CN103880150B - 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 order to reduce disinfection byproduct (DBP) concentration in drinking water disinfection, chloramines is usually used for alternative free chlorine disinfectant
[1]but because chloramines oxidisability is more weak, cause it longer for the oxidization time needed for 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 that is 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 alternative free chlorine disinfectant, but its oxidisability is more weak, is difficult to remove Organic substance in water.Ultrasonic technology is a kind of water technology novel in recent years, at the pollutent Be very effective 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 to remain (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 has other secondary metabolites to generate
[8], thus safely great threat is formed to drinking-water quality, thus, control to be necessary to its removal.
Reference:
[1]Singer,P.C.,Ed,Formation and control of disinfection byproducts indrinking Water[M]American Water Works Association:Denver,CO,1999。
[2]Snyder SA,Wert EC,Lei H,Westerhoff P,Yoon Y,Removal of EDCs andpharmaceuticals in drinking and reuse treatment processes[M].AWWA ResearchFoundation,IWA Publishing,London,2007。
[3]Adolfsson-Erici M,Pettersson M,Parkkonen J.Triclosan,a commonly usedbactericide 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 waterand wastewater[J],Ultrasonics Sonochemistry,2008(15):689–694。
[5]Yao JJ,Gao NY,Li C,Mechanism and kinetics of parathion degradation underultrasonic irradiation[J],Journal of Hazardous Materials,2010(175):138–145。
[6]Mehrdad A,Hashemzadeh R,Ultrasonic degradation of Rhodamine B in thepresence of hydrogen peroxide and some metal oxide[J],UltrasonicsSonochemistry,2010(17):168–172。
[7]Bester K,Fate of triclosan and triclosan-methyl in sewage treatment plantsand surface waters[J].Arch Environ Contam Toxicol,2005,49:9–17。
[8]Ramaswamy BR,Shanmugam G,Velu G,GC–MS analysis and ecotoxicological riskassessment of triclosan,carbamazepine and parabens in Indian rivers,Journal ofHazardous Materials[J]2011,186:1586–1593。
Summary of the invention
The object of the invention is to effectively to remove the problems such as the TCS in water body for chloramines disinfection in existing water technology, there is provided 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 the TCS in water body effectively be removed.
Described strengthening chloramines disinfection is used for water treatment device and 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;
The entrance of described first recycle pump is located in chloramine solution deposit pond, first circulation pump outlet is successively in the first valve and under meter access reaction tank, the side, bottom 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 the side, top 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 is used for the method for water treatment, and adopt described strengthening chloramines disinfection 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 ultrasound cavitation effect and can generate hydroxyl radical free radical (OH) simultaneously in chloramine solution under hyperacoustic effect, thus except the TCS in anhydrating, complete water treatment.
The present invention adopts ultrasonic with chloramines coupling technique, except ultrasonic wave has except certain destruction to target substance, the more important thing is that chloramines comparatively fast can be decomposed into hypochlorous acid under hyperacoustic effect, target substance is oxidized to small molecules by hypochlorous acid, it is made to be easier to be removed by ultrasonic wave, in addition, ultrasonic wave and chloramines coupling technique higher to the palliating degradation degree of target contaminant, oxidation products is generally the small-molecular-weight oxygenatedchemicals be easily biodegradable, or carbonic acid gas and water.
The present invention can solve existing water purification technology to the problem effectively cannot removing 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.
Accompanying drawing explanation
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 chloramine concentrations 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
Following examples will the present invention is further illustrated by reference to the accompanying drawings.
See Fig. 1, described strengthening chloramines disinfection is used for water treatment device embodiment and is provided with chloramine solution deposit pond 1, first recycle pump 2, first valve 3, under meter 4, second valve 5, the 3rd valve 6, second recycle pump 7, the 4th valve 8, processor for ultrasonic wave B.The entrance of described 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, the side, bottom 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, 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 the side, top 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 is used for the method for water treatment, and adopt described strengthening chloramines disinfection 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 ultrasound cavitation effect and can generate hydroxyl radical free radical (OH) simultaneously in chloramine solution under hyperacoustic effect, thus except the TCS in anhydrating, complete water treatment.
Below provide optimum of operation and influence factor:
1 ultrasonic wave is on the impact of Chlorine in Solution amine solubility
Get two glasss of 1L pure water in test, respectively add chloramine solution to 2.65mg/L, wherein one glass of chloramine solution is under 600w Ultrasonic Conditions, another glass of static placement, whole process ice bath, finally in the time point determining Chlorine in Solution amine concentration of setting.Investigate ultrasonic wave to the impact of Chlorine in Solution amine concentration, the results are shown in Figure 2.As shown in Figure 2, when 30min, 60min, 90min, under Ultrasonic Conditions only lower by 6.8% than static chloramines surplus ratio, 11.3%, 9.8%.Chloramines static placement 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 on the impact of Chlorine in Solution amine concentration, and chloramines major part under Ultrasonic Conditions is preserved, and also shows that chloramines is relatively stable under Ultrasonic Conditions simultaneously.
The impact that 2 ultrasonic powers are removed TCS
Get the TCS solution that 1L starting point concentration is 200 μ g/L in test, add the chloramine solution of 3mg/L, regulate processor for ultrasonic wave power, investigate 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.When ultrasonic power is 240W, after reaction 120min, the clearance of TCS only has 55.5%, and when ultrasonic power is 360W, 480W, 600W, after reaction 120min, the clearance of TCS rises to 65.7%, 80.2%, 83.5%.Test shows, improves the clearance that ultrasonic power can increase TCS.Due under ul-trasonic irradiation, aqueous solution generation cavitation effect impels water-molecule dissociation to become 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 hybridsonophotochemical 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, thus add OH concentration in solution and improve the clearance of TCS.TCS degradation curve presents the feature of first order reaction, and parameter is in table 1.
Process degradation TCS curve first order kinetics mathematic(al) parameter is combined under table 1 different capacity
3 chloramine concentrations are on the impact of TCS clearance
Get the TCS solution that 1L starting point concentration is 200 μ g/L in test, arranging ultrasonic power is 600w, adds a certain amount of chloramine solution, and the concentration investigating chloramine solution, on the impact of TCS clearance, the results are shown in Figure 4.As shown in Figure 4, the clearance of TCS raises with chloramine concentrations and presents the trend first raising and reduce afterwards.During independent ultrasonic degradation TCS, TCS clearance only has 50%.When after the chloramine solution adding 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%.Concentration to the clearance of 10mg/L, TCS that adds continuing to increase chloramine solution is reduced to 80.4%.Test shows: it is bad that ultrasonic wave removes separately TCS effect, adds the clearance that a certain amount of chloramine solution can improve TCS, and the clearance of TCS raises with chloramine concentrations and presents the trend first raising and reduce afterwards.Chloramines is relatively stable, is difficult to oxidative degradation TCS.But under hyperacoustic effect, chloramines and ultrasonic wave act synergistically, and considerably improve the clearance of TCS.This may be due under Ultrasonic Conditions, the TCS in solution and chloramines generation mechanical vibration, adds TCS and chloramines effective collision number of times, improves the clearance of TCS.Along with the increase of chloramine concentrations, the effective collision number of times of TCS and chloramines also obviously increases, and when chloramine concentrations reaches 5mg/L, TCS clearance reaches and is up to 90.8%.But when 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 is relative with chloramines effective collision number of times to be reduced, and causes the clearance of TCS to decline.
4TCS starting point concentration is on the impact of TCS clearance
Choose the TCS solution of the different starting point concentration of 1L in test, add the chloramine solution of 3mg/L, at 600w ul-trasonic irradiation, investigate the different starting point concentration of TCS to the impact of 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.The removal effect impact of visible TCS starting point concentration distich technique is larger.It can thus be appreciated that ultrasonic wave and chloramines coupling technique better can remove 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.
Process degradation TCS curve first order kinetics mathematic(al) parameter is combined under the different starting point concentration of table 2TCS
5pH value is on the impact of TCS clearance
Get the TCS solution that 1L starting point concentration is 200 μ g/L in test, arranging ultrasonic power is 600W, adds the chloramine solution of 3mg/L, adjustment solution ph, investigates solution ph to the impact of clearance, the results are shown in Figure 6.As shown in Figure 6, TCS clearance raises with pH value and raises.When pH value is 6.7, TCS clearance is 72.0%.When pH value is 7.2,8.7 and 9.4, TCS clearance is respectively 76.9%, 83.5%, 92.4%.When pH value is 10.7, reaction terminates the concentration of TCS in rear solution lower than detectability.Test shows: TCS clearance raises with pH value and raises.This may be because chloramines generation acid catalysis effect in the aqueous solution causes chloramines to generate dichlormaine, 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 chloramine concentrations declines and 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 free ion trapping agents are on the impact of clearance
Get the TCS solution that 1L starting point concentration is 200 μ g/L in test, arranging ultrasonic power is 600w, adds the chloramine solution of 3mg/L, simulates radical scavenger with TBA, investigates radical scavenger to the impact of clearance, the results are shown in Figure 7.As shown in Figure 7, TCS degradation rate rises with TBA concentration and declines.Add TBA0.001,0.01,0.05 and 0.1mol/L time, 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, if add radical scavenger and cause chemical degradation rate decline just show this reaction process comprise free radical participate 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, formationand 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 remove TCS in water, and processor for ultrasonic wave output rating and chloramine concentrations are to the clearance correlation of TCS.Water ionic strength distich technique has micro-promoter action.Wherein in neutral conditions, processor for ultrasonic wave output rating is 600w, and when adding 5mg/L chloramine solution, after running processor for ultrasonic wave 120min, TCS clearance reaches 90.8%.
Test shows: ultrasonic wave and chloramines coupling have synergistic effect, have good removal effect to TCS.
Claims (4)
1. strengthen chloramines disinfection and be used for a water treatment device, it 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 first recycle pump is located in chloramine solution deposit pond, first circulation pump outlet is successively in the first valve and under meter access reaction tank, the side, bottom 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 the side, top 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 used for water treatment device as claimed in claim 1, it is characterized in that the frequency of described processor for ultrasonic wave is 20kHz.
3. a kind of strengthening chloramines disinfection is used for water treatment device as claimed in claim 1, it is characterized in that described ultrasonic transducer stretches into the liquid level of solution 2 ~ 5cm to be measured in reaction tank, ensures solution-stabilized temperature with ice bath.
4. strengthen the method for chloramines disinfection for water treatment, it is characterized in that adopting if described a kind of chloramines disinfection of strengthening arbitrary in claims 1 to 3 is for water treatment device, concrete steps are as follows:
In the reaction tank that solution to be measured is housed, add chloramine solution, then the ultrasonic transducer of processor for ultrasonic wave is goed deep into reaction soln liquid level 2 ~ 5cm, maintain the stable temperature of reaction soln with ice bath; Open processor for ultrasonic wave, ultrasound cavitation effect can occur the chloramines under hyperacoustic effect in solution can generate hydroxyl radical free radical (OH) simultaneously, thus except the triclosan in anhydrating, completes water treatment.
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