CN113075374B - Method for evaluating generation of byproduct NDMA in water disinfection process - Google Patents
Method for evaluating generation of byproduct NDMA in water disinfection process Download PDFInfo
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Abstract
The invention discloses a method for evaluating the generation of a byproduct NDMA in a water disinfection process, which mainly comprises the following steps: collecting and arranging relevant data generated by a byproduct NDMA in a water system disinfection process; obtaining a regression model by using SPSS software; calculating the addition amount of the disinfectant, and measuring the temperature in the disinfection tank; substituting the data into a model equation; the NDMA production under different disinfection modes is obtained through model calculation; the disinfectant, the disinfectant concentration and the temperature are selected according to actual conditions, and a regression model is established by considering that the disinfectant generates different amounts of byproducts and is respectively related to the temperature and the concentration. The invention regresses from the actual disinfection effect, has more practical significance, and reduces the deviation between the theoretical condition and the actual operation.
Description
Technical Field
The invention belongs to the field of water system disinfection, and particularly relates to a method for evaluating generation of a disinfection by-product NDMA (Newcastle disease Virus MA) in a water disinfection process by using ammonium monochloride, dichloramine and ozone.
Background
N-dimethylnitrosamine NDMA (named NDMA) is a chemical substance with strong carcinogenicity, and can enter an animal body in various forms of respiratory tract inhalation, digestive tract intake, subcutaneous intramuscular injection, skin contact and the like to cause tumors. The use of chloramine disinfectants and the increase in ammonia nitrogen concentration during disinfection is an important cause of the production of NDMA, a disinfection by-product. In addition, due to the use of polyepichlorohydrin dimethylamine and polydimethyldiallylammonium chloride flocculants in large quantities, NDMA is generated in the subsequent chloramine disinfection process.
The mechanism of ammonium chloride disinfection is as follows: chloramine is hydrolyzed in water to generate hypochlorous acid, so that the aim of disinfection is fulfilled. Research shows that chloramine can react with amino acid to prevent protein synthesis and biological activity with protein as substrate, so as to reach disinfection effect. Chloramine can reduce the generation amount of disinfection byproducts such as trihalomethane, haloacetic acid and the like compared with free chlorine, has good stability in a water supply system, and can inhibit the propagation of bacteria in water for a long time. The adoption of chloramine for disinfection can control smell and taste and keep the drinking water to have good mouthfeel. More and more waterworks have therefore adopted chloramine disinfection instead of free chlorine disinfection.
The ozone disinfection mechanism is as follows: ozone is a strong oxidant, after dissolved in water, inorganic matter and organic matter in water are oxidized directly or indirectly by using a large amount of hydroxyl free radicals and nascent oxygen generated in the reaction, and the oxidized organic matter enters cells of bacteria to oxidize intracellular organic matter, so that the aims of sterilization, disinfection and water quality purification are achieved.
In the disinfection process, dimethylamine in the water body meets ozone, is firstly oxidized into hydrocarbon amine, then the hydrocarbon amine reacts with the dimethylamine to generate UDMH, and then is oxidized to generate NDMA.
The modeling of the invention adopts a sps nonlinear regression model. The sps nonlinear regression is a method for establishing a nonlinear relationship between a dependent variable and a series of independent variables, and unlike the linear regression for estimating a linear model, the nonlinear regression estimates a model having an arbitrary relationship between an independent variable and a dependent variable by using an iterative estimation algorithm.
Disclosure of Invention
The object of the present invention is to overcome the drawbacks of the prior art by providing, by means of modelling, the production of NDMA (Newcastle disease Virus) as a byproduct is researched on the premise of adopting three disinfectants, namely, monoammonium chloride, dichloramine and ozone for disinfection. The method comprises the steps of measuring the temperature of a water body, the adding amount of a disinfectant and the generation amount of a disinfection by-product NDMA (Newcastle disease Virus-associated antigen), and evaluating the generation amount of the disinfection by-product in the disinfection process by establishing a multiple regression model.
The technical scheme of the invention is as follows: the method for evaluating the generation of the byproduct NDMA in the water disinfection process mainly comprises the following steps:
1) Collecting and arranging relevant data generated by a byproduct NDMA in a water system disinfection process;
2) Obtaining a regression model by using SPSS software according to the data;
3) Calculating the addition amount of the disinfectant, and measuring the temperature in the disinfection tank;
4) Substituting the data into a model equation;
5) The NDMA production under different disinfection modes is obtained through model calculation;
6) Selecting the disinfectant, the disinfectant concentration and the temperature according to actual conditions, and establishing a regression model by considering different disinfectants producing different amounts of byproducts which are respectively related to the temperature and the concentration.
Furthermore, the invention takes the generation amount of a disinfection by-product NDMA as a dependent variable and the temperature and the adding amount of the disinfectant as independent variables to establish a model: the generation amount of NDMA in the disinfection process of ammonium monochloride and ozone is related to two factors of temperature and disinfectant adding amount, and SPSS nonlinear regression analysis is selected to obtain a binary equation.
Further, the model equation of the NDMA generation amount changing with the temperature of the disinfection water body and the adding amount of the disinfectant in the ammonium chloride disinfection process is constructed as follows:
f＝-36.45×T 3 +0.417×T 2 ×c 1 -8.189×T×c 1 2 +2366.962×T 2 +4.858×T×c 1 +35.455×c 1 2 +164.404×c 1 -42756.992×T+159146.674
wherein f is the NDMA production amount, and the unit is mu g/L;
t is the temperature of the disinfection water body, and the unit is;
c 1 the dosage is the dosage of ammonium chloride, and the unit is mg/L.
Further, the model equation of the NDMA generation amount, the temperature of the disinfection water body and the change of the disinfectant adding amount in the ozone disinfection process is constructed as follows:
f＝-40.349×T 3 -8.099×c 3 3 -0.812×T 2 ×c 3 -0.303×T×c 3 2 +2622.484×T 2 +20.076×c 3 2 +28.472×T×c 3 +58.6×c 3 -47402.617×T+176477.299
wherein f is the NDMA production amount, and the unit is mu g/L;
t is the temperature of the sterilized water body, and the unit is;
c 3 the unit of the ozone dosage is mmol/L.
Further, the invention has the advantages that for dichloramine disinfection, the NDMA generation amount is only obviously related to the dichloramine adding amount, and a unitary equation is established.
Further, the model equation of the change of the NDMA generation amount and the disinfectant adding amount in the ammonium dichloride disinfection process is constructed as follows:
f＝1607.5c 2 3 -4101c 2 2 +2966.3c 2 +11.088
wherein f is the NDMA production amount, and the unit is mu g/L;
c 2 the dosage of the ammonium dichloride is in mmol/L.
Compared with the prior art, the invention has the beneficial effects that:
1. compared with an equation derived by dynamics, the model regresses from the actual disinfection effect, has more practical significance, and reduces the deviation between the theoretical condition and the actual operation.
2. The model considers the generation amount of a disinfection by-product NDMA under the condition of removing the stability of the novel coronavirus, and establishes a multiple regression model, and a model aiming at the condition is not provided before.
3. The model is comprehensively considered in many aspects, and can give consideration to time, dosage, time cost of disinfection efficiency, economic benefit of disinfectant dosage and environmental benefit.
4. The model is not required to be subjected to complex experiments, but is actually applied through the existing data and the established model according to the formula obtained by the model, and the model is simple and convenient and has practical value.
Drawings
FIG. 1 is a flow chart of the experimental development procedure;
FIG. 2 is a multiple line graph of NDMA production as a function of monochloramine dosing and temperature;
FIG. 3 is a graph of NDMA production as a function of dichloramine dosage;
FIG. 4 is a multiple line graph of NDMA production as a function of ozone dosage and temperature.
Detailed Description
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
First, a large review of the literature, looking at relevant data collected and collated about the production of byproduct NDMA during disinfection of water systems for monochloramine, dichloramine and ozone disinfection, is presented, with some examples of data as follows:
TABLE 1 partial data of NDMA formation during water disinfection with monochloronium chloride (data source: reference [2 ])
TABLE 2 partial data of the amount of NDMA produced during Water Disinfection with ammonium dichloride (data source: reference [2 ])
TABLE 3 partial data of the amount of NDMA produced during the water disinfection with ozone (data source: reference [2 ])
Then, in this example, NDMA, which is a byproduct generated during the water sterilization process using monochloramine, dichloramine, and ozone, was selected as a research object, and a model was established based on the above-mentioned collated data.
The general idea of the model is as follows: and establishing a model by taking the generation amount of the disinfection by-product NDMA as a dependent variable and the temperature and the disinfectant addition amount as independent variables. Because the NDMA generation amount in the disinfection process of the ammonium monochloride and the ozone is related to two factors of temperature and disinfectant addition amount, the SPSS nonlinear regression analysis is selected to obtain the following binary equations (1) and (3).
For dichloramine disinfection, the comparison of the established models shows that the NDMA production is only significantly related to the dichloramine addition, so that a unitary equation is established as shown in (2) below.
The model was constructed as follows:
(1) a model equation of the NDMA generation quantity changing with the temperature of the disinfection water body and the addition quantity of the disinfectant in the ammonium chloride disinfection process:
f＝-36.45×T 3 +0.417×T 2 ×c 1 -8.189×T×c 1 2 +2366.962×T 2 +4.858×T×c 1 +35.455×c 1 2 +164.404×c 1 -42756.992×T+159146.674
wherein f is the NDMA production amount, and the unit is mu g/L;
t is the temperature of the disinfection water body, and the unit is;
c 1 the dosage is the dosage of ammonium chloride, and the unit is mg/L.
(2) The model equation of the change of the NDMA generation amount and the disinfectant adding amount in the ammonium dichloride disinfection process is as follows:
f＝1607.5c 2 3 -4101c 2 2 +2966.3c 2 +11.088
wherein f is the NDMA production amount, and the unit is mu g/L;
c 2 the dosage is the dosage of ammonium dichloride and the unit is mmol/L.
(3) A model equation of the NDMA generation amount, the temperature of the disinfection water body and the change of the disinfectant adding amount in the ozone disinfection process is as follows:
f＝-40.349×T 3 -8.099×c 3 3 -0.812×T 2 ×c 3 -0.303×T×c 3 2 +2622.484×T 2 +20.076×c 3 2 +28.472×T×c 3 +58.6×c 3 -47402.617×T+176477.299
wherein f is the NDMA production amount, and the unit is mu g/L;
t is the temperature of the disinfection water body, and the unit is;
c 3 the unit of the ozone dosage is mmol/L.
A multiple line graph of the NDMA production amount with respect to the ammonium monochloride addition amount and the temperature is shown in FIG. 2, a graph of the NDMA production amount with respect to the dichloramine addition amount is shown in FIG. 3, and a multiple line graph of the NDMA production amount with respect to the ozone addition amount and the temperature is shown in FIG. 4.
And the test shows that the prediction effect of the model basically meets the requirement. Wherein R of an ammonium chloride disinfection model 2 
0.898, R of Disinfection model of Dichloroamine 2 0.975, R of ozone sterilization model 2 And was 0.995. It is generally considered that R 2 If the fitting effect is better than 0.8, the three models meet the requirements. A large number of references are made to documents for the collection and interpretation of relevant data generated by NDMA, a by-product of a water system disinfection process, for ammonium monochloride, ammonium dichloride and ozone disinfection.
The NDMA limit value in the drinking water quality criterion of the world health organization is 0.1 mug/L, and the NDMA limit value is substituted into the ammonium monochloride disinfection and ozone disinfection model to obtain a relational expression of the temperature and the disinfectant dosage which meet the limit of the drinking water quality criterion of the world health organization; substituting into a dichloramine disinfection model to directly calculate the using amount of dichloramine;
measuring the temperature in the disinfection tank for use as real-time data;
substituting the data into the model, and calculating to obtain the addition of the disinfectant in different disinfection modes at the temperature of the pool;
the proper disinfectant is selected according to actual conditions.
Reference documents:
[1] a study of nitrosamine disinfection by-product precursors in lake water and their removal characteristics [ D ]. University of qinghua, 2014 is also known.
[2] Research on the generation rule and influencing factors of invar loyalty, N-nitrosodimethylamine in the water treatment process [ D ]. Harbin university of industry, 2007.
[3] World health organization, drinking water quality criteria [ M ].4 edition, shanghai: shanghai university of transportation, 2014.
Claims (1)
1. The method for evaluating the generation of the by-product N-dimethylnitrosamine NDMA in the water disinfection process is characterized by mainly comprising the following steps:
1) Collecting and arranging relevant data generated by a byproduct N-dimethyl nitrosamine NDMA in a relevant water system disinfection process;
2) Obtaining a regression model by using SPSS software according to the data;
3) Calculating the addition amount of the disinfectant, and measuring the temperature in the disinfection tank;
4) Substituting the data into a model equation;
5) The production amount of the N-dimethyl nitrosamine NDMA in different disinfection modes is obtained through model calculation;
6) Selecting a disinfectant, disinfectant concentration and temperature according to actual conditions, and establishing a regression model by considering that the quantities of byproducts generated by different disinfectants are different and are respectively related to the temperature and the concentration;
establishing a model by taking the generation amount of a disinfection by-product N-dimethylnitrosamine NDMA as a dependent variable and the temperature and the adding amount of a disinfectant as independent variables: the generation amount of N-dimethyl nitrosamine NDMA in the disinfection process of ammonium monochloride and ozone is related to two factors of temperature and disinfectant adding amount, and SPSS nonlinear regression analysis is selected to obtain a binary equation;
a model equation of the generation quantity of N-dimethyl nitrosamine NDMA in the process of ammonium chloride disinfection along with the change of the disinfection water body temperature and the disinfectant addition quantity is constructed as follows:
f＝-36.45×T 3 +0.417×T 2 ×c 1 -8.189×T×c 1 2 +2366.962×T 2 +4.858×T×c 1 +35.455×c 1 2 +164.404×c 1 -42756.992×T+159146.674
wherein f is the NDMA production amount, and the unit is mu g/L;
t is the temperature of the sterilized water body, and the unit is;
c 1 the dosage is the dosage of ammonium chloride, and the unit is mg/L;
or
A model equation of the generation amount of N-dimethyl nitrosamine NDMA in the ozone disinfection process, the disinfection water body temperature and the disinfectant adding amount change is established as follows:
f＝-40.349×T 3 -8.099×c 3 3 -0.812×T 2 ×c 3 -0.303×T×c 3 2 +2622.484×T 2 +20.076×c 3 2 +28.472×T×c 3 +58.6×c 3 -47402.617×T+176477.299
wherein f is the NDMA production amount, and the unit is mu g/L;
t is the temperature of the disinfection water body, and the unit is;
c 3 the dosage of ozone is mmol/L;
or
The model equation of the change of the generation amount of the N-dimethylnitrosamine NDMA and the addition amount of the disinfectant in the ammonium dichloride disinfection process is constructed as follows:
f＝1607.5c 2 3 -4101c 2 2 +2966.3c 2 +11.088
wherein f is the NDMA production amount, and the unit is mu g/L;
c 2 the dosage is the dosage of ammonium dichloride and the unit is mmol/L.
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