CN104370390B - A kind of method cut down water treatment disinfection byproduct (DBP) and generate - Google Patents
A kind of method cut down water treatment disinfection byproduct (DBP) and generate Download PDFInfo
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- CN104370390B CN104370390B CN201410647876.5A CN201410647876A CN104370390B CN 104370390 B CN104370390 B CN 104370390B CN 201410647876 A CN201410647876 A CN 201410647876A CN 104370390 B CN104370390 B CN 104370390B
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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
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
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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
- 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
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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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
- 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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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- Organic Chemistry (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The present invention discloses a kind of method cut down water treatment disinfection byproduct (DBP) and generate, and concrete steps comprise the ferrate adding 0.5-20mg/L in pending water and stir 10-30min, pH scope for 6-12 with the rotating speed of 200-500r/min; Adding the coagulating agent of 5-15mg/L, stir 10-30min with the speed of 20-60r/min after stirring 3-5min with the rotating speed of 150-250r/min, standing 30-60min makes it precipitate; After precipitation, at liquid level 1-3cm place Aspirate supernatant; Adding in chlorine bleach liquor to supernatant liquor and sterilize, wherein the addition of clorox is 3-12.8mg/L. Compared with common process, employing Ferrate Pre-Oxidation Positive enhanced coagulation provided by the invention+clorox sterilization, it is possible to guarantee that tap water is under the prerequisite meeting sterilisation effect, significantly big reduction disinfection byproduct (DBP) content; This method is simple to operate, invests little, and without the need to existing water factory technique is carried out large-scale redevelopment.
Description
Technical field
The present invention relates to water technology, particularly relate to a kind of method cut down water treatment disinfection byproduct (DBP) and generate.
Background technology
Increase due to China's population and the quickening of urbanization process, the development of industrial or agricultural; particularly a large amount of uses of agricultural chemical fertilizer and agricultural chemicals; making to enter the nutritive substances such as lake, the nitrogen of reservoir, phosphorus, potassium to increase, there is extensive algal bloom in each big lake of 2007-2009, causes Urban water supply crisis. Along with environmental pollution increasingly sharpens, various places, Fujian Province supply water sources algal bloom event is broken out again and again.
In source water, a large amount of breedings of algae, seriously have impact on drinking-water quality, threaten human health. Early stage research shows, frustule can produce a large amount of containing carbon class disinfection byproduct (DBP) (C-DBPs) in chlorination, chloramines process, compared with natural organic matter humic acid, fulvic acid in water, algae may be more directly more important to the contribution of C-DBPs in preoxidation process. The test of Hoehn etc. shows, 4 kinds of algaes in different vegetative period after chlorination maximum chloroform output exceeded humic acid. Algae secondary metabolite contains the pollutent of a large amount of nitrogen-containing group (such as Microcystin, phycocyanin, Phycocyanins, C-etc.) as a class, tap water preoxidation process all likely participates in reacting and generates the nitrogenous class disinfection byproduct (DBP) with strong genetoxic, and then produce bigger drinking water quality health risk. Research shows: containing a large amount of organonitrogens (such as protein, amino acid, amine class), hydroaropic substance and aromatic series organism, free amino acid and aromatic series type organic in the organism contained in frustule is then the important precursor species generating N-DBPs in preoxidation process. Therefore how effectively removal frustule and disinfection by-products formation potential are the emphasis of research.
Conventional water treatment process comprises coagulation-flocculation-precipitation-filtration-sterilization.But owing to algae surface is usually electronegative, not easily charge neutrality is with de-steady, and coagulation effect is poor; Algae metablite and frustule break the algae substances being released into water body such as saccharic acid etc., can react with coagulating agent in coagulation process, thus reduction process effect; Owing to algae cell density is little, sedimentation effect is poor, also can significantly increase Water purification difficulty.
Preoxidation technique can strengthen, as a kind of, the effective means that in coagulation, frustule is removed, it can change frustule apparent structure, hinder the motion of frustule, degradable extracellular organism and preoxidation after frustule organism contribute to flocculation, and be widely used in urgent technique. Conventional chemical agent comprises chlorine, dioxide peroxide, chloramines, potassium permanganate, ozone etc. Wherein chloride class preoxidation agent causes more if methyl halide class (THMs) and halogen are for the generation of acetic acid class (HAAs) disinfection byproduct (DBP), thus is restricted use. Ozone, as a kind of novel preoxidation agent, when processing containing iodine and containing bromine water body, easily generates iodo and bromine for disinfection byproduct (DBP), and for the high algae water of nitrogen content, easily generates more nitrogenous disinfection byproduct (DBP). Potassium permanganate, as metal preoxidation agent, has the advantage that abatement disinfection byproduct (DBP) generates, but due to redox potential not high, preoxidation speed is slow, causes a certain amount of purple of residue in water, therefore is also restricted to a certain extent. The method that disinfection byproduct (DBP) generates can be effectively cut down it is thus desirable to a kind of.
Summary of the invention
It is an object of the invention to overcome the deficiency of prior art, it is provided that a kind of method cut down water treatment disinfection byproduct (DBP) and generate, it is possible to solve disinfection byproduct (DBP) content in current water and be difficult to a difficult problem for stably reaching standard.
The technical solution adopted for the present invention to solve the technical problems is:. a kind of method cutting down the generation of water treatment disinfection byproduct (DBP) comprises the following steps:
(1) in pending water, add the ferrate of 0.5-20mg/L and stir 10-30min, pH scope for 6-12 with the rotating speed of 200-500r/min.
(2) adding the coagulating agent of 5-15mg/L, stir 10-30min with the speed of 20-60r/min after stirring 3-5min with the rotating speed of 150-250r/min, standing 30-60min makes it precipitate;
(3) after precipitation, at liquid level 1-3cm place Aspirate supernatant;
(4) sterilizing in interpolation chlorine bleach liquor to supernatant liquor, wherein the addition of clorox is 3-12.8mg/L.
Preferably, described ferrate is Na2Fe04, potassium ferrate or its mixture.
Preferably, described coagulating agent is polymerize aluminum chloride, iron(ic) chloride or Tai-Ace S 150.
Preferably, in step (4), sterilization carries out in dark condition, and the reaction times is 2-4 days.
Preferably, containing microcystic aeruginosa or the little ring algae of plum Buddhist nun in described pending water.
Preferably, described supernatant liquor adopts the S-WAT cancellation of 0.5M.
Preferably, in step (3), also comprise dissolved organic carbon concentration (DOC), the potassium concentration (K of test supernatant liquor+) and 254nm under ultraviolet absorption value (UV254).
Preferably, in step (4), also comprise test trichloromethane concentration (TCMFP).
Preferably, in step (2), stir 1min at 250rpm, after being reduced to 150rpm stirring 3min, then stir 15min under 60rpm.
Preferably, described ferrate is liquid ferrate or solid-state ferrate.
The invention has the beneficial effects as follows,
(1) ferrate of the present invention is the sexavalence form of iron, and oxidation capacity is strong and is suitable for being applied in water treatment, it can effective disinfection by-products formation potential in oxidative degradation water, and halogenated disinfection by-products can not be produced;
(2) ferrate that the present invention adopts a kind of integrates oxidation, flocculates, helps the multifunctional water treating agent coagulated, the reduction product Fe (OH) that it generates after oxidising process terminates3Also precipitate together with the organic-inorganic pollutent in water body, water body and environment can not be produced secondary pollution;
(3) the present invention adopts ferrate liquid oxidizer, it is possible to overcomes gaseous oxidant and adds the operational difficulty brought and the unequal problem of gas-vapor mix, thus improve the efficiency of preoxidation, and product is easy to add, storage, transport and management;
(4) Ferrate Pre-Oxidation Positive enhanced flocculation+cholorination technique that the present invention proposes, simple to operate, it is not necessary to increase equipment or existing water factory technique is carried out upgrading.
Below in conjunction with drawings and Examples, the present invention is described in further detail; But a kind of method cutting down the generation of water treatment disinfection byproduct (DBP) of the present invention is not limited to embodiment.
Accompanying drawing explanation
Fig. 1 be in the embodiment of the present invention 2 different ferrate dosage to the effect diagram of microcystic aeruginosa TCM growing amount after Ferrate Pre-Oxidation Positive-enhanced coagulation-cholorination.
Fig. 2 is the comparison diagram that in the embodiment of the present invention 3,2 kinds of frustules are generated TCM by Ferrate Pre-Oxidation Positive-enhanced coagulation-oxychlorination, and wherein two kinds of frustules are respectively microcystic aeruginosa and the little ring algae of Mei Ni.
Embodiment
Embodiment 1
Reaction is, at one, 1L microcystic aeruginosa cell suspending liquid (7.32 �� 10 is housed7Cell/L) six coagulations stir in instrument and complete, and concrete steps are as follows:
(1) preoxidation stage: Xiang Shuizhong adds the potassium ferrate (0.5-20mg/L) of doses, and with the rotating speed rapid reaction 10min of 200r/min, reaction pH controls at 6-12; Preoxidation terminates, and samples 50mL in 2cm place under water, with the S-WAT cancellation of 0.5M, with 0.45 ��m of membrane filtration, tests dissolved organic carbon concentration (DOC), potassium concentration (K respectively+) and ultraviolet absorption value (UV under 254nm254)��
(2) preoxidation-coagulation assisted stage: in the water sample that step (1) obtains, dosing coagulant polymerize aluminum chloride (PAC, 10mg/L), first stirs 3min fast with the rotating speed of 200r/min, slowly 15min is stirred again, then quiet heavy 30min with 40r/min; Quiet heavy after in 2cm place water sampling 50mL under water, with the S-WAT cancellation of 0.5M, with 0.45 ��m of membrane filtration, test DOC, turbidity, K respectively+And UV254��
See table 1, after preoxidation, along with potassium ferrate adds the increase of concentration, larger molecular organics is oxidized to intermediate product by the strong oxidation of potassium ferrate, UV254And DOC concentration raises. After enhanced coagulation, ferrate oxidation Organic substance in water is reduction product Fe (OH) simultaneously3Flocculation sediment is participated in so that wadding body congregational rate is stronger, and structure is more fine and close, contrast preoxidation, the UV of water outlet after enhanced coagulation as flocculation agent254Value decrease respectively 83%, 96% and 95%, DOC concentration reduce 21%, 21% and 10% respectively. Ferrate Pre-Oxidation Positive-enhanced coagulation effectively eliminates the organism in water, especially the material of the fragrance same clan, and sedimentation effect is good.
Table 1 Ferrate Pre-Oxidation Positive-enhanced coagulation is to K in microcystic aeruginosa cell solution+��DOC��UV254With the impact of turbidity
Embodiment 2
Reaction is, at one, 1L frustule suspension (microcystic aeruginosa (7.32 �� 10 is housed7Cell/L) six coagulations) stir in instrument and complete, Xiang Shuizhong add doses potassium ferrate (0,0.5,1.0,2.0mg/L, 5.0mg/L, 10.0mg/L, 20.0mg/L), with the rotating speed rapid reaction 30min of 250r/min, pH controls at 6-12;Dosing coagulant polymerize aluminum chloride (PAC, 10mg/L), first stir 3min fast with the rotating speed of 200r/min, slowly 15min is stirred (when high ferro dosage is increased to more than 5mg/L again with 40r/min, reaction times disappears as the reaction end time using solution purple), then quiet heavy 30min; Quiet heavy after in 2cm place water sampling 100mL under water, add clorox (12.8mg/L is in available chlorine) and carry out chlorination, dark reaction 3d, survey its trichloromethane concentration (TCMFP).
As shown in Figure 1, compared to simple coagulating sedimentation, when potassium ferrate dosage is when 0.5-20mg/L, TCM reduces 10%, 26%, 38,52,78 and 82% respectively. Visible Ferrate Pre-Oxidation Positive-enhanced coagulation can reduce the TCM precursor substance of coagulating sedimentation water outlet, and special in potassium ferrate dosage increases, the concentration of TCM reduces obviously. Visible Ferrate Pre-Oxidation Positive can effectively promote that the enhanced coagulation stage is to the removal of extract before TCM, but the increase along with liquid ferrate concentration, and reaction solution pH increases, and is up to 13, and speed of response becomes slow, and the reaction times increases.
Embodiment 3
Reaction respectively 1L microcystic aeruginosa (7.32 �� 10 is being housed7Cell/L) cell suspending liquid and the little ring algae (2.06 �� 10 of plum Buddhist nun is housed7Cell/L) six coagulations of cell suspending liquid stir in instrument and complete, the water respectively to different frustule suspension adds doses potassium ferrate (0,0.5,1.0,2.0mg/L), with the rotating speed rapid reaction 30min of 250r/min; Dosing coagulant polymerize aluminum chloride (PAC, 10mg/L), first stirs 3min fast with the rotating speed of 200r/min, then stirs 15min slowly with 40r/min, then quiet heavy 30min; Quiet heavy after in 2cm place water sampling 100mL under water, add clorox (12.8mg/L is in available chlorine) and carry out chlorination, dark reaction 3d, survey its TCMFP.
As shown in Figure 2, after adding ferrate, in 2 kinds of frustule enhanced coagulation processes, TCM precursor is all effectively removed. Ferrate has extremely strong oxidisability in water, can take off steady multiple algae, and the secondary metabolite of the algae in oxidation removal water source and frustule break and the solvability organic pollutant discharged time dead.
Embodiment 4
Former water takes from Zhejiang Jiaxing water factory, the liquid ferrate (289mg/L) of different volumes is added in the former aqueous solution of 1L, 30min is stirred at 250rpm, after adding 10mg/LPAC, continue to stir 1min at 250rpm, after being reduced to 150rpm stirring 3min, 15min is stirred again under 60rpm, after precipitation 30min, get 1cm��3cm supernatant liquor under liquid level, measure pH and UV254. Experimental result is as follows:
The different preoxidation dosage of table 2 removes turbidity and UV for flocculation sediment254Impact
Phenomenon is it can be observed that add after liquid high ferro carries out preoxidation by experiment, then adds the wadding body that flocculation agent produces and become many and body volume of wadding a quilt with cotton becomes big, and 0.5 and 0.77mL the most obvious. Data from table, it can be seen that add the UV of the water sample that Na2Fe04 can obviously reduce in water254, there is the effect of certain enhanced flocculation, during high ferro dosage 15mL, UV254Substantially can't detect.
Embodiment 5
Adding the liquid Na2Fe04 of 0.5-2.0mg/L in pending water, with the rotating speed rapid reaction 20min of 200r/min, reaction pH controls at 6-12; Add the coagulating agent iron(ic) chloride of 5mg/L, first stir 5min fast with the rotating speed of 150r/min, then stir 30min slowly with 20r/min, then quiet heavy 45min;Quiet heavy after get supernatant liquor 50mL in 2cm place under water, add clorox (3mg/L is in available chlorine) and carry out chlorination, dark reaction 2d.
Embodiment 6
Adding the solid-state Na2Fe04 of 0.5-20.0mg/L in pending water, with the rotating speed rapid reaction 10min of 500r/min, reaction pH controls at 6-12; Add the aluminum sulfate coagulant of 15mg/L, first stir 4min fast with the rotating speed of 250r/min, then stir 60min slowly with 60r/min, then quiet heavy 60min; Quiet heavy after get supernatant liquor 50mL in 2cm place under water, add clorox (8mg/L is in available chlorine) and carry out chlorination, dark reaction 4d.
Although the foregoing describing the specific embodiment of the present invention; but it is familiar with those skilled in the art to be to be understood that; specific embodiment described by us just explanation property; instead of the restriction for the scope to the present invention; those of ordinary skill in the art in the modification of the equivalence done according to the spirit of the present invention and change, in the scope that the claim that all should be encompassed in the present invention is protected.
Claims (6)
1. the method cut down water treatment disinfection byproduct (DBP) and generate, it is characterised in that comprise the following steps:
(1) in pending water, add the ferrate of 0.5-20mg/L and stir 10-30min, pH scope for 6-12 with the rotating speed of 200-500r/min, containing microcystic aeruginosa or the little ring algae of plum Buddhist nun in described pending water;
(2) adding the coagulating agent of 5-15mg/L, stir 1min at 250rpm, after being reduced to 150rpm stirring 3min, then stir 15min under 60rpm, standing 30-60min makes it precipitate, and described coagulating agent is polymerize aluminum chloride, iron(ic) chloride or Tai-Ace S 150;
(3) after precipitation, at liquid level 1-3cm place Aspirate supernatant, this supernatant liquor adopts the S-WAT cancellation of 0.5M;
(4) sterilizing in interpolation chlorine bleach liquor to supernatant liquor, wherein the addition of clorox is 3-12.8mg/L.
2. the method that abatement water treatment disinfection byproduct (DBP) according to claim 1 generates, it is characterised in that: described ferrate is Na2Fe04, potassium ferrate or its mixture.
3. the method that abatement water treatment disinfection byproduct (DBP) according to claim 1 generates, it is characterised in that: in step (4), sterilization carries out in dark condition, and the reaction times is 2-4 days.
4. the method that abatement water treatment disinfection byproduct (DBP) according to claim 1 generates, it is characterised in that: in step (3), also comprise the ultraviolet absorption value under dissolved organic carbon concentration, potassium concentration and the 254nm testing supernatant liquor.
5. the method that abatement water treatment disinfection byproduct (DBP) according to claim 1 generates, it is characterised in that: in step (4), also comprise test trichloromethane and generate gesture concentration.
6. the method that abatement water treatment disinfection byproduct (DBP) according to claim 1 generates, it is characterised in that: described ferrate is liquid ferrate or solid-state ferrate.
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| CN105502608A (en) * | 2016-01-28 | 2016-04-20 | 吴江华衍水务有限公司 | Method for removing precusor substance of disinfection by-product in water |
| CN105967384A (en) * | 2016-05-24 | 2016-09-28 | 同济大学 | Method for controlling generation of iodo-trihalomethanes in drinking water |
| CN105923879A (en) * | 2016-06-22 | 2016-09-07 | 陈朝民 | Water body purification method |
| CN106946302A (en) * | 2017-05-09 | 2017-07-14 | 天津亿利科能源科技发展股份有限公司 | It is a kind of to reduce the inorganic agent of COD of sewage value |
| CN107879522A (en) * | 2017-10-18 | 2018-04-06 | 天津大学 | The processing method of halogenated disinfection by-products in a kind of control drinking water |
| KR20210038417A (en) * | 2018-03-16 | 2021-04-07 | 더 텍사스 에이 앤드 엠 유니버시티 시스템 | Activated ferrate composition |
| CN108419918A (en) * | 2018-05-04 | 2018-08-21 | 江苏螯龙水产养殖科技有限公司 | A kind of resisting stress compound formulation and preparation method thereof |
| CN111362497B (en) * | 2020-03-20 | 2021-07-16 | 同济大学 | Method for treating brominated disinfection by-product precursor by combining magnetic ion exchange resin with nanofiltration |
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| CN101774711A (en) * | 2010-01-29 | 2010-07-14 | 深圳市深水宝安水务有限公司 | Method for reducing chlorite as disinfection by-product of drinking water |
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| CN101774711A (en) * | 2010-01-29 | 2010-07-14 | 深圳市深水宝安水务有限公司 | Method for reducing chlorite as disinfection by-product of drinking water |
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| 梁好 等.高铁酸盐去除水中消毒副产物前体物的研究.《环境科学与技术》.2004,第27卷(第2期), * |
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