CN110362963A - A kind of throwing chlorine method regenerating water sterilization - Google Patents

A kind of throwing chlorine method regenerating water sterilization Download PDF

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Publication number
CN110362963A
CN110362963A CN201910800221.XA CN201910800221A CN110362963A CN 110362963 A CN110362963 A CN 110362963A CN 201910800221 A CN201910800221 A CN 201910800221A CN 110362963 A CN110362963 A CN 110362963A
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chlorine
equation
water
concentration
concn
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CN110362963B (en
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李思玉
蔡言安
陈锋
毕学军
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Qingdao University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F30/00—Computer-aided design [CAD]
    • G06F30/20—Design optimisation, verification or simulation
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06Q—INFORMATION AND COMMUNICATION TECHNOLOGY [ICT] SPECIALLY ADAPTED FOR ADMINISTRATIVE, COMMERCIAL, FINANCIAL, MANAGERIAL OR SUPERVISORY PURPOSES; SYSTEMS OR METHODS SPECIALLY ADAPTED FOR ADMINISTRATIVE, COMMERCIAL, FINANCIAL, MANAGERIAL OR SUPERVISORY PURPOSES, NOT OTHERWISE PROVIDED FOR
    • G06Q10/00—Administration; Management
    • G06Q10/04—Forecasting or optimisation specially adapted for administrative or management purposes, e.g. linear programming or "cutting stock problem"
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06Q—INFORMATION AND COMMUNICATION TECHNOLOGY [ICT] SPECIALLY ADAPTED FOR ADMINISTRATIVE, COMMERCIAL, FINANCIAL, MANAGERIAL OR SUPERVISORY PURPOSES; SYSTEMS OR METHODS SPECIALLY ADAPTED FOR ADMINISTRATIVE, COMMERCIAL, FINANCIAL, MANAGERIAL OR SUPERVISORY PURPOSES, NOT OTHERWISE PROVIDED FOR
    • G06Q50/00—Systems or methods specially adapted for specific business sectors, e.g. utilities or tourism
    • G06Q50/06—Electricity, gas or water supply
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/04—Disinfection
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F2111/00—Details relating to CAD techniques
    • G06F2111/10—Numerical modelling

Abstract

The present invention relates to recycled water disinfection technology field more particularly to a kind of throwing chlorine methods for regenerating water sterilization.The following steps are included: (1) detection obtains NH in recycled water4 +- N concentration x1With the humic acid fluorescence intensity x that need to decline2Substituted into the cl concn A value that equation (1) obtains participating in chlorination reaction: (2) bring the A value obtained by equation (1) into chlorine attenuation coefficient ︱ k ︱ and participate in the governing equation (2) of the cl concn A of chlorination reaction, then can calculate chlorine attenuation coefficient ︱ k ︱；(3) Chlorine Decay First order dynamic model (3) will be substituted by the A value and ︱ k ︱ value that equation (1) and equation (2) obtain, then residual chlorine concentration C can be obtained and sterilize the governing equation of time of contact t.The present invention by establishing the throwing chlorine method of science, can carrying out disinfection to recycled water with economical and efficient, and can be provided safeguard for the control of chlorine residue with prediction.

Description

A kind of throwing chlorine method regenerating water sterilization
Technical field
The present invention relates to recycled water disinfection technology field more particularly to a kind of throwing chlorine methods for regenerating water sterilization.
Background technique
To guarantee recycled water terminal water water quality safety, it is remaining in water to increase that when recycled water plant effluent, need to add sodium hypochlorite Cl concn, so chlorine residue is the important indicator of guarantee recycled water terminal water water quality safety, but after the transport of longer pipe network Chlorine residue consumption is fast, not can guarantee terminal water water quality, it is therefore desirable to carry out secondary sterilization.Standard of reclaimed water (SL368- 2006) its residual chlorine concentration minimum requirements of the different reuse approach of recycled water is different in, wherein being used as cooling water and landscape water rule Determine residual chlorine concentration >=0.05mg/L, is used as urban reclaimed water and provides pipe network end residual chlorine concentration >=0.2mg/L.
Regeneration water sterilization both at home and abroad at present is still to carry out throwing chlorine using the Disinfect mechanism of water supply, but recycled water water quality is complicated, The specification that oneself need to be established is speculated and is controlled to residual chlorine concentration remaining in recycled water disinfecting process.
Summary of the invention
Present invention solves the technical problem that being that domestic and international regeneration water sterilization is still to be carried out using the Disinfect mechanism of water supply at present Chlorine is thrown, but recycled water water quality is complicated, need to establish the specification of oneself, residual chlorine concentration remaining in recycled water disinfecting process is speculated And control.
To solve the above problems, the present invention devises a kind of throwing chlorine method for regenerating water sterilization, by analyzing different chlorine doses And the Chlorine Decay rule under different main reactant concentration conditions realizes the science disinfection of recycled water, is a kind of according to regeneration Water water quality and storage residence time carry out the mode that science throws chlorine, can guarantee that recycled water terminal water water quality and economical and efficient disappear Poison.
In order to achieve the above objectives, the following technical solution is employed by the present invention: a kind of throwing chlorine method regenerating water sterilization adds Disinfectant be sodium hypochlorite, the Chlorine Decay rule then analyzed under different chlorine doses and different main reactant concentration conditions is come Realize the science disinfection of recycled water；Comprising the following steps:
(1) detection obtains NH in recycled water4 +- N concentration x1With the humic acid fluorescence intensity x that need to decline2, substituted into equation (1) obtain participating in the cl concn A value of chlorination reaction:
A=6.38-6.39 (0.18^x1)-0.63(0.98^x2) (1)
In formula: A- participates in the cl concn of entire chlorination reaction process, mg/L；
x1NH in recycled water4 +- N concentration, mg/L；
x2The humic acid fluorescence intensity that need to decline.
Wherein, the determination process of each parameter is as follows:
1. participating in the cl concn A value of entire reaction process in order to obtain, need to study the pass of reactant in chlorine consumption and water System, carry out water sampling while surveying chlorine residue, measure the different residence times be lauched in NH4 +-N、PO4 2-- P, COD, TOC, three Fluorescence is tieed up, wherein NH4 +- N concentration and humic acid fluorescence intensity moment decline and slippage maximum after adding sodium hypochlorite.
2. with NH4 +- N concentration and humic acid fluorescence intensity are parameter index, are throwing chlorine by being studied with ultrapure water water distribution The relationship between 0h chlorine consumption and reactant concentration variable quantity afterwards, as shown in Figure 1, it is anti-to obtain participation chlorination according to fit equation Answer the cl concn A of process and the functional relation of initial ammonia nitrogen concentration and humic acid concentration fluorescence intensity slippage, square journey (1).
A=y1+y2
A=6.38-6.39 (0.18^x1)-0.63(0.98^x2) (1)
In formula: the cl concn of the entire chlorination reaction process of A-participation, mg/L；
X1-ammonia nitrogen consumption, mg/L；
X2-humic acid fluorescence intensity slippage.
(2) it brings the A value obtained by equation (1) into chlorine attenuation coefficient ︱ k ︱ and participates in the pass of the cl concn A of chlorination reaction It is equation (2), then can calculates chlorine attenuation coefficient ︱ k ︱.
︱ k ︱=0.953-0.093 × A (2)
In formula: ︱ k ︱-chlorine attenuation coefficient；
A- participates in the cl concn of entire chlorination reaction process, mg/L.
Wherein, the determination process of each parameter is as follows:
1. experimental provision is that pure 304 stainless steel of 4 volumes covers heat preservation drum, number 1#, 2#, 3#, 4#, such as Fig. 2 institute Show.During test, 5L experimental water is separately added into 4 devices first；Secondly, using the NaClO solution of 1.55mol/L 4,6,8 and 10mg/L gradient is set by the initial free chlorine residual concentration of recycled water, stirs 30s；It is taken in the different residence times Sample measures free chlorine, total chlorine, NH4 +-N、PO4 2-- P, COD, TOC, three-dimensional fluorescence.
Wherein, it includes water inlet line 1, the throwing chlorine pipeline 2 above staving that the stainless steel, which covers heat preservation drum, is set in staving Blender 3, lower section are equipped with water outlet 4；Water inlet line 1 is accessed experimental water in staving by water pump, is added by throwing chlorine pipeline Enter NaClO solution, then stirred evenly with blender, is discharged water by the water outlet of water outlet 4, sample detection.
2. dynamics fitting is carried out with the variation of residence time to free chlorine residual, as shown in figure 3, the degree of correlation of all curves R2All 0.98 or more, illustrate that the decaying reaction of chlorine residue can be indicated with First order dynamic model, square journey (3).
C=C0+A×exp(k×t) (3)
In formula: residual chlorine concentration corresponding to C-t moment, mg/L；
C0- in decaying latter stage have neither part nor lot in the chlorine residue of reaction, mg/L；
T-disinfection time of contact, h；
The cl concn of the entire chlorination reaction process of A-participation, mg/L；
K-chlorine attenuation coefficient.
3. it obtains chlorine attenuation coefficient ︱ k ︱ according to the curve that equation 3 fits and participates in the cl concn A of entire chlorination reaction, The two is fitted, as shown in figure 4, the governing equation of ︱ k ︱ and A is obtained, it is then dense in the known chlorine for participating in chlorination reaction It spends under A value, carries it into the governing equation of ︱ k ︱ and A, then can calculate attenuation coefficient ︱ k ︱.
(3) Chlorine Decay First order dynamic model will be substituted by the A value and ︱ k ︱ value that equation (1) and equation (2) obtain (3), then residual chlorine concentration C can be obtained and sterilize the governing equation of time of contact t.
C=C0+ A × exp (- ︱ k ︱ × t) (3)
In formula: residual chlorine concentration corresponding to C-t moment, mg/L；
C0- in decaying latter stage the chlorine residue of reaction is had neither part nor lot in, it can when 0.15,19~23 DEG C desirable when water temperature is 15~18 DEG C 0.01, mg/L is taken, can be adjusted according to the actual situation；
T-disinfection time of contact, h；
The cl concn of the entire chlorination reaction process of A-participation, mg/L；
︱ k ︱-chlorine attenuation coefficient.
Suggest flow chart by throwing chlorine, i.e., shown in Fig. 5, can finally extrapolate chlorine residue corresponding when the disinfection contact t time Concentration, and the time required when chlorine residue is down to below required standard, so that the control and prediction for chlorine residue provide safeguard, separately It outside can also be by that need to store the residence time, deduce satisfactory secondary chlorine-throwed quantity with water terminal chlorine residue requirement condition.
The beneficial effects of the present invention are:
(1) NH has been determined by the relationship of reactant in chlorine consumption and water4 +- N and humic acid fluorescence intensity, which are used as, to be commented The factor of valence oxygen demand.
(2) Chlorine Decay First order dynamic model is established, it is corresponding when by calculating the available disinfection contact t time Residual chlorine concentration, and time required when chlorine residue is down to below required standard.
(3) by Chlorine Decay First order dynamic model and the residence time need to can be stored, with water terminal chlorine residue requirement item Part deduces satisfactory secondary chlorine-throwed quantity.
Detailed description of the invention
Fig. 1 is NH4 +The matched curve figure of-N and humic acid fluorescence intensity and chlorine consumption；
Fig. 2 is that stainless steel covers heat preservation drum structural schematic diagram；
Fig. 3 is the dynamic fitting curve of free chlorine residual and residence time；
Fig. 4 is the relationship fitted figure of ︱ k ︱ and A；
Fig. 5 is to throw chlorine to suggest flow chart；
Fig. 6 is chlorine residue measured value figure compared with predicted value；
In figure, water inlet line 1 throws chlorine pipeline 2, blender 3, water outlet 4.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with implementation of the invention Example, is clearly and completely described technical solution of the present invention.Obviously, described embodiment is that a part of the invention is real Example is applied, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creation Property labour under the premise of every other embodiment obtained, shall fall within the protection scope of the present invention.
Embodiment 1:
The secondary throwing chlorine disinfection method of recycled water provided by the present invention, Integral Thought are as follows: when recycled water is being transported or stored up Water quality deterioration during depositing learns NH in recycled water when need to carry out secondary sterilization to guarantee terminal water water quality4 +- N concentration and need The humic acid fluorescence intensity of decline can then be obtained according to the relation equation (1) between the cl concn A and reactant for participating in chlorination reaction To A value, ︱ k ︱ value then can be obtained further according to the relation equation (2) of chlorine attenuation coefficient ︱ k ︱ and the cl concn A for participating in chlorination reaction, Chlorine attenuation coefficient ︱ k ︱ value and the cl concn A value for participating in chlorination reaction substitute into model (3), then obtain residual chlorine concentration C and contact with disinfection The governing equation of time t, therefore corresponding residual chlorine concentration when can calculate the disinfection contact t time are the control of chlorine residue and pre- Survey provides guarantee.
It is using the recycled water of Hai Bohe sewage treatment plant, Qingdao City as experimental subjects, Process for Effluent water quality reaches " city dirt Water reuse (treatment utilization-water for scenic environment use water quality " (GB/T18921-2002) non-contact class water standard, the disinfectant added is secondary Sodium chlorate.
Following, NH is limited for Chlorine Decay to detection4 +-N(x1) concentration is 2.26mg/L, the humic acid fluorescence that need to decline is strong Spend (x2) it is 150, therefore the recycled water of secondary sterilization need to be carried out.Throwing chlorination is carried out by device shown in Fig. 2.Pass through equation A=6.38-6.39 (0.18^x1)-0.63(0.98^x2) the cl concn A ≈ 6.11mg/L for participating in chlorination reaction is calculated, A It substitutes into equation ︱ k ︱=0.953-0.093 × A and obtains chlorine attenuation coefficient ︱ k ︱ ≈ 0.38, obtain equation (3) C=0.01+6.11e^ (- 0.38t), by comparison actual measurement residual chlorine concentration and prediction residual chlorine concentration, each check post chlorine residue measured value and model calculation value ratio It is closer to, the goodness of fit is higher, sees Fig. 3.Therefore science is carried out by the method and throws chlorination, realized in recycled water disinfecting process The supposition and control of remaining residual chlorine concentration provide scientific basis for the secondary sterilization of recycled water.
The above, only the preferred embodiment of the present invention, protection scope of the present invention are not limited merely to above-mentioned reality Example is applied, all technical solutions belonged under the invention thinking all belong to the scope of protection of the present invention.It should be pointed out that being led for this technology For the technical staff in domain, also it is considered as protection scope of the present invention in any improvement for not departing from the principle of the invention.

Claims (4)

1. a kind of throwing chlorine method for regenerating water sterilization, it is characterised in that: the following steps are included:
(1) detection obtains NH in recycled water4 +- N concentration x1With the humic acid fluorescence intensity x that need to decline2, substituted into equation (1) and obtained To participate in chlorination reaction cl concn A value:
A=6.38-6.39 (0.18^x1)-0.63(0.98^x2) (1)
In formula: A- participates in the cl concn of entire chlorination reaction process, mg/L；
x1NH in recycled water4 +- N concentration, mg/L；
x2The humic acid fluorescence intensity that need to decline；
(2) it brings the A value obtained by equation (1) into chlorine attenuation coefficient ︱ k ︱ and participates in the relationship side of the cl concn A of chlorination reaction Formula (2) can then calculate chlorine attenuation coefficient ︱ k ︱:
︱ k ︱=0.953-0.093 × A (2)
In formula: ︱ k ︱-chlorine attenuation coefficient；
A- participates in the cl concn of entire chlorination reaction process, mg/L；
(3) Chlorine Decay First order dynamic model (3) will be substituted by the A value and ︱ k ︱ value that equation (1) and equation (2) obtain, then Residual chlorine concentration C can be obtained and sterilize the governing equation of time of contact t:
C=C0+A × exp (- ︱ k ︱ × t) (3)
In formula: residual chlorine concentration corresponding to C-t moment, mg/L；
C0-has neither part nor lot in the chlorine residue of reaction in decaying latter stage, and water temperature takes 0.01 when taking 0.15,19~23 DEG C when being 15~18 DEG C, mg/L；
T-disinfection time of contact, h；
The cl concn of the entire chlorination reaction process of A-participation, mg/L；
︱ k ︱-chlorine attenuation coefficient；
Corresponding residual chlorine concentration when can finally extrapolate the disinfection contact t time, and when chlorine residue is down to below required standard The required time；By above formula and the residence time need to be stored, met the requirements with water terminal chlorine residue requirement condition to deduce Secondary chlorine-throwed quantity.
2. a kind of throwing chlorine method for regenerating water sterilization as described in claim 1, it is characterised in that: the parameter of equation (1) calculates Method is as follows: with NH4 +- N concentration and humic acid fluorescence intensity are parameter index, by being studied after throwing chlorine with ultrapure water water distribution 0h chlorine consumption and reactant concentration variable quantity between relationship, according to fit equation obtain participate in chlorination reaction process chlorine it is dense Spend the functional relation of A and initial ammonia nitrogen concentration and humic acid concentration fluorescence intensity slippage.
3. a kind of throwing chlorine method for regenerating water sterilization as described in claim 1, it is characterised in that: the parameter of equation (2) calculates Method is as follows:
1. being taken as pure 304 stainless steel of 4 volumes covers heat preservation drum, number 1#, 2#, 3#, 4#, during test, first 4 5L experimental water is separately added into a device；Secondly, using the NaClO solution of 1.55mol/L by the initial free remaining of recycled water Cl concn is set as 4,6,8 and 10mg/L gradient, stirs 30s；
2. carrying out dynamics fitting, the degree of correlation R of all curves with the variation of residence time to free chlorine residual2All 0.98 or more, Illustrate that the decaying reaction of chlorine residue can be indicated with First order dynamic model, square journey (3):
C=C0+A×exp(k×t) (3)
In formula: residual chlorine concentration corresponding to C-t moment, mg/L；
C0- in decaying latter stage have neither part nor lot in the chlorine residue of reaction, mg/L；
T-disinfection time of contact, h；
The cl concn of the entire chlorination reaction process of A-participation, mg/L；
K-chlorine attenuation coefficient；
3. obtaining chlorine attenuation coefficient ︱ k ︱ according to the curve that equation 3 fits and participating in the cl concn A of entire chlorination reaction, to two Person is fitted, and obtains the governing equation of ︱ k ︱ and A, then under the known cl concn A value for participating in chlorination reaction, by its band Enter the governing equation of ︱ k ︱ and A, then can calculate attenuation coefficient ︱ k ︱.
4. a kind of throwing chlorine method for regenerating water sterilization as claimed in claim 3, it is characterised in that: the stainless steel covers heat preservation Drum includes water inlet line, the throwing chlorine pipeline above staving, sets blender in staving, lower section is equipped with water outlet.
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CN113075374A (en) * 2021-03-24 2021-07-06 天津大学 Method for evaluating generation of byproduct NDMA in water disinfection process

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