination of metal ion, complexation: by defeated for the soluble salt solutions of metal ion
Deliver to through step 2 process after polypropylene hollow fiber membrane assembly in, control metal ion can
The flow velocity of soluble solution and the flow direction in polypropylene hollow fiber membrane assembly, carry out one
Coordination, the complex reaction fixed time form chelate, make metal ion immobilized in through step 2 place
The surface of the polypropylene hollow fiber membrane assembly after reason；
Step 4, washing: ethanol water is transported to the hollow polypropylene after step 3 processes
In fiber film component, control ethanol water flowing side in polypropylene hollow fiber membrane assembly
To, circulation washing 6～12 hours, then be transported to deionized water wash through ethanol water circulation
In polypropylene hollow fiber membrane assembly after washing, wash 6～10 hours with deionized water recirculation；
Step 5, be dried: the polypropylene hollow fiber membrane assembly after step 4 is cleaned, 50～
At a temperature of 80 DEG C after drying, i.e. can get the polypropylene hollow fiber membrane group that antipollution is modified
Part；
Described polypropylene hollow fiber membrane assembly need to be installed in antipollution reforming apparatus, by anti-
Pollute reforming apparatus and carry out step 1,2,3 and 4；
Described antipollution reforming apparatus includes:
Be provided with the fluid reservoir (1) of agitating device, flow control mechanism, liquid delivery pump (4),
Pressure control mechanism, flow direction control mechanism；
Described flow direction control mechanism includes:
It is located at the flow divider (7) of the liquid feeding side of polypropylene hollow fiber membrane assembly,
It is located at the converging valve (9) of the tapping side of polypropylene hollow fiber membrane assembly,
Between inlet and the fluid reservoir (1) of flow divider (7), by liquid flow direction successively
Flow control mechanism, liquid delivery pump (4), pressure control mechanism are set,
Between liquid outlet and the fluid reservoir (1) of converging valve (9), by being provided with the 3rd valve (10)
Pipeline connect；
In step 2, modified compound is polymine, polylysine, poly arginine, group ammonia
The mixture of one or more any proportionings in acid, ethanolamine, lysine or arginine；
Any one during the soluble salt solutions of metal ion is following solution in step 3:
Cu2+Acetic acid, nitric acid, hydrochloric acid or sulfuric acid solution, or Ag+Salpeter solution.
2. the side that polypropylene hollow fiber membrane assembly antipollution as claimed in claim 1 is modified
Method, it is characterised in that described polypropylene hollow fiber membrane assembly is prepared in the following ways: take
Polypropylene hollow fiber membrane first with soak with ethanol 4～12 hours, then with deionized water clean 2～
5 times, remove the absorption impurity on polypropylene hollow fiber membrane surface, be subsequently placed in 50～80 DEG C
In baking oven, it is packaged into polypropylene hollow fiber membrane assembly after drying.
3. the side that polypropylene hollow fiber membrane assembly antipollution as claimed in claim 1 is modified
Method, it is characterised in that described flow control mechanism, is included successively by liquid flow direction: stream
Gauge (2), the first valve (3).
4. the side that polypropylene hollow fiber membrane assembly antipollution as claimed in claim 1 is modified
Method, it is characterised in that described pressure control mechanism, is included successively by liquid flow direction: pressure
Power table (5) and the second valve (6).
5. the side that polypropylene hollow fiber membrane assembly antipollution as claimed in claim 1 is modified
Method, it is characterised in that described polypropylene hollow fiber membrane assembly is installed to antipollution reforming apparatus
Concrete connected mode be:
The liquid feeding side of polypropylene hollow fiber membrane assembly (8) be provided with shaft orientation liquid feeding hole (8-1) and
Lateral inlet opening (8-2),
The tapping side of polypropylene hollow fiber membrane assembly (8) be provided with Axial-running Out fluid apertures (8-4) and
Lateral liquid outlet (8-3),
First outlet of flow divider (7) is connected with shaft orientation liquid feeding hole (8-1),
Second outlet of flow divider (7) is connected with lateral inlet opening (8-2)；
First import of converging valve (9) is connected with Axial-running Out fluid apertures (8-4),
Second import of converging valve (9) is connected with lateral liquid outlet (8-3).
6. the side that polypropylene hollow fiber membrane assembly antipollution as claimed in claim 1 is modified
Method, it is characterised in that described fluid reservoir (1), according to the carrying out of antipollution modification procedure, divides
Yong Yu not store cross-linking agent solution, modified compound solution, the soluble salt solutions of metal ion,
Ethanol water and deionized water, or it is respectively provided with some special containers, store cross-linking agent respectively
Solution, modified compound solution, the soluble salt solutions of metal ion, ethanol water and go
Ionized water, according to the carrying out of antipollution modification procedure, is connected into antipollution by different special containers
Reforming apparatus.
7. the side that polypropylene hollow fiber membrane assembly antipollution as claimed in claim 1 is modified
Method, it is characterised in that described modified compound solution, the soluble salt solutions of metal ion,
Ethanol water and deionized water flow direction in polypropylene hollow fiber membrane assembly (8)
All consistent with the flow direction of cross-linking agent solution in pretreatment.
8. the polypropylene hollow fiber membrane assembly antipollution as described in claim 1 or 7 is modified
Method, it is characterised in that by control flow direction realize to polypropylene hollow fiber membrane group
The process of part inner surface, or realize the process to polypropylene hollow fiber membrane module outer surface, or
Realize polypropylene hollow fiber membrane assembly is carried out simultaneously the place of inner surface, outer surface and fenestra
Reason.
9. the side that polypropylene hollow fiber membrane assembly antipollution as claimed in claim 8 is modified
Method, it is characterised in that described realization is to the process of polypropylene hollow fiber membrane module inner
Concretely comprise the following steps:
Make inlet and first outlet of flow divider (7), make the first of converging valve (9)
Import connects with liquid outlet, and keeping other valves in antipollution reforming apparatus is open mode.
10. the side that polypropylene hollow fiber membrane assembly antipollution as claimed in claim 8 is modified
Method, it is characterised in that described realization is to the process of polypropylene hollow fiber membrane module outer surface
Concretely comprise the following steps:
Make inlet and second outlet of flow divider (7), make the second of converging valve (9)
Import connects with liquid outlet, and keeping other valves in antipollution reforming apparatus is open mode.
The side that 11. polypropylene hollow fiber membrane assembly antipollutions as claimed in claim 8 are modified
Method, it is characterised in that described realization polypropylene hollow fiber membrane assembly is carried out simultaneously inner surface,
Concretely comprising the following steps of the process of outer surface and fenestra:
Make inlet and first outlet of flow divider (7), make the second of converging valve (9)
Import connects with liquid outlet, and keeping other valves in antipollution reforming apparatus is open mode.
The side that 12. polypropylene hollow fiber membrane assembly antipollutions as claimed in claim 1 are modified
Method, it is characterised in that the cross-linking agent in step 1 is formaldehyde, glutaraldehyde, butanedial, second two
Aldehyde or ethylene glycol bis glycidyl ether.
The side that 13. polypropylene hollow fiber membrane assembly antipollutions as claimed in claim 1 are modified
Method, it is characterised in that in step 1, the mass concentration of cross-linking agent solution is 10～50%.
The side that 14. polypropylene hollow fiber membrane assembly antipollutions as claimed in claim 1 are modified
Method, it is characterised in that in step 1, the flow velocity of cross-linking agent solution is 1～50ml/min, dynamically follows
The time of ring is 2～6 hours.
The side that 15. polypropylene hollow fiber membrane assembly antipollutions as claimed in claim 1 are modified
Method, it is characterised in that in step 2, the mass concentration of modified compound solution is 1%～15%.
The side that 16. polypropylene hollow fiber membrane assembly antipollutions as claimed in claim 1 are modified
Method, it is characterised in that in step 2, the flow velocity of modified compound solution is 1～50ml/min, hands over
Connection, the time of absorption are 1～4 hour.
The side that 17. polypropylene hollow fiber membrane assembly antipollutions as claimed in claim 1 are modified
Method, it is characterised in that in step 3 mass concentration of the soluble salt solutions of metal ion be 1%～
15%.
The side that 18. polypropylene hollow fiber membrane assembly antipollutions as claimed in claim 1 are modified
Method, it is characterised in that in step 3 flow velocity of the soluble salt solutions of metal ion be 1～
50ml/min, carries out being coordinated, the time of complex reaction is 1～4 hour.
19. polypropylene hollow fiber membrane assembly antipollutions as claimed in claim 1 modifications
Method, it is characterised in that in step 4, the mass concentration of ethanol water is 40～90%.
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| CN106256414B (en) * | 2015-06-18 | 2019-05-31 | 中国石油化工股份有限公司 | A kind of preparation method of the hollow fiber film assembly of Selective Separation metal ion |
| CN105642126B (en) * | 2016-01-04 | 2018-04-27 | 华东理工大学 | A kind of method of modifying of polypropylene hollow fiber membrane and its application in exhaust gas demercuration |
| CN105727752B (en) | 2016-05-11 | 2018-08-14 | 贵州省材料产业技术研究院 | A kind of preparation method and product of high-intensity anti-pollution antibacterial hollow fiber nanofiltration membrane |
| CN110394065B (en) * | 2018-04-25 | 2022-10-21 | 中国石油化工股份有限公司 | Composite nanofiltration membrane and preparation method and application thereof |
| CN111729617B (en) * | 2020-08-06 | 2020-11-17 | 山东九章膜技术有限公司 | Jet device for interfacial polymerization reaction |
| CN112892236B (en) * | 2021-03-09 | 2022-04-22 | 江苏厚生新能源科技有限公司 | High-strength polyethylene composite membrane for water treatment and preparation method thereof |
| CN113274880A (en) * | 2021-06-24 | 2021-08-20 | 厦门嘉戎技术股份有限公司 | Modification process of DTRO (draw texturing yarn) assembly membrane |
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