CN102914510A - 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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CN102914510A
CN102914510A CN2012103609883A CN201210360988A CN102914510A CN 102914510 A CN102914510 A CN 102914510A CN 2012103609883 A CN2012103609883 A CN 2012103609883A CN 201210360988 A CN201210360988 A CN 201210360988A CN 102914510 A CN102914510 A CN 102914510A
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chlorine
injector
water
reaction
concentration
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CN102914510B (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) attitude chlorine demand
Technical field
The invention belongs to water treatment sterilization field, particularly a kind of on-line determination is processed the Apparatus and method for of hydrodynamic(al) attitude chlorine demand.
Background technology
Sterilization is requisite link in the 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 the water delivery process.In order to guarantee the microbial safety of water quality, the throwing amount of sanitizer will guarantee that the pipe network tip has certain sanitizer level, otherwise may cause pipe network tip and water,tap microbial safety to be difficult to ensure.When in processing water, containing higher organism and during the DBPs precursor such as bromine, sanitizer can react with it generate have carcinogenic, teratogenesis, the halogenated disinfection by-products of mutagenesis, and Drinking Water in China standard (GB5749-2006) limits wherein 26 kinds of DBPs.In order to guarantee the chemical safety of water quality, the throwing amount of sanitizer will be lower than certain limit, the excessive waste that not only causes economically of dosage, and can cause exceeding standard of DBPs, in addition, using chloramines as the water supply plant of secondary sterilization agent for part, all is to add ammonia nitrogen after adding a period of time of chlorine generally, if add the surplus that the chlorine deficiency can cause ammonia nitrogen, add excessive three chloramines etc. that then 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 at present waterworks adjustment adds chlorine dose mainly contains empirical method, adjusts chlorine dosage, adjusts chlorine dosage, adjusts chlorine dosage according to the concentration of pipe network tip effective chlorine according to clear water reserviors water delivering orifice chlorine content according to the water yield, but all there is certain defective in above several method.The restriction that empirical method can be subject to artificial subjective factor is larger, tends to cause huge error; Change the impact that the method for adjusting chlorine dosage is not considered variation water quality according to the water yield, and on the dosage of determining the unit mass sanitizer, also have very large difficulty; 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 as required chlorination system (number of patent application: CN201020682570.0), its main technical schemes is to be provided with ammonia nitrogen on-line monitoring instrument at the chlorination place, thereby hydraulic detention time is that rapid feedback and the adjusting that chlorine residue on-line monitoring instrument is realized chlorine demand established in 4-6 minute position behind the chlorination point.But still belonging to, the method lag behind to regulate, in the unusual big ups and downs of water quality and limit by technology to be difficult to take fast can cause the situation not up to standard that supplies water in the situation of the measure of regulating.In addition, the method has only considered to consume with in a short time (4-6 minute) reaction of chlorine the material of chlorine, thereby and not have to consider can with the material of chlorine slow reaction consumption chlorine, still there is risk in this for the water factory of the remote transmission ﹠ distribution of needs.Therefore, exploitation can be carried out the short-term chlorine demand of front end adjusting, simultaneously computing water and the dosage control technology of long-term chlorine demand according to processing water water quality situation, is the difficulties of needing solution during present Research And Engineering is used badly.
The residence spectrum technology be a kind of can the realization response thing between rapid mixing and measure its in a short time technology of concentration change.First residence spectrum equipment is based on the research (Biochem.J.Vol.91 of Gibson and Milnes, 161 (1964)), afterwards at Alan Queen(patent No. US4399101), the Christopher Bull(patent No.: US5098186) etc. realized the functions such as controllable adjustment, computer linking automation control of complete rapid mixing, reaction tank capacity under people's the updating, according to the people's such as Echigo and Minear be sharp research (Environ.Sci.﹠amp; Technol.Vol.53 (2006)), position with the chlorine reaction in the natural organic matter in the water body can be divided into rapid reaction position and slow reaction position, therefore measures short-term chlorine demand and the long-term chlorine demand of processing water for the residence spectrum technology theoretical foundation is provided.
The present invention utilizes online residence spectrum equipment to carry out chlorine and processes reaction between the water, accurately chlorine detection and the consumption in processing water a period of time, and draw the speed that the position of processing the amount that can consume with the needs of chlorine rapid reaction component chlorine in the water and slow reaction consumes chlorine by certain dynamics the Fitting Calculation, thereby the chlorine demand of computing water is guaranteed safety, economy, stable water supply fast.
Summary of the invention
One of purpose of the present invention provides a kind of line that can be implemented in and measures the equipment of processing hydrodynamic(al) attitude chlorine demand.
Two of purpose of the present invention provides the method that a kind of on-line determination is processed hydrodynamic(al) attitude chlorine demand, in the hope of short-term chlorine demand and the long-term chlorine demand of can on-line determination processing water, thereby determine to provide theoretical foundation for what add chlorine dose to water treatment, and when water quality occurs than great fluctuation process, 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 the line traffic control unit, namely forms so-called online residence spectrum equipment.Utilize described online residence spectrum equipment on-line Accurate Measurement chlorine and the concentration of processing water residue effective chlorine after experiencing one period reaction time, and by logarithm value and the linear regression fit in reaction time of the concentration of residue effective chlorine are divided into rapid reaction and slow reaction with the reaction of chlorine and processing water, and set up accordingly the computing formula of the long-term chlorine demand of the short-term chlorine demand of quick phase process water and slow reaction phase process water, and according to the requirement of pipe network tip place chlorine content and residence Time Calculation are added the dynamic chlorine demand that chlorine point is processed water, thereby can realize adding the control in early stage of 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) attitude chlorine demand is residence spectrum unit and the On-line Control unit that online residence spectrum equipment comprises the four-way road; Utilize the concentration of residence spectrum unit Accurate Measurement chlorine and the effective chlorine after processing water reaction a period of time on described four-way road, and utilize described On-line Control unit to realize real-time, automatic, on-line determination processing hydrodynamic(al) attitude 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, stop controller, uviol lamp, monochromator and UV-detector with the pulling flow type of transfer valve; Described On-line Control unit comprises COD Mn(permanganate index) on-line monitoring instrument, T-valve, computing machine and the automation controller that is connected with the residence spectrum unit on described four-way road.
The structure of described four-way road injector is copied existing instrument: comprise 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.
Described pulling flow type with transfer valve stops the structure of controller, comprises a reactive end and a waste liquid end.
The reactive end of described four reactive end with the first path injector in the pulling flow type injector of transfer valve, alternate path injector and the reactive end of four-way road injector are connected with an end of described rapid mixing container by pipeline respectively; The other end of described rapid mixing container is connected with an end of described reaction tank by pipeline, and the other end of described reaction tank is connected with described four reactive end with the three-way injector in the pulling flow type injector of transfer valve with the reactive end that described pulling flow type with transfer valve stops controller by pipeline respectively; 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 described pulling flow type with transfer valve stops controller is equipped with the waste liquid vent pipe; The sample introduction end of described three-way injector is connected with the 3rd pure water pot with the developer hold-up vessel respectively by the sample channel with the 3rd T-valve.
The sample introduction end of described the first 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 MnThe on-line monitoring instrument is connected, and at this sample channel processing water water intaking valve is installed; Described COD MnThe on-line monitoring instrument by sample channel be connected with the sampling water spot of processing the water water inlet pipe; 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.
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 described the 4th T-valve all are connected with automation controller by signal wire; 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, described four volumes with the pulling flow type injector of transfer valve all arrange finish after, the max cap. that the max cap. of described reaction tank should be set to described reaction tank is described four capacity sums with the pulling flow type injector of transfer valve.The volume of described reaction tank stops controller control by described pulling flow type with transfer valve.
Described four identical with the volume of described alternate path injector with described the first 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) attitude chlorine demand carries out on-line determination to be processed the principle of the method for hydrodynamic(al) attitude chlorine demand and be: according to processing the different of material and chlorine reaction velocity in the water, the material in the processing water can be divided into rapid reaction material and slow reaction material.The rapid reaction material is mainly in the reaction of initial reaction stage stage and chlorine and consumed rapidly, its corresponding chlorine demand is called as the 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 that meets about cl concn and rapid reaction material as; And the slow reaction material mainly reacts and is consumed slowly at medium-term and long-term stage and the chlorine of reaction, its corresponding chlorine demand is called as long-term chlorine demand herein, this stage midium or long term is called as the slow reaction stage, because in the disinfecting process of processing water, it is not enough far away that the throwing amount of chlorine is compared the stoichiometry of processing slow reaction material in the water, therefore the reaction in this slow reaction stage can be regarded the pseudo first order reaction kinetics relation that meets 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 the first order reaction kinetics constant, and unit is h -1
Ln (C) is linear with reaction time t as can be known behind the integration, and linear fit can get the value of its first order reaction kinetic constant k, is that equal-volume mixes because of solutions of chlorine with processing water again, and the concentration of chlorine and processing water is all diluted half for original concentration after mixing.Calculate accordingly the equation that changes 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) attitude chlorine demand, unit is mg/L;
D is the short-term chlorine demand, and unit is mg/L;
T is the rapid reaction stage and slow reaction stage chlorine and the T.T. of processing water and contacting, and unit is h;
t 0The time that rapid reaction stage chlorine contacts with processing water, unit is h.
Can obtain D, k, t by following (2.3) step the Fitting Calculation 0Value, and obtain to process water according to the technology characteristics of water factory and arrive disinfecting time t that pipe network tip place needs and the concentration C of this required effective chlorine constantly, can retrodict out adds 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) attitude chlorine demand carries out on-line determination processing hydrodynamic(al) attitude chlorine demand may further comprise the 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, the concentration of filling it up with in the developer hold-up vessel as developer is the N of 2mM, N-diethyl-1,4-phenylenediamine (DPD aqueous solution) aqueous solution or 2,2-connection nitrogen-two-(3-ethyl-benzothiazole-6-sulfonic acid)-di-ammonium salts (ABTS aqueous solution) aqueous solution; When with the DPD aqueous solution during as developer, in the buffer solution hold-up vessel, fill it up with the phosphate buffer solution as the 2mM pH6.5 of buffer solution, when with the ABTS aqueous solution during as developer, in the buffer solution hold-up vessel, fill it up with pH as buffer solution and be 1.8 ~ 2.3 inorganic acid aqueous solution (for example hydrochloric acid solution of 0.01mol/L); Open and process the water water intaking valve, make process water from sample point by processing water water inlet pipe and the COD that flows through MnThe on-line monitoring instrument joins in the processing water store tank and fills it up with; Utilize COD MnThe on-line monitoring instrument is measured the COD that processes water MnValue;
(2), on-line determination is processed hydrodynamic(al) attitude chlorine demand
(2.1) drawing standard curve
(2.11) four of four-way road injector are set with the volume identical (preferably be 80 ~ 120 μ Ls) of the first path injector in the pulling flow type injector of transfer valve with the alternate path injector, the volume identical (preferably being 70 ~ 100 μ L) of three-way injector and four-way road injector; Be installed in described four transfer valves with the pulling flow type injector of transfer valve by control, 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, when making aqueous sodium hypochlorite solution in step (1) the chlorine storing solution hold-up vessel in entering described the first path injector, the concentration of effective chlorine is respectively six points among 0.1 ~ 3mg/L in the aqueous sodium hypochlorite solution, and in the aqueous sodium hypochlorite solution 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, when making developer (DPD aqueous solution or ABTS aqueous solution) in step (1) the developer hold-up vessel in entering described three-way injector, the concentration of developer is calculated according to sampling volume, and making the ratio of developer and the volumetric molar concentration of effective chlorine in reaction tank is 8:1 ~ 15:1; When making buffer solution in step (1) the buffer solution hold-up vessel in entering described four-way road injector, the concentration of the buffer solution that adds is decided according to the kind of described developer, when developer is the 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, so that the concentration of buffer solution is calculated according to sampling volume in the injector of described four-way road, making developer in reaction tank and the molar concentration rate of buffer solution is 1:1, when developer is the ABTS aqueous solution, adjustment is 1.8 ~ 2.3 inorganic acid aqueous solution and the sample introduction ratio of pure water as the pH of buffer solution, so that the concentration of damping fluid is calculated according to sampling volume in the injector of described four-way road, the pH that makes the mixed liquor in reaction tank is 3;
(2.12) by described four transfer valves with the pulling flow type injector of transfer valve of control, the sample introduction end of four described pulling flow type injectors with transfer valve is connected with sample channel respectively, makes in the step (2.11) liquid in four path injectors enter reaction tank; Sample introduction sequentially is: described the first path injector and described alternate path injector be sample introduction at first simultaneously, so that aqueous sodium hypochlorite solution and pure water enter in the reaction tank after mixing by the rapid mixing container, 0.5 after ~ 2 seconds, described three-way injector and described four-way road injector be sample introduction simultaneously, so that developer directly enters reaction tank, buffer solution enters reaction tank by the rapid mixing container, chlorine and developer react in buffer solution and generate the coloured product of tool, and be respectively six points among 0.1 ~ 3mg/L with the concentration that ultraviolet spectrum is measured respectively selected effective chlorine, and in the aqueous sodium hypochlorite solution 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 decided according to developer, when developer is the DPD aqueous solution, the ultraviolet determination wavelength is 515nm, when developer was the ABTS aqueous solution, the ultraviolet determination wavelength was 728nm; Described ultraviolet determination wavelength is regulated by monochromator;
The intensity A of corresponding ultraviolet absorptivity was as transverse axis when the concentration of effective chlorine was respectively six points among 0.1 ~ 3mg/L and 0mg/L in the aqueous sodium hypochlorite solution of (2.13) measuring with step (2.12), with the concentration C of the effective chlorine among the liquor natrii hypochloritis in corresponding described the first path injector 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 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 rear concentration that remains effective chlorine of chlorine and actual water body reaction
(2.21) by described four transfer valves with the pulling flow type injector of transfer valve of control, the sample introduction end of four described pulling flow type injectors with transfer valve is connected respectively with sample channel; Utilize COD MnThe on-line monitoring instrument is measured the COD that processes water MnValue; If COD MnValue then makes processing water directly enter in the described alternate path injector, if COD between 2 ~ 6mg/L 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, is 2 ~ 6mg/L so that enter the concentration of the processing water in the described alternate path injector then; If COD MnValue＜2mg/L will process the water rotary evaporation and be concentrated into 2 ~ 6mg/L, and it is joined in the described alternate path injector; Adjust the sample introduction ratio of chlorine storing solution and pure water by the first T-valve on the sample channel of controlling the first path injector, when making aqueous sodium hypochlorite solution in step (1) the chlorine storing solution hold-up vessel in entering described the first path injector, the concentration of effective chlorine and COD in the aqueous sodium hypochlorite solution MnBe worth identical; Enter solution in described three-way injector and the described four-way road injector and each path injector control method and divided by on enter concentration and the COD of effective chlorine in described the first path injector MnBe worth identical outside, other condition is all identical with (2.11) in the step (2.1);
(2.22) by described four transfer valves with the pulling flow type injector of transfer valve of control, the sample introduction end of four described pulling flow type injectors with transfer valve is connected with sample channel respectively, makes in the step (2.21) liquid in four path injectors enter reaction tank; The sample introduction order is identical with (2.12) in the step (2.1), it is at first simultaneously sample introduction of described the first path injector and described alternate path injector, so that entering after mixing by the rapid mixing container, aqueous sodium hypochlorite solution and processing water begins reaction in the reaction tank, after chlorine and the processing water process certain reaction time (t), described three-way injector and described four-way road injector be sample introduction simultaneously, so that developer directly enters reaction tank, buffer solution enters reaction tank by the rapid mixing container, chlorine and developer react in buffer solution and generate the coloured product of tool, and with the intensity of its ultraviolet absorptivity of ultraviolet spectroscopy; Concrete ultraviolet determination wavelength will be decided according to developer, and when developer was the DPD aqueous solution, the ultraviolet determination wavelength was 515nm, and when developer was the ABTS aqueous solution, the ultraviolet determination wavelength was 728nm; Described ultraviolet determination wavelength is regulated by monochromator; Chlorine is set at least 10 interior reaction time points of 0.1s ~ 15min scope with the reaction time (t) of processing water;
The expression formula C=a of the described typical curve that (2.13) in the intensity A substitution step (2.1) of the ultraviolet absorptivity of (2.23) (2.22) at least 10 reaction time points of step being measured are set up * A+b calculates chlorine and the concentration C of processing water corresponding effective chlorine behind at least 10 reaction time points of experience;
(2.3) the Fitting Calculation is processed the dynamic chlorine demand of water
(2.31) with at least 10 reaction time points (t) in step (2.22) chlorine that arranges and the reaction time of processing water as transverse axis, with step (2.23) chlorine with process water concentration of corresponding residue effective chlorine behind at least 10 reaction time points of experience and draw ln (C) ~ t as the longitudinal axis and scheme;
(2.32) middle three the longest points of reaction time of at least 10 reaction time points (t) begin to carry out linear regression fit among the ln (C) that step (2.31) is drawn ~ t figure, as the related coefficient (R of fitting result 2) be lower than 0.99, repeating step (2.22) then, increase chlorine and process the time point in the reaction time (t) of water, so that the reaction time of the time point that increases is 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) begin to carry out linear regression fit among the ln (C) that again step (2.31) is drawn ~ t figure, until the related coefficient (R of its fitting result 2) greater than 0.99;
(2.33) as the related coefficient (R of the fitting result of step (2.32) 2) greater than 0.99, then from least 10 reaction time points (t), choose a longest point of reaction time in the 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) still greater than 0.99, then from least 10 reaction time points (t), choose a longest point of reaction time in the point except the point that step (2.32) and this step have been chosen, be increased in this step point that match has been chosen last time and proceed linear regression fit; As related coefficient (R 2) still greater than 0.99, then continue this operation;
(2.34) as the related coefficient (R of the linear regression fit of step (2.33) 2) less than 0.99, ending step (2.33); Satisfy at last linear regression fit result's related coefficient (R 2) the point of choosing from least 10 reaction time points (t) that increases greater than 0.99 namely thought that by approximate the rapid reaction stage finishes the point that begins with the slow reaction stage, the reaction time of this point is set as t by the approximate time of thinking the rapid reaction stage that chlorine consumes 0, and the consumption of this chlorine is set as D namely by the approximate short-term chlorine demand of thinking to process water; And last related coefficient (R 2) the k value of match greater than 0.99 is namely by the approximate kinetic constant of thinking slow reaction stage pseudo first order reaction;
(2.35) obtain to process water according to the technology characteristics of water factory and arrive disinfecting time t that pipe network tip place needs and the concentration C of this required effective chlorine constantly, and with D, the k, the t that obtain in the 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 0Thereby can realize processing the more accurate estimation of hydrodynamic(al) attitude 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 that calculates, 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 " drinking water sanitary standard " (GB5749-2006) to the requirement of potable water network tip chlorine residue, be unlikely to again the excessive sanitizer that adds.
Equipment and method that on-line determination of the present invention is processed hydrodynamic(al) attitude chlorine demand have following technique effect:
(1) before adding chlorine, measures 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, namely under the concentration prerequisite that guarantees effective chlorine after certain reaction time, process the chlorine demand of water;
(3) processing water short-term chlorine demand and long-term chlorine demand can be measured simultaneously, different sterilization strategies can be served;
(4) after repeatedly measuring, can obtain in follow-up mensuration, can simplify the mensuration program about processing a large amount of water quality informations of water, namely reduce the time point that chlorine consumes; And can utilize historical data that the variation water quality of processing water is carried out reasonable prediction, before the water quality big ups and downs, carry out emergent the preparation;
(5) on-line determination, robotization control reduces personal error;
(6) do not need original water treatment building is carried out large-scale redevelopment, only need establish a sampled point and carry out sampling and measuring, cost is low, uses simple to operate.
Description of drawings
Fig. 1. on-line determination of the present invention is processed the equipment synoptic diagram of hydrodynamic(al) attitude chlorine demand.
Reference numeral
1. the first path injector 2. alternate path injectors 3. three-way injectors
4. four-way road injector 5. rapid mixing containers 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
12. the first pure water pot 13. second pure water pots 14. are 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 pipes 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. is processed the water water intaking valve
27. automation controller 28. computing machines
Embodiment
Embodiment 1
As research object, the flow of inlet water of water supply plant is 6200m to present embodiment with certain waterworks settling basin water outlet 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) attitude chlorine demand as shown in Figure 1 to carry out on-line determination processing hydrodynamic(al) attitude chlorine demand.The equipment of described on-line determination processing hydrodynamic(al) attitude 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, the 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 machines and the automation controller that is connected with the residence spectrum unit on described four-way road.
Described four-way road injector comprises 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 described pulling flow type injector with transfer valve, sample introduction end or the reactive end that can guarantee four described pulling flow type injectors with transfer valve only have an end to be connected with pipeline, be that the sample introduction end is when being connected with sample channel, reactive end is closed, and reactive end is when being connected with pipeline, and the sample introduction end is closed; Wherein, the described reactive end of 3 described pulling flow type injectors with transfer valve is connected by pipeline with reaction tank with the rapid mixing container; Sample channel at first is connected with the sample introduction end of described pulling flow type injector with transfer valve, and sample is entered in the sample channel, and afterwards, sample enters rapid mixing container and the reaction tank that is connected with reactive end through sample channel; Transfer valve is by computer control.The pulling flow type syringe is used for realizing that sample enters and flows out pipeline.
Described pulling flow type with transfer valve stops the structure of controller, comprises a reactive end and a waste liquid end; The reactive end that described pulling flow type with transfer valve stops controller at first is connected with reaction tank by pipeline, making reacted waste liquid enter described pulling flow type with transfer valve stops in the controller, simultaneously described pulling flow type stop controller with transfer valve can be controlled the solvent in the described reaction tank, afterwards, reacted waste liquid is discharged through the waste liquid vent pipe that is connected with waste liquid end that described pulling flow type with transfer valve stops controller.
The reactive end of described four reactive end with the first path injector 1 in the pulling flow type injector of transfer valve, alternate path injector 2 and the reactive end of four-way road injector 4 are connected with an end of described rapid mixing container 5 by pipeline respectively; The other end of described rapid mixing container is connected with an end of described reaction tank 6 by pipeline, and the other end of described reaction tank 6 is connected with described four reactive end with the three-way injector 3 in the pulling flow type injector of transfer valve with the reactive end that described pulling flow type with transfer valve stops controller 7 by pipeline respectively; 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 described pulling flow type with transfer valve stops controller 7 is equipped 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 described the first path injector 1 is connected with chlorine storing solution hold-up vessel the 11 and first pure water pot 12 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 processed the flow of water and pure water in order to control; Described processing water store tank 14 is by sample channel and described COD MnOn-line monitoring instrument 15 is connected, and at this sample channel processing water water intaking valve 26, described COD is installed MnOn-line monitoring instrument 15 by sample channel be connected with the sampling water spot of processing water water inlet pipe 16; 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.
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 described the 4th T-valve all are connected with automation controller 27 by signal wire; 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 described the 4th 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 described four capacity sums with the pulling flow type injector of transfer valve.
Described four identical with the volume of described alternate path injector with described the first 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) attitude chlorine demand carries out the method that on-line determination is processed hydrodynamic(al) attitude chlorine demand: use the 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, filling it up with in developer hold-up vessel 20 as the concentration of developer is the DPD aqueous solution of 2mM, fills it up with the phosphate buffer solution as the 2mM pH6.5 of buffer solution in buffer solution hold-up vessel 18; Open and process water water intaking valve 26, make process water from sample point by processing water water inlet pipe 16 and the COD that flows through MnOn-line monitoring instrument 15 joins in the processing water store tank 14 and fills it up with; Utilize COD MnThe on-line monitoring instrument is measured the COD that processes water MnValue;
When the volume of the liquid in above chlorine storing solution hold-up vessel 11, developer hold-up vessel 20, buffer solution hold-up vessel 18 and the processing water store tank 14 is lower than tank body volume 1/3, think to 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) attitude chlorine demand
(2.1) drawing standard curve
(2.11) it is identical with the volume of alternate path injector 2 with the first path injector 1 in the pulling flow type injector of transfer valve four of four-way road injector to be set, be 80 μ L, it is identical with the volume of four-way road injector 4 that three-way injector 3 is set, and is 70 μ L; Be installed in described four transfer valves with the pulling flow type injector of transfer valve by control, the sample introduction end of four described pulling flow type injectors with transfer valve is connected with sample channel respectively, and by the T-valve on the sample channel of four path injectors of control, aqueous sodium hypochlorite solution in the control chlorine storing solution hold-up vessel 11, developer in the developer hold-up vessel 20, buffer solution in the buffer solution hold-up vessel 18, process the processing water in the 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 reaction tank 6 in pure water in the 3rd pure water pot 21 and the 4th pure water pot 17 makes the stock solution of pure water and step (1) preparation enter 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, when making aqueous sodium hypochlorite solution in step (1) the chlorine storing solution hold-up vessel 11 in entering described the first path injector, the concentration of effective chlorine is respectively 0mg/L(in contrast in the aqueous sodium hypochlorite solution), 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, when making developer DPD aqueous solution in step (1) the developer hold-up vessel 20 in entering described three-way injector, the concentration of developer is calculated according to sampling volume, and making the ratio of DPD aqueous solution and the volumetric molar concentration of effective chlorine in reaction tank 6 is 8:1; When making buffer solution in step (1) the 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, so that the concentration of buffer solution is calculated according to sampling volume in the injector of described four-way road, making DPD aqueous solution in reaction tank 6 and the molar concentration rate of buffer solution is 1:1;
(2.12) by described four transfer valves with the pulling flow type injector of transfer valve of control, the sample introduction end of four described pulling flow type injectors with transfer valve is connected with sample channel respectively, makes in the step (2.11) liquid in four path injectors enter reaction tank; Sample introduction sequentially is: described the first path injector and described alternate path injector be sample introduction at first simultaneously, so that aqueous sodium hypochlorite solution and pure water enter in the reaction tank after mixing by the rapid mixing container, 0.5 after second, described three-way injector and described four-way road injector be sample introduction simultaneously, so that the DPD aqueous solution directly enters reaction tank, the buffer solution of pH6.5 enters reaction tank by the rapid mixing container, chlorine and DPD aqueous solution are reacted in buffer solution and are generated the coloured product of tool, and the concentration of measuring respectively selected effective chlorine under the 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 is regulated by monochromator;
(2.13) concentration of effective chlorine is respectively 0mg/L(in contrast in the aqueous sodium hypochlorite solution of measuring with step (2.12)), 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, with the concentration C of the effective chlorine among the liquor natrii hypochloritis in corresponding described the first path injector 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 rear concentration that remains effective chlorine of chlorine and actual water body reaction
(2.21) by described four transfer valves with the pulling flow type injector of transfer valve of control, the sample introduction end of four described pulling flow type injectors with transfer valve 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 directly enters in the alternate path injector processing water between 2 ~ 6mg/L; Adjust the sample introduction ratio of chlorine storing solution and pure water by the first T-valve 22 on the sample channel of controlling the first path injector 1, when making aqueous sodium hypochlorite solution in step (1) the chlorine storing solution hold-up vessel 11 in entering described the first path injector, the concentration of effective chlorine is 2mg/L in the aqueous sodium hypochlorite solution; Enter solution in described three-way injector and the described four-way road injector and each path injector control method and divided by on enter concentration and the COD of effective chlorine in described the first path injector MnBe worth identical outside, other condition is all identical with (2.11) in the step (2.1);
(2.22) by described four transfer valves with the pulling flow type injector of transfer valve of control, the sample introduction end of four described pulling flow type injectors with transfer valve is connected with sample channel respectively, makes in the step (2.21) liquid in four path injectors enter reaction tank; Sample introduction order is identical with (2.12) in the step (2.1), i.e. described the first path injector and described alternate path injector sample introduction at first simultaneously begins reaction so that aqueous sodium hypochlorite solution and processing water enter after mixing by the rapid mixing container in the reaction tank, after chlorine and the processing water process certain reaction time (t), described three-way injector and described four-way road injector be sample introduction simultaneously, so that the DPD aqueous solution directly enters reaction tank, buffer solution enters reaction tank by the rapid mixing container, chlorine is set to 0.1s, 0.2s, 0.5s with the reaction time (t) of processing water, 1s, 2s, 5s, 10s, 20s, 30s, 40s, 50s, 60s, 90s, 120s, 150s, 180s, 210s, 240s, 270s, a series of times such as 300s, chlorine and DPD aqueous solution are reacted in the buffer solution of pH6.5 and are generated red product, measure the intensity A of ultraviolet absorptivity of the product of gained redness under 515nm, and it is identical that the condition determination of ultraviolet absorptivity etc. are described during with above-mentioned drawing standard curve;
The expression formula C=a of the described typical curve that (2.13) in the intensity A substitution step (2.1) of the ultraviolet absorptivity of (2.23) (2.22) 20 reaction time points of step being measured are set up * A+b calculates chlorine and the concentration C of processing water corresponding residue effective chlorine behind 20 reaction time points of experience;
(2.3) the Fitting Calculation is processed the dynamic chlorine demand of water
(2.31) with 20 reaction time points (t) in step (2.22) chlorine that arranges and the reaction time of processing water as transverse axis, with step (2.23) chlorine with process water concentration C of corresponding residue effective chlorine behind 20 reaction time points of experience and draw ln (C) ~ t as the longitudinal axis and scheme;
(2.32) ln (C) of 240s, 270s, three points of 300s ~ t data are carried out linear regression fit among the ln (C) that step (2.31) is drawn ~ t figure, its related coefficient (R 2) be 0.999 (〉 0.99), then continue to increase the experimental data of 210s time point the ln (C) of above four points ~ t data are carried out linear fit, its related coefficient (R 2) be 0.998 (〉 0.99), continue above operation, the related coefficient (R that carries out match when the experimental point that increases 60s 2) be 0.995 (〉 0.99), and increase the related coefficient (R that carries out match behind the experimental point of 50s 2) be 0.986 (＜0.99), stop match.Satisfy at last the related coefficient (R of fitting result 2) the point that increases (reaction time 60s point) greater than 0.99 namely thought the point that rapid reaction end and slow reaction begin by approximate, 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 namely by the approximate short-term chlorine demand of thinking to process water; And last related coefficient (R 2) the k value (0.160h of match greater than 0.99 -1) namely by the approximate kinetic constant of thinking slow reaction stage pseudo first order reaction.Obtain to process water according to the technology characteristics of water factory 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 with 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 × ( 24 - 0.01667 ) ) + 0.32 = 2.64 mg / L
On the basis of the chlorine demand that calculates, carry out the scene according to 120% ratio and add the chlorine operation, chlorine-throwed quantity is 3.2mg/L, the concentration of pipe network tip effective chlorine is 0.06mg/L, error satisfies and to meet " drinking water sanitary standard " (GB5749-2006) to the requirement of potable water network tip chlorine residue in allowed band.
Embodiment 2
As research object, the flow of inlet water of water supply plant is 3800m to present embodiment with certain waterworks settling basin water outlet 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) attitude chlorine demand of embodiment 1 to carry out on-line determination processing hydrodynamic(al) attitude chlorine demand; Wherein: described four identical with the volume of described alternate path injector with described the first 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) attitude chlorine demand carries out the method that on-line determination is processed hydrodynamic(al) attitude chlorine demand: use the 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 and the typical curve that step (2.1) is set up.
The different technical scheme later for present embodiment and the step (2.2) of embodiment 1 is:
(2.2) measure the rear concentration that remains effective chlorine of chlorine and actual water body reaction
(2.21) by described four transfer valves with the pulling flow type injector of transfer valve of control, the sample introduction end of four described pulling flow type injectors with transfer valve 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 directly enters in the alternate path injector processing water between 2 ~ 6mg/L; Adjust the sample introduction ratio of chlorine storing solution and pure water by the first T-valve 22 on the sample channel of controlling the first path injector 1, when making aqueous sodium hypochlorite solution in step (1) the chlorine storing solution hold-up vessel 11 in entering described the first path injector, the concentration of effective chlorine is 2.5mg/L in the aqueous sodium hypochlorite solution; Enter solution in described three-way injector and the described four-way road injector and each path injector control method and divided by on enter concentration and the COD of effective chlorine in described the first path injector MnBe worth identical outside, other condition is all identical with (2.11) in the step (2.1);
(2.22) by described four transfer valves with the pulling flow type injector of transfer valve of control, the sample introduction end of four described pulling flow type injectors with transfer valve is connected with sample channel respectively, makes in the step (2.21) liquid in four path injectors enter reaction tank; Sample introduction order is identical with (2.12) in the step (2.1), i.e. described the first path injector and described alternate path injector sample introduction at first simultaneously begins reaction so that aqueous sodium hypochlorite solution and processing water enter after mixing by the rapid mixing container in the reaction tank, after chlorine and the processing water process certain reaction time (t), described three-way injector and described four-way road injector be sample introduction simultaneously, so that the DPD aqueous solution directly enters reaction tank, buffer solution enters reaction tank by the rapid mixing container, chlorine is set to 0.1s, 0.2s, 0.5s with the reaction time (t) of processing water, 1s, 2s, 5s, 10s, 20s, 30s, 40s, 50s, 60s, 90s, 120s, 150s, 180s, 210s, 240s, 270s, a series of times such as 300s, chlorine and DPD aqueous solution are reacted in the buffer solution of pH6.5 and are generated red product, measure the intensity A of ultraviolet absorptivity of the product of gained redness under 515nm, and it is identical that the condition determination of ultraviolet absorptivity etc. are described during with above-mentioned drawing standard curve;
The expression formula C=a of the described typical curve that (2.13) in the intensity A substitution step (2.1) of the ultraviolet absorptivity of (2.23) (2.22) 20 reaction time points of step being measured are set up * A+b calculates chlorine and the concentration C of processing water corresponding residue effective chlorine behind 20 reaction time points of experience;
(2.3) the Fitting Calculation is processed the dynamic chlorine demand of water
(2.31) with 20 reaction time points (t) in step (2.22) chlorine that arranges and the reaction time of processing water as transverse axis, with step (2.23) chlorine with process water concentration C of corresponding residue effective chlorine behind 20 reaction time points of experience and draw ln (C) ~ t as the longitudinal axis and scheme;
(2.32) ln (C) of 240s, 270s, three points of 300s ~ t data are carried out linear regression fit among the ln (C) that step (2.31) is drawn ~ t figure, its related coefficient (R 2) be 0.999 (〉 0.99), then continue to increase the experimental data of 210s time point the ln (C) of above four points ~ t data are carried out linear fit, its R 2Be 0.999 (〉 0.99), continue above operation, the R that carries out match when the experimental point that increases 30s 2Be 0.994 (〉 0.99), and increase the R that carries out match behind the experimental point of 20s 2Be 0.985 (＜0.99), stop match.Satisfy at last the R of fitting result 2The point that increases greater than 0.99 (reaction time 30s point) namely is similar to thinks the point that rapid reaction end and slow reaction begin, 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 namely by the approximate short-term chlorine demand of thinking to process water; And last R 2K value (the 0.146h of the match greater than 0.99 -1) namely by the approximate kinetic constant of thinking slow reaction stage pseudo first order reaction.Obtain to process water according to the technology characteristics of water factory 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 with 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 × ( 30 - 0.00833 ) ) + 0.35 = 4.37 mg / L
On the basis of the chlorine demand that calculates, carry out the scene according to 120% ratio and add the chlorine operation, chlorine-throwed quantity is 5.2mg/L, the concentration of pipe network tip effective chlorine is 0.07mg/L, error satisfies and to meet " drinking water sanitary standard " (GB5749-2006) to the requirement of potable water network tip chlorine residue in allowed band.
Embodiment 3
As research object, the flow of inlet water of water supply plant is 4600m to present embodiment with certain waterworks settling basin water outlet 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) attitude chlorine demand of embodiment 1 to carry out on-line determination processing hydrodynamic(al) attitude chlorine demand; Wherein: described four identical with the volume of described alternate path injector with described the first 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) attitude chlorine demand carries out the method that on-line determination is processed hydrodynamic(al) attitude chlorine demand: use the 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 and the typical curve that step (2.1) is set up.
The different technical scheme later for present embodiment and the step (2.2) of embodiment 1 is:
(2.2) measure the rear concentration that remains effective chlorine of chlorine and actual water body reaction
(2.21) by described four transfer valves with the pulling flow type injector of transfer valve of control, the sample introduction end of four described pulling flow type injectors with transfer valve 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 will process the water rotary evaporation and be concentrated into 3mg/L and enter in the alternate path injector; Adjust the sample introduction ratio of chlorine storing solution and pure water by the first T-valve 22 on the sample channel of controlling the first path injector 1, when making aqueous sodium hypochlorite solution in step (1) the chlorine storing solution hold-up vessel 11 in entering described the first path injector, the concentration of effective chlorine is 3mg/L in the aqueous sodium hypochlorite solution; Enter solution in described three-way injector and the described four-way road injector and each path injector control method and divided by on enter concentration and the COD of effective chlorine in described the first path injector MnBe worth identical outside, other condition is all identical with (2.11) in the step (2.1);
(2.22) by described four transfer valves with the pulling flow type injector of transfer valve of control, the sample introduction end of four described pulling flow type injectors with transfer valve is connected with sample channel respectively, makes in the step (2.21) liquid in four path injectors enter reaction tank; (2.12) in the step (2.1) of sample introduction order and embodiment 1 are identical, it is at first simultaneously sample introduction of described the first path injector and described alternate path injector, so that entering after mixing by the rapid mixing container, aqueous sodium hypochlorite solution and processing water begins reaction in the reaction tank, after chlorine and the processing water process certain reaction time (t), described three-way injector and described four-way road injector be sample introduction simultaneously, so that the DPD aqueous solution directly enters reaction tank, buffer solution enters reaction tank by the 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 times such as 500s, chlorine and DPD aqueous solution are reacted in the buffer solution of pH6.5 and are generated red product, measure the intensity A of ultraviolet absorptivity of the product of gained redness under 515nm, and it is identical that the condition determination of ultraviolet absorptivity etc. are described during with above-mentioned drawing standard curve;
The expression formula C=a of the described typical curve that (2.13) in the intensity A substitution step (2.1) of the ultraviolet absorptivity of (2.23) (2.22) 22 reaction time points of step being measured are set up * A+b calculates chlorine and the concentration C of processing water corresponding residue effective chlorine behind 22 reaction time points of experience;
(2.3) the Fitting Calculation is processed the dynamic chlorine demand of water
(2.31) with 22 reaction time points (t) in step (2.22) chlorine that arranges and the reaction time of processing water as transverse axis, with step (2.23) chlorine with process water concentration C of corresponding residue effective chlorine behind 22 reaction time points of experience and draw ln (C) ~ t as the longitudinal axis and scheme;
(2.32) ln (C) of 240s, 270s, three points of 300s ~ t data are carried out linear regression fit among the ln (C) that step (2.31) is drawn ~ t figure, its related coefficient (R 2) be 0.999 (〉 0.99), then continue to increase the experimental data of 210s time point the ln (C) of above four points ~ t data are carried out linear fit, its R 2Be 0.997 (〉 0.99), continue above operation, the R that carries out match when the experimental point that increases 90s 2Be 0.993 (〉 0.99), and increase the R that carries out match behind the experimental point of 60s 2Be 0.982 (＜0.99), stop match.Satisfy at last the R of fitting result 2The point that increases greater than 0.99 (reaction time 90s point) namely is similar to thinks the point that rapid reaction end and slow reaction begin, 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 namely by the approximate short-term chlorine demand of thinking to process water; And last R 2K value (the 0.180h of the match greater than 0.99 -1) namely by the approximate kinetic constant of thinking slow reaction stage pseudo first order reaction.Obtain to process water according to the technology characteristics of water factory 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 with 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 × ( 24 - 0.025 ) ) + 0.41 = 4.15 mg / L
Initial chlorine demand is 2.10mg/L before concentrated, on the basis of the chlorine demand that calculates, carry out the scene according to 120% ratio and add the chlorine operation, chlorine-throwed quantity is 2.5mg/L, the concentration of pipe network tip effective chlorine is 0.055mg/L, error satisfies and to meet " drinking water sanitary standard " (GB5749-2006) to the requirement of potable water network tip chlorine residue in allowed band.
Embodiment 4
As research object, the flow of inlet water of water supply plant is 5200m to present embodiment with certain waterworks settling basin water outlet 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) attitude chlorine demand of embodiment 1 to carry out on-line determination processing hydrodynamic(al) attitude chlorine demand; Wherein: described four identical with the volume of described alternate path injector with described the first 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) attitude chlorine demand carries out the method that on-line determination is processed hydrodynamic(al) attitude chlorine demand: use the 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 and the typical curve that step (2.1) is set up.
The different technical scheme later for present embodiment and the step (2.2) of embodiment 1 is:
(2.2) measure the rear concentration that remains effective chlorine of chlorine and actual water body reaction
(2.21) by described four transfer valves with the pulling flow type injector of transfer valve of control, the sample introduction end of four described pulling flow type injectors with transfer valve 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 directly enters in the alternate path injector processing water between 2 ~ 6mg/L; Adjust the sample introduction ratio of chlorine storing solution and pure water by the first T-valve 22 on the sample channel of controlling the first path injector 1, when making aqueous sodium hypochlorite solution in step (1) the chlorine storing solution hold-up vessel 11 in entering described the first path injector, the concentration of effective chlorine is 4mg/L in the aqueous sodium hypochlorite solution; Enter solution in described three-way injector and the described four-way road injector and each path injector control method and divided by on enter concentration and the COD of effective chlorine in described the first 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 described four transfer valves with the pulling flow type injector of transfer valve of control, the sample introduction end of four described pulling flow type injectors with transfer valve is connected with sample channel respectively, makes in the step (2.21) liquid in four path injectors enter reaction tank; The sample introduction order is identical with (2.12) in the step (2.1), it is at first simultaneously sample introduction of described the first path injector and described alternate path injector, so that entering after mixing by the rapid mixing container, aqueous sodium hypochlorite solution and processing water begins reaction in the reaction tank, after chlorine and the processing water process certain reaction time (t), described three-way injector and described four-way road injector be sample introduction simultaneously, so that the DPD aqueous solution directly enters reaction tank, buffer solution enters reaction tank by the 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 times such as 600s, chlorine and DPD aqueous solution are reacted in the buffer solution of pH6.5 and are generated red product, measure the intensity A of ultraviolet absorptivity of the product of gained redness under 515nm, it is identical that the condition determination of ultraviolet absorptivity etc. are described during with above-mentioned drawing standard curve;
The expression formula C=a of the described typical curve that (2.13) in the intensity A substitution step (2.1) of the ultraviolet absorptivity of (2.23) (2.22) 23 reaction time points of step being measured are set up * A+b calculates chlorine and the concentration C of processing water corresponding residue effective chlorine behind 23 reaction time points of experience;
(2.3) the Fitting Calculation is processed the dynamic chlorine demand of water
(2.31) with 23 reaction time points (t) in step (2.22) chlorine that arranges and the reaction time of processing water as transverse axis, with step (2.23) chlorine with process water concentration C of corresponding residue effective chlorine behind 23 reaction time points of experience and draw ln (C) ~ t as the longitudinal axis and scheme;
(2.32) ln (C) of 400s, 500s, three points of 600s ~ t data are carried out linear regression fit among the ln (C) that step (2.31) is drawn ~ t figure, its related coefficient (R 2) be 1.0000 (〉 0.99), then continue to increase the experimental data of 300s time point the ln (C) of above four points ~ t data are carried out linear fit, its R 2Be 0.999 (〉 0.99), continue above operation, the R that carries out match when the experimental point that increases 120s 2Be 0.995 (〉 0.99), and increase the R that carries out match behind the experimental point of 90s 2Be 0.988 (＜0.99), stop match.Satisfy at last the R of fitting result 2The point that increases greater than 0.99 (reaction time 120s point) namely is similar to thinks the point that rapid reaction end and slow reaction begin, 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 namely by the approximate short-term chlorine demand of thinking to process water; And last R 2K value (the 0.184h of the match greater than 0.99 -1) namely by the approximate kinetic constant of thinking slow reaction stage pseudo first order reaction.Obtain to process water according to the technology characteristics of water factory 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 with 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 × ( 12 - 0.0333 ) ) + 0.46 = 0.91 mg / L
It carries out the scene according to 120% ratio and adds the chlorine operation on the basis of the chlorine demand that calculates, chlorine-throwed quantity is 1.1mg/L, the concentration of pipe network tip effective chlorine is 0.06mg/L, its value satisfies and to meet " drinking water sanitary standard " (GB5749-2006) to the requirement of potable water network tip chlorine residue in allowed band.
Embodiment 5
As research object, the flow of inlet water of water supply plant is 2800m to present embodiment with certain waterworks settling basin water outlet 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) attitude chlorine demand of embodiment 1 to carry out on-line determination processing hydrodynamic(al) attitude chlorine demand; Wherein: described four identical with the volume of described alternate path injector with described the first 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) attitude chlorine demand carries out the method that on-line determination is processed hydrodynamic(al) attitude chlorine demand: use the 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
Fill it up with the aqueous sodium hypochlorite solution that concentration is 10mg/L in chlorine storing solution hold-up vessel, filling it up with in the developer hold-up vessel as the concentration of developer is the ABTS aqueous solution of 2mM; In the 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 the water water intaking valve, make process water from sample point by processing water water inlet pipe and the COD that flows through MnThe on-line monitoring instrument joins in the processing water store tank and fills it up with; Utilize COD MnThe on-line monitoring instrument is measured the COD that processes water MnValue;
(2), on-line determination is processed hydrodynamic(al) attitude chlorine demand
(2.1) drawing standard curve
(2.11) it is identical with the volume of alternate path injector 2 with the first path injector 1 in the pulling flow type injector of transfer valve four of four-way road injector to be set, be 100 μ L, it is identical with the volume of four-way road injector 4 that three-way injector 3 is set, and is 90 μ L; Be installed in described four transfer valves with the pulling flow type injector of transfer valve by control, the sample introduction end of four described pulling flow type injectors with transfer valve is connected with sample channel respectively, and by the T-valve on the sample channel of four path injectors of control, aqueous sodium hypochlorite solution in the control chlorine storing solution hold-up vessel 11, developer in the developer hold-up vessel 20, buffer solution in the buffer solution hold-up vessel 18, process the processing water in the 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 reaction tank 6 in pure water in the 3rd pure water pot 21 and the 4th pure water pot 17 makes the stock solution of pure water and step (1) preparation enter 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, when making aqueous sodium hypochlorite solution in step (1) the chlorine storing solution hold-up vessel 11 in entering described the first path injector, the concentration of effective chlorine is respectively 0mg/L(in contrast in the aqueous sodium hypochlorite solution), 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, when making developer ABTS aqueous solution in step (1) the developer hold-up vessel 20 in entering described three-way injector, the concentration of developer is calculated according to sampling volume, and making the ratio of ABTS aqueous solution and the volumetric molar concentration of effective chlorine in reaction tank 6 is 10:1; When making buffer solution in step (1) the 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, so that the concentration of buffer solution is calculated according to sampling volume in the injector of described four-way road, the pH that makes mixed liquor in reaction tank 6 is 3;
(2.12) by described four transfer valves with the pulling flow type injector of transfer valve of control, the sample introduction end of four described pulling flow type injectors with transfer valve is connected with sample channel respectively, makes in the step (2.11) liquid in four path injectors enter reaction tank; Sample introduction sequentially is: described the first path injector and described alternate path injector be sample introduction at first simultaneously, so that aqueous sodium hypochlorite solution and pure water enter in the reaction tank after mixing by the rapid mixing container, after 1 second, described three-way injector and described four-way road injector be sample introduction simultaneously, so that the ABTS aqueous solution directly enters reaction tank, 0.01mol/L hydrochloric acid buffer solution enter reaction tank by the rapid mixing container, chlorine and ABTS aqueous solution are reacted in buffer solution and are generated blue product, and the concentration of measuring respectively selected effective chlorine under the 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 is regulated by monochromator;
(2.13) concentration of effective chlorine is respectively 0mg/L(in contrast in the aqueous sodium hypochlorite solution of measuring with step (2.12)), 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, with the concentration C of the effective chlorine among the liquor natrii hypochloritis in corresponding described the first path injector 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 rear concentration that remains effective chlorine of chlorine and actual water body reaction
(2.21) by described four transfer valves with the pulling flow type injector of transfer valve of control, the sample introduction end of four described pulling flow type injectors with transfer valve 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 directly enters in the alternate path injector processing water between 2 ~ 6mg/L; Adjust the sample introduction ratio of chlorine storing solution and pure water by the first T-valve 22 on the sample channel of controlling the first path injector 1, when making aqueous sodium hypochlorite solution in step (1) the chlorine storing solution hold-up vessel 11 in entering described the first path injector, the concentration of effective chlorine is 4.5mg/L in the aqueous sodium hypochlorite solution; Enter solution in described three-way injector and the described four-way road injector and each path injector control method and divided by on enter concentration and the COD of effective chlorine in described the first path injector MnBe worth identical outside, other condition is all identical with (2.11) in the step (2.1);
(2.22) by described four transfer valves with the pulling flow type injector of transfer valve of control, the sample introduction end of four described pulling flow type injectors with transfer valve is connected with sample channel respectively, makes in the step (2.21) liquid in four path injectors enter reaction tank; The sample introduction order is identical with (2.12) in the step (2.1), it is at first simultaneously sample introduction of described the first path injector and described alternate path injector, so that entering after mixing by the rapid mixing container, aqueous sodium hypochlorite solution and processing water begins reaction in the reaction tank, after chlorine and the processing water process certain reaction time (t), described three-way injector and described four-way road injector be sample introduction simultaneously, so that the ABTS aqueous solution directly enters reaction tank, buffer solution enters reaction tank by the rapid mixing container, chlorine is set to 0.1s, 0.2s, 0.5s with the reaction time (t) of processing water, 1s, 2s, 5s, 10s, 20s, 30s, 40s, 50s, 60s, 90s, 120s, 150s, 180s, 210s, 240s, 270s, 300s, 400s, 500s, 600s, a series of times such as 900s, chlorine and ABTS aqueous solution are reacted in the mixed liquor of pH3 and are generated blue product, measure the intensity A of ultraviolet absorptivity of the product of gained blueness under 515nm, and it is identical that the condition determination of ultraviolet absorptivity etc. are described during with above-mentioned drawing standard curve;
The expression formula C=a of the described typical curve that (2.13) in the intensity A substitution step (2.1) of the ultraviolet absorptivity of (2.23) (2.22) 24 reaction time points of step being measured are set up * A+b calculates chlorine and the concentration C of processing water corresponding residue effective chlorine behind 24 reaction time points of experience;
(2.3) the Fitting Calculation is processed the dynamic chlorine demand of water
(2.31) with 24 reaction time points (t) in step (2.22) chlorine that arranges and the reaction time of processing water as transverse axis, with step (2.23) chlorine with process water concentration C of corresponding residue effective chlorine behind 24 reaction time points of experience and draw ln (C) ~ t as the longitudinal axis and scheme;
(2.32) ln (C) of 500s, 600s, three points of 900s ~ t data are carried out linear regression fit among the ln (C) that step (2.31) is drawn～t figure, its related coefficient (R 2) be 0.999 (〉 0.99), then continue to increase the experimental data of 400s time point the ln (C) of above four points ~ t data are carried out linear fit, its R 2Be 0.999 (〉 0.99), continue above operation, the R that carries out match when the experimental point that increases 120s 2Be 0.994 (〉 0.99), and increase the R that carries out match behind the experimental point of 90s 2Be 0.982 (＜0.99), stop match.Satisfy at last the R of fitting result 2The point that increases greater than 0.99 (reaction time 120s point) namely is similar to thinks the point that rapid reaction end and slow reaction begin, 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 namely by the approximate short-term chlorine demand of thinking to process water; And last R 2K value (the 0.190h of the match greater than 0.99 -1) namely by the approximate kinetic constant of thinking slow reaction stage pseudo first order reaction.Obtain to process water according to the technology characteristics of water factory 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 with 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 × ( 20 - 0.0333 ) ) + 0.49 = 2.71 mg / L
On the basis of the chlorine demand that calculates, carry out the scene according to 120% ratio and add the chlorine operation, chlorine-throwed quantity is 3.3mg/L, the concentration of pipe network tip effective chlorine is 0.07mg/L, its value satisfies and to meet " drinking water sanitary standard " (GB5749-2006) to the requirement of potable water network tip chlorine residue in allowed band.
Embodiment 6
As research object, the flow of inlet water of water supply plant is 4800m to present embodiment with certain waterworks settling basin water outlet 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) attitude chlorine demand of embodiment 1 to carry out on-line determination processing hydrodynamic(al) attitude chlorine demand; Wherein: described four identical with the volume of described alternate path injector with described the first 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) attitude chlorine demand carries out the method that on-line determination is processed hydrodynamic(al) attitude chlorine demand: use the ABTS aqueous solution as developer, 0.01mol/L hydrochloric acid solution as buffer solution, it is 728nm that UV-detector is measured wavelength, and utilizes the stock solution of step (1) preparation of embodiment 5 and the typical curve that step (2.1) is set up.
The different technical scheme later for present embodiment and the step (2.2) of embodiment 5 is:
(2.2) measure the rear concentration that remains effective chlorine of chlorine and actual water body reaction
(2.21) by described four transfer valves with the pulling flow type injector of transfer valve of control, the sample introduction end of four described pulling flow type injectors with transfer valve 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 directly enters in the alternate path injector processing water between 2 ~ 6mg/L; Adjust the sample introduction ratio of chlorine storing solution and pure water by the first T-valve 22 on the sample channel of controlling the first path injector 1, when making aqueous sodium hypochlorite solution in step (1) the chlorine storing solution hold-up vessel 11 in entering described the first path injector, the concentration of effective chlorine is 5mg/L in the aqueous sodium hypochlorite solution; Enter solution in described three-way injector and the described four-way road injector and each path injector control method and divided by on enter concentration and the COD of effective chlorine in described the first 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 described four transfer valves with the pulling flow type injector of transfer valve of control, the sample introduction end of four described pulling flow type injectors with transfer valve is connected with sample channel respectively, makes in the step (2.21) liquid in four path injectors enter reaction tank; (2.12) in the step (2.1) of sample introduction order and embodiment 5 are identical, it is at first simultaneously sample introduction of described the first path injector and described alternate path injector, so that entering after mixing by the rapid mixing container, aqueous sodium hypochlorite solution and processing water begins reaction in the reaction tank, after chlorine and the processing water process certain reaction time (t), described three-way injector and described four-way road injector be sample introduction simultaneously, so that the ABTS aqueous solution directly enters reaction tank, buffer solution enters reaction tank by the 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 times such as 600s, chlorine and ABTS aqueous solution are that reaction generates blue product in 3 the mixed liquor at pH, measure the intensity A of ultraviolet absorptivity of the product of gained blueness under 728nm, it is identical that the condition determination of ultraviolet absorptivity etc. are described during with above-mentioned drawing standard curve;
The expression formula C=a of the described typical curve that (2.13) in the intensity A substitution step (2.1) of the ultraviolet absorptivity of (2.23) (2.22) 23 reaction time points of step being measured are set up * A+b calculates chlorine and the concentration C of processing water corresponding residue effective chlorine behind 23 reaction time points of experience;
(2.3) the Fitting Calculation is processed the dynamic chlorine demand of water
(2.31) with 23 reaction time points (t) in step (2.22) chlorine that arranges and the reaction time of processing water as transverse axis, with step (2.23) chlorine with process water concentration C of corresponding residue effective chlorine behind 23 reaction time points of experience and draw ln (C) ~ t as the longitudinal axis and scheme;
(2.32) ln (C) of 400s, 500s, three points of 600s ~ t data are carried out linear regression fit among the ln (C) that step (2.31) is drawn ~ t figure, its related coefficient (R 2) be 0.998 (〉 0.99), then continue to increase the experimental data of 300s time point the ln (C) of above four points ~ t data are carried out linear fit, its R 2Be 0.996 (〉 0.99), continue above operation, the R that carries out match when the experimental point that increases 60s 2Be 0.992 (〉 0.99), and increase the R that carries out match behind the experimental point of 50s 2Be 0.985 (＜0.99), stop match.Satisfy at last the R of fitting result 2The point that increases greater than 0.99 (reaction time 60s point) namely is similar to thinks the point that rapid reaction end and slow reaction begin, 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 namely by the approximate short-term chlorine demand of thinking to process water; And last R 2K value (the 0.156h of the match greater than 0.99 -1) namely by the approximate kinetic constant of thinking slow reaction stage pseudo first order reaction.Obtain to process water according to the technology characteristics of water factory 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 with 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 × ( 27 - 0.01667 ) ) + 0.48 = 3.85 mg / L
On the basis of the chlorine demand that calculates, carry out the scene according to 120% ratio and add the chlorine operation, chlorine-throwed quantity is 4.6mg/L, the concentration of pipe network tip effective chlorine is 0.08mg/L, error satisfies and to meet " drinking water sanitary standard " (GB5749-2006) to the requirement of potable water network tip chlorine residue in allowed band.
Embodiment 7
As research object, the flow of inlet water of water supply plant is 3600m to present embodiment with certain waterworks settling basin water outlet 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) attitude chlorine demand of embodiment 1 to carry out on-line determination processing hydrodynamic(al) attitude chlorine demand; Wherein: described four identical with the volume of described alternate path injector with described the first 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) attitude chlorine demand carries out the method that on-line determination is processed hydrodynamic(al) attitude chlorine demand: use the 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 for present embodiment and the step (2) of embodiment 1 is:
(2), on-line determination is processed hydrodynamic(al) attitude chlorine demand
(2.1) drawing standard curve
(2.11) it is identical with the volume of alternate path injector 2 with the first path injector 1 in the pulling flow type injector of transfer valve four of four-way road injector to be set, be 85 μ L, it is identical with the volume of four-way road injector 4 that three-way injector 3 is set, and is 75 μ L; Be installed in described four transfer valves with the pulling flow type injector of transfer valve by control, the sample introduction end of four described pulling flow type injectors with transfer valve is connected with sample channel respectively, and by the T-valve on the sample channel of four path injectors of control, aqueous sodium hypochlorite solution in the control chlorine storing solution hold-up vessel 11, developer in the developer hold-up vessel 20, buffer solution in the buffer solution hold-up vessel 18, process the processing water in the 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 reaction tank 6 in pure water in the 3rd pure water pot 21 and the 4th pure water pot 17 makes the stock solution of pure water and step (1) preparation enter 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, when making aqueous sodium hypochlorite solution in step (1) the chlorine storing solution hold-up vessel 11 in entering described the first path injector, the concentration of effective chlorine is respectively 0mg/L(in contrast in the aqueous sodium hypochlorite solution), 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, when making developer DPD aqueous solution in step (1) the developer hold-up vessel 20 in entering described three-way injector, the concentration of developer is calculated according to sampling volume, and making the ratio of DPD aqueous solution and the volumetric molar concentration of effective chlorine in reaction tank 6 is 15:1; When making buffer solution in step (1) the 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, so that the concentration of buffer solution is calculated according to sampling volume in the injector of described four-way road, making DPD aqueous solution in reaction tank 6 and the molar concentration rate of buffer solution is 1:1;
(2.12) by described four transfer valves with the pulling flow type injector of transfer valve of control, the sample introduction end of four described pulling flow type injectors with transfer valve is connected with sample channel respectively, makes in the step (2.11) liquid in four path injectors enter reaction tank; Sample introduction sequentially is: described the first path injector and described alternate path injector be sample introduction at first simultaneously, so that aqueous sodium hypochlorite solution and pure water enter in the reaction tank after mixing by the rapid mixing container, after 2 seconds, described three-way injector and described four-way road injector be sample introduction simultaneously, so that the DPD aqueous solution directly enters reaction tank, the buffer solution of pH6.5 enters reaction tank by the rapid mixing container, chlorine and DPD aqueous solution are reacted in buffer solution and are generated the coloured product of tool, and the concentration of measuring respectively selected effective chlorine under the 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 is regulated by monochromator;
(2.13) concentration of effective chlorine is respectively 0mg/L(in contrast in the aqueous sodium hypochlorite solution of measuring with step (2.12)), 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, with the concentration C of the effective chlorine among the liquor natrii hypochloritis in corresponding described the first path injector 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 rear concentration that remains effective chlorine of chlorine and actual water body reaction
(2.21) by described four transfer valves with the pulling flow type injector of transfer valve of control, the sample introduction end of four described pulling flow type injectors with transfer valve 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 directly enters in the alternate path injector processing water between 2 ~ 6mg/L; Adjust the sample introduction ratio of chlorine storing solution and pure water by the first T-valve 22 on the sample channel of controlling the first path injector 1, when making aqueous sodium hypochlorite solution in step (1) the chlorine storing solution hold-up vessel 11 in entering described the first path injector, the concentration of effective chlorine is 6mg/L in the aqueous sodium hypochlorite solution; Enter solution in described three-way injector and the described four-way road injector and each path injector control method and divided by on enter concentration and the COD of effective chlorine in described the first path injector MnBe worth identical outside, other condition is all identical with (2.11) in the step (2.1);
(2.22) by described four transfer valves with the pulling flow type injector of transfer valve of control, the sample introduction end of four described pulling flow type injectors with transfer valve is connected with sample channel respectively, makes in the step (2.21) liquid in four path injectors enter reaction tank; Sample introduction order is identical with (2.12) in the step (2.1), i.e. described the first path injector and described alternate path injector sample introduction at first simultaneously begins reaction so that aqueous sodium hypochlorite solution and processing water enter after mixing by the rapid mixing container in the reaction tank, after chlorine and the processing water process certain reaction time (t), described three-way injector and described four-way road injector be sample introduction simultaneously, so that the DPD aqueous solution directly enters reaction tank, buffer solution enters reaction tank by the rapid mixing container, and chlorine is set to 0.1s, 0.2s with the reaction time (t) of processing water, 0.5s, 1s, 2s, 5s, 10s, 20s, 30s, 40s, 50s, 60s, 90s, 120s, 150s, 180s, 210s, 240s, 270s, 300s, a series of times such as 400s, chlorine and DPD aqueous solution are reacted in the buffer solution of pH6.5 and are generated red product, measure the intensity A of ultraviolet absorptivity of the product of gained redness under 515nm, it is identical that the condition determination of ultraviolet absorptivity etc. are described during with above-mentioned drawing standard curve;
The expression formula C=a of the described typical curve that (2.13) in the intensity A substitution step (2.1) of the ultraviolet absorptivity of (2.23) (2.22) 21 reaction time points of step being measured are set up * A+b calculates chlorine and the concentration C of processing water corresponding residue effective chlorine behind 21 reaction time points of experience;
(2.3) the Fitting Calculation is processed the dynamic chlorine demand of water
(2.31) with 21 reaction time points (t) in step (2.22) chlorine that arranges and the reaction time of processing water as transverse axis, with step (2.23) chlorine with process water concentration C of corresponding residue effective chlorine behind 21 reaction time points of experience and draw ln (C) ~ t as the longitudinal axis and scheme;
(2.32) ln (C) of 270s, 300s, three points of 400s ~ t data are carried out linear regression fit among the ln (C) that step (2.31) is drawn ~ t figure, its related coefficient (R 2) be 0.996 (〉 0.99), then continue to increase the experimental data of 240s time point the ln (C) of above four points ~ t data are carried out linear fit, its R 2Be 0.996 (〉 0.99), continue above operation, the R that carries out match when the experimental point that increases 40s 2Be 0.993 (〉 0.99), and increase the R that carries out match behind the experimental point of 30s 2Be 0.983 (＜0.99), stop match.Satisfy at last the R of fitting result 2The point that increases greater than 0.99 (reaction time 40s point) namely is similar to thinks the point that rapid reaction end and slow reaction begin, 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 namely by the approximate short-term chlorine demand of thinking to process water; And last R 2K value (the 0.150h of the match greater than 0.99 -1) namely by the approximate kinetic constant of thinking slow reaction stage pseudo first order reaction.Obtain to process water according to the technology characteristics of water factory 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 with 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 × ( 30 - 0.01111 ) ) + 0.53 = 5.02 mg / L
On the basis of the chlorine demand that calculates, carry out the scene according to 120% ratio and add the chlorine operation, chlorine-throwed quantity is 6mg/L, the concentration of pipe network tip effective chlorine is 0.065mg/L, its value satisfies and to meet " drinking water sanitary standard " (GB5749-2006) to the requirement of potable water network tip chlorine residue in allowed band.
Embodiment 8
As research object, the flow of inlet water of water supply plant is 3600m to present embodiment with certain waterworks settling basin water outlet 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) attitude chlorine demand of embodiment 1 to carry out on-line determination processing hydrodynamic(al) attitude chlorine demand; Wherein: described four identical with the volume of described alternate path injector with described the first 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) attitude chlorine demand carries out the method that on-line determination is processed hydrodynamic(al) attitude chlorine demand: use the 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 and the typical curve that embodiment 7 steps (2.1) are set up.
The different technical scheme later for present embodiment and the step (2.2) of embodiment 7 is:
(2.2) measure the rear concentration that remains effective chlorine of chlorine and actual water body reaction
(2.21) by described four transfer valves with the pulling flow type injector of transfer valve of control, the sample introduction end of four described pulling flow type injectors with transfer valve 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, then process the sample introduction ratio of water and pure water inlet by the second T-valve adjustment on the sample channel of control alternate path injector, to enter the concentration of the processing water in the described alternate path injector be 6mg/L and enter in the alternate path injector; Adjust the sample introduction ratio of chlorine storing solution and pure water by the first T-valve 22 on the sample channel of controlling the first path injector 1, when making aqueous sodium hypochlorite solution in step (1) the chlorine storing solution hold-up vessel 11 in entering described the first path injector, the concentration of effective chlorine is 6mg/L in the aqueous sodium hypochlorite solution; Enter solution in described three-way injector and the described four-way road injector and each path injector control method and divided by on enter concentration and the COD of effective chlorine in described the first path injector MnBe worth identical outside, other condition is all identical with (2.11) in embodiment 7 steps (2.1);
(2.22) by described four transfer valves with the pulling flow type injector of transfer valve of control, the sample introduction end of four described pulling flow type injectors with transfer valve is connected with sample channel respectively, makes in the step (2.21) liquid in four path injectors enter reaction tank; The sample introduction order is identical with (2.12) in the step (2.1), it is at first simultaneously sample introduction of described the first path injector and described alternate path injector, so that entering after mixing by the rapid mixing container, aqueous sodium hypochlorite solution and processing water begins reaction in the reaction tank, after chlorine and the processing water process certain reaction time (t), described three-way injector and described four-way road injector be sample introduction simultaneously, so that the DPD aqueous solution directly enters reaction tank, buffer solution enters reaction tank by the rapid mixing container, and 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 times such as 120s, chlorine and DPD aqueous solution are reacted in the buffer solution of pH6.5 and are generated red product, measure the intensity A of ultraviolet absorptivity of the product of gained redness under 515nm, and it is identical that the condition determination of ultraviolet absorptivity etc. are described during with above-mentioned drawing standard curve;
The expression formula C=a of the described typical curve that (2.13) in the intensity A substitution step (2.1) of the ultraviolet absorptivity of (2.23) (2.22) 14 reaction time points of step being measured are set up * A+b calculates chlorine and the concentration C of processing water corresponding residue effective chlorine behind 14 reaction time points of experience;
(2.3) the Fitting Calculation is processed the dynamic chlorine demand of water
(2.31) with 14 reaction time points (t) in step (2.22) chlorine that arranges and the reaction time of processing water as transverse axis, with step (2.23) chlorine with process water concentration C of corresponding residue effective chlorine behind 14 reaction time points of experience and draw ln (C) ~ t as the longitudinal axis and scheme;
(2.32) ln (C) of 60s, 90s, three points of 120s ~ t data are carried out linear regression fit among the ln (C) that step (2.31) is drawn ~ t figure, its related coefficient (R 2) be 0.988 (＜0.99), do not conform to symbol match requirement, then continue to increase the experimental data of 150s time point, the ln (C) of 90s, 120s, three points of 150s ~ t data are carried out linear fit, its R 2Be 0.992 (〉 0.99), continue to increase the data of 180s, 210s, three experimental points of 240s and be that the ln (C) ~ t data of 6 points of 90s, 120s, 150s, 180s, 210s, 240s carries out linear fit, its R to the reaction time 2Be 0.998 (〉 0.99).Satisfy the R of fitting result 2Minimum time point greater than 0.99 (reaction time 90s point) namely is similar to thinks the point that rapid reaction end and slow reaction begin, 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 namely by the approximate short-term chlorine demand of thinking to process water; And the k value (0.165h of the match that 6 experimental points between 90s ~ 240s are carried out -1) namely by the approximate kinetic constant of thinking slow reaction stage pseudo first order reaction.Obtain to process water according to the technology characteristics of water factory 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 with 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 × ( 20 - 0.025 ) ) + 0.45 = 1.80 mg / L
Must process hydrodynamic(al) attitude chlorine demand before the dilution is 2.4mg/L.On the basis of the chlorine demand that calculates, carry out the scene according to 120% ratio and add the chlorine operation, chlorine-throwed quantity is 2.9mg/L, the concentration of pipe network tip effective chlorine is 0.07mg/L, error satisfies and to meet " drinking water sanitary standard " (GB5749-2006) to the requirement of potable water network tip chlorine residue in allowed band.

Claims (5)

1. an on-line determination is processed the equipment of hydrodynamic(al) attitude 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, stops controller, uviol lamp, monochromator and UV-detector with the pulling flow type of transfer valve; Described On-line Control unit comprises COD MnOn-line monitoring instrument, T-valve, computing machine and the automation controller that is connected with the residence spectrum unit on described four-way road;
Described four-way road injector comprises 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;
Described pulling flow type with transfer valve stops controller and comprises a reactive end and a waste liquid end;
The reactive end of described four reactive end with the first path injector in the pulling flow type injector of transfer valve, alternate path injector and the reactive end of four-way road injector are connected with an end of described rapid mixing container by pipeline respectively; The other end of described rapid mixing container is connected with an end of described reaction tank by pipeline, and the other end of described reaction tank is connected with described four reactive end with the three-way injector in the pulling flow type injector of transfer valve with the reactive end that described pulling flow type with transfer valve stops controller by pipeline respectively; 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 described pulling flow type with transfer valve stops controller is equipped with the waste liquid vent pipe; The sample introduction end of described three-way injector is connected with the 3rd pure water pot with the developer hold-up vessel respectively by the sample channel with the 3rd T-valve;
The sample introduction end of described the first 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 MnThe on-line monitoring instrument is connected, and at this sample channel processing water water intaking valve is installed; Described COD MnThe on-line monitoring instrument by sample channel be connected with the sampling water spot of processing the water water inlet pipe; 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;
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 described the 4th T-valve all are connected with automation controller by signal wire; Described computing machine by signal wire respectively with described automation controller, described online COD MnMonitor and described UV-detector are connected.
2. on-line determination according to claim 1 is processed the equipment of hydrodynamic(al) attitude chlorine demand, and it is characterized in that: the max cap. of described reaction tank is described four 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) attitude chlorine demand, it is characterized in that: described four identical with the volume of described alternate path injector with described the first 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) attitude 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. an equipment that utilizes the described on-line determination of claim 1 ~ 4 any one to process hydrodynamic(al) attitude chlorine demand carries out the method that on-line determination is processed hydrodynamic(al) attitude chlorine demand, it is characterized in that described method may further comprise the 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, the concentration of filling it up with in the developer hold-up vessel as developer is the N of 2mM, N-diethyl-Isosorbide-5-Nitrae-phenylenediamine aqueous solution or 2,2-connection nitrogen-two-(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 the 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-two-(3-ethyl-benzothiazole-6-sulfonic acid)-di-ammonium salts aqueous solution is during as developer, fills it up with pH as buffer solution and be 1.8 ~ 2.3 inorganic acid aqueous solution in the buffer solution hold-up vessel; Open and process the water water intaking valve, make process water from sample point by processing water water inlet pipe and the COD that flows through MnThe on-line monitoring instrument joins in the processing water store tank and fills it up with; Utilize COD MnThe on-line monitoring instrument is measured the COD that processes water MnValue;
(2), on-line determination is processed hydrodynamic(al) attitude chlorine demand
(2.1) drawing standard curve
(2.11) it is identical with the volume of alternate path injector with the first path injector in the pulling flow type injector of transfer valve four of four-way road injector to be set, and the three-way injector is identical with the volume of four-way road injector; Be installed in described four transfer valves with the pulling flow type injector of transfer valve by control, 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, when making aqueous sodium hypochlorite solution in step (1) the chlorine storing solution hold-up vessel in entering described the first path injector, the concentration of effective chlorine is respectively six points among 0.1 ~ 3mg/L in the aqueous sodium hypochlorite solution, and the concentration of effective chlorine is 0mg/L in the aqueous sodium hypochlorite solution; 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-two-(3-ethyl-benzothiazole-6-sulfonic acid)-di-ammonium salts aqueous solution and pure water, when making developer in step (1) the developer hold-up vessel in entering described three-way injector, the concentration of developer is calculated according to sampling volume, and making the ratio of developer and the volumetric molar concentration of effective chlorine in reaction tank is 8:1 ~ 15:1; When making buffer solution in step (1) the buffer solution hold-up vessel in entering described four-way road injector, the concentration of the buffer solution that adds is decided 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, so that the concentration of buffer solution is calculated according to sampling volume in the injector of described four-way road, making developer in reaction tank and the molar concentration rate of buffer solution is 1:1, when developer is 2, during 2-connection nitrogen-two-(3-ethyl-benzothiazole-6-sulfonic acid)-di-ammonium salts aqueous solution, adjustment is 1.8 ~ 2.3 inorganic acid aqueous solution and the sample introduction ratio of pure water as the pH of buffer solution, so that the concentration of damping fluid is calculated according to sampling volume in the injector of described four-way road, the pH that makes the mixed liquor in reaction tank is 3;
(2.12) by described four transfer valves with the pulling flow type injector of transfer valve of control, the sample introduction end of four described pulling flow type injectors with transfer valve is connected with sample channel respectively, makes in the step (2.11) liquid in four path injectors enter reaction tank; Sample introduction sequentially is: described the first path injector and described alternate path injector be sample introduction at first simultaneously, so that aqueous sodium hypochlorite solution and pure water enter in the reaction tank after mixing by the rapid mixing container, 0.5 after ~ 2 seconds, described three-way injector and described four-way road injector be sample introduction simultaneously, so that developer directly enters reaction tank, buffer solution enters reaction tank by the rapid mixing container, chlorine and developer react in buffer solution and generate the coloured product of tool, and be respectively six points among 0.1 ~ 3mg/L with the concentration that ultraviolet spectrum is measured respectively selected effective chlorine, and the concentration of effective chlorine is the intensity of the ultraviolet absorptivity of the coloured product of 0mg/L gained tool in the aqueous sodium hypochlorite solution, concrete ultraviolet determination wavelength will be decided according to developer, when developer is N, N-diethyl-1, during 4-phenylenediamine aqueous solution, the ultraviolet determination wavelength is 515nm, when developer is 2, during 2-connection nitrogen-two-(3-ethyl-benzothiazole-6-sulfonic acid)-di-ammonium salts aqueous solution, the ultraviolet determination wavelength is 728nm;
The intensity of corresponding ultraviolet absorptivity was as transverse axis when the concentration of effective chlorine was respectively six points among 0.1 ~ 3mg/L and 0mg/L in the aqueous sodium hypochlorite solution of (2.13) measuring with step (2.12), with the concentration of the effective chlorine among the liquor natrii hypochloritis in corresponding described the first path injector 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 rear concentration that remains effective chlorine of chlorine and actual water body reaction
(2.21) by described four transfer valves with the pulling flow type injector of transfer valve of control, the sample introduction end of four described pulling flow type injectors with transfer valve is connected respectively with sample channel; Utilize COD MnThe on-line monitoring instrument is measured the COD that processes water MnValue; If COD MnValue then makes processing water directly enter in the described alternate path injector, if COD between 2 ~ 6mg/L 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, is 2 ~ 6mg/L so that enter the concentration of the processing water in the described alternate path injector then; If COD MnValue＜2mg/L will process the water rotary evaporation and be concentrated into 2 ~ 6mg/L, and it is joined in the described alternate path injector; Adjust the sample introduction ratio of chlorine storing solution and pure water by the first T-valve on the sample channel of controlling the first path injector, when making aqueous sodium hypochlorite solution in step (1) the chlorine storing solution hold-up vessel in entering described the first path injector, the concentration of effective chlorine and COD in the aqueous sodium hypochlorite solution MnBe worth identical; Enter solution in described three-way injector and the described four-way road injector and each path injector control method and divided by on enter concentration and the COD of effective chlorine in described the first path injector MnBe worth identical outside, other condition is all identical with (2.11) in the step (2.1);
(2.22) by described four transfer valves with the pulling flow type injector of transfer valve of control, the sample introduction end of four described pulling flow type injectors with transfer valve is connected with sample channel respectively, makes in the step (2.21) liquid in four path injectors enter reaction tank; The sample introduction order: described the first path injector and described alternate path injector be sample introduction at first simultaneously, so that entering after mixing by the rapid mixing container, aqueous sodium hypochlorite solution and processing water begins reaction in the reaction tank, after chlorine and the processing water process certain reaction time (t), described three-way injector and described four-way road injector be sample introduction simultaneously, so that developer directly enters reaction tank, buffer solution enters reaction tank by the rapid mixing container, chlorine and developer react in buffer solution and generate the coloured product of tool, and with the intensity of its ultraviolet absorptivity of ultraviolet spectroscopy; Concrete ultraviolet determination wavelength will be decided according to developer, when developer is N, N-diethyl-1, during 4-phenylenediamine aqueous solution, the ultraviolet determination wavelength is 515nm, when developer was 2,2-connection nitrogen-two-(3-ethyl-benzothiazole-6-sulfonic acid)-di-ammonium salts aqueous solution, the ultraviolet determination wavelength was 728nm; Chlorine is set at least 10 interior reaction time points of 0.1s ~ 15min scope with the reaction time (t) of processing water;
The expression formula C=a of the described typical curve that (2.13) in the intensity A substitution step (2.1) of the ultraviolet absorptivity of (2.23) (2.22) at least 10 reaction time points of step being measured are set up * A+b calculates chlorine and the concentration C of processing water corresponding effective chlorine behind at least 10 reaction time points of experience;
(2.3) the Fitting Calculation is processed the dynamic chlorine demand of water
(2.31) with at least 10 reaction time points (t) in step (2.22) chlorine that arranges and the reaction time of processing water as transverse axis, with step (2.23) chlorine with process water concentration of corresponding residue effective chlorine behind at least 10 reaction time points of experience and draw ln (C) ~ t as the longitudinal axis and scheme;
(2.32) middle three the longest points of reaction time of at least 10 reaction time points (t) begin to carry out linear regression fit among the ln (C) that step (2.31) is drawn ~ t figure, as the related coefficient (R of fitting result 2) be lower than 0.99, repeating step (2.22) then, increase chlorine and process the time point in the reaction time (t) of water, so that the reaction time of the time point that increases is 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) begin to carry out linear regression fit among the ln (C) that again step (2.31) is drawn ~ t figure, until the related coefficient (R of its fitting result 2) greater than 0.99;
(2.33) as the related coefficient (R of the fitting result of step (2.32) 2) greater than 0.99, then from least 10 reaction time points (t), choose a longest point of reaction time in the 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) still greater than 0.99, then from least 10 reaction time points (t), choose a longest point of reaction time in the point except the point that step (2.32) and this step have been chosen, be increased in this step point that match has been chosen last time and proceed linear regression fit; As related coefficient (R 2) still greater than 0.99, then continue this operation;
(2.34) as the related coefficient (R of the linear regression fit of step (2.33) 2) less than 0.99, ending step (2.33); Satisfy at last linear regression fit result's related coefficient (R 2) greater than the approximate point of thinking that the end of rapid reaction stage and slow reaction stage begin of 0.99 the point of from least 10 reaction time points (t), choosing that increases quilt, the reaction time of this point is set as t by the approximate time of thinking the rapid reaction stage that chlorine consumes 0, and the consumption of this chlorine is set as D by the approximate short-term chlorine demand of thinking to process water; And last related coefficient (R 2) the k value of match greater than 0.99 is by the approximate kinetic constant of thinking slow reaction stage pseudo first order reaction;
(2.35) obtain to process water according to the technology characteristics of water factory and arrive disinfecting time t that pipe network tip place needs and the concentration C of this required effective chlorine constantly, and with D, the k, the t that obtain in the step (2.34) 0Value substitution formula (4) calculates and adds the dynamic chlorine demand C that chlorine point is processed water 0
C 0 = C exp ( - k × ( t - t 0 ) ) + D - - - ( 4 )
Wherein: C is the concentration of effective chlorine, the mg/L of unit;
K is the first order reaction kinetics constant, and unit is h -1
C 0Be that on-line determination is processed hydrodynamic(al) attitude chlorine demand, unit is mg/L;
D is the short-term chlorine demand, and unit is mg/L;
T is the rapid reaction stage and slow reaction stage chlorine and the T.T. of processing water and contacting, and unit is h;
t 0Be the time that rapid reaction stage chlorine contacts with processing water, unit is h.
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CN107727586A (en) * 2017-09-11 2018-02-23 华侨大学 A kind of method that permanganate indices in water is determined with DPD
CN108414465B (en) * 2018-02-05 2020-07-10 清华大学 Method for measuring and predicting chlorine active substances and residual chlorine attenuation in reclaimed water
CN108414465A (en) * 2018-02-05 2018-08-17 清华大学 The measurement and prediction technique of chlorine active material and Chlorine Decay in a kind of recycled water
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