CN106693715A - Electric field coating process of ultrafiltration membrane - Google Patents
Electric field coating process of ultrafiltration membrane Download PDFInfo
- Publication number
- CN106693715A CN106693715A CN201611024233.0A CN201611024233A CN106693715A CN 106693715 A CN106693715 A CN 106693715A CN 201611024233 A CN201611024233 A CN 201611024233A CN 106693715 A CN106693715 A CN 106693715A
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- electric field
- milipore filter
- tio
- membrane
- coating process
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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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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to an electric field coating process of an ultrafiltration membrane. The electric field coating process of the ultrafiltration membrane belongs to the technical field of water treatment membrane preparation, and comprises the steps of placing coating liquid containing negative charge TiO2 in a coating pond; immersing an ultrafiltration membrane component and a stainless steel plate electrode in the coating liquid; respectively connecting the ultrafiltration membrane component and the stainless steel plate electrode to positive and negative electrodes of a direct-current power supply; carrying out electric field coating under the electric field intensity being 30V/cm to obtain a coating modified ultrafiltration membrane with a TiO2 granular layer on the ultrafiltration membrane surface based on the ultrafiltration membrane component. The prepared modified ultrafiltration membrane can separate a colloidand a macromolecular organic compound, playing a leading role on membrane pollution, from a membrane surface by depending on the functions of adsorption and interception of a precoated layer on a pollutant, so that the membrane pollution is greatly reduced. During backwashing, the pollutant falls off from the membrane surface along with the precoated layer, the backwashing resistance of the membrane is reduced, and a backwashing effect is improved.
Description
Technical field
The invention belongs to the preparing technical field of membrane for water treatment.
Background technology
It is particularly prominent that increasingly strict environmental standard causes that the advantage that membrane technology is applied to efficient water treatment technology shows
Go out.But fouling membrane is to limit its wide variety of key factor.Membrane fouling rate is reduced, improving film service life turns into
Study hotspot.Research on reducing fouling membrane both at home and abroad is focused primarily upon and seeks the strong membrane material of contamination resistance, improves material
The filtrability and design of liquid preferably filtering fluidised form etc..
In recent years, in the industry it is proposed that the film of the fine particle directly contact reduction fouling membrane in preventing film and feed liquid is pre-
Coating concept, existing many researchs show that milipore filter precoated shet is that one kind is effective and improves Membrane Filtration Flux, reduces fouling membrane speed
Rate, the technology for improving some contaminants removal effects, but the factor of influence precoated shet effect has a lot, general precoated shet work
The powdery paints that skill is used all is easier sedimentation in water, substantial amounts of coating is had in pre-coating process and deposits to membrane cisterna
Bottom, increased the sludge output of membrane cisterna, have impact on the quality of precoated shet, even if increase stirring facility, between coating and film
Combination degree also more difficult control.In addition, milipore filter precoated shet technological requirement coating should easily deposit to film surface forms precoating
Layer, easily comes off in backwash from film surface again so that coating screening difficulty, precoated shet complex process and is difficult to.
The content of the invention
The present invention seeks to propose that a kind of controllability is good, adaptable milipore filter electric field coating process.
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 painting feed liquid, hyperfiltration membrane assembly and stainless steel plate electrode is connected the both positive and negative polarity of dc source respectively, in electric-field intensity
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 modified ultrafiltration membrane being made of the inventive method can be acted on pollutant absorption and retention etc. by precoated shet will
The colloid and larger molecular organicses played a major role to fouling membrane are isolated with film surface, so as to fouling membrane is greatly lowered.This hair
Bright dependence electrically charged particle forms precoated shet isolation causes the colloid of fouling membrane and larger molecular organicses material direct with milipore filter
Contact, during backwash, pollutant comes off with precoated shet from film surface, and the backwash resistance of film reduces, and backwash effect is improved.
Compared with other precoated shet modified techniques, the present invention has following clear superiority：
1st, the present invention replaces conventional water suction force that coating is coated into film surface using electric field force, and the coating of formation is looser,
Not only operating process is easily-controllable, and through charged modified TiO2Dispersive property in water is obviously improved.
2nd, under DC Electric Field, charged TiO2Can be quickly be coated to ultrafiltration membrane surface, by voltage and precoating
The regulation of layer time can very easily obtain certain thickness precoated shet.
3rd, in the membrane filtration course of work, the milipore filter cake layer after precoated shet is looser, irreversible membrane fouling institute accounting
Example significantly reduces, and the milipore filter backwash membrane flux after precoated shet is more easy to recover.
Further, negative electrical charge TiO in painting feed liquid of the present invention2Particle diameter be 0.5~1 μm.Ultrafiltration fenestra is used in experiment
Footpath is 0.1 μm, modified TiO2Particle diameter is 0% less than 0.188 μm of proportion, and particle diameter substantially rises in 1.000 μm or so place's ratios
Height, so TiO during precoated shet2Mainly adsorb and form cake layer on film surface, will not be resulted in blockage into fenestra.
The negative electrical charge TiO in the painting feed liquid2Concentration be 2g/L.Other group experiments are compareed, coating liquid concentration is precoated
During for 2g/L, precoated shet milipore filter flux depression in filter process is the slowest, and backwashed rear membrane flux is extensive
Multiple better off.
In order to realize quick, uniform coating formation, stainless steel plate electrode of the present invention is two pieces, is respectively symmetrically arrangement
In the outside of hyperfiltration membrane assembly.
The time of precoated shet is not less than 10min in the process.Other group experiments are compareed, the precoated shet time is 10min
When, precoated shet milipore filter flux depression in filter process is the slowest, and backwash after membrane flux recovery situation more
It is good.
The present invention has been further defined containing negative electrical charge TiO2Painting feed liquid specific preparation method：In magnetic agitation bar
Under part, by TiO2Be dissolved in the aqueous solution of calgon, with dilute acid for adjusting pH value 6 after, add neopelex,
Then disperse 1 hour under the conditions of temperature constant magnetic stirring, separated acquirement solid phase, dried 2 hours at 105 DEG C, it is ground, take
Obtain graininess negative electrical charge TiO2.With pure water dilution graininess negative electrical charge TiO2Formed and contain negative electrical charge TiO2Painting feed liquid.
The TiO2It is 20: 1 with the mixing quality ratio of calgon in the aqueous solution of calgon.
The neopelex and TiO2Mixing quality ratio be 3: 20.It is modified through neopelex
TiO2Zeta potential be -29.58mV, modified TiO2 carried charges are more, are more easy to move under the electric field.
Brief description of the drawings
Fig. 1 is charged TiO2Electric field precoated shet formed after State concept schematic diagram.
Fig. 2 is the conceptual schematic view of membrane filtration state.
Fig. 3 is the conceptual schematic view of backwash state.
Membrane flux comparison diagram when Fig. 4 is for 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 representation of hyperfiltration membrane assembly of the present invention.
Specific embodiment
First, flat plate ultrafiltration membrane module structure：
As shown in fig. 7, comprises being clamped with milipore filter 6 by geometrical clamp 7, the milipore filter 6 is polyvinyladine floride milipore filter, nominal pore
Footpath is 0.1 μm, and geometrical clamp 7 is made up of ABS resin.
In the inner chamber of milipore filter 6, flow-guiding cloth 5 is set, in the graphite silk screen 4 that the inner chamber density of setting of flow-guiding cloth 5 is 60 mesh,
In the inner chamber of graphite silk screen 4, deflector 3 is set.
Electrically connected with the inner of one group of wire 1 in graphite silk screen 4, the middle part of wire 1 passes through the gap of deflector 3, wire 1
Outer end be arranged on the outside of milipore filter 6, then by epoxy sealing on geometrical clamp 7.
Water outlet mouthpiece 2 is set on geometrical clamp 7, is set and water outlet mouthpiece 2 between the deflector 3 of the inner chamber of graphite silk screen 4
Between connect exhalant canal 8.
Exhalant canal 8 can be made up of an interconnection and a vertical passageway, and interconnection is located on deflector 3
Side, sets curb corresponding with the gap before each deflector 3, one end of vertical passageway and interconnection on interconnection
It is connected, the other end is connected with the lower end of water outlet mouthpiece 2, so that the liquid for leaching is passed through successively by the gap before deflector 3
Curb is collected to the interconnection of exhalant canal 8, then causes water outlet mouthpiece 2 through vertical passageway.
2nd, modified technique：
1st, graininess negative electrical charge TiO is prepared2：
Under the conditions of magnetic agitation, by the TiO of 100g2It is dissolved in the aqueous solution of 500mL calgons（Wherein hexa metaphosphoric acid
Sodium 5g）, with dilute acid for adjusting pH value 6 after, 15g neopelexes are added, then under the conditions of temperature constant magnetic stirring point
Dissipate 1 hour, separated acquirement solid phase, dried 2 hours at 105 DEG C, it is ground, obtain the particle that 120g particle diameters are 0.5~1 μm
Shape negative electrical charge TiO2。
2nd, preparing has negative electrical charge TiO2Painting feed liquid：
Take 2g graininess negative electrical charges TiO2It is diluted in 1L pure water, is formed and contain negative electrical charge TiO2Painting feed liquid, the coating being made into
Negative electrical charge TiO in liquid2Concentration be 2g/L.
3rd, 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 is immersed in painting feed liquid,
And two pieces of stainless steel plate electrodes is arranged symmetrically in two outsides of hyperfiltration membrane assembly.
The positive pole of dc source is connected on hyperfiltration membrane assembly, dc source is all connected on two pieces of stainless steel plate electrodes
Negative pole, more than electric field coating 10min is carried out under conditions of electric-field intensity is 30V/cm, and then venting is remaining applies feed liquid, obtains
Ultrafiltration membrane surface based on hyperfiltration membrane assembly has TiO2The modified ultrafiltration membrane of stratum granulosum.
3rd, application test and result：
Take the modified ultrafiltration membrane component being made carries out film process into source water：The suction pump of milipore filter is opened, precoated shet is by negative
Pressure suction operation.At the end of a filter cycle, suction pump is closed, opening recoil pump carries out film backwash, and now precoated shet takes off
Fall.After backwash terminates, power-on carries out electric field precoated shet, repeats above-mentioned job step.
Charged TiO when the 1st, using present invention treatment source water2Carry out the state of film during electric field precoated shet：
The charged TiO that will be prepared2Apply feed liquid and add membrane cisterna, the TiO of bear electricity in the presence of extra electric field2Particle is moved to super
Filter membrane surface forms coating.Charged TiO2View after electric field precoated shet is formed is as shown in Figure 1.
The filtration condition of film when the 2nd, using present invention treatment source water：
Open peristaltic pump to be filtered, larger molecular organicses and suspension are trapped within precoated shet, and hydrone is then passed through
Precoated shet milipore filter.View during membrane filtration is as shown in Figure 2.
The state of film when being backwashed when the 3rd, using present invention treatment source water：
During backwash, peristaltic pump is rotated backward, pollutant is come off with part precoated shet from film surface, and precoated shet milipore filter is had
Effect cleaning.The view of film is as shown in Figure 3 during backwash.
Influence when the 4th, using present invention treatment source water to membrane flux：
Modified ultrafiltration membrane and pure water are made into the concentrated solution that mass concentration is 2g/l, to ultrafiltration before starting first filter cycle
Film carries out electric field precoated shet, and coating electric-field intensity is 30V/cm, coating time period 10min.Coating starts to filter raw water after terminating.If
The membrane filtration of non-coating treatment is check experiment group, and it is as shown in Figure 4 that membrane flux changes over time rule.
As shown in Figure 4, control group（I.e. non-modified milipore filter）Flux depression it is rapid, with the carrying out of filtering,
Membrane flux is in continuous downward trend.After terminating first filter cycle, membrane flux is only the 56% of initial pure water flux, instead
Membrane flux only recovers to the 67% of initial pure water flux after flushing.After five cycles are run, the membrane flux through backwashing only recovers
To the 58% of initial pure water flux.
The milipore filter of 10min is precoated after terminating first filter cycle, membrane flux is the 73.5% of initial pure water flux,
Membrane flux can return to the 91.2% of initial pure water flux after backwash.When operation to the 5th cycle, the membrane flux after backwash
Can recover to the 76.5% of initial pure water flux, 18.5% is improve than control group.
Influence when the 5th, using present invention treatment source water to turbidity removal effect：
Experiment is as shown in Figure 5 to the removal effect of turbidity.The turbidity of test pill water is 5 ~ 105 NTU.It is super after electric field precoated shet
Filter membrane delivery turbidity is 0.17~0.55NTU, and the change of influent turbidity influences smaller, clearance to delivery turbidity>92%, precoating
Milipore filter after layer shows good stability to the removal effect of turbidity.Concurrent control group（I.e. non-modified milipore filter）
Delivery turbidity is 0.62~1.62 NTU.
Influence when the 6th, using present invention treatment source water to permanganate index removal effect：
Experiment is as shown in Figure 6 to the removal effect of permanganate index.The mean concentration of raw water permanganate index during experiment
It is 4.93mg/L, control group（I.e. non-modified milipore filter）The mean concentration of water outlet permanganate index is 2.32mg/L, is put down
Equal clearance is 52.9%.The mean concentration of modified milipore filter water outlet permanganate index is 1.79mg/L, and average removal rate is
63.6%, 10.7% is improve compared with control group.
Claims (9)
1. the electric field coating process of a kind of milipore filter, 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 painting feed liquid, hyperfiltration membrane assembly and stainless steel plate electrode are connected respectively
The both positive and negative polarity of dc source is connect, electric field coating is carried out under conditions of electric-field intensity is 30V/cm, obtained and be based on hyperfiltration membrane assembly
Ultrafiltration membrane surface there is TiO2The coating modified milipore filter of stratum granulosum.
2. the electric field coating process of milipore filter according to claim 1, it is characterised in that：Negative electrical charge TiO in the painting feed liquid2
Particle diameter be 0.5~1 μm.
3. the electric field coating process of milipore filter 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 milipore filter according to claim 1, it is characterised in that：The stainless steel plate electrode is two
Block, is respectively symmetrically the outside for being arranged in hyperfiltration membrane assembly.
5. the electric field coating process of milipore filter according to claim 1, it is characterised in that：The time of the electric field coating is not small
In 10min.
6. according to claim 1 or 2 or 3 or 4 or 5 milipore filter electric field coating process, it is characterised in that：In magnetic agitation
Under the conditions of, by TiO2Be dissolved in the aqueous solution of calgon, with dilute acid for adjusting pH value 6 after, add DBSA
Sodium, then disperses 1 hour, separated acquirement solid phase under the conditions of temperature constant magnetic stirring, is dried 2 hours at 105 DEG C, through grinding
Mill, obtains graininess negative electrical charge TiO2；With pure water dilution graininess negative electrical charge TiO2Formed and contain negative electrical charge TiO2Painting feed liquid.
7. the electric field coating process of milipore filter according to claim 6, it is characterised in that：The TiO2With calgon
The mixing quality ratio of calgon is 20: 1 in the aqueous solution.
8. the electric field coating process of milipore filter according to claim 5, it is characterised in that：The neopelex and
TiO2Mixing quality ratio be 3: 20.
9. according to claim 1 or 2 or 3 or 4 or 5 milipore filter electric field coating process, it is characterised in that：The milipore filter
Component includes the milipore filter clamped by geometrical clamp, and water outlet mouthpiece is set on geometrical clamp；In milipore filter inner chamber, flow-guiding cloth is set,
Graphite silk screen is set in flow-guiding cloth inner chamber, deflector is set in graphite silk screen inner chamber, the inner of one group of wire is connected electrically in graphite
On silk screen, the outer end of wire is arranged on milipore filter outside, set between the deflector of graphite silk screen inner chamber with water outlet mouthpiece it
Between exhalant canal is set.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611024233.0A CN106693715B (en) | 2016-11-22 | 2016-11-22 | A kind of electric field coating process of ultrafiltration membrane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611024233.0A CN106693715B (en) | 2016-11-22 | 2016-11-22 | A kind of electric field coating process of ultrafiltration membrane |
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| Publication Number | Publication Date |
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| CN106693715A true CN106693715A (en) | 2017-05-24 |
| CN106693715B CN106693715B (en) | 2019-05-10 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108014654A (en) * | 2017-12-15 | 2018-05-11 | 南京工业大学 | One kind is used for intensive polar solvent and is dehydrated separated molecular screen membrane method of modifying |
| CN116078177A (en) * | 2023-03-06 | 2023-05-09 | 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 for surface optical catalytic film of metal substrate |
| CN102050955A (en) * | 2009-10-28 | 2011-05-11 | 北京化工大学 | Preparation method of polystyrene-based mesoporous silica film |
-
2016
- 2016-11-22 CN CN201611024233.0A patent/CN106693715B/en active Active
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 for surface optical catalytic film of metal substrate |
| CN102050955A (en) * | 2009-10-28 | 2011-05-11 | 北京化工大学 | Preparation method of polystyrene-based mesoporous silica film |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108014654A (en) * | 2017-12-15 | 2018-05-11 | 南京工业大学 | One kind is used for intensive polar solvent and is dehydrated separated molecular screen membrane method of modifying |
| 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 |
| CN116078177A (en) * | 2023-03-06 | 2023-05-09 | 华电水务装备(天津)有限公司 | Hollow fiber forward osmosis membrane, preparation method and application |
| 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 |
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| CN106693715B (en) | 2019-05-10 |
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