CN102914510B - Device and method for online measurement of dynamic chlorine demand of conditioning water - Google Patents

Device and method for online measurement of dynamic chlorine demand of conditioning water Download PDF

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CN102914510B
CN102914510B CN201210360988.3A CN201210360988A CN102914510B CN 102914510 B CN102914510 B CN 102914510B CN 201210360988 A CN201210360988 A CN 201210360988A CN 102914510 B CN102914510 B CN 102914510B
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chlorine
injector
water
concentration
reaction
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CN102914510A (en
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曲久辉
田川
刘锐平
刘会娟
兰华春
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Research Center for Eco Environmental Sciences of CAS
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Abstract

The invention belongs to the field of water supply treatment and disinfection, and particularly relates to a device and a method for online measurement of dynamic chlorine demand of conditioning water. The technical scheme disclosed by the invention is that the existing four-way stay spectrometer is improved, and an online control unit is added to form an online stay spectrum device. The method comprises the following steps: accurately measuring the concentration of residual effective chlorine of the chlorine and the conditioning water after a period of time of reaction by the online stay spectrum device on line; dividing reaction of the chlorine and the conditioning water into rapid reaction and slow reaction by linear regression fitting of a logarithmic value and reaction time of the residual effective chlorine; building a calculation formula of short-term chlorine demand on the conditioning water at the rapid reaction stage and long-term chlorine demand on the conditioning water at the slow reaction stage; and calculating the dynamic chlorine demand of the conditioning water according to the demand on a residual chlorine value at the tail end of a pipe network and the stay time, thus the pre-stage control of the fed chlorine can be achieved; the economical efficiency and the security of the fed chlorine are achieved, and water supply security is effectively guaranteed.

Description

A kind of on-line determination is processed the Apparatus and method for of hydrodynamic(al) state chlorine demand
Technical field
The invention belongs to Water Disinfection field, particularly a kind of on-line determination is processed the Apparatus and method for of hydrodynamic(al) state chlorine demand.
Background technology
Sterilization is requisite link in drinking water treatment technological process, be last one barrier that ensures drinking water safety, and chlorine or hypochlorite remains the sanitizer that Chinese most water supply plant adopts at present.The primary goal of sterilization is to realize the deactivation of the pathogenic microorganisms such as Escherichia coli, virus, and regrowth and the biomembranous growth of tube wall of controlling microorganism in water delivery process.In order to guarantee the microbial safety of water quality, the throwing amount of sanitizer will guarantee that pipe network tip has certain sanitizer level, otherwise may cause pipe network tip and water,tap microbial safety to be difficult to ensure.While containing higher organism in processing water and during the DBPs precursor such as bromine, sanitizer can react with it generate there is carcinogenic, teratogenesis, the halogenated disinfection by-products of mutagenesis, and Drinking Water in China standard (GB5749-2006) limits 26 kinds of DBPs wherein.In order to guarantee the chemical safety of water quality, the throwing amount of sanitizer will be lower than certain limit, the excessive waste not only causing economically of dosage, and can cause exceeding standard of DBPs, in addition, for part, using chloramines as the water supply plant of secondary sterilization agent, is generally all to add ammonia nitrogen after adding a period of time of chlorine, if add the surplus that chlorine deficiency can cause ammonia nitrogen, add excessive three chloramines etc. that may generate of chlorine and cause secondary pollution.Therefore, the throwing amount of sanitizer is the key factor of maintaining water supply microbial safety and chemical safety.
The method that waterworks adjustment at present adds chlorine dose mainly contains empirical method, according to the water yield, adjusts chlorine dosage, according to clear water reserviors water delivering orifice chlorine content, adjusts chlorine dosage, according to the concentration of pipe network tip effective chlorine, adjusts chlorine dosage, but above several method all exists certain defect.The restriction that empirical method can be subject to artificial subjective factor is larger, tends to cause huge error; The method that changes adjustment chlorine dosage according to the water yield is not considered the impact of variation water quality, and on the dosage of determining unit mass sanitizer, has very large difficulty yet; The method of adjusting chlorine dosage according to the concentration of clear water reserviors water delivering orifice and pipe network tip effective chlorine exists hysteresis quality, is difficult to grasp suitable dosage when the fluctuation of water quality situation is larger.The people such as Cao Deming have proposed chlorination system (number of patent application: CN201020682570.0) as required, its main technical schemes is at chlorination place, to be provided with ammonia nitrogen on-line monitoring instrument, thereby rapid feedback and the adjusting that chlorine residue on-line monitoring instrument is realized chlorine demand established in the position that is 4-6 minute at the rear hydraulic detention time of chlorination point.But the method still belongs to and lag behind regulating, in the abnormal big ups and downs of water quality and limit by technology to be difficult to take to regulate measure fast in the situation that, can cause water supply situation not up to standard.In addition, the method only considered can with chlorine in a short time (4-6 minute) react and consume the material of chlorine, thereby and do not have to consider to consume the material of chlorine with chlorine slow reaction, for the water factory of the remote transmission & distribution of needs, still there is risk in this.Therefore, exploitation can be carried out front end adjusting, the short-term chlorine demand of the water of computing simultaneously and the dosage control technology of long-term chlorine demand according to processing water water quality situation, is in current Research And Engineering application, to need the difficulties of solution badly.
Residence spectrum technology be a kind of can realization response thing between rapid mixing measure its technology of concentration change in a short time.First residence spectrum equipment is the research (Biochem.J.Vol.91 based on Gibson and Milnes, 161 (1964)), afterwards at Alan Queen(patent No. US4399101), the Christopher Bull(patent No.: US5098186) etc. realized complete rapid mixing under people's updating, the controllable adjustment of reaction tank capacity, the functions such as computer linking automation control, according to the people's such as Echigo and Minear profit research (Environ.Sci. & Technol.Vol.53 (2006)), the position of reacting with chlorine in the natural organic matter in water body can be divided into rapid reaction position and slow reaction position, therefore short-term chlorine demand and the long-term chlorine demand for residence spectrum technology mensuration processing water provides theoretical foundation.
The present invention utilizes online residence spectrum equipment to carry out chlorine and processes the reaction between water, accurately chlorine detection and the consumption of processing water in a period of time, and draw and process the speed that can consume chlorine with the amount that need to consume chlorine of chlorine rapid reaction component and the position of slow reaction in water by certain dynamics the Fitting Calculation, thereby the chlorine demand of computing water, guarantees safety, economy, stable water supply fast.
Summary of the invention
One of object of the present invention is to provide a kind of equipment that can realize on-line determination processing hydrodynamic(al) state chlorine demand.
Two of object of the present invention is to provide a kind of method that on-line determination is processed hydrodynamic(al) state chlorine demand, to can on-line determination processing short-term chlorine demand and the long-term chlorine demand of water, thereby for definite theoretical foundation that provides of chlorine dose is provided to water treatment, and when water quality generation larger fluctuation, can judge in advance and adjust the dosage of chlorine.
Technical scheme of the present invention is, existing four-way road residence spectrum instrument is transformed, and is increased in line traffic control unit, forms so-called online residence spectrum equipment.Utilize described online residence spectrum equipment on-line Accurate Measurement chlorine and processing water after one period of reaction time of experience, to remain the concentration of effective chlorine, and by the logarithm value of concentration of residue effective chlorine and the linear regression fit in reaction time are divided into rapid reaction and slow reaction by chlorine with reacting of water of processing, and set up accordingly the computing formula of the short-term chlorine demand of quick phase process water and the long-term chlorine demand of slow reaction phase process water, and according to the requirement of pipe network tip place chlorine content and residence Time Calculation are added to the dynamic chlorine demand that chlorine point is processed water, thereby can realize the control in early stage that adds chlorine, realization adds economy and the safety of chlorine, effective guarantee water supply security.
The equipment that on-line determination of the present invention is processed hydrodynamic(al) state chlorine demand is residence spectrum unit and the On-line Control unit that online residence spectrum equipment comprises four-way road; Utilize the residence spectrum unit Accurate Measurement chlorine on described four-way road to react the concentration of the effective chlorine after a period of time with processing water, and the described On-line Control unit of utilization is realized in real time, automatic, on-line determination processing hydrodynamic(al) state chlorine demand.
(structure is copied existing residence spectrum instrument: stopped-flow spectrometer in the residence spectrum unit on described four-way road, SX20, Applied physics Co., UK) comprise four-way road injector, rapid mixing container, reaction tank, with the pulling flow type of transfer valve, stop controller, uviol lamp, monochromator and UV-detector; Described On-line Control unit comprises COD mn(permanganate index) on-line monitoring instrument, T-valve, computing machine and the automation controller being connected with the residence spectrum unit on described four-way road.
The structure of described four-way road injector is copied existing instrument: comprise that four with the pulling flow type injector of transfer valve, each pulling flow type injector with transfer valve comprises a sample introduction end and a reactive end.
The described pulling flow type with transfer valve stops the structure of controller, comprises a reactive end and a waste liquid end.
Described four with the reactive end of the first path injector in the pulling flow type injector of transfer valve, the reactive end of the reactive end of alternate path injector and four-way road injector by pipeline, be connected with one end of described rapid mixing container respectively; The other end of described rapid mixing container is connected with one end of described reaction tank by pipeline, and the reactive end that the other end of described reaction tank stops controller by pipeline and the described pulling flow type with transfer valve is respectively connected with described four reactive end with the three-way injector in the pulling flow type injector of transfer valve; Described monochromator is installed above described reaction tank, described uviol lamp is installed above described monochromator; Described UV-detector is installed below described reaction tank.
The waste liquid end that the described pulling flow type with transfer valve stops controller is provided with waste liquid vent pipe; The sample introduction end of described three-way injector is connected with the 3rd pure water pot with developer hold-up vessel respectively by the sample channel with the 3rd T-valve.
The sample introduction end of the first described path injector is connected with chlorine storing solution hold-up vessel and the first pure water pot respectively by the sample channel with the first T-valve; The sample introduction end of described alternate path injector is connected with the second pure water pot and processing water store tank respectively by the sample channel with the second T-valve; Described processing water store tank is by sample channel and described COD mnon-line monitoring instrument is connected, and processing water water intaking valve is installed on this sample channel; Described COD mnon-line monitoring instrument is connected with the sampling water spot with processing water water inlet pipe by sample channel; The sample introduction end of described four-way road injector is connected with the 4th pure water pot and buffer solution hold-up vessel respectively by the sample channel with the 4th T-valve.
The first described path injector, described alternate path injector, described three-way injector, described four-way road injector, described stop controller, described uviol lamp, described monochromator, described UV-detector, described COD mnon-line monitoring instrument, the first described T-valve, the second described T-valve, the 3rd described T-valve are all connected with automation controller by signal wire with the 4th described T-valve; Described computing machine by signal wire respectively with described automation controller, described online COD mnmonitor and described UV-detector are connected.
The volume of described reaction tank can be adjusted automatically, and equal total sample size in this moment, be that sample introduction solution is just filled with reaction tank, after described four volumes with the pulling flow type injector of transfer valve have all arranged, the max cap. that the max cap. of described reaction tank should be set to described reaction tank is four described capacity sums with the pulling flow type injector of transfer valve.The volume of described reaction tank stops controller by the described pulling flow type with transfer valve and controls.
Described four identical with the volume of described alternate path injector with the first described path injector in the pulling flow type injector of transfer valve, be preferably 80 ~ 120 μ L.
Described four identical with the volume of described four-way road injector with the described three-way injector in the pulling flow type injector of transfer valve, be preferably 70 ~ 100 μ L.
The equipment that utilizes on-line determination of the present invention to process hydrodynamic(al) state chlorine demand carries out on-line determination to be processed the square ratio juris of hydrodynamic(al) state chlorine demand and is: according to processing the different of material in water and chlorine reaction velocity, the material in processing water can be divided into rapid reaction material and slow reaction material.Rapid reaction material mainly reacts with chlorine in the initial reaction stage stage and is consumed rapidly, its corresponding chlorine demand is called as short-term chlorine demand in the present invention, this initial stage is called as the rapid reaction stage, and its reaction can be regarded the second order reaction kinetics relation meeting about cl concn and rapid reaction material as; And slow reaction material mainly in reaction the long-term stage react with chlorine and consumed slowly, its corresponding chlorine demand is called as long-term chlorine demand herein, this medium-term and long-term stage is called as the slow reaction stage, due in processing the disinfecting process of water, the stoichiometry that the throwing amount of chlorine is compared slow reaction material in processing water is not enough far away, therefore the reaction in this slow reaction stage can be regarded the pseudo first order reaction kinetics relation meeting about cl concn as, that is:
dC/dt=-kC (1)
Wherein, C is the concentration of effective chlorine, the mg/L of unit;
K is first order reaction kinetics constant, and unit is h -1;
After integration, known ln (C) is linear with reaction time t, and linear fit can obtain the value of its first order reaction kinetic constant k, is that equal-volume mixes again because of solutions of chlorine with processing water, and after mixing, the concentration of chlorine and processing water is all diluted half for original concentration.Calculate accordingly the equation changing with reaction time t in the concentration C of slow reaction stage effective chlorine, that is:
1/2C=(1/2C 0-1/2D)exp(-k(t-t 0)) (2)
Be reduced to: C=(C 0-D) exp (k (t-t 0)) (3)
C 0 = C exp ( - k × ( t - t 0 ) ) + D - - - ( 4 )
Wherein, the same formula of the meaning of C and k and unit (1);
C 0be that on-line determination is processed hydrodynamic(al) state chlorine demand, unit is mg/L;
D is short-term chlorine demand, and unit is mg/L;
T is the T.T. contacting with processing water with slow reaction stage chlorine in the rapid reaction stage, and unit is h;
T 0the time that rapid reaction stage chlorine contacts with processing water, unit is h.
By following (2.3) step the Fitting Calculation, can obtain D, k, t 0value, and obtain and process water and arrive disinfecting time t that pipe network tip place needs and the concentration C of this required effective chlorine constantly according to the technology characteristics of water factory, can retrodict out and add the dynamic chlorine demand C of chlorine point 0.
The method that the equipment that utilizes on-line determination of the present invention to process hydrodynamic(al) state chlorine demand carries out on-line determination processing hydrodynamic(al) state chlorine demand comprises the following steps:
(1), preparation stock solution
In chlorine storing solution hold-up vessel, fill it up with the aqueous sodium hypochlorite solution that concentration is 10mg/L, in developer hold-up vessel, fill it up with the N that the concentration as developer is 2mM, N-diethyl-1,4-phenylenediamine (DPD aqueous solution) aqueous solution or 2,2-connection nitrogen-bis--(3-ethyl-benzothiazole-6-sulfonic acid)-di-ammonium salts (ABTS aqueous solution) aqueous solution; When usining DPD aqueous solution during as developer, in buffer solution hold-up vessel, fill it up with the phosphate buffer solution as the 2mM pH6.5 of buffer solution, when usining ABTS aqueous solution during as developer, in buffer solution hold-up vessel, fill it up with the inorganic acid aqueous solution (for example hydrochloric acid solution of 0.01mol/L) that the pH as buffer solution is 1.8 ~ 2.3; Open and process water water intaking valve, make to process water from sample point by processing water water inlet pipe the COD that flows through mnon-line monitoring instrument joins to be processed in water store tank and fills it up with; Utilize COD mnon-line monitoring instrument is measured the COD that processes water mnvalue;
(2), on-line determination is processed hydrodynamic(al) state chlorine demand
(2.1) drawing standard curve
(2.11) four of four-way road injector are set with the first path injector in the pulling flow type injector of transfer valve identical with the volume of alternate path injector (being preferably 80 ~ 120 μ L), three-way injector identical with the volume of four-way road injector (being preferably 70 ~ 100 μ L), by control, be arranged on four described transfer valves with the pulling flow type injector of transfer valve, the stock solution of pure water and step (1) preparation is entered respectively in four pulling flow type injectors with transfer valve by preset proportion, wherein, adjust the sample introduction ratio of chlorine storing solution and pure water, while making aqueous sodium hypochlorite solution in step (1) chlorine storing solution hold-up vessel in entering the first described path injector, in aqueous sodium hypochlorite solution, the concentration of effective chlorine is respectively six points in 0.1 ~ 3mg/L, and in aqueous sodium hypochlorite solution the concentration of effective chlorine be 0mg/L(in contrast), in described alternate path injector, add pure water, adjust the sample introduction ratio of developer (DPD aqueous solution or ABTS aqueous solution) and pure water, while making developer (DPD aqueous solution or ABTS aqueous solution) in step (1) developer hold-up vessel in entering described three-way injector, the concentration of developer is calculated according to sampling volume, and making the developer in reaction tank is 8:1 ~ 15:1 with the ratio of the volumetric molar concentration of effective chlorine, while making buffer solution in step (1) buffer solution hold-up vessel in entering described four-way road injector, the concentration of the buffer solution adding is determined according to the kind of described developer, when developer is DPD aqueous solution, adjustment is as the sample introduction ratio of phosphate buffer solution and the pure water of the 2mM pH6.5 of buffer solution, the concentration of buffer solution in described four-way road injector is calculated according to sampling volume, making developer in reaction tank and the molar concentration rate of buffer solution is 1:1, when developer is ABTS aqueous solution, the inorganic acid aqueous solution that adjustment is 1.8 ~ 2.3 as the pH of buffer solution and the sample introduction ratio of pure water, the concentration of damping fluid in described four-way road injector is calculated according to sampling volume, the pH that makes the mixed liquor in reaction tank is 3,
(2.12) by controlling four described transfer valves with the pulling flow type injector of transfer valve, the sample introduction end of the pulling flow type injector with transfer valve described in four is connected with sample channel respectively, makes the liquid in four path injectors in step (2.11) enter reaction tank, sample introduction is sequentially: the first described path injector and described alternate path injector be sample introduction first simultaneously, after being mixed by rapid mixing container, aqueous sodium hypochlorite solution and pure water enter in reaction tank, after 0.5 ~ 2 second, described three-way injector and described four-way road injector while sample introduction, make developer directly enter reaction tank, buffer solution enters reaction tank by rapid mixing container, chlorine reacts in buffer solution with developer and generates the coloured product of tool, and be respectively six points in 0.1 ~ 3mg/L by the concentration that ultraviolet spectrum is measured respectively selected effective chlorine, and in aqueous sodium hypochlorite solution the concentration of effective chlorine be 0mg/L(in contrast) intensity of the ultraviolet absorptivity of the coloured product of gained tool, concrete ultraviolet determination wavelength will be determined according to developer, when developer is DPD aqueous solution, ultraviolet determination wavelength is 515nm, when developer is ABTS aqueous solution, ultraviolet determination wavelength is 728nm, described ultraviolet determination wavelength regulates by monochromator,
(2.13) using the intensity A of the corresponding ultraviolet absorptivity while being respectively six points in 0.1 ~ 3mg/L and 0mg/L of the concentration of effective chlorine in the aqueous sodium hypochlorite solution that step (2.12) measures as transverse axis, the concentration C of the effective chlorine in the liquor natrii hypochloritis of usining in corresponding the first described path injector is as longitudinal axis drawing standard curve, the line linearity of going forward side by side returns, and sets up the expression formula of typical curve of the cl concn of the effective chlorine in ultraviolet absorptivity and described the first path injector:
C=a×A+b (5)
Wherein, the meaning of C is identical with formula (1), is the concentration of the effective chlorine as the longitudinal axis, the mg/L of unit;
A is the intensity as the ultraviolet absorptivity of transverse axis, and unit is cm -1;
A is the slope of typical curve, and unit is cm * mg/L;
B is the transversal distance of typical curve, and unit is mg/L;
(2.2) measure the concentration that remains effective chlorine after chlorine reacts with actual water body
(2.21) by controlling four described transfer valves with the pulling flow type injector of transfer valve, the sample introduction end of the pulling flow type injector with transfer valve described in four is connected respectively with sample channel; Utilize COD mnon-line monitoring instrument is measured the COD that processes water mnvalue; If COD mnvalue, between 2 ~ 6mg/L, makes to process water and directly enters in described alternate path injector, if COD mnvalue >6mg/L,, by the second T-valve adjustment processing water on the sample channel of control alternate path injector and the sample introduction ratio of pure water inlet, making the concentration of the processing water in the alternate path injector described in entering is 2 ~ 6mg/L; If COD mnvalue <2mg/L, is concentrated into 2 ~ 6mg/L by processing water rotary evaporation, and is joined in described alternate path injector; By controlling the first T-valve on the sample channel of the first path injector, adjust the sample introduction ratio of chlorine storing solution and pure water, while making aqueous sodium hypochlorite solution in step (1) chlorine storing solution hold-up vessel in entering the first described path injector, the concentration of effective chlorine and COD in aqueous sodium hypochlorite solution mnbe worth identical; Enter the control method of solution in described three-way injector and described four-way road injector and each path injector and divided by the concentration and the COD that above enter effective chlorine in the first described path injector mnbe worth identical outside, other condition is all identical with (2.11) in step (2.1);
(2.22) by controlling four described transfer valves with the pulling flow type injector of transfer valve, the sample introduction end of the pulling flow type injector with transfer valve described in four is connected with sample channel respectively, makes the liquid in four path injectors in step (2.21) enter reaction tank, sample introduction order is identical with (2.12) in step (2.1), the first path injector described in and described alternate path injector be sample introduction first simultaneously, make aqueous sodium hypochlorite solution and process after water mixes by rapid mixing container to enter in reaction tank and start to react, chlorine and processing water are after certain reaction time (t), described three-way injector and described four-way road injector while sample introduction, make developer directly enter reaction tank, buffer solution enters reaction tank by rapid mixing container, chlorine reacts in buffer solution with developer and generates the coloured product of tool, and by the intensity of its ultraviolet absorptivity of ultraviolet spectroscopy, concrete ultraviolet determination wavelength will be determined according to developer, and when developer is DPD aqueous solution, ultraviolet determination wavelength is 515nm, and when developer is ABTS aqueous solution, ultraviolet determination wavelength is 728nm, described ultraviolet determination wavelength regulates by monochromator, chlorine is set at least 10 reaction time points within the scope of 0.1s ~ 15min with the reaction time (t) of processing water,
(2.23) the expression formula C=a * A+b of the described typical curve that (2.13) in the intensity A substitution step (2.1) of the ultraviolet absorptivity of (2.22) at least 10 reaction time points of step being measured are set up, calculates chlorine and the concentration C of processing water corresponding effective chlorine after at least 10 reaction time points of experience;
(2.3) the Fitting Calculation is processed the dynamic chlorine demand of water
(2.31) using chlorine that step (2.22) arranges with at least 10 reaction time points (t) in reaction time of processing water as transverse axis, using step (2.23) chlorine with process water concentration of corresponding residue effective chlorine after at least 10 reaction time points of experience and as the longitudinal axis, draw ln (C) ~ t and scheme;
(2.32) in ln (C) ~ t figure step (2.31) being drawn, at least 10 reaction time points (t), three the longest points of reaction time start to carry out linear regression fit, as the related coefficient (R of fitting result 2) lower than 0.99, repeating step (2.22), increase chlorine and the time point of processing the reaction time (t) of water, make the reaction time of the time point of increase be greater than the maximal value in original at least 10 reaction time point, then repeating step (2.31), and middle three the longest points of reaction time of at least 10 reaction time points (t) start to carry out linear regression fit in ln (the C) ~ t figure again step (2.31) being drawn, until the related coefficient (R of its fitting result 2) be greater than 0.99;
(2.33) as the related coefficient (R of the fitting result of step (2.32) 2) be greater than 0.99, from least 10 reaction time points (t), choose a longest point of reaction time in a point except the point that step (2.32) has been chosen, be increased in the point that step (2.32) chosen and proceed linear regression fit; As related coefficient (R 2) be still greater than 0.99, from at least 10 reaction time points (t), choose a longest point of reaction time in a point except the point that step (2.32) and this step have been chosen, be increased in this step point that matching has been chosen last time and proceed linear regression fit; As related coefficient (R 2) be still greater than 0.99, continue this operation;
(2.34) as the related coefficient (R of the linear regression fit of step (2.33) 2) be less than 0.99, end step (2.33); Finally meet the related coefficient (R of linear regression fit result 2) be greater than 0.99 the point of choosing increasing by approximate, thought that the rapid reaction stage finishes the point starting with the slow reaction stage from least 10 reaction time points (t), the reaction time of this point, by the approximate time of thinking the rapid reaction stage that chlorine consumes, is set as t 0, and the consumption of this chlorine is by the approximate short-term chlorine demand of thinking to process water, is set as D; And last related coefficient (R 2) be greater than 0.99 matching k value by the approximate kinetic constant of thinking slow reaction stage pseudo first order reaction;
(2.35) according to the technology characteristics of water factory, obtain and process water and arrive disinfecting time t that pipe network tip place needs and the concentration C of this required effective chlorine constantly, and by D, the k, the t that obtain in step (2.34) 0the value above-mentioned formula of substitution (4), calculates and adds the dynamic chlorine demand C that chlorine point is processed water 0; Thereby can realize processing the more accurate estimation of hydrodynamic(al) state chlorine demand.When processing water dilutes or is concentrated, calculate in proportion the chlorine demand of the front water sample of dilution.When practical operation, on the basis of the chlorine demand calculating, additionally add 20% to improve the margin of safety more, so that the concentration of pipe network tip effective chlorine remains on 0.05mg/L ~ 1mg/L, thereby meet the requirement of < < drinking water sanitary standard > > (GB5749-2006) to the chlorine residue of potable water network tip, be unlikely to again the excessive sanitizer that adds.
Equipment and method that on-line determination of the present invention is processed hydrodynamic(al) state chlorine demand have following technique effect:
(1) before adding chlorine, measure the chlorine demand of processing water, can realize front-end control and adjusting, when big ups and downs appear in water quality, can judge in advance and regulate.
(2) can measure the dynamic chlorine demand of processing water, under the concentration prerequisite that guarantees effective chlorine after certain reaction time, process the chlorine demand of water;
(3) can measure simultaneously and process water short-term chlorine demand and long-term chlorine demand, can serve different sterilization strategies;
(4) after repeatedly measuring, can obtain about processing a large amount of water quality informations of water, in follow-up mensuration, can simplify mensuration program, reduce the time point that chlorine consumes; And can utilize historical data to carry out reasonable prediction to processing the variation water quality of water, before water quality big ups and downs, carry out emergent preparation;
(5) on-line determination, robotization is controlled, and reduces personal error;
(6) do not need original water treatment building to carry out large-scale redevelopment, only need to establish a sampled point and carry out sampling and measuring, cost is low, uses simple to operate.
Accompanying drawing explanation
Fig. 1. on-line determination of the present invention is processed the equipment schematic diagram of hydrodynamic(al) state chlorine demand.
Reference numeral
1. the first path injector 2. alternate path injector 3. three-way injectors
4. four-way road injector 5. rapid mixing container 6. reaction tanks
7. the pulling flow type with transfer valve stops controller 8. uviol lamps
9. monochromator 10. UV-detector 11. chlorine storing solution hold-up vessels
The pure water pot 14. of 12. first pure water pot 13. second is processed water store tank
15.COD mnon-line monitoring instrument 16. is processed water water inlet pipe 17. the 4th pure water pot
18. buffer solution hold-up vessel 19. waste liquid vent pipe 20. developer hold-up vessels
21. the 3rd pure water pot 22. first T-valve 23. second T-valve
24. the 3rd T-valve 25. the 4th T-valve 26. are processed water water intaking valve
27. automation controller 28. computing machines
Embodiment
Embodiment 1
The present embodiment is usingd certain waterworks settling basin water outlet as research object, and the flow of inlet water of water supply plant is 6200m 3/ h, the COD of settling basin water outlet mnvalue is 2mg/L, and ammonia nitrogen is 0.17mg/L, and the pipe network tip residence time is 24 hours, and the concentration requirement of pipe network tip effective chlorine is 0.05mg/L.
Utilize the equipment of on-line determination processing hydrodynamic(al) state chlorine demand as shown in Figure 1 to carry out on-line determination processing hydrodynamic(al) state chlorine demand.The equipment of described on-line determination processing hydrodynamic(al) state chlorine demand comprises residence spectrum unit and the On-line Control unit on four-way road.
(structure is copied existing residence spectrum instrument: stopped-flow spectrometer in the residence spectrum unit on described four-way road, SX20, Applied physics Co., UK) comprise that a four-way road injector, a rapid mixing container, a reaction tank, a pulling flow type with transfer valve stop controller, a uviol lamp, a monochromator and a UV-detector; Described On-line Control unit comprises COD mn(permanganate index) on-line monitoring instrument, four T-valve, computing machine and the automation controller being connected with the residence spectrum unit on described four-way road.
Described four-way road injector comprises that four with the pulling flow type injector of transfer valve, and each pulling flow type injector with transfer valve comprises a sample introduction end and a reactive end, and described sample introduction end is connected by pipeline respectively with hold-up vessel and pure water pot; The transfer valve of the described pulling flow type injector with transfer valve, sample introduction end or the reactive end that can guarantee the pulling flow type injector with transfer valve described in four only have one end to be connected with pipeline, be that sample introduction end is when be connected with sample channel, reactive end is closed, and reactive end is when be connected with pipeline, sample introduction end is closed; Wherein, the described reactive end of the pulling flow type injector with transfer valve described in 3 is connected by pipeline with reaction tank with rapid mixing container; First sample channel is connected with the sample introduction end of the described pulling flow type injector with transfer valve, and sample is entered in sample channel, and afterwards, sample enters rapid mixing container and the reaction tank being connected with reactive end through sample channel; Transfer valve is by computer control.Pulling flow type syringe is used for realizing sample and enters and flow out pipeline.
The described pulling flow type with transfer valve stops the structure of controller, comprises a reactive end and a waste liquid end; First the reactive end that the described pulling flow type with transfer valve stops controller is connected with reaction tank by pipeline, making reacted waste liquid enter the described pulling flow type with transfer valve stops in controller, the described pulling flow type with transfer valve stops controller and can control the solvent in described reaction tank simultaneously, afterwards, reacted waste liquid stops through the pulling flow type with transfer valve with described the waste liquid vent pipe that the waste liquid end of controller is connected and discharges.
Described four with the reactive end of the first path injector 1 in the pulling flow type injector of transfer valve, the reactive end of the reactive end of alternate path injector 2 and four-way road injector 4 by pipeline, be connected with one end of described rapid mixing container 5 respectively; The other end of described rapid mixing container is connected with one end of described reaction tank 6 by pipeline, and the reactive end that the other end of described reaction tank 6 stops controller 7 by pipeline and the described pulling flow type with transfer valve is respectively connected with described four reactive end with the three-way injector 3 in the pulling flow type injector of transfer valve; Described monochromator 9 is installed above described reaction tank, described uviol lamp 8 is installed above described monochromator 9; Described UV-detector 10 is installed below described reaction tank.
The waste liquid end that the described pulling flow type with transfer valve stops controller 7 is provided with waste liquid vent pipe 19; The sample introduction end of described three-way injector 3 is connected with the 3rd pure water pot 21 with developer hold-up vessel 20 respectively by the sample channel with the 3rd T-valve 24, and wherein the 3rd T-valve 24 is in order to control the flow of developer and pure water.
The sample introduction end of the first described path injector 1 is connected with the pure water pot 12 of chlorine storing solution hold-up vessel 11 and first respectively by the sample channel with the first T-valve 22, and wherein the first T-valve 22 is in order to control the flow of chlorine storing solution and pure water; The sample introduction end of described alternate path injector 2 is connected with the second pure water pot 13 and processing water store tank 14 with dilution respectively by the sample channel with the second T-valve 23, and wherein the second T-valve 23 is in order to control the flow of processing water and pure water; Described processing water store tank 14 is by sample channel and described COD mnon-line monitoring instrument 15 is connected, and processing water water intaking valve 26, described COD are installed on this sample channel mnon-line monitoring instrument 15 is connected with the sampling water spot with processing water water inlet pipe 16 by sample channel; The sample introduction end of described four-way road injector 4 is connected with the 4th pure water pot 17 and buffer solution hold-up vessel 18 with dilution respectively by the sample channel with the 4th T-valve 25, and wherein the 4th T-valve 25 is in order to control the flow of buffer solution and pure water.
The first described path injector, described alternate path injector, described three-way injector, described four-way road injector, described stop controller, described uviol lamp, described monochromator, described UV-detector, described COD mnon-line monitoring instrument, the first described T-valve, the second described T-valve, the 3rd described T-valve are all connected with automation controller 27 by signal wire with the 4th described T-valve; Described computing machine 28 by signal wire respectively with described automation controller 27, described online COD mnmonitor and described UV-detector are connected.By computer realization to described the first path injector, described alternate path injector, described three-way injector, described four-way road injector, described stop controller, described uviol lamp, described monochromator, described UV-detector, described COD mnon-line monitoring instrument, described the first T-valve, described the second T-valve, described the 3rd T-valve and the 4th described T-valve carry out robotization control, and described COD mnthe signal feedback of on-line monitoring instrument and described UV-detector is to computing machine.
The max cap. of described reaction tank is set to four described capacity sums with the pulling flow type injector of transfer valve.
Described four identical with the volume of described alternate path injector with the first described path injector in the pulling flow type injector of transfer valve, be 80 ~ 120 μ L.
Described four identical with the volume of described four-way road injector with the described three-way injector in the pulling flow type injector of transfer valve, be 70 ~ 100 μ L.
The equipment that utilizes above-mentioned on-line determination to process hydrodynamic(al) state chlorine demand carries out the method that on-line determination is processed hydrodynamic(al) state chlorine demand: use DPD aqueous solution as developer, the phosphate buffer solution of pH6.5 is as buffer solution, and it is 515nm that UV-detector is measured wavelength.
(1), preparation stock solution
In chlorine storing solution hold-up vessel 11, fill it up with the aqueous sodium hypochlorite solution that concentration is 10mg/L, in developer hold-up vessel 20, fill it up with the DPD aqueous solution that the concentration as developer is 2mM, in buffer solution hold-up vessel 18, fill it up with the phosphate buffer solution as the 2mM pH6.5 of buffer solution; Open and process water water intaking valve 26, make to process water from sample point by processing water water inlet pipe 16 COD that flows through mnon-line monitoring instrument 15 joins to be processed in water store tank 14 and fills it up with; Utilize COD mnon-line monitoring instrument is measured the COD that processes water mnvalue;
When above chlorine storing solution hold-up vessel 11, developer hold-up vessel 20, buffer solution hold-up vessel 18 and the volume of processing the liquid in water store tank 14, think during lower than tank body volume 1/3 and surpass warning line, need to repeat above corresponding steps corresponding hold-up vessel is filled it up with.
(2), on-line determination is processed hydrodynamic(al) state chlorine demand
(2.1) drawing standard curve
(2.11) four of four-way road injector are set identical with the volume of alternate path injector 2 with the first path injector 1 in the pulling flow type injector of transfer valve, be 80 μ L, three-way injector 3 is set identical with the volume of four-way road injector 4, is 70 μ L, by control, be arranged on four described transfer valves with the pulling flow type injector of transfer valve, the sample introduction end of the pulling flow type injector with transfer valve described in four is connected with sample channel respectively, and by the T-valve on the sample channel of four path injectors of control, control the aqueous sodium hypochlorite solution in chlorine storing solution hold-up vessel 11, developer in developer hold-up vessel 20, buffer solution in buffer solution hold-up vessel 18, process the processing water in water store tank 14, pure water in the first pure water pot 12, pure water in the second pure water pot 13, the ratio of pure water in pure water in the 3rd pure water pot 21 and the 4th pure water pot 17 in reaction tank 6, the stock solution of pure water and step (1) preparation is entered respectively in four pulling flow type injectors with transfer valve by preset proportion, wherein, adjust the sample introduction ratio of chlorine storing solution and pure water, while making aqueous sodium hypochlorite solution in step (1) chlorine storing solution hold-up vessel 11 in entering the first described path injector, in aqueous sodium hypochlorite solution, the concentration of effective chlorine is respectively 0mg/L(in contrast), 0.1mg/L, 0.2mg/L, 0.5mg/L, 1mg/L, 2mg/L and 3mg/L, in described alternate path injector, add pure water, adjust the sample introduction ratio of developer DPD aqueous solution and pure water, while making developer DPD aqueous solution in step (1) developer hold-up vessel 20 in entering described three-way injector, the concentration of developer is calculated according to sampling volume, and making the DPD aqueous solution in reaction tank 6 is 8:1 with the ratio of the volumetric molar concentration of effective chlorine, while making buffer solution in step (1) buffer solution hold-up vessel 18 in entering described four-way road injector, adjustment is as the sample introduction ratio of phosphate buffer solution and the pure water of the 2mM pH6.5 of buffer solution, the concentration of buffer solution in described four-way road injector is calculated according to sampling volume, and making DPD aqueous solution in reaction tank 6 and the molar concentration rate of buffer solution is 1:1,
(2.12) by controlling four described transfer valves with the pulling flow type injector of transfer valve, the sample introduction end of the pulling flow type injector with transfer valve described in four is connected with sample channel respectively, makes the liquid in four path injectors in step (2.11) enter reaction tank, sample introduction is sequentially: the first described path injector and described alternate path injector be sample introduction first simultaneously, after being mixed by rapid mixing container, aqueous sodium hypochlorite solution and pure water enter in reaction tank, after 0.5 second, described three-way injector and described four-way road injector while sample introduction, make DPD aqueous solution directly enter reaction tank, the buffer solution of pH6.5 enters reaction tank by rapid mixing container, chlorine reacts and generates the coloured product of tool with DPD aqueous solution in buffer solution, and the concentration of measuring respectively selected effective chlorine under 515nm wavelength is respectively 0mg/L(in contrast), 0.1mg/L, 0.2mg/L, 0.5mg/L, 1mg/L, the intensity A of the ultraviolet absorptivity of 2mg/L and the coloured product of 3mg/L gained tool, described ultraviolet determination wavelength regulates by monochromator,
(2.13) usining the concentration of effective chlorine in the aqueous sodium hypochlorite solution that step (2.12) measures is respectively 0mg/L(in contrast), when 0.1mg/L, 0.2mg/L, 0.5mg/L, 1mg/L, 2mg/L and 3mg/L the intensity A of corresponding ultraviolet absorptivity as transverse axis, the concentration C of the effective chlorine in the liquor natrii hypochloritis of usining in corresponding the first described path injector is as longitudinal axis drawing standard curve, the line linearity of going forward side by side returns, and sets up the expression formula of typical curve of the cl concn of the effective chlorine in ultraviolet absorptivity and described the first path injector:
C=a×A+b (5)
Wherein, C is the concentration as the effective chlorine of the longitudinal axis, the mg/L of unit;
A is the intensity as the ultraviolet absorptivity of transverse axis, and unit is cm -1;
A is the slope of typical curve, and unit is cm * mg/L;
B is the transversal distance of typical curve, and unit is mg/L;
(2.2) measure the concentration that remains effective chlorine after chlorine reacts with actual water body
(2.21) by controlling four described transfer valves with the pulling flow type injector of transfer valve, the sample introduction end of the pulling flow type injector with transfer valve described in four is connected respectively with sample channel; Utilize COD mnon-line monitoring instrument 15 is measured the COD that processes water mnvalue is 2mg/L, COD mnvalue, between 2 ~ 6mg/L, makes to process water and directly enters in alternate path injector; By controlling the first T-valve 22 on the sample channel of the first path injector 1, adjust the sample introduction ratio of chlorine storing solutions and pure water, while making aqueous sodium hypochlorite solution in step (1) chlorine storing solution hold-up vessel 11 in entering the first described path injector, in aqueous sodium hypochlorite solution, the concentration of effective chlorine is 2mg/L; Enter the control method of solution in described three-way injector and described four-way road injector and each path injector and divided by the concentration and the COD that above enter effective chlorine in the first described path injector mnbe worth identical outside, other condition is all identical with (2.11) in step (2.1);
(2.22) by controlling four described transfer valves with the pulling flow type injector of transfer valve, the sample introduction end of the pulling flow type injector with transfer valve described in four is connected with sample channel respectively, makes the liquid in four path injectors in step (2.21) enter reaction tank, sample introduction order is identical with (2.12) in step (2.1), the first path injector described in and described alternate path injector be sample introduction first simultaneously, make aqueous sodium hypochlorite solution and process after water mixes by rapid mixing container to enter in reaction tank and start to react, chlorine and processing water are after certain reaction time (t), described three-way injector and described four-way road injector while sample introduction, make DPD aqueous solution directly enter reaction tank, buffer solution enters reaction tank by rapid mixing container, chlorine is set to 0.1s with the reaction time (t) of processing water, 0.2s, 0.5s, 1s, 2s, 5s, 10s, 20s, 30s, 40s, 50s, 60s, 90s, 120s, 150s, 180s, 210s, 240s, 270s, a series of time such as 300s, chlorine reacts in the buffer solution of pH6.5 with DPD aqueous solution and generates red product, under 515nm, measure the intensity A of ultraviolet absorptivity of the product of gained redness, it is identical that the condition determinations of ultraviolet absorptivity etc. are described during with above-mentioned drawing standard curve,
(2.23) the expression formula C=a * A+b of the described typical curve that (2.13) in the intensity A substitution step (2.1) of the ultraviolet absorptivity of (2.22) 20 reaction time points of step being measured are set up, calculates chlorine and the concentration C of processing water corresponding residue effective chlorine after 20 reaction time points of experience;
(2.3) the Fitting Calculation is processed the dynamic chlorine demand of water
(2.31) using chlorine that step (2.22) arranges with 20 reaction time points (t) in reaction time of processing water as transverse axis, using step (2.23) chlorine with process water concentration C of corresponding residue effective chlorine after 20 reaction time points of experience and as the longitudinal axis, draw ln (C) ~ t and scheme;
(2.32) in ln (C) ~ t figure step (2.31) being drawn, ln (the C) ~ t data of 240s, 270s, tri-points of 300s are carried out linear regression fit, its related coefficient (R 2) be 0.999 (>0.99), then continue the experimental data of increase 210s time point and the ln of above four points (C) ~ t data are carried out to linear fit, its related coefficient (R 2) be 0.998 (>0.99), continue above operation, as the related coefficient (R that increases the experimental point of 60s and carry out matching 2) be 0.995 (>0.99), and increase the related coefficient (R that carries out matching after the experimental point of 50s 2) be 0.986 (<0.99), stop matching.Finally meet the related coefficient (R of fitting result 2) be greater than 0.99 the point increasing (reaction time 60s point) and by approximate, thought that rapid reaction finishes the point starting with slow reaction, the reaction time of this point (60s) is similar to the time in the quick stage of thinking that chlorine consumes, and the consumption of this chlorine (0.320mg/L) is by the approximate short-term chlorine demand of thinking to process water; And last related coefficient (R 2) be greater than the k value (0.160h of 0.99 matching -1) by the approximate kinetic constant of thinking slow reaction stage pseudo first order reaction.According to the technology characteristics of water factory, obtain and process water and arrive the disinfecting time t(24h that pipe network tip place needs) and the concentration C (0.05mg/L) of the required effective chlorine in this moment, and by above-mentioned data substitution aforementioned formula (4), calculate accordingly at the dynamic chlorine demand C that adds chlorine point processing water 0, that is:
C 0 = 0.05 exp ( - 0.160 &times; ( 24 - 0.01667 ) ) + 0.32 = 2.64 mg / L
On the basis of the chlorine demand calculating, according to 120% ratio, carry out scene and add chlorine operation, chlorine-throwed quantity is 3.2mg/L, the concentration of pipe network tip effective chlorine is 0.06mg/L, error, in allowed band, meets and meets the requirement of < < drinking water sanitary standard > > (GB5749-2006) to the chlorine residue of potable water network tip.
Embodiment 2
The present embodiment is usingd certain waterworks settling basin water outlet as research object, and the flow of inlet water of water supply plant is 3800m 3/ h, the COD of settling basin water outlet mnvalue is 2.5mg/L, and ammonia nitrogen is 0.21mg/L, and the pipe network tip residence time is 30 hours, and the concentration requirement of pipe network tip effective chlorine is 0.05mg/L.
Utilize the equipment of the on-line determination processing hydrodynamic(al) state chlorine demand of embodiment 1 to carry out on-line determination processing hydrodynamic(al) state chlorine demand; Wherein: described four identical with the volume of described alternate path injector with the first described path injector in the pulling flow type injector of transfer valve, be 80 μ L; Described four identical with the volume of described four-way road injector with the described three-way injector in the pulling flow type injector of transfer valve, be 70 μ L.
The equipment that utilizes above-mentioned on-line determination to process hydrodynamic(al) state chlorine demand carries out the method that on-line determination is processed hydrodynamic(al) state chlorine demand: use DPD aqueous solution as developer, the phosphate buffer solution of pH6.5 is as buffer solution, it is 515nm that UV-detector is measured wavelength, and utilizes the stock solution of step (1) preparation and the typical curve of step (2.1) foundation of embodiment 1.
The different technical scheme later from the step (2.2) of embodiment 1 for the present embodiment is:
(2.2) measure the concentration that remains effective chlorine after chlorine reacts with actual water body
(2.21) by controlling four described transfer valves with the pulling flow type injector of transfer valve, the sample introduction end of the pulling flow type injector with transfer valve described in four is connected respectively with sample channel; Utilize COD mnon-line monitoring instrument 15 is measured the COD that processes water mnvalue is 2.5mg/L, COD mnvalue, between 2 ~ 6mg/L, makes to process water and directly enters in alternate path injector; By controlling the first T-valve 22 on the sample channel of the first path injector 1, adjust the sample introduction ratio of chlorine storing solutions and pure water, while making aqueous sodium hypochlorite solution in step (1) chlorine storing solution hold-up vessel 11 in entering the first described path injector, in aqueous sodium hypochlorite solution, the concentration of effective chlorine is 2.5mg/L; Enter the control method of solution in described three-way injector and described four-way road injector and each path injector and divided by the concentration and the COD that above enter effective chlorine in the first described path injector mnbe worth identical outside, other condition is all identical with (2.11) in step (2.1);
(2.22) by controlling four described transfer valves with the pulling flow type injector of transfer valve, the sample introduction end of the pulling flow type injector with transfer valve described in four is connected with sample channel respectively, makes the liquid in four path injectors in step (2.21) enter reaction tank, sample introduction order is identical with (2.12) in step (2.1), the first path injector described in and described alternate path injector be sample introduction first simultaneously, make aqueous sodium hypochlorite solution and process after water mixes by rapid mixing container to enter in reaction tank and start to react, chlorine and processing water are after certain reaction time (t), described three-way injector and described four-way road injector while sample introduction, make DPD aqueous solution directly enter reaction tank, buffer solution enters reaction tank by rapid mixing container, chlorine is set to 0.1s with the reaction time (t) of processing water, 0.2s, 0.5s, 1s, 2s, 5s, 10s, 20s, 30s, 40s, 50s, 60s, 90s, 120s, 150s, 180s, 210s, 240s, 270s, a series of time such as 300s, chlorine reacts in the buffer solution of pH6.5 with DPD aqueous solution and generates red product, under 515nm, measure the intensity A of ultraviolet absorptivity of the product of gained redness, it is identical that the condition determinations of ultraviolet absorptivity etc. are described during with above-mentioned drawing standard curve,
(2.23) the expression formula C=a * A+b of the described typical curve that (2.13) in the intensity A substitution step (2.1) of the ultraviolet absorptivity of (2.22) 20 reaction time points of step being measured are set up, calculates chlorine and the concentration C of processing water corresponding residue effective chlorine after 20 reaction time points of experience;
(2.3) the Fitting Calculation is processed the dynamic chlorine demand of water
(2.31) using chlorine that step (2.22) arranges with 20 reaction time points (t) in reaction time of processing water as transverse axis, using step (2.23) chlorine with process water concentration C of corresponding residue effective chlorine after 20 reaction time points of experience and as the longitudinal axis, draw ln (C) ~ t and scheme;
(2.32) in ln (C) ~ t figure step (2.31) being drawn, ln (the C) ~ t data of 240s, 270s, tri-points of 300s are carried out linear regression fit, its related coefficient (R 2) be 0.999 (>0.99), then continue the experimental data of increase 210s time point and the ln of above four points (C) ~ t data are carried out to linear fit, its R 2be 0.999 (>0.99), continue above operation, as the R that increases the experimental point of 30s and carry out matching 2be 0.994 (>0.99), and increase the R that carries out matching after the experimental point of 20s 2be 0.985 (<0.99), stop matching.Finally meet the R of fitting result 2be greater than 0.99 the point increasing (reaction time 30s point) and by approximate, thought that rapid reaction finishes the point starting with slow reaction, the reaction time of this point (30s) is similar to the time in the quick stage of thinking that chlorine consumes, and the consumption of this chlorine (0.350mg/L) is by the approximate short-term chlorine demand of thinking to process water; And last R 2be greater than the k value (0.146h of 0.99 matching -1) by the approximate kinetic constant of thinking slow reaction stage pseudo first order reaction.According to the technology characteristics of water factory, obtain and process water and arrive the disinfecting time t(30h that pipe network tip place needs) and the concentration C (0.05mg/L) of the required effective chlorine in this moment, and by above-mentioned data substitution aforementioned formula (4), calculate accordingly at the dynamic chlorine demand C that adds chlorine point processing water 0, that is:
C 0 = 0.05 exp ( - 0.146 &times; ( 30 - 0.00833 ) ) + 0.35 = 4.37 mg / L
On the basis of the chlorine demand calculating, according to 120% ratio, carry out scene and add chlorine operation, chlorine-throwed quantity is 5.2mg/L, the concentration of pipe network tip effective chlorine is 0.07mg/L, error, in allowed band, meets and meets the requirement of < < drinking water sanitary standard > > (GB5749-2006) to the chlorine residue of potable water network tip.
Embodiment 3
The present embodiment is usingd certain waterworks settling basin water outlet as research object, and the flow of inlet water of water supply plant is 4600m 3/ h, the COD of settling basin water outlet mnvalue is 1.5mg/L, and ammonia nitrogen is 0.14mg/L, and the pipe network tip residence time is 24 hours, and the concentration requirement of pipe network tip effective chlorine is 0.05mg/L.
Utilize the equipment of the on-line determination processing hydrodynamic(al) state chlorine demand of embodiment 1 to carry out on-line determination processing hydrodynamic(al) state chlorine demand; Wherein: described four identical with the volume of described alternate path injector with the first described path injector in the pulling flow type injector of transfer valve, be 100 μ L; Described four identical with the volume of described four-way road injector with the described three-way injector in the pulling flow type injector of transfer valve, be 85 μ L.
The equipment that utilizes above-mentioned on-line determination to process hydrodynamic(al) state chlorine demand carries out the method that on-line determination is processed hydrodynamic(al) state chlorine demand: use DPD aqueous solution as developer, the phosphate buffer solution of pH6.5 is as buffer solution, it is 515nm that UV-detector is measured wavelength, and utilizes the stock solution of step (1) preparation and the typical curve of step (2.1) foundation of embodiment 1.
The different technical scheme later from the step (2.2) of embodiment 1 for the present embodiment is:
(2.2) measure the concentration that remains effective chlorine after chlorine reacts with actual water body
(2.21) by controlling four described transfer valves with the pulling flow type injector of transfer valve, the sample introduction end of the pulling flow type injector with transfer valve described in four is connected respectively with sample channel; Utilize COD mnon-line monitoring instrument 15 is measured the COD that processes water mnvalue is 1.5mg/L, COD mnvalue <2mg/L, is concentrated into 3mg/L by processing water rotary evaporation and enters in alternate path injector; By controlling the first T-valve 22 on the sample channel of the first path injector 1, adjust the sample introduction ratio of chlorine storing solutions and pure water, while making aqueous sodium hypochlorite solution in step (1) chlorine storing solution hold-up vessel 11 in entering the first described path injector, in aqueous sodium hypochlorite solution, the concentration of effective chlorine is 3mg/L; Enter the control method of solution in described three-way injector and described four-way road injector and each path injector and divided by the concentration and the COD that above enter effective chlorine in the first described path injector mnbe worth identical outside, other condition is all identical with (2.11) in step (2.1);
(2.22) by controlling four described transfer valves with the pulling flow type injector of transfer valve, the sample introduction end of the pulling flow type injector with transfer valve described in four is connected with sample channel respectively, makes the liquid in four path injectors in step (2.21) enter reaction tank, (2.12) in the step (2.1) of sample introduction order and embodiment 1 are identical, the first path injector described in and described alternate path injector be sample introduction first simultaneously, make aqueous sodium hypochlorite solution and process after water mixes by rapid mixing container to enter in reaction tank and start to react, chlorine and processing water are after certain reaction time (t), described three-way injector and described four-way road injector while sample introduction, make DPD aqueous solution directly enter reaction tank, buffer solution enters reaction tank by rapid mixing container, chlorine is set to 0.1s with the reaction time (t) of processing water, 0.2s, 0.5s, 1s, 2s, 5s, 10s, 20s, 30s, 40s, 50s, 60s, 90s, 120s, 150s, 180s, 210s, 240s, 270s, 300s, 400s, a series of time such as 500s, chlorine reacts in the buffer solution of pH6.5 with DPD aqueous solution and generates red product, under 515nm, measure the intensity A of ultraviolet absorptivity of the product of gained redness, it is identical that the condition determinations of ultraviolet absorptivity etc. are described during with above-mentioned drawing standard curve,
(2.23) the expression formula C=a * A+b of the described typical curve that (2.13) in the intensity A substitution step (2.1) of the ultraviolet absorptivity of (2.22) 22 reaction time points of step being measured are set up, calculates chlorine and the concentration C of processing water corresponding residue effective chlorine after 22 reaction time points of experience;
(2.3) the Fitting Calculation is processed the dynamic chlorine demand of water
(2.31) using chlorine that step (2.22) arranges with 22 reaction time points (t) in reaction time of processing water as transverse axis, using step (2.23) chlorine with process water concentration C of corresponding residue effective chlorine after 22 reaction time points of experience and as the longitudinal axis, draw ln (C) ~ t and scheme;
(2.32) in ln (C) ~ t figure step (2.31) being drawn, ln (the C) ~ t data of 240s, 270s, tri-points of 300s are carried out linear regression fit, its related coefficient (R 2) be 0.999 (>0.99), then continue the experimental data of increase 210s time point and the ln of above four points (C) ~ t data are carried out to linear fit, its R 2be 0.997 (>0.99), continue above operation, as the R that increases the experimental point of 90s and carry out matching 2be 0.993 (>0.99), and increase the R that carries out matching after the experimental point of 60s 2be 0.982 (<0.99), stop matching.Finally meet the R of fitting result 2be greater than 0.99 the point increasing (reaction time 90s point) and by approximate, thought that rapid reaction finishes the point starting with slow reaction, the reaction time of this point (90s) is similar to the time in the quick stage of thinking that chlorine consumes, and the consumption of this chlorine (0.41mg/L) is by the approximate short-term chlorine demand of thinking to process water; And last R 2be greater than the k value (0.180h of 0.99 matching -1) by the approximate kinetic constant of thinking slow reaction stage pseudo first order reaction.According to the technology characteristics of water factory, obtain and process water and arrive the disinfecting time t(24h that pipe network tip place needs) and the concentration C (0.05mg/L) of the required effective chlorine in this moment, and by above-mentioned data substitution aforementioned formula (4), calculate accordingly at the dynamic chlorine demand C that adds chlorine point processing water 0, that is:
C 0 = 0.05 exp ( - 0.180 &times; ( 24 - 0.025 ) ) + 0.41 = 4.15 mg / L
Before concentrated, initial chlorine demand is 2.10mg/L, on the basis of the chlorine demand calculating, according to 120% ratio, carry out scene and add chlorine operation, chlorine-throwed quantity is 2.5mg/L, the concentration of pipe network tip effective chlorine is 0.055mg/L, error, in allowed band, meets and meets the requirement of < < drinking water sanitary standard > > (GB5749-2006) to the chlorine residue of potable water network tip.
Embodiment 4
The present embodiment is usingd certain waterworks settling basin water outlet as research object, and the flow of inlet water of water supply plant is 5200m 3/ h, the COD of settling basin water outlet mnvalue is 4mg/L, and ammonia nitrogen is 0.17mg/L, and the pipe network tip residence time is 12 hours, and the concentration requirement of pipe network tip effective chlorine is 0.05mg/L.
Utilize the equipment of the on-line determination processing hydrodynamic(al) state chlorine demand of embodiment 1 to carry out on-line determination processing hydrodynamic(al) state chlorine demand; Wherein: described four identical with the volume of described alternate path injector with the first described path injector in the pulling flow type injector of transfer valve, be 120 μ L; Described four identical with the volume of described four-way road injector with the described three-way injector in the pulling flow type injector of transfer valve, be 100 μ L.
The equipment that utilizes above-mentioned on-line determination to process hydrodynamic(al) state chlorine demand carries out the method that on-line determination is processed hydrodynamic(al) state chlorine demand: use DPD aqueous solution as developer, the phosphate buffer solution of pH6.5 is as buffer solution, it is 515nm that UV-detector is measured wavelength, and utilizes the stock solution of step (1) preparation and the typical curve of step (2.1) foundation of embodiment 1.
The different technical scheme later from the step (2.2) of embodiment 1 for the present embodiment is:
(2.2) measure the concentration that remains effective chlorine after chlorine reacts with actual water body
(2.21) by controlling four described transfer valves with the pulling flow type injector of transfer valve, the sample introduction end of the pulling flow type injector with transfer valve described in four is connected respectively with sample channel; Utilize COD mnon-line monitoring instrument 15 is measured the COD that processes water mnvalue is 4mg/L, COD mnvalue, between 2 ~ 6mg/L, makes to process water and directly enters in alternate path injector; By controlling the first T-valve 22 on the sample channel of the first path injector 1, adjust the sample introduction ratio of chlorine storing solutions and pure water, while making aqueous sodium hypochlorite solution in step (1) chlorine storing solution hold-up vessel 11 in entering the first described path injector, in aqueous sodium hypochlorite solution, the concentration of effective chlorine is 4mg/L; Enter the control method of solution in described three-way injector and described four-way road injector and each path injector and divided by the concentration and the COD that above enter effective chlorine in the first described path injector mnbe worth identical outside, other condition is all identical with (2.11) in the step (2.1) of embodiment 1;
(2.22) by controlling four described transfer valves with the pulling flow type injector of transfer valve, the sample introduction end of the pulling flow type injector with transfer valve described in four is connected with sample channel respectively, makes the liquid in four path injectors in step (2.21) enter reaction tank, sample introduction order is identical with (2.12) in step (2.1), the first path injector described in and described alternate path injector be sample introduction first simultaneously, make aqueous sodium hypochlorite solution and process after water mixes by rapid mixing container to enter in reaction tank and start to react, chlorine and processing water are after certain reaction time (t), described three-way injector and described four-way road injector while sample introduction, make DPD aqueous solution directly enter reaction tank, buffer solution enters reaction tank by rapid mixing container, chlorine is set to 0.1s with the reaction time (t) of processing water, 0.2s, 0.5s, 1s, 2s, 5s, 10s, 20s, 30s, 40s, 50s, 60s, 90s, 120s, 150s, 180s, 210s, 240s, 270s, 300s, 400s, 500s, a series of time such as 600s, chlorine reacts in the buffer solution of pH6.5 with DPD aqueous solution and generates red product, under 515nm, measure the intensity A of ultraviolet absorptivity of the product of gained redness, it is identical that the condition determinations of ultraviolet absorptivity etc. are described during with above-mentioned drawing standard curve,
(2.23) the expression formula C=a * A+b of the described typical curve that (2.13) in the intensity A substitution step (2.1) of the ultraviolet absorptivity of (2.22) 23 reaction time points of step being measured are set up, calculates chlorine and the concentration C of processing water corresponding residue effective chlorine after 23 reaction time points of experience;
(2.3) the Fitting Calculation is processed the dynamic chlorine demand of water
(2.31) using chlorine that step (2.22) arranges with 23 reaction time points (t) in reaction time of processing water as transverse axis, using step (2.23) chlorine with process water concentration C of corresponding residue effective chlorine after 23 reaction time points of experience and as the longitudinal axis, draw ln (C) ~ t and scheme;
(2.32) in ln (C) ~ t figure step (2.31) being drawn, ln (the C) ~ t data of 400s, 500s, tri-points of 600s are carried out linear regression fit, its related coefficient (R 2) be 1.0000 (>0.99), then continue the experimental data of increase 300s time point and the ln of above four points (C) ~ t data are carried out to linear fit, its R 2be 0.999 (>0.99), continue above operation, as the R that increases the experimental point of 120s and carry out matching 2be 0.995 (>0.99), and increase the R that carries out matching after the experimental point of 90s 2be 0.988 (<0.99), stop matching.Finally meet the R of fitting result 2be greater than 0.99 the point increasing (reaction time 120s point) and by approximate, thought that rapid reaction finishes the point starting with slow reaction, the reaction time of this point (120s) is similar to the time in the quick stage of thinking that chlorine consumes, and the consumption of this chlorine (0.46mg/L) is by the approximate short-term chlorine demand of thinking to process water; And last R 2be greater than the k value (0.184h of 0.99 matching -1) by the approximate kinetic constant of thinking slow reaction stage pseudo first order reaction.According to the technology characteristics of water factory, obtain and process water and arrive the disinfecting time t(12h that pipe network tip place needs) and the concentration C (0.05mg/L) of the required effective chlorine in this moment, and by above-mentioned data substitution aforementioned formula (4), calculate accordingly at the dynamic chlorine demand C that adds chlorine point processing water 0, that is:
C 0 = 0.05 exp ( - 0.184 &times; ( 12 - 0.0333 ) ) + 0.46 = 0.91 mg / L
It carries out scene according to 120% ratio and adds chlorine operation on the basis of the chlorine demand calculating, chlorine-throwed quantity is 1.1mg/L, the concentration of pipe network tip effective chlorine is 0.06mg/L, its value, in allowed band, meets and meets the requirement of < < drinking water sanitary standard > > (GB5749-2006) to the chlorine residue of potable water network tip.
Embodiment 5
The present embodiment is usingd certain waterworks settling basin water outlet as research object, and the flow of inlet water of water supply plant is 2800m 3/ h, the COD of settling basin water outlet mnvalue is 4.5mg/L, and ammonia nitrogen is 0.26mg/L, and the pipe network tip residence time is 20 hours, and the concentration requirement of pipe network tip effective chlorine is 0.05mg/L.
Utilize the equipment of the on-line determination processing hydrodynamic(al) state chlorine demand of embodiment 1 to carry out on-line determination processing hydrodynamic(al) state chlorine demand; Wherein: described four identical with the volume of described alternate path injector with the first described path injector in the pulling flow type injector of transfer valve, be 100 μ L; Described four identical with the volume of described four-way road injector with the described three-way injector in the pulling flow type injector of transfer valve, be 90 μ L.
The equipment that utilizes above-mentioned on-line determination to process hydrodynamic(al) state chlorine demand carries out the method that on-line determination is processed hydrodynamic(al) state chlorine demand: use ABTS aqueous solution as developer, the hydrochloric acid solution of 0.01mol/L is as buffer solution, and it is 728nm that UV-detector is measured wavelength.
(1), preparation stock solution
In chlorine storing solution hold-up vessel, fill it up with the aqueous sodium hypochlorite solution that concentration is 10mg/L, in developer hold-up vessel, fill it up with the ABTS aqueous solution that the concentration as developer is 2mM; In buffer solution hold-up vessel, fill it up with the hydrochloric acid solution (pH is 2) as the 0.01mol/L of buffer solution; Open and process water water intaking valve, make to process water from sample point by processing water water inlet pipe the COD that flows through mnon-line monitoring instrument joins to be processed in water store tank and fills it up with; Utilize COD mnon-line monitoring instrument is measured the COD that processes water mnvalue;
(2), on-line determination is processed hydrodynamic(al) state chlorine demand
(2.1) drawing standard curve
(2.11) four of four-way road injector are set identical with the volume of alternate path injector 2 with the first path injector 1 in the pulling flow type injector of transfer valve, be 100 μ L, three-way injector 3 is set identical with the volume of four-way road injector 4, is 90 μ L, by control, be arranged on four described transfer valves with the pulling flow type injector of transfer valve, the sample introduction end of the pulling flow type injector with transfer valve described in four is connected with sample channel respectively, and by the T-valve on the sample channel of four path injectors of control, control the aqueous sodium hypochlorite solution in chlorine storing solution hold-up vessel 11, developer in developer hold-up vessel 20, buffer solution in buffer solution hold-up vessel 18, process the processing water in water store tank 14, pure water in the first pure water pot 12, pure water in the second pure water pot 13, the ratio of pure water in pure water in the 3rd pure water pot 21 and the 4th pure water pot 17 in reaction tank 6, the stock solution of pure water and step (1) preparation is entered respectively in four pulling flow type injectors with transfer valve by preset proportion, wherein, adjust the sample introduction ratio of chlorine storing solution and pure water, while making aqueous sodium hypochlorite solution in step (1) chlorine storing solution hold-up vessel 11 in entering the first described path injector, in aqueous sodium hypochlorite solution, the concentration of effective chlorine is respectively 0mg/L(in contrast), 0.1mg/L, 0.2mg/L, 0.5mg/L, 1mg/L, 2mg/L and 3mg/L, in described alternate path injector, add pure water, adjust the sample introduction ratio of developer ABTS aqueous solution and pure water, while making developer ABTS aqueous solution in step (1) developer hold-up vessel 20 in entering described three-way injector, the concentration of developer is calculated according to sampling volume, and making the ABTS aqueous solution in reaction tank 6 is 10:1 with the ratio of the volumetric molar concentration of effective chlorine, while making buffer solution in step (1) buffer solution hold-up vessel 18 in entering described four-way road injector, adjustment is as the sample introduction ratio of hydrochloric acid solution and the pure water of the 0.01mol/L of buffer solution, the concentration of buffer solution in described four-way road injector is calculated according to sampling volume, and the pH that makes mixed liquor in reaction tank 6 is 3,
(2.12) by controlling four described transfer valves with the pulling flow type injector of transfer valve, the sample introduction end of the pulling flow type injector with transfer valve described in four is connected with sample channel respectively, makes the liquid in four path injectors in step (2.11) enter reaction tank, sample introduction is sequentially: the first described path injector and described alternate path injector be sample introduction first simultaneously, after being mixed by rapid mixing container, aqueous sodium hypochlorite solution and pure water enter in reaction tank, after 1 second, described three-way injector and described four-way road injector while sample introduction, make ABTS aqueous solution directly enter reaction tank, the hydrochloric acid buffer solution of 0.01mol/L enters reaction tank by rapid mixing container, chlorine reacts and generates blue product with ABTS aqueous solution in buffer solution, and the concentration of measuring respectively selected effective chlorine under 728nm wavelength is respectively 0mg/L(in contrast), 0.1mg/L, 0.2mg/L, 0.5mg/L, 1mg/L, the intensity A of the ultraviolet absorptivity of the product of 2mg/L and 3mg/L gained blueness, described ultraviolet determination wavelength regulates by monochromator,
(2.13) usining the concentration of effective chlorine in the aqueous sodium hypochlorite solution that step (2.12) measures is respectively 0mg/L(in contrast), when 0.1mg/L, 0.2mg/L, 0.5mg/L, 1mg/L, 2mg/L and 3mg/L the intensity A of corresponding ultraviolet absorptivity as transverse axis, the concentration C of the effective chlorine in the liquor natrii hypochloritis of usining in corresponding the first described path injector is as longitudinal axis drawing standard curve, the line linearity of going forward side by side returns, and sets up the expression formula of typical curve of the cl concn of the effective chlorine in ultraviolet absorptivity and described the first path injector:
C=a×A+b (5)
Wherein, C is the concentration as the effective chlorine of the longitudinal axis, the mg/L of unit;
A is the intensity as the ultraviolet absorptivity of transverse axis, and unit is cm -1;
A is the slope of typical curve, and unit is cm * mg/L;
B is the transversal distance of typical curve, and unit is mg/L;
(2.2) measure the concentration that remains effective chlorine after chlorine reacts with actual water body
(2.21) by controlling four described transfer valves with the pulling flow type injector of transfer valve, the sample introduction end of the pulling flow type injector with transfer valve described in four is connected respectively with sample channel; Utilize COD mnon-line monitoring instrument 15 is measured the COD that processes water mnvalue is 4.5mg/L, COD mnvalue, between 2 ~ 6mg/L, makes to process water and directly enters in alternate path injector; By controlling the first T-valve 22 on the sample channel of the first path injector 1, adjust the sample introduction ratio of chlorine storing solutions and pure water, while making aqueous sodium hypochlorite solution in step (1) chlorine storing solution hold-up vessel 11 in entering the first described path injector, in aqueous sodium hypochlorite solution, the concentration of effective chlorine is 4.5mg/L; Enter the control method of solution in described three-way injector and described four-way road injector and each path injector and divided by the concentration and the COD that above enter effective chlorine in the first described path injector mnbe worth identical outside, other condition is all identical with (2.11) in step (2.1);
(2.22) by controlling four described transfer valves with the pulling flow type injector of transfer valve, the sample introduction end of the pulling flow type injector with transfer valve described in four is connected with sample channel respectively, makes the liquid in four path injectors in step (2.21) enter reaction tank, sample introduction order is identical with (2.12) in step (2.1), the first path injector described in and described alternate path injector be sample introduction first simultaneously, make aqueous sodium hypochlorite solution and process after water mixes by rapid mixing container to enter in reaction tank and start to react, chlorine and processing water are after certain reaction time (t), described three-way injector and described four-way road injector while sample introduction, make ABTS aqueous solution directly enter reaction tank, buffer solution enters reaction tank by rapid mixing container, chlorine is set to 0.1s with the reaction time (t) of processing water, 0.2s, 0.5s, 1s, 2s, 5s, 10s, 20s, 30s, 40s, 50s, 60s, 90s, 120s, 150s, 180s, 210s, 240s, 270s, 300s, 400s, 500s, 600s, a series of time such as 900s, chlorine reacts in the mixed liquor of pH3 with ABTS aqueous solution and generates blue product, under 515nm, measure the intensity A of ultraviolet absorptivity of the product of gained blueness, it is identical that the condition determinations of ultraviolet absorptivity etc. are described during with above-mentioned drawing standard curve,
(2.23) the expression formula C=a * A+b of the described typical curve that (2.13) in the intensity A substitution step (2.1) of the ultraviolet absorptivity of (2.22) 24 reaction time points of step being measured are set up, calculates chlorine and the concentration C of processing water corresponding residue effective chlorine after 24 reaction time points of experience;
(2.3) the Fitting Calculation is processed the dynamic chlorine demand of water
(2.31) using chlorine that step (2.22) arranges with 24 reaction time points (t) in reaction time of processing water as transverse axis, using step (2.23) chlorine with process water concentration C of corresponding residue effective chlorine after 24 reaction time points of experience and as the longitudinal axis, draw ln (C) ~ t and scheme;
(2.32) in ln (C)～t figure step (2.31) being drawn, ln (the C) ~ t data of 500s, 600s, tri-points of 900s are carried out linear regression fit, its related coefficient (R 2) be 0.999 (>0.99), then continue the experimental data of increase 400s time point and the ln of above four points (C) ~ t data are carried out to linear fit, its R 2be 0.999 (>0.99), continue above operation, as the R that increases the experimental point of 120s and carry out matching 2be 0.994 (>0.99), and increase the R that carries out matching after the experimental point of 90s 2be 0.982 (<0.99), stop matching.Finally meet the R of fitting result 2be greater than 0.99 the point increasing (reaction time 120s point) and by approximate, thought that rapid reaction finishes the point starting with slow reaction, the reaction time of this point (120s) is similar to the time in the quick stage of thinking that chlorine consumes, and the consumption of this chlorine (0.490mg/L) is by the approximate short-term chlorine demand of thinking to process water; And last R 2be greater than the k value (0.190h of 0.99 matching -1) by the approximate kinetic constant of thinking slow reaction stage pseudo first order reaction.According to the technology characteristics of water factory, obtain and process water and arrive the disinfecting time t(20h that pipe network tip place needs) and the concentration C (0.05mg/L) of the required effective chlorine in this moment, and by above-mentioned data substitution aforementioned formula (4), calculate accordingly at the dynamic chlorine demand C that adds chlorine point processing water 0, that is:
C 0 = 0.05 exp ( - 0.190 &times; ( 20 - 0.0333 ) ) + 0.49 = 2.71 mg / L
On the basis of the chlorine demand calculating, according to 120% ratio, carry out scene and add chlorine operation, chlorine-throwed quantity is 3.3mg/L, the concentration of pipe network tip effective chlorine is 0.07mg/L, its value, in allowed band, meets and meets the requirement of < < drinking water sanitary standard > > (GB5749-2006) to the chlorine residue of potable water network tip.
Embodiment 6
The present embodiment is usingd certain waterworks settling basin water outlet as research object, and the flow of inlet water of water supply plant is 4800m 3/ h, the COD of settling basin water outlet mnvalue is 5mg/L, and ammonia nitrogen is 0.15mg/L, and the pipe network tip residence time is 27 hours, and the concentration requirement of pipe network tip effective chlorine is 0.05mg/L.
Utilize the equipment of the on-line determination processing hydrodynamic(al) state chlorine demand of embodiment 1 to carry out on-line determination processing hydrodynamic(al) state chlorine demand; Wherein: described four identical with the volume of described alternate path injector with the first described path injector in the pulling flow type injector of transfer valve, be 100 μ L; Described four identical with the volume of described four-way road injector with the described three-way injector in the pulling flow type injector of transfer valve, be 90 μ L.
The equipment that utilizes above-mentioned on-line determination to process hydrodynamic(al) state chlorine demand carries out the method that on-line determination is processed hydrodynamic(al) state chlorine demand: use ABTS aqueous solution as developer, the hydrochloric acid solution of 0.01mol/L is as buffer solution, it is 728nm that UV-detector is measured wavelength, and utilizes the stock solution of step (1) preparation and the typical curve of step (2.1) foundation of embodiment 5.
The different technical scheme later from the step (2.2) of embodiment 5 for the present embodiment is:
(2.2) measure the concentration that remains effective chlorine after chlorine reacts with actual water body
(2.21) by controlling four described transfer valves with the pulling flow type injector of transfer valve, the sample introduction end of the pulling flow type injector with transfer valve described in four is connected respectively with sample channel; Utilize COD mnon-line monitoring instrument 15 is measured the COD that processes water mnvalue is 5mg/L, COD mnvalue, between 2 ~ 6mg/L, makes to process water and directly enters in alternate path injector; By controlling the first T-valve 22 on the sample channel of the first path injector 1, adjust the sample introduction ratio of chlorine storing solutions and pure water, while making aqueous sodium hypochlorite solution in step (1) chlorine storing solution hold-up vessel 11 in entering the first described path injector, in aqueous sodium hypochlorite solution, the concentration of effective chlorine is 5mg/L; Enter the control method of solution in described three-way injector and described four-way road injector and each path injector and divided by the concentration and the COD that above enter effective chlorine in the first described path injector mnbe worth identical outside, other condition is all identical with (2.11) in the step (2.1) of embodiment 5;
(2.22) by controlling four described transfer valves with the pulling flow type injector of transfer valve, the sample introduction end of the pulling flow type injector with transfer valve described in four is connected with sample channel respectively, makes the liquid in four path injectors in step (2.21) enter reaction tank, (2.12) in the step (2.1) of sample introduction order and embodiment 5 are identical, the first path injector described in and described alternate path injector be sample introduction first simultaneously, make aqueous sodium hypochlorite solution and process after water mixes by rapid mixing container to enter in reaction tank and start to react, chlorine and processing water are after certain reaction time (t), described three-way injector and described four-way road injector while sample introduction, make ABTS aqueous solution directly enter reaction tank, buffer solution enters reaction tank by rapid mixing container, chlorine is set to 0.1s with the reaction time (t) of processing water, 0.2s, 0.5s, 1s, 2s, 5s, 10s, 20s, 30s, 40s, 50s, 60s, 90s, 120s, 150s, 180s, 210s, 240s, 270s, 300s, 400s, 500s, a series of time such as 600s, in the mixed liquor that chlorine is 3 with ABTS aqueous solution at pH, react and generate blue product, under 728nm, measure the intensity A of ultraviolet absorptivity of the product of gained blueness, it is identical that the condition determinations of ultraviolet absorptivity etc. are described during with above-mentioned drawing standard curve,
(2.23) the expression formula C=a * A+b of the described typical curve that (2.13) in the intensity A substitution step (2.1) of the ultraviolet absorptivity of (2.22) 23 reaction time points of step being measured are set up, calculates chlorine and the concentration C of processing water corresponding residue effective chlorine after 23 reaction time points of experience;
(2.3) the Fitting Calculation is processed the dynamic chlorine demand of water
(2.31) using chlorine that step (2.22) arranges with 23 reaction time points (t) in reaction time of processing water as transverse axis, using step (2.23) chlorine with process water concentration C of corresponding residue effective chlorine after 23 reaction time points of experience and as the longitudinal axis, draw ln (C) ~ t and scheme;
(2.32) in ln (C) ~ t figure step (2.31) being drawn, ln (the C) ~ t data of 400s, 500s, tri-points of 600s are carried out linear regression fit, its related coefficient (R 2) be 0.998 (>0.99), then continue the experimental data of increase 300s time point and the ln of above four points (C) ~ t data are carried out to linear fit, its R 2be 0.996 (>0.99), continue above operation, as the R that increases the experimental point of 60s and carry out matching 2be 0.992 (>0.99), and increase the R that carries out matching after the experimental point of 50s 2be 0.985 (<0.99), stop matching.Finally meet the R of fitting result 2be greater than 0.99 the point increasing (reaction time 60s point) and by approximate, thought that rapid reaction finishes the point starting with slow reaction, the reaction time of this point (60s) is similar to the time in the quick stage of thinking that chlorine consumes, and the consumption of this chlorine (0.48mg/L) is by the approximate short-term chlorine demand of thinking to process water; And last R 2be greater than the k value (0.156h of 0.99 matching -1) by the approximate kinetic constant of thinking slow reaction stage pseudo first order reaction.According to the technology characteristics of water factory, obtain and process water and arrive the disinfecting time t(27h that pipe network tip place needs) and the concentration C (0.05mg/L) of the required effective chlorine in this moment, and by above-mentioned data substitution aforementioned formula (4), calculate accordingly at the dynamic chlorine demand C that adds chlorine point processing water 0, that is:
C 0 = 0.05 exp ( - 0.156 &times; ( 27 - 0.01667 ) ) + 0.48 = 3.85 mg / L
On the basis of the chlorine demand calculating, according to 120% ratio, carry out scene and add chlorine operation, chlorine-throwed quantity is 4.6mg/L, the concentration of pipe network tip effective chlorine is 0.08mg/L, error, in allowed band, meets and meets the requirement of < < drinking water sanitary standard > > (GB5749-2006) to the chlorine residue of potable water network tip.
Embodiment 7
The present embodiment is usingd certain waterworks settling basin water outlet as research object, and the flow of inlet water of water supply plant is 3600m 3/ h, the COD of settling basin water outlet mnvalue is 6mg/L, and ammonia nitrogen is 0.21mg/L, and the pipe network tip residence time is 30 hours, and the concentration requirement of pipe network tip effective chlorine is 0.05mg/L.
Utilize the equipment of the on-line determination processing hydrodynamic(al) state chlorine demand of embodiment 1 to carry out on-line determination processing hydrodynamic(al) state chlorine demand; Wherein: described four identical with the volume of described alternate path injector with the first described path injector in the pulling flow type injector of transfer valve, be 85 μ L; Described four identical with the volume of described four-way road injector with the described three-way injector in the pulling flow type injector of transfer valve, be 75 μ L.
The equipment that utilizes above-mentioned on-line determination to process hydrodynamic(al) state chlorine demand carries out the method that on-line determination is processed hydrodynamic(al) state chlorine demand: use DPD aqueous solution as developer, the phosphate buffer solution of pH6.5 is as buffer solution, it is 515nm that UV-detector is measured wavelength, and utilizes the stock solution of step (1) preparation of embodiment 1.
The different technical scheme later from the step (2) of embodiment 1 for the present embodiment is:
(2), on-line determination is processed hydrodynamic(al) state chlorine demand
(2.1) drawing standard curve
(2.11) four of four-way road injector are set identical with the volume of alternate path injector 2 with the first path injector 1 in the pulling flow type injector of transfer valve, be 85 μ L, three-way injector 3 is set identical with the volume of four-way road injector 4, is 75 μ L, by control, be arranged on four described transfer valves with the pulling flow type injector of transfer valve, the sample introduction end of the pulling flow type injector with transfer valve described in four is connected with sample channel respectively, and by the T-valve on the sample channel of four path injectors of control, control the aqueous sodium hypochlorite solution in chlorine storing solution hold-up vessel 11, developer in developer hold-up vessel 20, buffer solution in buffer solution hold-up vessel 18, process the processing water in water store tank 14, pure water in the first pure water pot 12, pure water in the second pure water pot 13, the ratio of pure water in pure water in the 3rd pure water pot 21 and the 4th pure water pot 17 in reaction tank 6, the stock solution of pure water and step (1) preparation is entered respectively in four pulling flow type injectors with transfer valve by preset proportion, wherein, adjust the sample introduction ratio of chlorine storing solution and pure water, while making aqueous sodium hypochlorite solution in step (1) chlorine storing solution hold-up vessel 11 in entering the first described path injector, in aqueous sodium hypochlorite solution, the concentration of effective chlorine is respectively 0mg/L(in contrast), 0.1mg/L, 0.2mg/L, 0.5mg/L, 1mg/L, 2mg/L and 3mg/L, in described alternate path injector, add pure water, adjust the sample introduction ratio of developer DPD aqueous solution and pure water, while making developer DPD aqueous solution in step (1) developer hold-up vessel 20 in entering described three-way injector, the concentration of developer is calculated according to sampling volume, and making the DPD aqueous solution in reaction tank 6 is 15:1 with the ratio of the volumetric molar concentration of effective chlorine, while making buffer solution in step (1) buffer solution hold-up vessel 18 in entering described four-way road injector, adjustment is as the sample introduction ratio of phosphate buffer solution and the pure water of the 2mM pH6.5 of buffer solution, the concentration of buffer solution in described four-way road injector is calculated according to sampling volume, and making DPD aqueous solution in reaction tank 6 and the molar concentration rate of buffer solution is 1:1,
(2.12) by controlling four described transfer valves with the pulling flow type injector of transfer valve, the sample introduction end of the pulling flow type injector with transfer valve described in four is connected with sample channel respectively, makes the liquid in four path injectors in step (2.11) enter reaction tank, sample introduction is sequentially: the first described path injector and described alternate path injector be sample introduction first simultaneously, after being mixed by rapid mixing container, aqueous sodium hypochlorite solution and pure water enter in reaction tank, after 2 seconds, described three-way injector and described four-way road injector while sample introduction, make DPD aqueous solution directly enter reaction tank, the buffer solution of pH6.5 enters reaction tank by rapid mixing container, chlorine reacts and generates the coloured product of tool with DPD aqueous solution in buffer solution, and the concentration of measuring respectively selected effective chlorine under 515nm wavelength is respectively 0mg/L(in contrast), 0.1mg/L, 0.2mg/L, 0.5mg/L, 1mg/L, the intensity A of the ultraviolet absorptivity of 2mg/L and the coloured product of 3mg/L gained tool, described ultraviolet determination wavelength regulates by monochromator,
(2.13) usining the concentration of effective chlorine in the aqueous sodium hypochlorite solution that step (2.12) measures is respectively 0mg/L(in contrast), when 0.1mg/L, 0.2mg/L, 0.5mg/L, 1mg/L, 2mg/L and 3mg/L the intensity A of corresponding ultraviolet absorptivity as transverse axis, the concentration C of the effective chlorine in the liquor natrii hypochloritis of usining in corresponding the first described path injector is as longitudinal axis drawing standard curve, the line linearity of going forward side by side returns, and sets up the expression formula of typical curve of the cl concn of the effective chlorine in ultraviolet absorptivity and described the first path injector:
C=a×A+b (5)
Wherein, C is the concentration as the effective chlorine of the longitudinal axis, the mg/L of unit;
A is the intensity as the ultraviolet absorptivity of transverse axis, and unit is cm -1;
A is the slope of typical curve, and unit is cm * mg/L;
B is the transversal distance of typical curve, and unit is mg/L;
(2.2) measure the concentration that remains effective chlorine after chlorine reacts with actual water body
(2.21) by controlling four described transfer valves with the pulling flow type injector of transfer valve, the sample introduction end of the pulling flow type injector with transfer valve described in four is connected respectively with sample channel; Utilize COD mnon-line monitoring instrument 15 is measured the COD that processes water mnvalue is 6mg/L, COD mnvalue, between 2 ~ 6mg/L, makes to process water and directly enters in alternate path injector; By controlling the first T-valve 22 on the sample channel of the first path injector 1, adjust the sample introduction ratio of chlorine storing solutions and pure water, while making aqueous sodium hypochlorite solution in step (1) chlorine storing solution hold-up vessel 11 in entering the first described path injector, in aqueous sodium hypochlorite solution, the concentration of effective chlorine is 6mg/L; Enter the control method of solution in described three-way injector and described four-way road injector and each path injector and divided by the concentration and the COD that above enter effective chlorine in the first described path injector mnbe worth identical outside, other condition is all identical with (2.11) in step (2.1);
(2.22) by controlling four described transfer valves with the pulling flow type injector of transfer valve, the sample introduction end of the pulling flow type injector with transfer valve described in four is connected with sample channel respectively, makes the liquid in four path injectors in step (2.21) enter reaction tank, sample introduction order is identical with (2.12) in step (2.1), the first path injector described in and described alternate path injector be sample introduction first simultaneously, make aqueous sodium hypochlorite solution and process after water mixes by rapid mixing container to enter in reaction tank and start to react, chlorine and processing water are after certain reaction time (t), described three-way injector and described four-way road injector while sample introduction, make DPD aqueous solution directly enter reaction tank, buffer solution enters reaction tank by rapid mixing container, chlorine is set to 0.1s with the reaction time (t) of processing water, 0.2s, 0.5s, 1s, 2s, 5s, 10s, 20s, 30s, 40s, 50s, 60s, 90s, 120s, 150s, 180s, 210s, 240s, 270s, 300s, a series of time such as 400s, chlorine reacts in the buffer solution of pH6.5 with DPD aqueous solution and generates red product, under 515nm, measure the intensity A of ultraviolet absorptivity of the product of gained redness, it is identical that the condition determinations of ultraviolet absorptivity etc. are described during with above-mentioned drawing standard curve,
(2.23) the expression formula C=a * A+b of the described typical curve that (2.13) in the intensity A substitution step (2.1) of the ultraviolet absorptivity of (2.22) 21 reaction time points of step being measured are set up, calculates chlorine and the concentration C of processing water corresponding residue effective chlorine after 21 reaction time points of experience;
(2.3) the Fitting Calculation is processed the dynamic chlorine demand of water
(2.31) using chlorine that step (2.22) arranges with 21 reaction time points (t) in reaction time of processing water as transverse axis, using step (2.23) chlorine with process water concentration C of corresponding residue effective chlorine after 21 reaction time points of experience and as the longitudinal axis, draw ln (C) ~ t and scheme;
(2.32) in ln (C) ~ t figure step (2.31) being drawn, ln (the C) ~ t data of 270s, 300s, tri-points of 400s are carried out linear regression fit, its related coefficient (R 2) be 0.996 (>0.99), then continue the experimental data of increase 240s time point and the ln of above four points (C) ~ t data are carried out to linear fit, its R 2be 0.996 (>0.99), continue above operation, as the R that increases the experimental point of 40s and carry out matching 2be 0.993 (>0.99), and increase the R that carries out matching after the experimental point of 30s 2be 0.983 (<0.99), stop matching.Finally meet the R of fitting result 2be greater than 0.99 the point increasing (reaction time 40s point) and by approximate, thought that rapid reaction finishes the point starting with slow reaction, the reaction time of this point (40s) is similar to the time in the quick stage of thinking that chlorine consumes, and the consumption of this chlorine (0.530mg/L) is by the approximate short-term chlorine demand of thinking to process water; And last R 2be greater than the k value (0.150h of 0.99 matching -1) by the approximate kinetic constant of thinking slow reaction stage pseudo first order reaction.According to the technology characteristics of water factory, obtain and process water and arrive the disinfecting time t(30h that pipe network tip place needs) and the concentration C (0.05mg/L) of the required effective chlorine in this moment, and by above-mentioned data substitution aforementioned formula (4), calculate accordingly at the dynamic chlorine demand C that adds chlorine point processing water 0, that is:
C 0 = 0.05 exp ( - 0.150 &times; ( 30 - 0.01111 ) ) + 0.53 = 5.02 mg / L
On the basis of the chlorine demand calculating, according to 120% ratio, carry out scene and add chlorine operation, chlorine-throwed quantity is 6mg/L, the concentration of pipe network tip effective chlorine is 0.065mg/L, its value, in allowed band, meets and meets the requirement of < < drinking water sanitary standard > > (GB5749-2006) to the chlorine residue of potable water network tip.
Embodiment 8
The present embodiment is usingd certain waterworks settling basin water outlet as research object, and the flow of inlet water of water supply plant is 3600m 3/ h, the COD of settling basin water outlet mnvalue is 8mg/L, and ammonia nitrogen is 0.21mg/L, and the pipe network tip residence time is 20 hours, and the concentration requirement of pipe network tip effective chlorine is 0.05mg/L.
Utilize the equipment of the on-line determination processing hydrodynamic(al) state chlorine demand of embodiment 1 to carry out on-line determination processing hydrodynamic(al) state chlorine demand; Wherein: described four identical with the volume of described alternate path injector with the first described path injector in the pulling flow type injector of transfer valve, be 90 μ L; Described four identical with the volume of described four-way road injector with the described three-way injector in the pulling flow type injector of transfer valve, be 80 μ L.
The equipment that utilizes above-mentioned on-line determination to process hydrodynamic(al) state chlorine demand carries out the method that on-line determination is processed hydrodynamic(al) state chlorine demand: use DPD aqueous solution as developer, the phosphate buffer solution of pH6.5 is as buffer solution, it is 515nm that UV-detector is measured wavelength, and utilizes the stock solution of step (1) preparation and the typical curve of embodiment 7 steps (2.1) foundation of embodiment 1.
The different technical scheme later from the step (2.2) of embodiment 7 for the present embodiment is:
(2.2) measure the concentration that remains effective chlorine after chlorine reacts with actual water body
(2.21) by controlling four described transfer valves with the pulling flow type injector of transfer valve, the sample introduction end of the pulling flow type injector with transfer valve described in four is connected respectively with sample channel; Utilize COD mnon-line monitoring instrument 15 is measured the COD that processes water mnvalue is 8mg/L, COD mnvalue >6mg/L, by the second T-valve adjustment on the sample channel of control alternate path injector, process the sample introduction ratio of water and pure water inlet, make the concentration that enters the processing water in described alternate path injector be 6mg/L and enter in alternate path injector; By controlling the first T-valve 22 on the sample channel of the first path injector 1, adjust the sample introduction ratio of chlorine storing solutions and pure water, while making aqueous sodium hypochlorite solution in step (1) chlorine storing solution hold-up vessel 11 in entering the first described path injector, in aqueous sodium hypochlorite solution, the concentration of effective chlorine is 6mg/L; Enter the control method of solution in described three-way injector and described four-way road injector and each path injector and divided by the concentration and the COD that above enter effective chlorine in the first described path injector mnbe worth identical outside, other condition is all identical with (2.11) in embodiment 7 steps (2.1);
(2.22) by controlling four described transfer valves with the pulling flow type injector of transfer valve, the sample introduction end of the pulling flow type injector with transfer valve described in four is connected with sample channel respectively, makes the liquid in four path injectors in step (2.21) enter reaction tank, sample introduction order is identical with (2.12) in step (2.1), the first path injector described in and described alternate path injector be sample introduction first simultaneously, make aqueous sodium hypochlorite solution and process after water mixes by rapid mixing container to enter in reaction tank and start to react, chlorine and processing water are after certain reaction time (t), described three-way injector and described four-way road injector while sample introduction, make DPD aqueous solution directly enter reaction tank, buffer solution enters reaction tank by rapid mixing container, chlorine is set to 0.1s with the reaction time (t) of processing water, 0.2s, 0.5s, 1s, 2s, 5s, 10s, 20s, 30s, 40s, 50s, 60s, 90s, a series of time such as 120s, chlorine reacts in the buffer solution of pH6.5 with DPD aqueous solution and generates red product, under 515nm, measure the intensity A of ultraviolet absorptivity of the product of gained redness, it is identical that the condition determinations of ultraviolet absorptivity etc. are described during with above-mentioned drawing standard curve,
(2.23) the expression formula C=a * A+b of the described typical curve that (2.13) in the intensity A substitution step (2.1) of the ultraviolet absorptivity of (2.22) 14 reaction time points of step being measured are set up, calculates chlorine and the concentration C of processing water corresponding residue effective chlorine after 14 reaction time points of experience;
(2.3) the Fitting Calculation is processed the dynamic chlorine demand of water
(2.31) using chlorine that step (2.22) arranges with 14 reaction time points (t) in reaction time of processing water as transverse axis, using step (2.23) chlorine with process water concentration C of corresponding residue effective chlorine after 14 reaction time points of experience and as the longitudinal axis, draw ln (C) ~ t and scheme;
(2.32) in ln (C) ~ t figure step (2.31) being drawn, ln (the C) ~ t data of 60s, 90s, tri-points of 120s are carried out linear regression fit, its related coefficient (R 2) be 0.988 (<0.99), do not conform to symbol matching requirement, then continue to increase the experimental data of 150s time point, ln (the C) ~ t data of 90s, 120s, tri-points of 150s are carried out to linear fit, its R 2be 0.992 (>0.99), continue to increase the data of 180s, 210s, tri-experimental points of 240s and to the reaction time, be that ln (the C) ~ t data of 6 points of 90s, 120s, 150s, 180s, 210s, 240s are carried out linear fit, its R 2be 0.998 (>0.99).Meet the R of fitting result 2be greater than 0.99 minimum time point (reaction time 90s point) and by approximate, thought that rapid reaction finishes the point starting with slow reaction, the reaction time of this point (90s) is similar to the time in the quick stage of thinking that chlorine consumes, and the consumption of this chlorine (0.450mg/L) is by the approximate short-term chlorine demand of thinking to process water; And the k value (0.165h of the matching that 6 experimental points between 90s ~ 240s are carried out -1) by the approximate kinetic constant of thinking slow reaction stage pseudo first order reaction.According to the technology characteristics of water factory, obtain and process water and arrive the disinfecting time t(30h that pipe network tip place needs) and the concentration C (0.05mg/L) of the required effective chlorine in this moment, and by above-mentioned data substitution aforementioned formula (4), calculate accordingly at the dynamic chlorine demand C that adds chlorine point processing water 0, that is:
C 0 = 0.05 exp ( - 0.165 &times; ( 20 - 0.025 ) ) + 0.45 = 1.80 mg / L
Before dilution, must process hydrodynamic(al) state chlorine demand is 2.4mg/L.On the basis of the chlorine demand calculating, according to 120% ratio, carry out scene and add chlorine operation, chlorine-throwed quantity is 2.9mg/L, the concentration of pipe network tip effective chlorine is 0.07mg/L, error, in allowed band, meets and meets the requirement of < < drinking water sanitary standard > > (GB5749-2006) to the chlorine residue of potable water network tip.

Claims (5)

1. on-line determination is processed an equipment for hydrodynamic(al) state chlorine demand, comprises residence spectrum unit and the On-line Control unit on four-way road; It is characterized in that:
The residence spectrum unit on described four-way road comprises four-way road injector, rapid mixing container, reaction tank, with the pulling flow type of transfer valve, stops controller, uviol lamp, monochromator and UV-detector; Described On-line Control unit comprises COD mnon-line monitoring instrument, T-valve, computing machine and the automation controller being connected with the residence spectrum unit on described four-way road;
Described four-way road injector comprises that four with the pulling flow type injector of transfer valve, and each pulling flow type injector with transfer valve comprises a sample introduction end and a reactive end;
The described pulling flow type with transfer valve stops controller and comprises a reactive end and a waste liquid end;
Described four with the reactive end of the first path injector in the pulling flow type injector of transfer valve, the reactive end of the reactive end of alternate path injector and four-way road injector by pipeline, be connected with one end of described rapid mixing container respectively; The other end of described rapid mixing container is connected with one end of described reaction tank by pipeline, and the reactive end that the other end of described reaction tank stops controller by pipeline and the described pulling flow type with transfer valve is respectively connected with described four reactive end with the three-way injector in the pulling flow type injector of transfer valve; Described monochromator is installed above described reaction tank, described uviol lamp is installed above described monochromator; Described UV-detector is installed below described reaction tank;
The waste liquid end that the described pulling flow type with transfer valve stops controller is provided with waste liquid vent pipe; The sample introduction end of described three-way injector is connected with the 3rd pure water pot with developer hold-up vessel respectively by the sample channel with the 3rd T-valve;
The sample introduction end of the first described path injector is connected with chlorine storing solution hold-up vessel and the first pure water pot respectively by the sample channel with the first T-valve; The sample introduction end of described alternate path injector is connected with the second pure water pot and processing water store tank respectively by the sample channel with the second T-valve; Described processing water store tank is by sample channel and described COD mnon-line monitoring instrument is connected, and processing water water intaking valve is installed on this sample channel; Described COD mnon-line monitoring instrument is connected with the sampling water spot with processing water water inlet pipe by sample channel; The sample introduction end of described four-way road injector is connected with the 4th pure water pot and buffer solution hold-up vessel respectively by the sample channel with the 4th T-valve;
The first described path injector, described alternate path injector, described three-way injector, described four-way road injector, described stop controller, described uviol lamp, described monochromator, described UV-detector, described COD mnon-line monitoring instrument, the first described T-valve, the second described T-valve, the 3rd described T-valve are all connected with automation controller by signal wire with the 4th described T-valve; Described computing machine by signal wire respectively with described automation controller, described COD mnon-line monitoring instrument and described UV-detector are connected.
2. on-line determination according to claim 1 is processed the equipment of hydrodynamic(al) state chlorine demand, it is characterized in that: the max cap. of described reaction tank is four described capacity sums with the pulling flow type injector of transfer valve.
3. on-line determination according to claim 1 and 2 is processed the equipment of hydrodynamic(al) state chlorine demand, it is characterized in that: described four identical with the volume of described alternate path injector with the first described path injector in the pulling flow type injector of transfer valve, be 80～120 μ L.
4. on-line determination according to claim 1 and 2 is processed the equipment of hydrodynamic(al) state chlorine demand, it is characterized in that: described four identical with the volume of described four-way road injector with the described three-way injector in the pulling flow type injector of transfer valve, be 70～100 μ L.
5. the equipment that utilizes on-line determination described in claim 1～4 any one to process hydrodynamic(al) state chlorine demand carries out the method that on-line determination is processed hydrodynamic(al) state chlorine demand, it is characterized in that, described method comprises the following steps:
(1), preparation stock solution
In chlorine storing solution hold-up vessel, fill it up with the aqueous sodium hypochlorite solution that concentration is 10mg/L, in developer hold-up vessel, fill it up with the N that the concentration as developer is 2mM, N-diethyl-Isosorbide-5-Nitrae-phenylenediamine aqueous solution or 2,2-connection nitrogen-bis--(3-ethyl-benzothiazole-6-sulfonic acid)-di-ammonium salts aqueous solution; When with N, N-diethyl-1,4-phenylenediamine aqueous solution is during as developer, in buffer solution hold-up vessel, fill it up with the phosphate buffer solution as the 2mM pH6.5 of buffer solution, when with 2,2-connection nitrogen-bis--(3-ethyl-benzothiazole-6-sulfonic acid)-di-ammonium salts aqueous solution is during as developer, fills it up with the inorganic acid aqueous solution that the pH as buffer solution is 1.8～2.3 in buffer solution hold-up vessel; Open and process water water intaking valve, make to process water from sample point by processing water water inlet pipe the COD that flows through mnon-line monitoring instrument joins to be processed in water store tank and fills it up with; Utilize COD mnon-line monitoring instrument is measured the COD that processes water mnvalue;
(2), on-line determination is processed hydrodynamic(al) state chlorine demand
(2.1) drawing standard curve
(2.11) four of four-way road injector are set identical with the volume of alternate path injector with the first path injector in the pulling flow type injector of transfer valve, three-way injector is identical with the volume of four-way road injector, by control, be arranged on four described transfer valves with the pulling flow type injector of transfer valve, the stock solution of pure water and step (1) preparation is entered respectively in four pulling flow type injectors with transfer valve by preset proportion, wherein, adjust the sample introduction ratio of chlorine storing solution and pure water, while making aqueous sodium hypochlorite solution in step (1) chlorine storing solution hold-up vessel in entering the first described path injector, in aqueous sodium hypochlorite solution, the concentration of effective chlorine is respectively six points in 0.1～3mg/L, and in aqueous sodium hypochlorite solution, the concentration of effective chlorine is 0mg/L, in described alternate path injector, add pure water, adjust developer N, N-diethyl-1,4-phenylenediamine aqueous solution or 2, the sample introduction ratio of 2-connection nitrogen-bis--(3-ethyl-benzothiazole-6-sulfonic acid)-di-ammonium salts aqueous solution and pure water, while making developer in step (1) developer hold-up vessel in entering described three-way injector, the concentration of developer is calculated according to sampling volume, and making the developer in reaction tank is 8:1～15:1 with the ratio of the volumetric molar concentration of effective chlorine, while making buffer solution in step (1) buffer solution hold-up vessel in entering described four-way road injector, the concentration of the buffer solution adding is determined according to the kind of described developer, when developer is N, N-diethyl-1, during 4-phenylenediamine aqueous solution, adjustment is as the sample introduction ratio of phosphate buffer solution and the pure water of the 2mM pH6.5 of buffer solution, the concentration of buffer solution in described four-way road injector is calculated according to sampling volume, making developer in reaction tank and the molar concentration rate of buffer solution is 1:1, when developer is 2, during 2-connection nitrogen-bis--(3-ethyl-benzothiazole-6-sulfonic acid)-di-ammonium salts aqueous solution, the inorganic acid aqueous solution that adjustment is 1.8～2.3 as the pH of buffer solution and the sample introduction ratio of pure water, the concentration of damping fluid in described four-way road injector is calculated according to sampling volume, the pH that makes the mixed liquor in reaction tank is 3,
(2.12) by controlling four described transfer valves with the pulling flow type injector of transfer valve, the sample introduction end of the pulling flow type injector with transfer valve described in four is connected with sample channel respectively, makes the liquid in four path injectors in step (2.11) enter reaction tank, sample introduction is sequentially: the first described path injector and described alternate path injector be sample introduction first simultaneously, after being mixed by rapid mixing container, aqueous sodium hypochlorite solution and pure water enter in reaction tank, after 0.5～2 second, described three-way injector and described four-way road injector while sample introduction, make developer directly enter reaction tank, buffer solution enters reaction tank by rapid mixing container, chlorine reacts in buffer solution with developer and generates the coloured product of tool, and be respectively six points in 0.1～3mg/L by the concentration that ultraviolet spectrum is measured respectively selected effective chlorine, and in aqueous sodium hypochlorite solution, the concentration of effective chlorine is the intensity of the ultraviolet absorptivity of the coloured product of 0mg/L gained tool, concrete ultraviolet determination wavelength will be determined according to developer, when developer is N, N-diethyl-1, during 4-phenylenediamine aqueous solution, ultraviolet determination wavelength is 515nm, when developer is 2, during 2-connection nitrogen-bis--(3-ethyl-benzothiazole-6-sulfonic acid)-di-ammonium salts aqueous solution, ultraviolet determination wavelength is 728nm,
(2.13) using the intensity of the corresponding ultraviolet absorptivity while being respectively six points in 0.1～3mg/L and 0mg/L of the concentration of effective chlorine in the aqueous sodium hypochlorite solution that step (2.12) measures as transverse axis, the concentration of the effective chlorine in the liquor natrii hypochloritis of usining in corresponding the first described path injector is as longitudinal axis drawing standard curve, the line linearity of going forward side by side returns, and sets up the expression formula of typical curve of the cl concn of the effective chlorine in ultraviolet absorptivity and described the first path injector:
C＝a×A+b (5)
Wherein, C is the concentration as the effective chlorine of the longitudinal axis, the mg/L of unit;
A is the intensity as the ultraviolet absorptivity of transverse axis, and unit is cm -1;
A is the slope of typical curve, and unit is cm * mg/L;
B is the transversal distance of typical curve, and unit is mg/L;
(2.2) measure the concentration that remains effective chlorine after chlorine reacts with actual water body
(2.21) by controlling four described transfer valves with the pulling flow type injector of transfer valve, the sample introduction end of the pulling flow type injector with transfer valve described in four is connected respectively with sample channel; Utilize COD mnon-line monitoring instrument is measured the COD that processes water mnvalue; If COD mnvalue, between 2～6mg/L, makes to process water and directly enters in described alternate path injector, if COD mnvalue >6mg/L,, by the second T-valve adjustment processing water on the sample channel of control alternate path injector and the sample introduction ratio of pure water inlet, making the concentration of the processing water in the alternate path injector described in entering is 2～6mg/L; If COD mnvalue <2mg/L, is concentrated into 2～6mg/L by processing water rotary evaporation, and is joined in described alternate path injector; By controlling the first T-valve on the sample channel of the first path injector, adjust the sample introduction ratio of chlorine storing solution and pure water, while making aqueous sodium hypochlorite solution in step (1) chlorine storing solution hold-up vessel in entering the first described path injector, the concentration of effective chlorine and COD in aqueous sodium hypochlorite solution mnbe worth identical; Enter the control method of solution in described three-way injector and described four-way road injector and each path injector and divided by the concentration and the COD that above enter effective chlorine in the first described path injector mnbe worth identical outside, other condition is all identical with (2.11) in step (2.1);
(2.22) by controlling four described transfer valves with the pulling flow type injector of transfer valve, the sample introduction end of the pulling flow type injector with transfer valve described in four is connected with sample channel respectively, makes the liquid in four path injectors in step (2.21) enter reaction tank, sample introduction order: the first described path injector and described alternate path injector be sample introduction first simultaneously, make aqueous sodium hypochlorite solution and process after water mixes by rapid mixing container to enter in reaction tank and start to react, chlorine and processing water are after certain reaction time (t), described three-way injector and described four-way road injector while sample introduction, make developer directly enter reaction tank, buffer solution enters reaction tank by rapid mixing container, chlorine reacts in buffer solution with developer and generates the coloured product of tool, and by the intensity of its ultraviolet absorptivity of ultraviolet spectroscopy, concrete ultraviolet determination wavelength will be determined according to developer, when developer is N, N-diethyl-1, during 4-phenylenediamine aqueous solution, ultraviolet determination wavelength is 515nm, when developer is 2,2-connection nitrogen-bis--(3-ethyl-benzothiazole-6-sulfonic acid)-di-ammonium salts aqueous solution, ultraviolet determination wavelength is 728nm, chlorine is set at least 10 reaction time points within the scope of 0.1s～15min with the reaction time (t) of processing water,
(2.23) the expression formula C=a * A+b of the described typical curve that (2.13) in the intensity A substitution step (2.1) of the ultraviolet absorptivity of (2.22) at least 10 reaction time points of step being measured are set up, calculates chlorine and the concentration C of processing water corresponding effective chlorine after at least 10 reaction time points of experience;
(2.3) the Fitting Calculation is processed the dynamic chlorine demand of water
(2.31) using chlorine that step (2.22) arranges with at least 10 reaction time points (t) in reaction time of processing water as transverse axis, using step (2.23) chlorine with process water concentration of corresponding residue effective chlorine after at least 10 reaction time points of experience and as the longitudinal axis, draw ln (C)～t and scheme;
(2.32) in ln (C)～t figure step (2.31) being drawn, at least 10 reaction time points (t), three the longest points of reaction time start to carry out linear regression fit, as the related coefficient (R of fitting result 2) lower than 0.99, repeating step (2.22), increase chlorine and the time point of processing the reaction time (t) of water, make the reaction time of the time point of increase be greater than the maximal value in original at least 10 reaction time point, then repeating step (2.31), and middle three the longest points of reaction time of at least 10 reaction time points (t) start to carry out linear regression fit in ln (the C)～t figure again step (2.31) being drawn, until the related coefficient (R of its fitting result 2) be greater than 0.99;
(2.33) as the related coefficient (R of the fitting result of step (2.32) 2) be greater than 0.99, from at least 10 reaction time points (t), choose a longest point of reaction time in a point except the point that step (2.32) has been chosen, be increased in the point that step (2.32) chosen and proceed linear regression fit; As related coefficient (R 2) be still greater than 0.99, from at least 10 reaction time points (t), choose a longest point of reaction time in a point except the point that step (2.32) and this step have been chosen, be increased in this step point that matching has been chosen last time and proceed linear regression fit; As related coefficient (R 2) be still greater than 0.99, continue this operation;
(2.34) as the related coefficient (R of the linear regression fit of step (2.33) 2) be less than 0.99, end step (2.33); Finally meet the related coefficient (R of linear regression fit result 2) be greater than 0.99 the point of choosing increasing thought that by approximate the rapid reaction stage finishes the point starting with the slow reaction stage from least 10 reaction time points (t), the reaction time of this point is thought rapid reaction stage chlorine and the time that processing water contacts, to be set as t by approximate 0, and the consumption of this chlorine is by the approximate short-term chlorine demand of thinking to process water, is set as D; And last related coefficient (R 2) be greater than 0.99 matching k value by the approximate kinetic constant of thinking slow reaction stage pseudo first order reaction;
(2.35) according to the technology characteristics of water factory, obtain and process water and arrive disinfecting time t that pipe network tip place needs and the concentration C of this required effective chlorine constantly, and by D, the k, the t that obtain in step (2.34) 0value substitution formula (4), calculates and adds the dynamic chlorine demand C that chlorine point is processed water 0; Described disinfecting time t is the T.T. contacting with processing water with slow reaction stage chlorine in the rapid reaction stage;
C 0 = C exp ( - k &times; ( t - t 0 ) ) + D - - - ( 4 )
Wherein: C is the concentration of effective chlorine, the mg/L of unit;
K is first order reaction kinetics constant, and unit is h -1;
C 0be that on-line determination is processed hydrodynamic(al) state chlorine demand, unit is mg/L;
D is short-term chlorine demand, and unit is mg/L;
T is the T.T. contacting with processing water with slow reaction stage chlorine in the rapid reaction stage, and unit is h;
T 0be the time that rapid reaction stage chlorine contacts with processing water, unit is h.
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