CN106830471A - A kind of method of organic micro-pollutantses in photocatalysis, ultrafiltration, nanofiltration group technology control drinking water - Google Patents
A kind of method of organic micro-pollutantses in photocatalysis, ultrafiltration, nanofiltration group technology control drinking water Download PDFInfo
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- CN106830471A CN106830471A CN201710098851.8A CN201710098851A CN106830471A CN 106830471 A CN106830471 A CN 106830471A CN 201710098851 A CN201710098851 A CN 201710098851A CN 106830471 A CN106830471 A CN 106830471A
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- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 52
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 36
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 35
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000005516 engineering process Methods 0.000 title claims abstract description 17
- 239000003651 drinking water Substances 0.000 title claims abstract description 14
- 235000020188 drinking water Nutrition 0.000 title claims abstract description 14
- 239000012528 membrane Substances 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 230000015556 catabolic process Effects 0.000 claims abstract description 6
- 238000006731 degradation reaction Methods 0.000 claims abstract description 6
- 239000005446 dissolved organic matter Substances 0.000 claims abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 230000000694 effects Effects 0.000 claims description 10
- 239000004408 titanium dioxide Substances 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000005416 organic matter Substances 0.000 claims description 8
- 239000008187 granular material Substances 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000007822 coupling agent Substances 0.000 claims description 6
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 6
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 230000004907 flux Effects 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 244000005700 microbiome Species 0.000 claims description 4
- 239000002957 persistent organic pollutant Substances 0.000 claims description 4
- 229910008558 TiSO4 Inorganic materials 0.000 claims description 3
- 241001296405 Tiso Species 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 238000003980 solgel method Methods 0.000 claims description 3
- 238000007711 solidification Methods 0.000 claims description 3
- 230000008023 solidification Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- MWKJTNBSKNUMFN-UHFFFAOYSA-N trifluoromethyltrimethylsilane Chemical compound C[Si](C)(C)C(F)(F)F MWKJTNBSKNUMFN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003643 water by type Substances 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 230000009849 deactivation Effects 0.000 claims description 2
- 239000003344 environmental pollutant Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 231100000719 pollutant Toxicity 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 238000001514 detection method Methods 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 238000005345 coagulation Methods 0.000 description 6
- 230000015271 coagulation Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001471 micro-filtration Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 description 2
- 229940106691 bisphenol a Drugs 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000002846 particulate organic matter Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000009287 sand filtration Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0532—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing sulfate-containing salts
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
- C02F1/325—Irradiation devices or lamp constructions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Water Supply & Treatment (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Physical Water Treatments (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The method of organic micro-pollutantses, belongs to water-treatment technology field in a kind of photocatalysis, ultrafiltration, nanofiltration group technology control drinking water.Using photocatalysis pond and ultrafiltration as nanofiltration membrane treatment pretreatment, by setting photocatalysis pond and ultrafiltration come degradation water before the nanofiltration membrane cisterna in dissolved organic matter and organic micro-pollutantses；By further absorption and the degraded of photocatalysis pond, mitigate the service life that ultrafiltration and NF membrane are improved to ultrafiltration and the pollution of NF membrane, by photocatalysis pond and ultrafiltration as the pretreatment unit of nanofiltration membrane treatment, mitigate ultrafiltration and nanofiltration membrane pollution.
Description
Technical field
The present invention relates to drinking water treatment technology, it is related specifically to a kind of ultrafiltration and nanofiltration bi-membrane method and photocatalysis is gone
The method of organic micro-pollutantses, belongs to water-treatment technology field in water removal.
Background technology
With the further raising of worsening shortages and the water standard of China's water resource, the further treatment technique of drinking water and
Research is urgent.Drinking water conventional treatment process, i.e. coagulation, precipitation, sand filtration and sterilization process, although clarification of water can be made, disappeared
Except part pathogenic bacteria, but have to the removal ability of many poisonous and hazardous organic pollution produced in process of industrialization
Limit, especially to medium or small-molecular-weight organic matter removal poor ability, there is very big threat in this to health.The opposing party
How face, with the raising and the appearance of national newest sanitary standard for drinking water (GB5749-2006) of people's quality of life, meet
High request high standard, will be subject matter that many water factories face.
In recent years, membrane filtration technology gradually large-scale application in drinking water treatment, including micro-filtration, ultrafiltration, nanofiltration, reverse osmosis filter
Film etc., wherein, ultrafiltration is very high to the retention removal ability of the particulate pollutant such as bacterium, virus, algae, colloid in water, and to molten
Solution property organic matter removal ability is very low, and traditional reverse osmosis membrane filtration journey needs to consume substantial amounts of energy, therefore, with ultrafiltration and
Counter-infiltration is compared, and the Nanofiltration Membrane Separation Technology that operating pressure is relatively low, permeation flux is larger arises at the historic moment.And utilize coagulation
Partial solubility organic matter can be converted into particulate organic matter by absorption, the volume effect of sweeping etc., and this can effectively improve ultrafiltration technology
To the removal ability of dissolubility larger molecular organicses.But, removal of the method to medium or small-molecular-weight the organic matter of raising
It is limited in one's ability.NF membrane has two significant advantages in the application：(1) retention relative molecular weight (MWCO) 200-1000 it
Between, therefore it is applicable to separate relative molecular weight more than 200, size is about the dissolved constituent of 1nm；(2) with stronger ion
Selectivity.The characteristic property of Nanofiltration-membrane technique causes that it has the irreplaceable status of other membrane technologies in many fields.
At present, the removal for organic micro-pollution in water is mainly used in conjunction using activated carbon with other method, such as ozone-work
Property charcoal technology removal organic pollutants, but there is following defect in the method：1. ozone Oxidation Treatment drinking water exists smelly
The defect such as coefficient of oxygen utilization is low, oxidability is not enough；2. ozone can effectively degrade has containing unsaturated bond or partial aromatic class
Organic pollutants, and be difficult to for the stability organic micro-pollutantses (such as agricultural chemicals, halogenated organic matters and nitro compound) of part
Oxidative degradation；3. larger molecular organicses can be oxidized to small organic molecule by ozone, the molecular mass of organic matter is diminished, will
It is unfavorable for the absorption of activated carbon, therefore, the deficiency for how avoiding the above method from existing, this is that the key of urgent need to resolve in engineering is asked
Topic.
The present invention proposes dual membrane system removal organic micro-pollutantses, i.e. ultrafiltration for organic micro-pollution excessive problem in water
With nanofiltration system, ultrafiltration as the pretreatment of nanofiltration system is further adsorbed by the photocatalytic oxidation of titanium dioxide
And degradation of organic substances, it is to avoid and mitigate the nanofiltration membrane pollution that microorganism is caused, improve the service life of film.
The content of the invention
The purpose of the present invention is to propose to organic micro- dirt in a kind of advanced oxidation, ultrafiltration, nanofiltration group technology control drinking water
The method for contaminating thing, and the method for effectively controlling fouling membrane.
The technical thought that the present invention takes is：Using photocatalysis pond and ultrafiltration as nanofiltration membrane treatment pretreatment, by
Photocatalysis pond is set before nanofiltration membrane cisterna and ultrafiltration comes dissolved organic matter and organic micro-pollutantses in degradation water；By photocatalysis pond
Further absorption and degraded, mitigate the service life that ultrafiltration and NF membrane are improved to ultrafiltration and the pollution of NF membrane, are urged by light
Change the pretreatment unit of pond and ultrafiltration as nanofiltration membrane treatment, mitigate ultrafiltration and nanofiltration membrane pollution.
The present invention is achieved by following technical solution：
A kind of method of organic micro-pollutantses in advanced oxidation, ultrafiltration, nanofiltration group technology control drinking water, its feature exists
In the device of use includes the pretreatment unit, photocatalysis pond, milipore filter, NF membrane, ultrafiltration membrane pool and the photocatalysis that are sequentially connected
Pond is provided separately, in order to avoid the service life of the irradiation influence milipore filter of uviol lamp；Raw water is by after pretreatment unit, water outlet enters
To photocatalysis pond, remaining dissolved organic matter and various micro quantity organic pollutants in further degradation water, photocatalysis pond water outlet are entered
Enter ultrafiltration membrane pool removal partial organic substances, ultrafiltration membrane pool water outlet is processed into NF membrane, obtains the treatment water of more high-quality.
Using online detecting system, according to the indices of detecting system, using different concentrate recirculation modes, determine
NF membrane concentrated water is to revert to photocatalysis pond or ultrafiltration membrane pool, improves the treatment effect of each technique unit, plays to different dirts
Dye thing uses different backflow approach.If for example, dense oxygen in water or COD (COD >=10mg/L) higher, illustrate that organic matter contains
Amount is higher, and in the reflowable pond to photocatalysis, if its content is not high, COD ＜ 10mg/L are reflowable to ultrafiltration membrane pool.
In photocatalysis pond, the larger organic matter of molecular weight is broken down into small organic molecule, or by small organic molecule without
Machine.
By photocatalysis pond and ultrafiltration as the pretreatment unit of nanofiltration membrane treatment, mitigate ultrafiltration and nanofiltration membrane pollution；
Described milipore filter, hyperfiltration membrane assembly used is external pressure immersion type membrane component, and material is polyvinyl chloride or poly- inclined
PVF；The pore diameter range of milipore filter is between 0.01~0.02 μm, the flux of milipore filter is 10~30L/m2H, can basis
Specific water quality is selected.Uviol lamp and titanium dioxide granule are placed in photocatalysis pond, uviol lamp increases photocatalysis effect, and
There is deactivation for microorganism in pond；Titanium dioxide granule particle diameter prepared by the present invention is 0.5~5 μm, and particle is larger, it is easy to
Dam and precipitate, milipore filter will not be produced too big dirty stifled.
Titanium dioxide granule used is synthesized using sol-gel process, with TiSO4It is titanium source, takes the TiSO of 15mL4Deposit
Liquid, 5mL glacial acetic acid, are added slowly in 30mL absolute ethyl alcohols, stirring while adding, and stirring 30min obtains A liquid；1mL acetic acid is taken again
It is added in 1mL deionized waters, and 20mL absolute ethyl alcohols, stirring while adding, stirring 15min obtains B liquid；It is stirred vigorously lower by B
Liquid dropwise instills A liquid, 5h is stirred at room temperature and obtains colloidal sol, then colloidal sol is moved into crystallizing kettle closing, is placed in insulating box at 120 DEG C
Crystallization 10h at room temperature, forms gel.The gel that will be prepared again is put into 100 DEG C of baking oven and dries 12h；Finally it is placed in tubular type
In stove, at 400 DEG C and 2h is heat-treated, the heating-up time is 40min, and heating rate is 10 degrees/min, will catalysis after natural cooling
Agent is placed in standby in drier.A certain amount of silicon fluoride coupling agent is taken, ethanol solution is dissolved in, is configured to 0.5g/L~10g/L's
Silicon fluoride coupling agent aqueous solution, at room temperature, takes the above-mentioned catalyst for preparing, and is soaked in 10h in this solution, afterwards, takes out
Rinsed well with deionized water, 2h taking-ups are dried under the conditions of being placed in 110 DEG C, then, be immersed in 0.5mmol/L~5mmol/
1h is soaked in the trifluoromethyl trimethylsilane aqueous solution of L, deionized water rinsing surface is used afterwards, it is rearmounted with deionized water rinsing
The dry solidification 2h in 110 DEG C of baking oven.
Drinking water is set up in order to improve the removal effect of organic micro-pollutantses of the invention, before ultrafiltration, and routinely pretreatment is single
Unit, improves removal effect；Described pretreatment unit can be one or more the group in coagulation, precipitation, sand filter
Close.
Drinking water is set up in order to improve the removal effect of organic micro-pollutantses of the invention, before ultrafiltration, and routinely pretreatment is single
Unit, improves removal effect；Described pretreatment unit can be one or more the group in coagulation, precipitation, sand filter
Close.
Advanced oxidation of the present invention, ultrafiltration, the method for nanofiltration group technology go micropollutants in water removal, with tradition
Ozone oxidation-BAC process compare, as the pretreatment unit photocatalysis pond of nanofiltration and ultrafiltration, not only make organic micro-
Contaminant degradation effect more preferably, and causes that microorganism and organic micro-pollutantses concentration are lower into the water of nanofiltration membrane cisterna, go out
The water quality of water more high-quality.
Fig. 1 is advanced oxidation of the present invention, ultrafiltration, nanofiltration group technology flow chart.
Specific embodiment
Name two examples and illustrate specific embodiment of the invention, but scope of the presently claimed invention is not limited to
In this.
Following examples titanium dioxide granule is synthesized using sol-gel process, with TiSO4It is titanium source, takes the TiSO of 15mL4
Storing solution, 5mL glacial acetic acid, are added slowly in 30mL absolute ethyl alcohols, stirring while adding, and stirring 30min obtains A liquid；1mL is taken again
Acetic acid is added in 1mL deionized waters, and 20mL absolute ethyl alcohols, stirring while adding, and stirring 15min obtains B liquid；It is stirred vigorously down
B liquid is dropwise instilled into A liquid, 5h is stirred at room temperature and is obtained colloidal sol, then colloidal sol is moved into crystallizing kettle closing, be placed in 120 in insulating box
Crystallization 10h at room temperature, forms gel at DEG C.The gel that will be prepared again is put into 100 DEG C of baking oven and dries 12h；Finally it is placed in
In tube furnace, at 400 DEG C and 2h is heat-treated, the heating-up time is 40min, and heating rate is 10 degrees/min, will after natural cooling
Catalyst is placed in standby in drier.A certain amount of silicon fluoride coupling agent is taken, ethanol solution is dissolved in, 0.5g/L~10g/ is configured to
The silicon fluoride coupling agent aqueous solution of L, at room temperature, takes the above-mentioned catalyst for preparing, and is soaked in 10h in this solution, afterwards, takes
Go out and rinsed well with deionized water, dried under the conditions of being placed in 110 DEG C 2h taking-up, then, be immersed in 0.5mmol/L~
1h is soaked in the trifluoromethyl trimethylsilane aqueous solution of 5mmol/L, deionized water rinsing surface is used afterwards, rushed with deionized water
Dry solidification 2h in 110 DEG C of baking oven is placed in after washing.
Embodiment 1：In the present embodiment, raw water uses laboratory water distribution, specific condition of water quality such as following table
| Water quality index | Unit | Numerical value |
| DOC | mg/L | 3.85 |
| Bisphenol-A | mg/L | 1.2 |
| Turbidity | NTU | 4.85 |
| Electrical conductivity | μs/cm | 5000 |
The pretreatment unit uses coagulation-precipitation-micro-filtration, and it is 12mg/L that coagulant uses aluminium polychloride dosage
(in terms of commercial quality).The coagulation stage uses pipe-line mixer, and the stage of reaction uses mechanical agitation mixing pit, precipitate phase to use
Tube settler, titanium dioxide particle diameter is 1.0 μm.
The ultrafiltration tubular membrane is PVDF tubular ultra-filtration membranes, molecular cut off 8000.1 hour is adsorbed in photocatalysis pond
Opening uviol lamp afterwards carries out photocatalysis, and water outlet carries out ultrafiltration, and ultrafiltration pressure is 0.08MPa, and ultrafiltration membrane area is 0.02m2,
Membrane flux 30L/ (m2.h), flow system flow is 2L/h.
The nanofiltration Flat Membrane is PES flat board NF membranes, and molecular cut off 800, nanofiltration membrane area is 28.6cm2.Super
Filter is filtered after carrying out about 60min, and nanofiltration operating pressure is 0.25MPa, and solution ph is 6.8, and the operating time is 120min, is received
The filter device rate of recovery is 75%.
To 0.021NTU, DOC is 1.25mg/L to final outflow water haze reduction, and organic pollution bisphenol A concentration is
0.055mg/L, clearance reaches 95%, and electrical conductivity is down to 2000 μ s/cm.
Embodiment 2：In the present embodiment, raw water uses laboratory water distribution, specific condition of water quality such as following table
| Water quality index | Unit | Numerical value |
| DOC | mg/L | 4.15 |
| Atrazine | mg/L | 0.5 |
| Turbidity | NTU | 5.95 |
| Electrical conductivity | μs/cm | 6000 |
The pretreatment unit uses coagulation-precipitation-micro-filtration, and it is 12mg/L that coagulant uses aluminium polychloride dosage
(in terms of commercial quality).The coagulation stage uses pipe-line mixer, and the stage of reaction uses mechanical agitation mixing pit, precipitate phase to use
Tube settler, titanium dioxide particle diameter is 1.0 μm.
The ultrafiltration tubular membrane is PVDF tubular ultra-filtration membranes, molecular cut off 8000.1 hour is adsorbed in photocatalysis pond
Opening uviol lamp afterwards carries out photocatalysis, and water outlet carries out ultrafiltration, and ultrafiltration pressure is 0.08MPa, and ultrafiltration membrane area is 0.02m2,
Membrane flux 30L/ (m2.h), flow system flow is 2L/h.
The nanofiltration Flat Membrane is PES flat board NF membranes, and molecular cut off 800, nanofiltration membrane area is 28.6cm2.Super
Filter is filtered after carrying out about 60min, and nanofiltration operating pressure is 0.25MPa, and solution ph is 6.8, and the operating time is 120min, is received
The filter device rate of recovery is 75%.
To 0.092NTU, DOC is 1.68mg/L to final outflow water haze reduction, and organic pollution atrazine concentration is
0.009mg/L, clearance reaches 98.2%, and electrical conductivity is down to 2300 μ s/cm.
Claims (7)
1. a kind of method that photocatalysis, ultrafiltration, nanofiltration group technology control organic micro-pollutantses in drinking water, it is characterised in that
The device of use includes the pretreatment unit, photocatalysis pond, milipore filter, the NF membrane that are sequentially connected, ultrafiltration membrane pool and photocatalysis pond
It is provided separately, in order to avoid the service life of the irradiation influence milipore filter of uviol lamp；Raw water is by after pretreatment unit, water outlet is entered into
Photocatalysis pond, remaining dissolved organic matter and various micro quantity organic pollutants in further degradation water, photocatalysis pond water outlet enters
Ultrafiltration membrane pool removes partial organic substances, and ultrafiltration membrane pool water outlet is processed into NF membrane, obtains the treatment water of more high-quality.
2., according to the method for claim 1, it is characterised in that use online detecting system, the detection according to detecting system refers to
Mark, using different concentrate recirculation modes, determines that NF membrane concentrated water is to revert to oxidation pond or ultrafiltration membrane pool, improves each technique
The treatment effect of unit, plays and uses different backflow approach to different pollutants.
3. according to the method for claim 2, it is characterised in that if dense oxygen in water or COD are higher, COD >=10mg/L says
Bright content of organics is higher, is back in photocatalysis pond, if its content is not high, COD ＜ 10mg/L are back to ultrafiltration membrane pool.
4., according to the method for claim 1, it is characterised in that in photocatalysis pond, the larger organic matter of molecular weight is broken down into small
Molecular organic, or small organic molecule is inorganization.
5. according to the method for claim 1, it is characterised in that the hyperfiltration membrane assembly used by milipore filter is external pressure submerged membrane group
Part, material is polyvinyl chloride or Kynoar；The pore diameter range of milipore filter be 0.01~0.02 μm between, the flux of milipore filter
It is 10~30L/m2·h。
6. it is purple according to the method for claim 1, it is characterised in that place uviol lamp and titanium dioxide granule in photocatalysis pond
Outer lamp increases photocatalysis effect, and has deactivation for microorganism in pond；Titanium dioxide granule particle diameter is 0.5~5 μm.
7. according to the method for claim 6, it is characterised in that titanium dioxide granule is synthesized using sol-gel process, with TiSO4For
Titanium source, takes the TiSO of 15mL4Storing solution, 5mL glacial acetic acid, are added slowly in 30mL absolute ethyl alcohols, stirring while adding, stirring
30min obtains A liquid；1mL acetic acid is taken again to be added in 1mL deionized waters, and 20mL absolute ethyl alcohols, stirring while adding, stirring
15min obtains B liquid；Be stirred vigorously it is lower B liquid is dropwise instilled into A liquid, 5h is stirred at room temperature and obtains colloidal sol, then colloidal sol is moved into crystallization
Kettle is closed, and is placed in insulating box crystallization 10h at 120 DEG C and at room temperature, is formed gel.The gel that will be prepared again is put into 100 DEG C
12h is dried in baking oven；Finally it is placed in tube furnace, at 400 DEG C and is heat-treated 2h, the heating-up time is 40min, and heating rate is
10 degrees/min, catalyst is placed in after natural cooling standby in drier.A certain amount of silicon fluoride coupling agent is taken, ethanol is dissolved in
Solution, is configured to 0.5~5g/L silicon fluoride coupling agent aqueous solutions, at room temperature, takes the above-mentioned catalyst for preparing, and is soaked in this
10h in solution, afterwards, taking-up is rinsed well with deionized water, and 2h taking-ups are dried under the conditions of being placed in 110 DEG C, then, is soaked
Soak 1h in 0.5~5mmol/L trifluoromethyl trimethylsilane aqueous solution, deionized water rinsing surface used afterwards, spend from
Sub- water is placed in dry solidification 2h in 110 DEG C of baking oven after rinsing.
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