CN105858955A - Method for removing disinfection by-products in water - Google Patents

Method for removing disinfection by-products in water Download PDF

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Publication number
CN105858955A
CN105858955A CN201610269195.9A CN201610269195A CN105858955A CN 105858955 A CN105858955 A CN 105858955A CN 201610269195 A CN201610269195 A CN 201610269195A CN 105858955 A CN105858955 A CN 105858955A
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water
membrane
base material
dbp
modified
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CN105858955B (en
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韩健健
陈顺权
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Guangzhou Institute of Advanced Technology of CAS
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Guangzhou Institute of Advanced Technology of CAS
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    • 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
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0006—Organic membrane manufacture by chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/34—Polyvinylidene fluoride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/36—Introduction of specific chemical groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/48—Antimicrobial properties
    • 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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/445—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by forward osmosis
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/02—Non-contaminated water, e.g. for industrial water supply
    • C02F2103/04—Non-contaminated water, e.g. for industrial water supply for obtaining ultra-pure water
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/42—Nature of the water, waste water, sewage or sludge to be treated from bathing facilities, e.g. swimming pools
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention relates to a method for removing disinfection by-products in water. The method is characterized by carrying out integrated membrane treatment after enhanced coagulation of a water sample to be treated, wherein the integrated membrane treatment method comprises the following steps: ultrafiltration: purifying the water sample subjected to enhanced coagulation by adopting an ultrafiltration membrane to obtain a first water sample; nanofiltration: purifying the first water sample by adopting a nanofiltration membrane to obtain a second water sample; pervaporation: purifying the second water sample by adopting a pervaporation membrane and then collecting the second water sample, thus removing the disinfection by-products in water. The method has the beneficial effects that the enhanced coagulation technology and the three-stage integrated membrane technology comprising ultrafiltration, nanofiltration and pervaporation are integrated to remove the disinfection by-products in water; through organic combination of the steps, the removal rate of the disinfection by-products is more than or equal to 90%, the disinfection by-products in water are effectively reduced and the water quality requirement of safe water is met; therefore the method has great significance to purifying chlorinated swimming pool water, drinking water, and the like.

Description

Remove the method for disinfection byproduct (DBP) in water
Technical field
The present invention relates to water process, particularly relate to a kind of remove the method for disinfection byproduct (DBP) in water.
Background technology
Cholorination is most popular disinfection way in the drinking water course of processing, has gone up the history of a century. But, cholorination mode, can inevitably produce Chlorination Disinfection By-products (DBPs).As far back as 1974 Year just studies have found that, DBPs has the effects such as strong carcinogenic, teratogenesis, mutagenesis, the serious harm mankind Health.
For ensureing mankind's water safety, the control of DBPs in water, obtain the great attention of countries in the world.Mesh Before, the U.S. reduces the THMs the highest permission mass concentration standard in drinking-water, carries out in two stages: first In the stage, THMs reduces to 80 μ g/L from 100 μ g/L；Second stage, drops to 40 μ g/L further by THMs. China is also made that strict regulation in the drinking water standard of calendar year 2001 to this: chloroform the highest Mass concentration is 60 μ g/L, and carbon tetrachloride is 2 μ g/L.
The research at present controlled DBPs in drinking water, is concentrated mainly on four aspects: (1) from Sources controlling, I.e. strengthen the protection to source water；(2) replacement disinfectant and sterilization method are used；(3) DBPs precursor Removal；(4) removal of DBPs.
Water head site environmental conservation, improving source water quality is to reduce the fundamental way of DBPs, but, portion of China The water environment of region-by-region has suffered severe contamination, so for the research of other three aspects, the most just seeming outstanding For necessity.
At present, the disinfectant and the method that substitute cholorination mainly have chloramines, ozone and ultraviolet etc.: research Find, the ratio of chlorine and ammonia nitrogen is down to 5, it is possible to the DBPs making independent chlorination be generated reduces 89%； Use pre-chloramination technique can not only reach effect of some pre-oxidation process, also extend chloramines disinfection simultaneously Time of contact, improve the microbial safety of drinking water, but, illinois university grain science system Genetic toxicity scholar Plewa J Michael research find, a kind of chloramines disinfection by-product is to find poison so far Property maximum；As a kind of strong oxidizer, sterilization and the oxidability of ozone are above chlorine, are current dosings Maximally effective disinfectant in sterilization, has an advantage in that and does not produces the disinfection byproduct (DBP) such as THMs, but ozone Unstability in water so that it is difficult to separately as disinfectant, for the sterilization of drinking water, and, Ozonization has the possibility producing the by-products such as bromate；The broad spectrum activity of ultraviolet sterilization, is the most all disappearing In poison technology the highest, it can effectively kill multiple chlorine and ozone can not be killed parasite type, as hidden Property cysticercus and giardia lamblia stiles etc., and there is no the generation of DBPs, but, ultraviolet penetrating in water Ability and the power of ultraviolet lamp tube and life-span, constrain the application in terms of drinking water disinfection of the ultraviolet disinfection mode.
In view of cholorination remains most popular disinfection way in the drinking water course of processing, to DBPs And the removal research of precursor, just seem most important.
Summary of the invention
Based on this, it is necessary to provide a kind of and remove the method for disinfection byproduct (DBP) in water.
A kind of remove the method for disinfection byproduct (DBP) in water, use coagulant, or, coagulant and flocculation aid are treated After process water sample carries out enhanced coagulation, then carrying out Integrated Films process, described Integrated Films processes and comprises the steps:
Ultrafiltration: use ultrafilter membrane that the water sample after enhanced coagulation is purified, obtain the first water sample；
Nanofiltration: use NF membrane that described first water sample is purified, obtain the second water sample；
Infiltration evaporation: after using infiltrating and vaporizing membrane that described second water sample is purified, collect.
Wherein in an embodiment, the preparation method of described ultrafilter membrane is as follows:
Ultrafilter membrane base material carries out charged modification, and described ultrafilter membrane base material is polysulfones (PSF), polyethersulfone resin (PES) or Kynoar (PVDF),
The method of described charged modification is: be dissolved in concentrated sulphuric acid by described ultrafilter membrane base material, adds chlorosulfonic acid (being slowly added to), reacts 20-25h at a temperature of 20-40 DEG C, control described chlorosulfonic acid and concentrated sulphuric acid Volume ratio be 1:1-3, in described concentrated sulphuric acid, the mass concentration of ultrafilter membrane base material is 8-12%；
With nanometer Ag+The SiO modified2Granule is blended with charged modified ultrafilter membrane base material as filler particles, Make the ultrafilter membrane of molecular cut off 10000-50000Da, described nanometer Ag+The SiO modified2Granule is in institute The mass concentration stated in charged modified ultrafilter membrane base material is 5-10%.
Wherein in an embodiment, in described concentrated sulphuric acid, the mass concentration of ultrafilter membrane base material is 8-10%；
The molecular cut off of described ultrafilter membrane is 10000-20000Da, described nanometer Ag+The SiO modified2Granule Mass concentration in described charged modified ultrafilter membrane base material is 7-9%.
Wherein in an embodiment, the preparation method of described NF membrane is as follows:
NF membrane base material carries out charged modification, and described NF membrane base material is polysulfones or polyethersulfone resin,
The method of described charged modification is: be dissolved in concentrated sulphuric acid by described NF membrane base material, adds chlorosulfonic acid (being slowly added to), reacts 20-25h at a temperature of 20-40 DEG C, control described chlorosulfonic acid and concentrated sulphuric acid Volume ratio be 1:1-3, in described concentrated sulphuric acid, the mass concentration of NF membrane base material is 8-12%；
With nanometer Ag+The SiO modified2Granule is blended with charged modified NF membrane base material as filler particles, Make the NF membrane of molecular cut off 500-600Da, described nanometer Ag+The SiO modified2Granule is described lotus Mass concentration in the NF membrane base material that electricity is modified is 5-10%.
Wherein in an embodiment, the molecular cut off of described NF membrane is 500-550Da, described nanometer Ag+The SiO modified2Granule mass concentration in described charged modified NF membrane base material is 8-10%.
Wherein in an embodiment, described Ag+The SiO modified2The diameter Distribution of granule is 30-80nm.
Wherein in an embodiment, the method for described infiltration evaporation is as follows:
Use the macromolecular material polydimethylsiloxane (PDMS) of hydrophobicity parent's haloform, polyacrylic acid Ethyl ester (PEA) or polyethyl methacrylate (HEMA) are membrane material, enter with activated carbon for filler particles Row is blended, and prepares hydrophobic infiltrating and vaporizing membrane, and described activated carbon is at described polydimethylsiloxane, polyacrylic acid Mass concentration in ethyl ester or polyethyl methacrylate is 5-10%, or,
Using hydrophilic macromolecular material polyvinyl alcohol is membrane material, prepares hydrophilic infiltrating and vaporizing membrane.
Wherein in an embodiment, the preparation method of described infiltrating and vaporizing membrane is as follows:
It is blended with polyethyl methacrylate as filler particles using activated carbon, prepares infiltrating and vaporizing membrane, described Activated carbon mass concentration in described polyethyl methacrylate is 7-9%.
The film build method of above-mentioned charged ultrafilter membrane, charged nanofiltration membrane and infiltrating and vaporizing membrane can use this area conventional Method.
Ag+-SiO2Granule can be prepared according to following method:
Take orthosilicic acid tetraalkyl ester (TAOS), ethanol, deionized water, ammonia successively in there-necked flask, Volume is respectively 12,200,20,15mL, stir 24h under room temperature, obtain milky SiO2Suspending liquid A； Take 0.85g AgNO3, prepare 25mmol/LAgNO3Ethanol solution, the N-aminoethyl-γ of addition 1.075g- Aminopropyl trimethoxysilane, lucifuge is stirred at room temperature 12h, by the yellow solution of gained, is slowly added into In suspending liquid A, lucifuge is stirred at room temperature 12h, is centrifuged, washs and is dried, to obtain final product.
Wherein in an embodiment, described coagulant is added water by the bodied ferric sulfate of iron-holder 15-25wt% and joins System forms, and concentration is 5-15mg/L；
Described flocculation aid is added water formulated by cationic-type polyacrylamide, and concentration is 20-25mg/L；
The method of described enhanced coagulation is: put in described pending water sample by described coagulant and flocculation aid, Dosage is followed successively by 40-50mg/L and 0.05-0.15mg/L, and tune pH value is 5-8, stirring,.
Wherein in an embodiment, described coagulant is added water by the bodied ferric sulfate of iron-holder 15-20wt% and joins System forms, and concentration is 14-15mg/L；
Described flocculation aid is added water formulated by the cationic-type polyacrylamide of molecular weight 3000kDa, concentration For 23-25mg/L；
The method of described enhanced coagulation is: put in described pending water sample by described coagulant and flocculation aid, Dosage is followed successively by 40-45mg/L and 0.09-0.1mg/L, and adjusting pH value is stirring after 6.3-7.6, stirring speed Degree is 60-400r/min, and mixing time is 15-20min, then stands 15-25min,.
Compared with prior art, the method have the advantages that
(1) present invention combines Mixing enhancement+, and is permeated, by ultrafiltration, nanofiltration and vaporization, three built Disinfection byproduct (DBP) in water is removed by level Integrated Membrane Technology, and each step organically combines, to disinfection byproduct (DBP) Removal efficiency reaches more than 90%, can effectively reduce the disinfection byproduct (DBP) in water, reach safe water water quality requirement, Significant for the swimming-pool water after purification cholorination, drinking water etc..
(2) by kind and the character of conservative control each step separation film, it is also possible to realize primary further super The preparation of pure water (removal efficiency more than 99%).
(3) by filling Ag+-SiO2Granule, can be effectively improved the resisting microbial contamination of ultrafiltration and NF membrane Can, extend the service life of both films.
(4) method of disinfection byproduct (DBP) during the present invention removes water, technique is advanced, improves water and processes work ring Border, it is achieved cleaning is carried out production strictly in line with rules and regulations, and removal effect is good, and systematic running cost is low, simple to operate, it is simple to industry Change big production.
Accompanying drawing explanation
Fig. 1 is the equipment and flow chart that one embodiment of the invention removes that in water, the method for disinfection byproduct (DBP) uses, Wherein,
1-the first water tank；2-hyperfiltration membrane assembly；3-the second water tank；4-nanofiltration membrane component；5-three-tank；6- Infiltration vaporization membrane module；7-cold-trap；8-the 4th water tank.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is removed the method work of disinfection byproduct (DBP) in water the most in detail Explanation.
Embodiment 1
The present embodiment is a kind of removes the method for disinfection byproduct (DBP) in water, its equipment used and flow process such as Fig. 1 institute Showing, pending water sample is the swimming-pool water after certain swimming sterilizing, and wherein the kind of DBPs is with THMs and HAAs (halogen acetic acid) is main, THMs and HAAs is respectively at 230 μ g/L-260 μ g/L, 140 μ g/L-420 μ g/L Between fluctuate, method comprises the steps:
(1) enhanced coagulation:
The bodied ferric sulfate of iron-holder 25wt% is added water and is made into the coagulant that concentration is 5mg/L；
Being added water by the cationic-type polyacrylamide of molecular weight 3000kDa and being configured to concentration is that helping of 20mg/L is solidifying Agent；
Described coagulant and flocculation aid are put in described pending water sample, dosage be followed successively by 50mg/L and 0.15mg/L, adjusting pH value is stirring after 8, and mixing speed is 400r/min, and mixing time is 15min, so Rear standing 25min；
(2) ultrafiltration:
Hyperfiltration membrane assembly 2 includes ultrafilter membrane, step (1) process after water sample through the first water tank 1 from ultrafilter membrane The downside of assembly 2 enters membrane cisterna, and the water through assembly does not sends back in the first water tank 1, through the water of assembly On the upside of hyperfiltration membrane assembly 2 out, most DBPs precursor and the part such as the most removable humic acid DBPs, obtains the first water sample, wherein,
Described ultrafilter membrane is charged filled-type ultrafilter membrane, and preparation method is as follows:
Kynoar is dissolved in concentrated sulphuric acid, is slowly added to chlorosulfonic acid, at a temperature of 30 DEG C, carry out sulfonation Reaction, the volume ratio controlling chlorosulfonic acid and concentrated sulphuric acid is 1:2, and in concentrated sulphuric acid, the mass concentration of Kynoar is 12%, response time 20h, prepare charged base material sulfonation Kynoar；
With nanometer Ag+The SiO modified2Granule (diameter Distribution is 30-80nm) as filler particles with charged Base material sulfonation polyvinylidene blending, uses conventional method to make the ultrafilter membrane of molecular cut off 50000Da, Described nanometer Ag+The SiO modified2Granule mass concentration in charged base material SPSF is 5%；
(3) nanofiltration:
Nanofiltration membrane component 4 includes NF membrane, the first water sample of step (2) through the second water tank 3 from NF membrane group The downside of part 4 enters membrane cisterna, and the water through assembly does not sends back in the second water tank 3, through assembly water from On the upside of nanofiltration membrane component 4 out, the most removable most DBPs, obtain the second water sample, wherein,
Described NF membrane is charged filled-type NF membrane, and preparation method is similar to the preparation of step (2) ultrafilter membrane, The molecular cut off preparing NF membrane is 600Da；
(4) infiltration evaporation:
Through process above, the DBPs entered in the water in infiltration vaporization membrane module 6 is a remaining little portion The neutral organic molecule THMs that fractionated molecule amount is less, infiltration vaporization membrane module 6 includes infiltrating and vaporizing membrane, should Infiltrating and vaporizing membrane uses the polydimethylsiloxane of hydrophobic parent THMs system to be blended with activated carbon as filler particles Becoming, wherein activated carbon mass concentration in polydimethylsiloxane is 15%,
Second water sample of step (3) through three-tank 5 from the upside of infiltration vaporization membrane module 6 enter membrane cisterna, During filtration, THMs dissolves and adsorbs on film, and penetrates into the downstream of film further, obtains in cold-trap 7 It is the concentrated solution of THMs, enters the water in the 4th water tank 8 and be the water of removing DBPs gained, in water DBPs clearance reaches more than 90%, can be used as swimming-pool water and uses.
Embodiment 2
The present embodiment is a kind of removes the method for disinfection byproduct (DBP) in water, as a example by pending water sample is certain city's tap water, THMs and HAAs respectively between 10 μ g/L-35 μ g/L, 1.4 μ g/L-4.5 μ g/L fluctuate, method step with Embodiment 1 is similar to, and difference is:
(1) enhanced coagulation:
The bodied ferric sulfate of iron-holder 15wt% is added water and is made into the coagulant that concentration is 15mg/L；
Being added water by the cationic-type polyacrylamide of molecular weight 3000kDa and being configured to concentration is that helping of 23mg/L is solidifying Agent；
Described coagulant and flocculation aid are put in described pending water sample, dosage be followed successively by 40mg/L and 0.10mg/L, adjusting pH value is stirring after 7.5, and mixing speed is 60r/min, and mixing time is 15min, so Rear standing 15min；
(2) ultrafiltration:
Hyperfiltration membrane assembly 2 includes that ultrafilter membrane, described ultrafilter membrane are charged filled-type ultrafilter membrane, and preparation method is such as Under:
Polysulfone resin is dissolved in concentrated sulphuric acid, is slowly added to chlorosulfonic acid, at a temperature of 30 DEG C, carry out sulfonation anti- Should, the volume ratio controlling chlorosulfonic acid and concentrated sulphuric acid is 1:2, and in concentrated sulphuric acid, the mass concentration of polyethersulfone resin is 8%, Response time 25h, prepares charged base material sulfonated polyether sulphone resin；
With nanometer Ag+The SiO modified2Granule (diameter Distribution is 30-80nm) as filler particles with charged Base material SPSF is blended, and uses conventional method to make the ultrafilter membrane of molecular cut off 20000Da, described in receive Rice Ag+The SiO modified2Granule mass concentration in charged base material SPSF is 8%；
(3) nanofiltration:
Nanofiltration membrane component 4 includes that NF membrane, described NF membrane are charged filled-type NF membrane, preparation method class Like the preparation of step (2) ultrafilter membrane, the molecular cut off preparing NF membrane is 500Da；
(4) infiltration evaporation:
Infiltration vaporization membrane module 6 includes infiltrating and vaporizing membrane, and this infiltrating and vaporizing membrane uses gathering of hydrophobic parent THMs Ethyl methacrylate and activated carbon are blended as filler particles and make, and wherein activated carbon is at polymethylacrylic acid Mass concentration in ethyl ester is 8%, and during filtration, THMs dissolves and adsorbs on film, and penetrates into film further Downstream, obtain in cold-trap 7 is the concentrated solution of THMs, and the water entered in the 4th water tank 8 is removing The water of DBPs gained, the DBPs clearance in water reaches more than 95%.
Embodiment 3
The present embodiment is a kind of removes the method for disinfection byproduct (DBP) in water, as a example by pending water sample is certain city's tap water, THMs and HAAs respectively between 10 μ g/L-35 μ g/L, 1.4 μ g/L-4.5 μ g/L fluctuate, method step with Embodiment 1 is similar to, and difference is:
(1) enhanced coagulation:
The bodied ferric sulfate of iron-holder 20wt% is added water and is made into the coagulant that concentration is 15mg/L；
Being added water by the cationic-type polyacrylamide of molecular weight 3000kDa and being configured to concentration is that helping of 24mg/L is solidifying Agent；
Described coagulant and flocculation aid are put in described pending water sample, dosage be followed successively by 45mg/L and 0.096mg/L, adjusting pH value is stirring after 6.41, and mixing speed is 200r/min, and mixing time is 20min, Then 20min is stood；
(2) ultrafiltration:
Hyperfiltration membrane assembly 2 includes that ultrafilter membrane, described ultrafilter membrane are charged filled-type ultrafilter membrane, and preparation method is such as Under:
Polysulfones is dissolved in concentrated sulphuric acid, is slowly added to chlorosulfonic acid, at a temperature of 30 DEG C, carry out sulfonating reaction, The volume ratio controlling chlorosulfonic acid and concentrated sulphuric acid is 1:2, and in concentrated sulphuric acid, the mass concentration of Kynoar is 10%, Response time 22h, prepares charged base material SPSF；
With nanometer Ag+The SiO modified2Granule (diameter Distribution is 30-80nm) as filler particles with charged Base material SPSF is blended, and uses conventional method to make the ultrafilter membrane of molecular cut off 10000Da, described in receive Rice Ag+The SiO modified2Granule mass concentration in charged base material SPSF is 8%；
(3) nanofiltration:
Nanofiltration membrane component 4 includes that NF membrane, described NF membrane are charged filled-type NF membrane, and preparation method is such as Under:
Polysulfones is dissolved in concentrated sulphuric acid, is slowly added to chlorosulfonic acid, at a temperature of 30 DEG C, carry out sulfonating reaction, The volume ratio controlling chlorosulfonic acid and concentrated sulphuric acid is 1:2, and in concentrated sulphuric acid, the concentration of polysulfones is 12%, the response time 23h, prepares charged base material SPSF；
With nanometer Ag+The SiO modified2Granule (diameter Distribution is 30-80nm) as filler particles with charged Base material SPSF is blended, and uses conventional method to make the NF membrane of molecular cut off 550Da, described nanometer Ag+The SiO modified2Granule mass concentration in charged base material SPSF is 10%；
(4) infiltration evaporation:
Infiltration vaporization membrane module 6 includes infiltrating and vaporizing membrane, and the active layer of this infiltrating and vaporizing membrane uses hydrophilic gathering Vinyl alcohol is made, and three-tank 5 has heater, and temperature is that to affect of infiltration evaporation flux important Factor, when producing ultra-pure water, can regulate temperature, the yield of regulation ultra-pure water, mistake by this heater During filter, water adsorbs on film, and penetrates into the downstream of film further, and obtain in cold-trap 7 is primary ultrapure Water, the DBPs clearance in water reaches more than 99.9%.
Comparative example
A kind of method of disinfection byproduct (DBP) in water, pending water sample and method step removed of this comparative example is with real Executing example 2, difference is: do not carry out collecting in described infiltration evaporation step, i.e. embodiment 2 three-tank 5 To water, DBPs clearance is only 80%.
Each technical characteristic of embodiment described above can combine arbitrarily, for making description succinct, the most right The all possible combination of each technical characteristic in above-described embodiment is all described, but, if these skills There is not contradiction in the combination of art feature, is all considered to be the scope that this specification is recorded.
Embodiment described above only have expressed the several embodiments of the present invention, and it describes more concrete and detailed, But can not therefore be construed as limiting the scope of the patent.It should be pointed out that, for this area For those of ordinary skill, without departing from the inventive concept of the premise, it is also possible to make some deformation and change Entering, these broadly fall into protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be with appended power Profit requires to be as the criterion.

Claims (10)

1. remove the method for disinfection byproduct (DBP) in water for one kind, it is characterised in that use coagulant, or, coagulation After agent and flocculation aid carry out enhanced coagulation to pending water sample, then carry out Integrated Films process, at described Integrated Films Reason comprises the steps:
Ultrafiltration: use ultrafilter membrane that the water sample after enhanced coagulation is purified, obtain the first water sample；
Nanofiltration: use NF membrane that described first water sample is purified, obtain the second water sample；
Infiltration evaporation: after using infiltrating and vaporizing membrane that described second water sample is purified, collect.
The method of disinfection byproduct (DBP) in removal water the most according to claim 1, it is characterised in that described The preparation method of ultrafilter membrane is as follows:
Ultrafilter membrane base material is carried out charged modification: described ultrafilter membrane base material is polysulfones, polyethersulfone resin or poly-inclined Fluorothene, the method for described charged modification is: be dissolved in concentrated sulphuric acid by described ultrafilter membrane base material, adds chlorine Sulfonic acid, reacts 20-25h at a temperature of 20-40 DEG C, control the volume ratio of described chlorosulfonic acid and concentrated sulphuric acid For 1:1-3, in described concentrated sulphuric acid, the mass concentration of ultrafilter membrane base material is 8-12%；
With nanometer Ag+The SiO modified2Granule is blended with charged modified ultrafilter membrane base material as filler particles, Make the ultrafilter membrane of molecular cut off 10000-50000Da, described nanometer Ag+The SiO modified2Granule is in institute The mass concentration stated in charged modified ultrafilter membrane base material is 5-10%.
The method of disinfection byproduct (DBP) in removal water the most according to claim 2, it is characterised in that described In concentrated sulphuric acid, the mass concentration of ultrafilter membrane base material is 8-10%；
The molecular cut off of described ultrafilter membrane is 10000-20000Da, described nanometer Ag+The SiO modified2Granule Mass concentration in described charged modified ultrafilter membrane base material is 7-9%.
The method of disinfection byproduct (DBP) in removal water the most according to claim 1, it is characterised in that described The preparation method of NF membrane is as follows:
NF membrane base material is carried out charged modification: described NF membrane base material is polysulfones or polyethersulfone resin, described The method of charged modification is: be dissolved in concentrated sulphuric acid by described NF membrane base material, adds chlorosulfonic acid, in 20-40 DEG C At a temperature of react 20-25h, the volume ratio controlling described chlorosulfonic acid and concentrated sulphuric acid is 1:1-3, described dense In sulphuric acid, the mass concentration of NF membrane base material is 8-12%；
With nanometer Ag+The SiO modified2Granule is blended with charged modified NF membrane base material as filler particles, Make the NF membrane of molecular cut off 500-600Da, described nanometer Ag+The SiO modified2Granule is described lotus Mass concentration in the NF membrane base material that electricity is modified is 5-10%.
The method of disinfection byproduct (DBP) in removal water the most according to claim 4, it is characterised in that described The molecular cut off of NF membrane is 500-550Da, described nanometer Ag+The SiO modified2Granule charged changes described The mass concentration in NF membrane base material after property is 8-10%.
6., according to the method for disinfection byproduct (DBP) in the removal water described in any one of claim 2-5, its feature exists In, described Ag+The SiO modified2A diameter of 30-80nm of granule.
The method of disinfection byproduct (DBP) in removal water the most according to claim 1, it is characterised in that described The preparation method of infiltrating and vaporizing membrane is as follows:
Using activated carbon as filler particles and polydimethylsiloxane, polyethyl acrylate or polymethylacrylic acid Ethyl ester is blended, and prepares infiltrating and vaporizing membrane, and described activated carbon is in described polydimethylsiloxane, polyacrylic acid second Mass concentration in ester or polyethyl methacrylate is 5-15%；Or,
Infiltrating and vaporizing membrane is prepared as base material using polyvinyl alcohol.
The method of disinfection byproduct (DBP) in removal water the most according to claim 7, it is characterised in that described The preparation method of infiltrating and vaporizing membrane is as follows:
It is blended with polyethyl methacrylate as filler particles using activated carbon, prepares infiltrating and vaporizing membrane, described Activated carbon mass concentration in described polyethyl methacrylate is 7-9%.
9. according to the method for disinfection byproduct (DBP) in the removal water described in claim 1-5 or any one of 7-8, its Being characterised by, described coagulant is added water formulated by the bodied ferric sulfate of iron-holder 15-25wt%, and concentration is 5-15mg/L；
Described flocculation aid is added water formulated by cationic-type polyacrylamide, and concentration is 20-25mg/L；
The method of described enhanced coagulation is: put in described pending water sample by described coagulant and flocculation aid, Dosage is followed successively by 40-50mg/L and 0.05-0.15mg/L, and tune pH value is 5-8, stirring,.
The method of disinfection byproduct (DBP) in removal water the most according to claim 9, it is characterised in that institute Stating coagulant and added water formulated by the bodied ferric sulfate of iron-holder 15-20wt%, concentration is 14-15mg/L；
Described flocculation aid is added water formulated by the cationic-type polyacrylamide of molecular weight 3000kDa, concentration For 23-25mg/L；
The method of described enhanced coagulation is: put in described pending water sample by described coagulant and flocculation aid, Dosage is followed successively by 40-45mg/L and 0.09-0.1mg/L, and adjusting pH value is stirring after 6.3-7.6, stirring speed Degree is 60-400r/min, and mixing time is 15-20min, then stands 15-25min,.
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