CN103880150A - Water treatment device for enhancing chloramine disinfection and treatment method thereof - Google Patents
Water treatment device for enhancing chloramine disinfection and treatment method thereof Download PDFInfo
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Abstract
The invention provides a water treatment device for enhancing chloramine disinfection and a treatment method thereof, and relates to water treatment. The device is provided with a chloramine solution storage pool, circulating pumps, valves, a flowmeter and an ultrasonic processor; the inlet of a first circulating pump is arranged in the chloramine solution storage pool, the outlet of the first circulating pump is connected into a reaction tank through a first valve and the flowmeter in sequence, a cooling water inlet is arranged on one side of the bottom of the reaction tank, a circulating water outlet is arranged on the bottom of the reaction tank, the circulating water outlet is connected into the reaction tank through a second valve, a second circulating pump and a fourth valve in sequence, circulating water is drained from the reaction tank through a second valve and a third valve, and a cooling water outlet is arranged on one side of the top of the reaction tank; and an ultrasonic transducer stretches into a solution to be tested in the reaction tank. A chloramine solution is added in the chloramine solution storage pool filled with the solution to be tested, the ultrasonic transducer stretches into the liquid level of the chloramine solution, and a stable temperature of the chloramine solution is maintained; and the ultrasonic processor is started to remove TCS in water under the action of ultrasonic.
Description
Technical field
The present invention relates to water treatment, especially relate to the one strengthening chloramines disinfection of municipal plumbing and environmental engineering for water treatment device and treatment process thereof.
Background technology
In drinking water disinfection, in order to reduce disinfection byproduct (DBP) concentration, chloramines is usually used for substituting free chlorine disinfectant
[1], but due to chloramines oxidisability a little less than, cause it longer for the required oxidization time of organism, removal ability is poor
[2], cause its result of use unsatisfactory.Because the harm of the micro-content organisms such as personal-care supplies in tap water becomes increasingly conspicuous, therefore, this invention technology can be widely used in the advanced treatment of tap water, also can be applicable to removal poisonous in water, difficult for biological degradation micro quantity organic pollutant simultaneously.
Chloramines is a kind of green disinfectant, the generation of less disinfection byproduct (DBP) in its sterilizing process, be commonly used to substitute free chlorine disinfectant, but its oxidisability a little less than, be difficult to remove organism in water.Ultrasonic technology is novel in recent years a kind of water technology, remarkable in the pollutent effect of removal water pollutant especially difficult degradation
[3～5].
Triclosan (Irgacare MP, Triclosan, TCS) is a kind of ubiquitous water environment pollution thing
[6].Investigator has carried out a large amount of investigation to the distribution situation of TCS in earth surface water source, and result shows: most surface water has TCS residual (μ g/L-ng/L), and the concentrations of TCS is even up to 5160ng/L
[7], show this type of material serious threat the water quality safety of tap water.But research shows that existing water technology is not good to the removal effect of TCS, and there are other secondary metabolites to generate
[8]thereby, drinking-water quality is formed safely to great threat, thereby, its removal control is necessary.
Reference:
[1]Singer,P.C.,Ed,Formation and control of disinfection byproducts in drinking Water[M]American Water Works Association:Denver,CO,1999。
[2]Snyder SA,Wert EC,Lei H,Westerhoff P,Yoon Y,Removal of EDCs and pharmaceuticals in drinking and reuse treatment processes[M].AWWA Research Foundation,IWA Publishing,London,2007。
[3]Adolfsson-Erici M,Pettersson M,Parkkonen J.Triclosan,a commonly used bactericide found in human milk and in the aquatic environment in Sweden[J].Chemosphere2002,46:1485–1489。
[4]Prado LS,Barro R,Jares CG,Sonochemical degradation of triclosan in water and wastewater[J],Ultrasonics Sonochemistry,2008(15):689–694。
[5]Yao JJ,Gao NY,Li C,Mechanism and kinetics of parathion degradation under ultrasonic irradiation[J],Journal of Hazardous Materials,2010(175):138–145。
[6]Mehrdad A,Hashemzadeh R,Ultrasonic degradation of Rhodamine B in the presence of hydrogen peroxide and some metal oxide[J],Ultrasonics Sonochemistry,2010(17):168–172。
[7]Bester K,Fate of triclosan and triclosan-methyl in sewage treatment plants and surface waters[J].Arch Environ Contam Toxicol,2005,49:9–17。
[8]Ramaswamy BR,Shanmugam G,Velu G,GC–MS analysis and ecotoxicological risk assessment of triclosan,carbamazepine and parabens in Indian rivers,Journal of Hazardous Materials[J]2011,186:1586–1593。
Summary of the invention
The object of the invention is to cannot effectively remove the problems such as the TCS in water body for chloramines disinfection in existing water technology, provide a kind of strengthening chloramines disinfection for water treatment device and treatment process thereof, the present invention is mainly applicable to municipal plumbing and environmental engineering, adopt the method for processor for ultrasonic wave and chloramines coupling, can effectively remove the TCS in water body.
Described strengthening chloramines disinfection is provided with chloramine solution deposit pond, the first recycle pump, the first valve, under meter, the second valve, the 3rd valve, the second recycle pump, the 4th valve, processor for ultrasonic wave for water treatment device;
The entrance of described the first recycle pump is located in chloramine solution deposit pond, the first circulation pump outlet is successively in the first valve and under meter access reaction tank, bottom one side of reaction tank is provided with cooling water intake, the bottom of reaction tank is provided with circulating water outlet, circulating water outlet is successively in the second valve, the second recycle pump and the 4th valve access reaction tank, circulating water outlet is discharged outside reaction tank through the second valve and the 3rd valve successively, and top one side of reaction tank is provided with cooling water outlet; The ultrasonic transducer of processor for ultrasonic wave stretches in the solution to be measured in reaction tank.
The frequency of described processor for ultrasonic wave can be 20kHz, and described ultrasonic transducer stretches into the liquid level of solution 2～5cm to be measured in reaction tank, and available ice bath ensures solution-stabilized temperature.
Described strengthening chloramines disinfection, for the method for water treatment, adopts described strengthening chloramines disinfection for water treatment device, and concrete steps are as follows:
In the chloramine solution deposit pond that solution to be measured is housed, add chloramine solution, then the ultrasonic transducer of processor for ultrasonic wave is goed deep into chloramine solution liquid level 2～5cm, maintain the stable temperature of chloramine solution with ice bath; Open processor for ultrasonic wave, can there is ultrasonic cavitation effect and can generate hydroxyl radical free radical (OH) simultaneously in chloramine solution under hyperacoustic effect, thereby except the TCS in anhydrating, complete water treatment.
The present invention adopts ultrasonic and chloramines coupling technique, except ultrasonic wave has certain destruction target substance, the more important thing is that chloramines can comparatively fast be decomposed into hypochlorous acid under hyperacoustic effect, target substance is oxidized to small molecules by hypochlorous acid, make it be easier to be removed by ultrasonic wave, in addition, the palliating degradation degree to target contaminant of ultrasonic wave and chloramines coupling technique is higher, oxidation products is generally the small molecules amount oxygenatedchemicals being easily biodegradable, or carbonic acid gas and water.
The present invention can solve existing water purification technology to cannot effectively removing the problem of micro quantity organic pollutant TCS in water body, has that technique is simple, the time is short, high to target compound degraded salinity, to advantages such as environmental requirement are lower.
Brief description of the drawings
Fig. 1 is the structure composition schematic diagram of strengthening chloramines disinfection of the present invention for water treatment device.
Fig. 2 is the impact of ultrasonic wave on chloramines.
Fig. 3 is the impact that ultrasonic power is removed TCS.
Fig. 4 is the impact that chloramines concentration is removed TCS.
Fig. 5 is the impact that starting point concentration is removed TCS.
Fig. 6 is the impact that pH value is removed TCS.
Fig. 7 is the impact that radical scavenger is removed TCS.
Embodiment
The present invention is further illustrated in connection with accompanying drawing for following examples.
Referring to Fig. 1, described strengthening chloramines disinfection is provided with chloramine solution deposit pond 1, the first recycle pump 2, the first valve 3, under meter 4, the second valve 5, the 3rd valve 6, the second recycle pump 7, the 4th valve 8, processor for ultrasonic wave B for water treatment device embodiment.The entrance of described the first recycle pump 2 is located in chloramine solution deposit pond 1, the outlet of the first recycle pump 2 accesses in reaction tank A through the first valve 3 and under meter 4 successively, bottom one side of reaction tank A is provided with cooling water intake 9, the bottom of reaction tank A is provided with circulating water outlet A1, circulating water outlet A1 accesses in reaction tank A through the second valve 5, the second recycle pump 7 and the 4th valve 8 successively, circulating water outlet A1 discharges outside reaction tank A through the second valve 5 and the 3rd valve 6 successively, and top one side of reaction tank A is provided with cooling water outlet 10; The ultrasonic transducer 11 of processor for ultrasonic wave B stretches in the solution to be measured in reaction tank A.
The frequency of described processor for ultrasonic wave can be 20kHz, and described ultrasonic transducer stretches into the liquid level of solution 2～5cm to be measured in reaction tank A, and available ice bath ensures solution-stabilized temperature.
Described strengthening chloramines disinfection, for the method for water treatment, adopts described strengthening chloramines disinfection for water treatment device, and concrete steps are as follows:
In the chloramine solution deposit pond that solution to be measured is housed, add chloramine solution, then the ultrasonic transducer of processor for ultrasonic wave is goed deep into chloramine solution liquid level 2～5cm, maintain the stable temperature of chloramine solution with ice bath; Open processor for ultrasonic wave, can there is ultrasonic cavitation effect and can generate hydroxyl radical free radical (OH) simultaneously in chloramine solution under hyperacoustic effect, thereby except the TCS in anhydrating, complete water treatment.
Below provide optimum of operation and influence factor:
The impact of 1 ultrasonic wave on Chlorine in Solution amine solubility
In test, get two glasss of 1L pure water, respectively add chloramine solution to 2.65mg/L, wherein one glass of chloramine solution under 600w Ultrasonic Conditions, another glass of static placement, whole process ice bath, the time point determining Chlorine in Solution amine concentration of finally setting.Investigate the impact of ultrasonic wave on Chlorine in Solution amine concentration, the results are shown in Figure 2.As shown in Figure 2, in the time of 30min, 60min, 90min, under Ultrasonic Conditions only lower by 6.8% than static chloramines surplus ratio, 11.3%, 9.8%.The static placement of chloramines 120min Chlorine in Solution amine surplus ratio is 96.6%, and chloramines 120min Chlorine in Solution amine surplus ratio under Ultrasonic Conditions is 86.8%.Both only differ from 9.8%, and result shows that ultrasonic wave is less to Chlorine in Solution amine concentration affects, and chloramines major part under Ultrasonic Conditions is preserved, and also show that chloramines is relatively stable under Ultrasonic Conditions simultaneously.
The impact that 2 ultrasonic powers are removed TCS
In test, getting 1L starting point concentration is the TCS solution of 200 μ g/L, adds the chloramine solution of 3mg/L, regulates processor for ultrasonic wave power, investigates the impact that ultrasonic power is removed TCS, the results are shown in Figure 3.As shown in Figure 3, improve ultrasonic power and can increase the clearance of coupling technique to TCS.In the time that ultrasonic power is 240W, after reaction 120min, the clearance of TCS only has 55.5%, and in the time that ultrasonic power is 360W, 480W, 600W, after reaction 120min, the clearance of TCS rises to 65.7%, 80.2%, 83.5%.Test shows, improving ultrasonic power can increase the clearance of TCS.Due under ul-trasonic irradiation, aqueous solution generation cavitation effect impels water molecules to resolve into hydroxyl radical free radical (OH) and hydrogen atom (H) (Adewuyi Y.G.Sonochemistry:environmental science and engineering applications, Ind.Eng.Chem.Res.2001,40 (22): 4681 – 4715; Adewuyi Y.G.Sonochemistry in environmental remediation.1.Combinative and hybrid sonophotochemical oxidation processes for the treatment of pollutants in water, Environ.Sci.Technol.2005,39 (10): 3409 – 3420), its reaction can be expressed as formula (1).
H
2O→H·+·OH （1）
When ultrasonic power increases, improve the speed of sonolysis water molecules, thereby increased OH concentration in solution and improved the clearance of TCS.TCS degradation curve presents the feature of first order reaction, and parameter is in table 1.
Under table 1 different capacity, combine process degradation TCS curve first order kinetics parameter
3 impacts of chloramines concentration on TCS clearance
In test, getting 1L starting point concentration is the TCS solution of 200 μ g/L, and it is 600w that ultrasonic power is set, and adds a certain amount of chloramine solution, and the impact of the concentration of investigation chloramine solution on TCS clearance, the results are shown in Figure 4.As shown in Figure 4, the clearance of TCS raises and presents the trend that first raises and reduce afterwards with chloramines concentration.When independent ultrasonic degradation TCS, TCS clearance only has 50%.When adding after the chloramine solution of 1.25mg/L, TCS clearance rises to 71%.Increase chloramine solution add concentration to 5mg/L time, the clearance of TCS reaches and is up to 90.8%.That continues increase chloramine solution adds concentration to 10mg/L, and the clearance of TCS is reduced to 80.4%.Test shows: it is bad that ultrasonic wave is removed separately TCS effect, adds a certain amount of chloramine solution and can improve the clearance of TCS, and the clearance of TCS raises and presents the trend that first raises and reduce afterwards with chloramines concentration.Chloramines is relatively stable, is difficult to oxidative degradation TCS.But under hyperacoustic effect, chloramines and ultrasonic wave act synergistically, and have improved significantly the clearance of TCS.This may be due under Ultrasonic Conditions, and the TCS in solution and chloramines generation mechanical vibration have increased TCS and chloramines effective collision number of times, have improved the clearance of TCS.Along with the increase of chloramines concentration, the effective collision number of times of TCS and chloramines also obviously increases, and in the time that chloramines concentration reaches 5mg/L, TCS clearance reaches and is up to 90.8%.But while continuing to increase the concentration of chloramines, Chlorine in Solution amine excessive concentration, to such an extent as under Ultrasonic Conditions between chloramines and chloramines collision frequency increase, but TCS and relative minimizing of chloramines effective collision number of times cause the clearance decline of TCS.
The impact of 4TCS starting point concentration on TCS clearance
In test, choose the TCS solution of the different starting point concentrations of 1L, add the chloramine solution of 3mg/L, at 600w ul-trasonic irradiation, investigate the impact of the different starting point concentrations of TCS on TCS clearance, the results are shown in Figure 5.As shown in Figure 5, when TCS starting point concentration is 108,212,323 and 527 μ g/L, TCS clearance is respectively 95.4%, 83.5%, 74.4% and 62%.Test shows: TCS clearance declines along with the rising of starting point concentration.Visible TCS starting point concentration distich is larger with the removal effect impact of technique.Ultrasonic wave that hence one can see that and chloramines coupling technique can better be removed the TCS of low concentration in water body.Wherein TCS degradation curve presents the feature of first order reaction, and parameter is in table 2.
Under the different starting point concentrations of table 2TCS, combine process degradation TCS curve first order kinetics parameter
The impact of 5pH value on TCS clearance
In test, getting 1L starting point concentration is the TCS solution of 200 μ g/L, and it is 600W that ultrasonic power is set, and adds the chloramine solution of 3mg/L, adjusts pH, investigates the impact of pH on clearance, the results are shown in Figure 6.As shown in Figure 6, TCS clearance raises with pH value.PH value is 6.7 o'clock, and TCS clearance is 72.0%.PH value is 7.2,8.7 and 9.4 o'clock, and TCS clearance is respectively 76.9%, 83.5%, 92.4%.In the time that pH value is 10.7, the concentration that reaction finishes TCS in rear solution is lower than detectability.Test shows: TCS clearance raises with pH value.This may be to generate dichlormaine because chloramines generation acid catalysis effect in the aqueous solution causes chloramines, its reaction can be expressed as formula (2) (3) (4) Valentine R L, Jafvert C T, General Acid Catalysis of Monochloramine Disproportionatlon[J], Environ.Scl.Technol.1088,22,691-696; Vikesland P J, Greyshock A E, Triclosan Reactivity in Chloraminated Waters[J], Environ.Sci.Technol.2006,40,2615-2622).Part chloramines is converted into dichlormaine, and chloramines density loss causes the clearance of TCS to decline.
NH
3Cl
++NH
2Cl→NHCl
2+NH
3+H
+ (3)
NH
2Cl+NH
2Cl→NHCl
2(4)
6 impacts of free ion trapping agent on clearance
In test, getting 1L starting point concentration is the TCS solution of 200 μ g/L, and it is 600w that ultrasonic power is set, and adds the chloramine solution of 3mg/L, with TBA simulation radical scavenger, investigates the impact of radical scavenger on clearance, the results are shown in Figure 7.As shown in Figure 7, TCS degradation rate rises and declines with TBA concentration.Add TBA0.001,0.01,0.05 and when 0.1mol/L, the clearance of TCS is 70.3%, 41.0%, 27.8% and 20.0%.Along with free radical capture agent concentration raises, TCS degradation rate declines on the contrary.Radical scavenger is usually used in confirming that reaction exists free radical reaction, cause chemical degradation rate to decline if add radical scavenger and just show that this reaction process comprises free radical and participates in degraded (Song W, Cruz A A, Rein K, O ' Shea K E, Ultrasonically induced degradation of microcystin-LR and-RR:identification of products, effect of pH, formation and destruction of peroxides[J], Environ.Sci.Technol.2006,40 (12): 3941 – 3946).Test shows have free radical to participate in degraded in coupling process degradation TCS reaction process.
Processor for ultrasonic wave and chloramines coupling technique can effectively be removed TCS in water, processor for ultrasonic wave output rating and the chloramines concentration clearance correlation to TCS.The distich of water intermediate ion intensity has micro-promoter action by technique.Wherein, under neutrallty condition, processor for ultrasonic wave output rating is 600w, and while adding 5mg/L chloramine solution, after operation processor for ultrasonic wave 120min, TCS clearance reaches 90.8%.
Test shows: ultrasonic wave and chloramines coupling have synergistic effect, and TCS is had to good removal effect.
Claims (4)
1. strengthening chloramines disinfection, for a water treatment device, is characterized in that being provided with chloramine solution deposit pond, the first recycle pump, the first valve, under meter, the second valve, the 3rd valve, the second recycle pump, the 4th valve, processor for ultrasonic wave;
The entrance of described the first recycle pump is located in chloramine solution deposit pond, the first circulation pump outlet is successively in the first valve and under meter access reaction tank, bottom one side of reaction tank is provided with cooling water intake, the bottom of reaction tank is provided with circulating water outlet, circulating water outlet is successively in the second valve, the second recycle pump and the 4th valve access reaction tank, circulating water outlet is discharged outside reaction tank through the second valve and the 3rd valve successively, and top one side of reaction tank is provided with cooling water outlet; The ultrasonic transducer of processor for ultrasonic wave stretches in the solution to be measured in reaction tank.
2. a kind of strengthening chloramines disinfection is for water treatment device as claimed in claim 1, and the frequency that it is characterized in that described processor for ultrasonic wave is 20kHz.
3. a kind of strengthening chloramines disinfection, for water treatment device, is characterized in that described ultrasonic transducer stretches into the liquid level of solution 2～5cm to be measured in reaction tank as claimed in claim 1, ensures solution-stabilized temperature with ice bath.
4. strengthen the method for chloramines disinfection for water treatment, it is characterized in that adopting if the described a kind of chloramines disinfection of strengthening arbitrary in claim 1～3 is for water treatment device, concrete steps are as follows:
In the chloramine solution deposit pond that solution to be measured is housed, add chloramine solution, then the ultrasonic transducer of processor for ultrasonic wave is goed deep into chloramine solution liquid level 2～5cm, maintain the stable temperature of chloramine solution with ice bath; Open processor for ultrasonic wave, can there is ultrasonic cavitation effect and can generate hydroxyl radical free radical (OH) simultaneously in chloramine solution under hyperacoustic effect, thereby except the TCS in anhydrating, complete water treatment.
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