CN106693715B - A kind of electric field coating process of ultrafiltration membrane - Google Patents
A kind of electric field coating process of ultrafiltration membrane Download PDFInfo
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- CN106693715B CN106693715B CN201611024233.0A CN201611024233A CN106693715B CN 106693715 B CN106693715 B CN 106693715B CN 201611024233 A CN201611024233 A CN 201611024233A CN 106693715 B CN106693715 B CN 106693715B
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- 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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/02—Electrophoretic coating characterised by the process with inorganic material
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Abstract
A kind of electric field coating process of ultrafiltration membrane, belongs to the preparation technical field of membrane for water treatment.Negative electrical charge TiO will be contained2Painting feed liquid be placed in coating pond, hyperfiltration membrane assembly and stainless steel plate electrode are immersed in and applied in feed liquid, hyperfiltration membrane assembly and stainless steel plate electrode are separately connected to the positive and negative anodes of DC power supply, electric field coating is carried out under conditions of electric field strength is 30V/cm, obtaining the ultrafiltration membrane surface based on hyperfiltration membrane assembly has TiO2The coating modified ultrafiltration membrane of stratum granulosum.The effects of manufactured modified ultrafiltration membrane can be adsorbed and be retained to pollutant by precoated shet is isolated by the colloid to play a major role to fouling membrane and larger molecular organics with film surface, so that fouling membrane be greatly lowered.When backwash, pollutant falls off with precoated shet from film surface, and the backwash resistance of film reduces, and backwash effect improves.
Description
Technical field
The invention belongs to the preparation technical fields of membrane for water treatment.
Background technique
The advantage that increasingly strict environmental standard makes membrane technology be applied to efficient water treatment technology shows especially prominent
Out.However fouling membrane is to limit its widely applied key factor.Membrane fouling rate is reduced, improving film service life becomes
Research hotspot.It is focused primarily upon both at home and abroad about the research for reducing fouling membrane and seeks the strong membrane material of contamination resistance, improve material
Filtrability and design preferably filtering fluidised form of liquid etc..
In recent years, in the industry it is proposed that the film for preventing film from directly contacting reduction fouling membrane with the fine particle in feed liquid is pre-
Coating concept is existing many research shows that ultrafiltration membrane precoated shet is the effective improvement Membrane Filtration Flux of one kind, reduces fouling membrane speed
Rate, the technology for improving certain contaminants removal effects, however influence many because being known as of precoated shet effect, general precoated shet work
Powdery paints used by skill in water be all easier to settle, a large amount of coating is had in pre-coating process and deposits to membrane cisterna
Bottom, increase the sludge output of membrane cisterna, affect the quality of precoated shet, even if increase stirring facility, between coating and film
Combination degree is also more difficult to control.In addition, ultrafiltration membrane precoating layer process requires coating that should be easy to deposit to film surface formation precoating
Layer is easy to fall off from film surface in backwash again, so that coating screening is difficult, precoated shet complex process and is difficult to realize.
Summary of the invention
Object of the present invention is to propose a kind of electric field coating process of good, the adaptable ultrafiltration membrane of controllability.
The present invention will contain negative electrical charge TiO2Painting feed liquid be placed in coating pond, by hyperfiltration membrane assembly and stainless steel plate electrode
It is immersed in and applies in feed liquid, hyperfiltration membrane assembly and stainless steel plate electrode are separately connected to the positive and negative anodes of DC power supply, in electric field strength
To carry out electric field coating under conditions of 30V/cm, obtaining the ultrafiltration membrane surface based on hyperfiltration membrane assembly has TiO2The painting of stratum granulosum
Layer modified ultrafiltration membrane.
The effects of pollutant being adsorbed and be retained by precoated shet using modified ultrafiltration membrane made of the method for the present invention, will
The colloid and larger molecular organics play a major role to fouling membrane is isolated with film surface, so that fouling membrane be greatly lowered.This hair
It is bright by electrically charged particle formed precoated shet isolation cause fouling membrane colloid and larger molecular organics substance and ultrafiltration membrane it is direct
Contact, when backwash, pollutant falls off with precoated shet from film surface, and the backwash resistance of film reduces, and backwash effect improves.
Compared with other precoated shet modified techniques, the present invention has following clear superiority:
1, the present invention replaces conventional water suction force that coating is coated to film surface using electric field force, and the coating of formation is more loose
It dissipates, not only operating process is easily-controllable, and through charged modified TiO2Dispersion performance in water is obviously improved.
2, under DC Electric Field, charged TiO2Cracking it can be coated to ultrafiltration membrane surface, pass through voltage and precoating
The adjusting of layer time can very easily obtain certain thickness precoated shet.
3, during film filtration, the ultrafiltration membrane cake layer after precoated shet is looser, irreversible membrane fouling institute accounting
Example substantially reduces, and the ultrafiltration membrane backwash membrane flux after precoated shet is easier to restore.
Further, negative electrical charge TiO in painting feed liquid of the present invention2Partial size be 0.5~1 μm.Test ultrafiltration fenestra
Diameter is 0.1 μm, modified TiO2Less than 0.188 μm proportion of partial size is 0%, and partial size obviously rises in 1.000 μm or so place's ratios
Height, so TiO when precoated shet2It is mainly adsorbed on film surface and forms cake layer, will not result in blockage into fenestra.
The negative electrical charge TiO in the painting feed liquid2Concentration be 2g/L.Other group tests are compareed, coating liquid concentration is precoated
When for 2g/L, flux depression is the slowest during the filtration process for precoated shet ultrafiltration membrane, and it is backwashed after membrane flux it is extensive
Multiple better off.
In order to realize that quick, uniform coating formation, stainless steel plate electrode of the present invention are two pieces, it is symmetrically arranged
In the outside of hyperfiltration membrane assembly.
The time of precoated shet is not less than 10min in the process.Other group tests are compareed, the precoated shet time is 10min
When, flux depression is the slowest during the filtration process for precoated shet ultrafiltration membrane, and backwash after membrane flux recovery situation more
It is good.
The present invention, which has further defined, contains negative electrical charge TiO2Painting feed liquid specific preparation method: in magnetic agitation item
Under part, by TiO2It is dissolved in the aqueous solution of calgon, after dilute acid for adjusting pH value 6, adds neopelex,
Then disperse 1 hour under the conditions of temperature constant magnetic stirring, obtain solid phase through separation, dried 2 hours at 105 DEG C, it is ground, it takes
Obtain graininess negative electrical charge TiO2.Graininess negative electrical charge TiO is diluted with pure water2It is formed and contains negative electrical charge TiO2Painting feed liquid.
The TiO2Mixing mass ratio with calgon in the aqueous solution of calgon is 20: 1.
The neopelex and TiO2Mixing mass ratio be 3: 20.It is modified through neopelex
TiO2Zeta potential be -29.58mV, modified TiO2 carried charge is more, is easier to move under the electric field.
Detailed description of the invention
Fig. 1 is charged TiO2Electric field precoated shet formed after State concept schematic diagram.
Fig. 2 is the conceptual schematic view of film filtration condition.
Fig. 3 is the conceptual schematic view of backwashing state.
Membrane flux comparison diagram when Fig. 4 is filtering.
Fig. 5 is turbidity removal effect contrast figure.
Fig. 6 is permanganate index removal effect comparison diagram.
Fig. 7 is a kind of structural schematic diagram of hyperfiltration membrane assembly of the present invention.
Specific embodiment
One, flat plate ultrafiltration membrane module structure:
As shown in fig. 7, comprises being clamped with ultrafiltration membrane 6 by fixing clamp 7, which is polyvinyladine floride ultrafiltration membrane, mark
Aperture is referred to as 0.1 μm, and fixing clamp 7 is made of ABS resin.
Ultrafiltration membrane 6 inner cavity be arranged flow-guiding cloth 5, flow-guiding cloth 5 inner cavity density of setting be 60 mesh graphite silk screen 4,
In the inner cavity of graphite silk screen 4, deflector 3 is set.
It is electrically connected in graphite silk screen 4 with the inner end of one group of conducting wire 1, the middle part of conducting wire 1 passes through the gap of deflector 3, conducting wire 1
Outer end the outside of ultrafiltration membrane 6 is set, be then sealed on fixing clamp 7 by epoxy resin.
Water outlet mouthpiece 2 is set on fixing clamp 7, setting and water outlet mouthpiece 2 between the deflector 3 of 4 inner cavity of graphite silk screen
Between the exhalant canal 8 that is connected to.
Exhalant canal 8 can be made of an interconnection and a vertical passageway, and interconnection is located on deflector 3
Curb corresponding with the gap before each deflector 3, one end of vertical passageway and interconnection is arranged in side on interconnection
It is connected, the other end is connected with the lower end of water outlet mouthpiece 2, so that the liquid filtered out is successively passed through by the gap before deflector 3
Curb is collected to the interconnection of exhalant canal 8, then leads to water outlet mouthpiece 2 through vertical passageway.
Two, modified technique:
1, graininess negative electrical charge TiO is prepared2:
Under the conditions of magnetic agitation, by the TiO of 100g2Be dissolved in the aqueous solution of 500mL calgon (wherein six partially
Sodium phosphate 5g), after dilute acid for adjusting pH value 6,15g neopelex is added, then in temperature constant magnetic stirring condition
Lower dispersion 1 hour obtains solid phase through separation, dries 2 hours at 105 DEG C, ground, and obtaining 120g partial size is 0.5~1 μm
Graininess negative electrical charge TiO2。
2, it is prepared with negative electrical charge TiO2Painting feed liquid:
Take 2g graininess negative electrical charge TiO2It is diluted in 1L pure water, is formed and contain negative electrical charge TiO2Painting feed liquid, the painting being made into
Negative electrical charge TiO in feed liquid2Concentration be 2g/L.
3, modified ultrafiltration membrane is prepared:
The painting feed liquid of preparation is placed in coating pond, hyperfiltration membrane assembly and two pieces of stainless steel plate electrodes are immersed in painting feed liquid
It is interior, and it is arranged symmetrically in two pieces of stainless steel plate electrodes on the outside of two of hyperfiltration membrane assembly.
The anode that DC power supply is connected on hyperfiltration membrane assembly, all connects DC power supply on two pieces of stainless steel plate electrodes
Cathode carries out electric field coating 10min or more under conditions of electric field strength is 30V/cm, and then venting residue applies feed liquid, obtains
Ultrafiltration membrane surface based on hyperfiltration membrane assembly has TiO2The modified ultrafiltration membrane of stratum granulosum.
Three, application test and result:
Modified ultrafiltration membrane component made of taking enters source water and carries out film process: open the suction pump of ultrafiltration membrane, precoated shet according to
It works by negative-pressure ward.At the end of a filter cycle, suction pump is closed, recoil pump is opened and carries out film backwash, precoat at this time
Layer falls off.After backwash, opens power supply and carry out electric field precoated shet, repeat above-mentioned work step.
1, charged TiO when using present invention processing source water2Carry out the state of film when electric field precoated shet:
By the charged TiO of preparation2It applies feed liquid and membrane cisterna, the TiO of bear electricity under the action of extra electric field is added2Particle is mobile
Coating is formed to ultrafiltration membrane surface.Charged TiO2Status diagram after electric field precoated shet is formed is as shown in Figure 1.
2, the filtration condition of film when handling source water using the present invention:
It opens peristaltic pump to be filtered, larger molecular organics and suspended matter are trapped on precoated shet, and hydrone is then smooth
Pass through precoated shet ultrafiltration membrane.Status diagram when film filters is as shown in Figure 2.
3, the state of film when being backwashed when handling source water using the present invention:
When backwash, peristaltic pump is rotated backward, pollutant falls off with part precoated shet from film surface, and precoated shet ultrafiltration membrane obtains
To effective cleaning.The status diagram of film is as shown in Figure 3 when backwash.
4, influence when handling source water using the present invention to membrane flux:
Modified ultrafiltration membrane and pure water are made into the concentrated solution that mass concentration is 2g/l, it is right before starting first filter cycle
Ultrafiltration membrane carries out electric field precoated shet, and coating electric field strength is 30V/cm, coating time period 10min.It is former to start filtering after coating
Water.If the film of non-coating treatment is filtered into check experiment group, membrane flux changes over time regular as shown in Figure 4.
As shown in Figure 4, the flux depression of control group (i.e. non-modified ultrafiltration membrane) is rapid, with the progress of filtering,
Membrane flux is in continuous downward trend.After first filter cycle, membrane flux is only the 56% of initial pure water flux, instead
Membrane flux only restores to the 67% of initial pure water flux after flushing.After running five periods, the membrane flux through backwashing only restores
To the 58% of initial pure water flux.
The ultrafiltration membrane of 10min is precoated after first filter cycle, membrane flux is the 73.5% of initial pure water flux,
Membrane flux can be restored to the 91.2% of initial pure water flux after backwash.When operation to the 5th period, the membrane flux after backwashing
It can restore to the 76.5% of initial pure water flux, improve 18.5% than control group.
5, influence when handling source water using the present invention to turbidity removal effect:
It tests as shown in Figure 5 to the removal effect of turbidity.The turbidity of test pill water is 5 ~ 105 NTU.After electric field precoated shet
Ultrafiltration membrane delivery turbidity be 0.17~0.55NTU, the variation of influent turbidity influences smaller, removal rate > 92% to delivery turbidity,
Ultrafiltration membrane after precoated shet shows good stability to the removal effect of turbidity.(i.e. non-modified is super for concurrent control group
Filter membrane) delivery turbidity be 0.62~1.62 NTU.
6, influence when handling source water using the present invention to permanganate index removal effect:
It tests as shown in Figure 6 to the removal effect of permanganate index.Raw water permanganate index is averaged during test
Concentration is 4.93mg/L, and the mean concentration that control group (i.e. non-modified ultrafiltration membrane) is discharged permanganate index is 2.32mg/
L, average removal rate 52.9%.The mean concentration of modified ultrafiltration membrane water outlet permanganate index is 1.79mg/L, average to remove
Rate is 63.6%, improves 10.7% compared with the control group.
Claims (8)
1. a kind of electric field coating process of ultrafiltration membrane, it is characterised in that: negative electrical charge TiO will be contained2Painting feed liquid be placed in coating pond
In, hyperfiltration membrane assembly and stainless steel plate electrode are immersed in and applied in feed liquid, hyperfiltration membrane assembly and stainless steel plate electrode are connected respectively
The positive and negative anodes for connecing DC power supply carry out electric field coating under conditions of electric field strength is 30V/cm, obtain and are based on hyperfiltration membrane assembly
Ultrafiltration membrane surface have TiO2The coating modified ultrafiltration membrane of stratum granulosum；Under the conditions of magnetic agitation, by TiO2It is dissolved in hexa metaphosphoric acid
In the aqueous solution of sodium, after being 6 with dilute acid for adjusting pH value, neopelex is added, then in temperature constant magnetic stirring item
Disperse 1 hour under part, obtains solid phase through separation, dried 2 hours at 105 DEG C, it is ground, obtain graininess negative electrical charge TiO2；
Graininess negative electrical charge TiO is diluted with pure water2It is formed and contains negative electrical charge TiO2Painting feed liquid.
2. the electric field coating process of ultrafiltration membrane according to claim 1, it is characterised in that: negative electrical charge TiO in the painting feed liquid2
Partial size be 0.5~1 μm.
3. the electric field coating process of ultrafiltration membrane according to claim 2, it is characterised in that: the negative electrical charge in the painting feed liquid
TiO2Concentration be 2g/L.
4. the electric field coating process of ultrafiltration membrane according to claim 1, it is characterised in that: the stainless steel plate electrode is two
Block is symmetrically arranged at the outside of hyperfiltration membrane assembly.
5. the electric field coating process of ultrafiltration membrane according to claim 1, it is characterised in that: the time of electric field coating is not less than
10min。
6. the electric field coating process of ultrafiltration membrane according to claim 1, it is characterised in that: the TiO2With calgon
The mixing mass ratio of calgon is 20: 1 in aqueous solution.
7. the electric field coating process of ultrafiltration membrane according to claim 1, it is characterised in that: the neopelex and
TiO2Mixing mass ratio be 3: 20.
8. the electric field coating process of according to claim 1 or 2 or 3 or 4 or 5 ultrafiltration membranes, it is characterised in that: the ultrafiltration membrane
Component includes the ultrafiltration membrane clamped by fixing clamp, and water outlet mouthpiece is arranged on fixing clamp；In ultrafiltration membrane inner cavity, flow-guiding cloth is set,
Graphite silk screen is set in flow-guiding cloth inner cavity, deflector is set in graphite silk screen inner cavity, the inner end of one group of conducting wire is connected electrically in graphite
On silk screen, the outer end of conducting wire is arranged on the outside of ultrafiltration membrane, and setting connects with water outlet mouthpiece between the deflector of graphite silk screen inner cavity
Logical exhalant canal.
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| CN201611024233.0A CN106693715B (en) | 2016-11-22 | 2016-11-22 | A kind of electric field coating process of ultrafiltration membrane |
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| CN201611024233.0A CN106693715B (en) | 2016-11-22 | 2016-11-22 | A kind of electric field coating process of ultrafiltration membrane |
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| CN108014654B (en) * | 2017-12-15 | 2023-08-18 | 南京工业大学 | Molecular sieve membrane modification method for dehydration separation of strong polar solvent |
| CN116078177B (en) * | 2023-03-06 | 2023-06-02 | 华电水务装备(天津)有限公司 | Hollow fiber forward osmosis membrane, preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1438069A (en) * | 2003-01-25 | 2003-08-27 | 福州大学 | Electrophoresis preparation method of metal substrate surface photocatalytic film |
| CN102050955A (en) * | 2009-10-28 | 2011-05-11 | 北京化工大学 | Preparation method of polystyrene-based mesoporous silica film |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1438069A (en) * | 2003-01-25 | 2003-08-27 | 福州大学 | Electrophoresis preparation method of metal substrate surface photocatalytic film |
| CN102050955A (en) * | 2009-10-28 | 2011-05-11 | 北京化工大学 | Preparation method of polystyrene-based mesoporous silica film |
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