CN101793820B - On-line monitoring method for double module linkage water quality - Google Patents
On-line monitoring method for double module linkage water quality Download PDFInfo
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- CN101793820B CN101793820B CN 200910119788 CN200910119788A CN101793820B CN 101793820 B CN101793820 B CN 101793820B CN 200910119788 CN200910119788 CN 200910119788 CN 200910119788 A CN200910119788 A CN 200910119788A CN 101793820 B CN101793820 B CN 101793820B
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- 238000000034 method Methods 0.000 title claims abstract description 81
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000012544 monitoring process Methods 0.000 title claims abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 44
- 230000008859 change Effects 0.000 claims abstract description 6
- 238000001514 detection method Methods 0.000 claims description 26
- 230000001419 dependent effect Effects 0.000 claims description 12
- 238000000825 ultraviolet detection Methods 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 239000010865 sewage Substances 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000012417 linear regression Methods 0.000 claims description 3
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- 238000012545 processing Methods 0.000 claims description 2
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Abstract
The invention mainly aims to solve the problem that a result measured by using a UV method needs comparing with the result of an international standard method, and discloses an on-line monitoring method for double module linkage water quality, which combines the UV method with a chemical method. The water quality can be measured (once every three seconds at a fastest speed) by using a UV method-based measuring module (a UV module for short); and simultaneously, a chemical method-based measuring module (a chemical measuring module for short) is used for measuring according to set time (measure once every 0.5 hours to 30 days according to water quality change condition). Data of the two methods are compared and a null-point measurement is used for determining correlativity between a UV value and the result measured by the chemical method of the international method so as to evaluate a linear relation. The linear relation is input into the UV module as an operational formula (calibrating relevant coefficients of the UV measuring module by using the chemical measuring module) of a COD or TOC value, so automatic comparison experiment between the UV method and the international method is achieved and the measuring instantaneity and correctness are ensured at the same time.
Description
Technical field
The present invention relates to a kind of on-line monitoring method for double module linkage water quality that UV method and chemical method are combined, and relate in particular to UV method and national standard method are realized that in instrument automatic on-line compares, calculates the method that correlationship is used for the COD On-line rapid measurement.
Background technology
Along with the development of China's economic, environmental pollution also is on the rise, and all there is pollution in various degree in present all kinds of water system major parts.Chemical oxygen demand (COD) (Chemical Oxygen Demand, be called for short COD) refer in the water body easily by the amount of the oxygenant that reducing substances consumed of strong oxidizer oxidation, the result is converted into the amount of oxygen, in mg/L, it is the composite target that characterizes reducing substances in the water body, is one of most important organic contamination overall target in the monitoring water environment.Total organic carbon (TOC) is the overall target that represents organism quality in the water body with the content of carbon, usually is used for estimating the degree of Organic Pollution in the water body.
COD on-line monitoring instrument in the market is very many, and detection method is divided according to principle, can be divided into Physical and chemical oxidization method.
Physical is ultraviolet absorptivity (Ultraviolet Absorbance, be called for short UVA, or UV) method, it utilizes organic compound to measure in the absorption at 254nm wavelength place, in order to reduce the impact of suspended material on measuring, generally all adopt dual wavelength to measure (254nm is for measuring wavelength, and 550nm is the buckle back scape).With the mensuration of chemical oxidization method in essence difference is arranged.It is pure physical optics method that the method is measured, and does not have chemical reaction, need not chemical reagent, does not have chemical reaction in the mensuration process, is not subjected to chloride ion interference, non-secondary pollution, and fast response time, the instrument failure rate is low, maintenance is little, is easy to accomplish on-line monitoring.But the UV method also exists the shortcoming of its method itself: when measuring COD with the UV method, often rely on the correlationship of UV and COD to calculate the numerical value of COD.And the wastewater treatment level of China is still not too high at present, and the comparison of ingredients of waste water water sample is complicated, when only calculating COD by the correlationship of UV and COD; If the water sample composition changes greatly, because the size of related coefficient and water sample composition have much relations, therefore need to often demarcate related coefficient by comparison, or need collect as much as possible the accuracy of the comparison data guarantee measurement of long period.Therefore, the on-line monitoring instrument of UV method is only applicable to the monitoring of more stable water quality, for the larger water quality of change of water quality, is difficult to guarantee accuracy.And the UV method is in the mensuration process, must and National Standard Method compare, data just have reliability.If only be the contrast experiment of UV method and National Standard Method with the laboratory, it is loaded down with trivial details that work will become, and workload is very large.
It also is in like manner that the UV method is measured TOC.
Chemical oxidization method is divided into: potassium dichromate oxidation (COD
Cr) and permanganate index (COD
Mn).Potassium dichromate oxidation (COD
Cr) be applicable to the mensuration of the COD of sewage.Permanganate index (COD
Mn) be applicable to the mensuration of the COD of clean water.Potassium dichromate oxidation (COD
Cr), mainly measure the COD content of sewage, measure accurately, but complicated operation measured once the fastest about 30 minutes, the time is longer, produces secondary pollution, and is subjected to the interference of chlorion in the water.Permanganate index (COD
Mn) can only measure clean water, measure once the fastest about 30 minutes, minute is longer, and the process more complicated can not realize real-time measurement.More than the COD on-line monitoring instrument of two kinds of chemical methodes, the structure relative complex, failure rate is higher, the daily servicing amount is larger, can only carry out sampled measurements to sewage every a period, can not Real-Time Monitoring.
Divide according to principle of work, the TOC analyser can be divided into combustion oxidation-non-dispersion infrared absorption process, conductance method, gas chromatography, wet oxidation-non-dispersion infrared absorption process etc.Wherein combustion oxidation-non-dispersion infrared absorption process only needs disposable conversion, and flow process is simple, favorable reproducibility, highly sensitive, so TOC on-line monitoring instrument mainly adopts combustion oxidation-non-dispersion infrared absorption process.But the method is subjected to chloride ion interference serious, and apparatus structure is complicated, long-term continuous coverage, and maintenance is large.
In the existing method, all be single a kind of Physical of use or chemical method, water quality is monitored, and these two kinds of methods itself all exist defective, can not satisfy the demand of monitoring water quality on line.
Summary of the invention
The present invention mainly is the problem that the result needs and National Standard Method is compared of measuring in order to solve the UV method.On-line monitoring method for double module linkage water quality combines the advantage of Physical and chemical method, has realized the robotization of the control experiment of UV method and national standard method, has guaranteed simultaneously real-time and the accuracy measured.
The present invention combines the mensuration module of the chemical method of the mensuration module of UV method and GB.Measurement module (hereinafter to be referred as the UV module) based on the UV method can be measured in real time to water quality (the fastest 3 seconds once); Simultaneously, measure (can set 0.5 hour-30 days measure once) based on the measurement module (hereinafter to be referred as the chemical measurement module) of chemical method by setting-up time, the data of two kinds of methods are compared, again in conjunction with Measurement Zero Point, determine result's the correlationship of the chemical determination of UV value and National Standard Method, thereby obtain linear relation, and be input to the UV module as the operational formula (being the demarcation that the UV measurement module carries out related coefficient with the chemical measurement module namely) of COD or TOC value.
Before next chemical measurement module was demarcated, the related coefficient that the UV module will utilize demarcated last time was used for COD or the TOC value of Real-time Measuring water gaging.
The on-line monitoring method for double module linkage water quality that a kind of UV method and chemical method combine may further comprise the steps:
(1) demarcation of instrument, wherein the UV method is carried out Zero calibration, measures the UV value of distilled water; Then detect same time water sample with chemical detection module and UV detection module respectively, two groups of data are carried out linear regression processing, calculate dependent equation:
COD or TOC=kUV+b
In the formula, UV represents the ultraviolet absorptivity value, and dimensionless or dimension are l/m; COD represents the chemical oxygen demand value, and dimension is mg/L; TOC represents the total organic carbon value, and dimension is mg/L; K represents the slope of linear equation; B represents the intercept of linear equation;
(2) dependent equation that calculates is input to the UV detection module, aqueous sample stream is through the UV detection module, and the UV module is carried out the real time measure, and every 3-30 measures once second, utilizes equation to calculate COD or TOC content;
(3) demarcate according to the time that sets, recomputate dependent equation.
According to the situation of change of water quality, can set the detection time (0.5 hour-30 days) of chemical detection module, again instrument is demarcated, determine dependent equation, guarantee the accuracy that next period UV measures.In the mensuration process, if UV value N continuous time (N＞3) has larger variation (wherein N＞3 are exemplary, and it only is for explanation that the present invention is made an explanation, and is not limitation of the present invention), illustrate that water quality changes, instrument will be demarcated automatically.The present invention can well solve the problem of comparing of UV method and National Standard Method in the on-line monitoring, has guaranteed simultaneously the accuracy that UV measures.
Description of drawings
Fig. 1 shows the demarcation process flow diagram of embodiments of the invention;
Fig. 2 shows the overhaul flow chart of embodiments of the invention.
Embodiment
Fig. 1 shows the demarcation process flow diagram of embodiments of the invention, wherein:
(1) the UV method is carried out Zero calibration, namely measures the UV value of distilled water;
(2) use respectively chemical detection module and UV detection module, detect the water sample of same period;
(3) two groups of data are carried out linear regression analysis, calculate dependent equation:
COD or TOC=kUV+b
In the formula, UV---ultraviolet absorptivity value (dimensionless, or l/m);
COD---chemical oxygen demand (COD) (mg/L);
TOC---total organic carbon (mg/L);
The slope of k---linear equation;
The intercept of b---linear equation.
Fig. 2 shows the overhaul flow chart of embodiments of the invention, wherein: after the demarcation, the dependent equation that calculates is input to the UV detection module, aqueous sample stream is through the UV detection module, the UV module is carried out the real time measure, every 3-30 measures once (i.e. the fastest 3 seconds data) second, utilizes equation to calculate COD or TOC content; (wherein N＞3 are exemplary when undergoing mutation when arriving setting-up time (can set 0.5 hour-30 days) or working as UV value N continuous time (N＞3), it only is for explanation that the present invention is made an explanation, and be not limitation of the present invention), can automatically demarcate, recomputate dependent equation.
As seen, according to the situation of change of water quality, can set the detection time of chemical detection module, again instrument be demarcated, determine dependent equation, guarantee the accuracy that next period UV measures.In the mensuration process, if UV value N continuous time (N＞3) is undergone mutation (wherein N＞3 are exemplary, and it only is for explanation that the present invention is made an explanation, and is not limitation of the present invention), illustrate that water quality changes, instrument will be demarcated automatically.
Different according to the water sample of measuring, different with the index of measuring, following mode can also be arranged:
In order to reduce the impact of suspended material on measuring, the UV detection module can adopt dual wavelength to measure (254nm is for measuring wavelength, and 550nm is the buckle back scape);
If the water quality of measuring is sewage, the chemical detection module can adopt the detection module of CODcr;
If the water quality of measuring is clean water or surface water, the chemical detection module can adopt the detection module of CODMn;
If the index that water quality need to be monitored is TOC, the chemical detection module can adopt the detection module of TOC;
Some other indexs that can use the UV method to detect, needs and standard chemical process are compared, and can change the corresponding chemical detection module into;
Measure the chemical detection module of same index, can adopt the chemical detection method of different national standards.
Double module linkage water quality on-line monitoring technique of the present invention combines the advantage of Physical and chemical method, has realized the robotization of the control experiment of UV method and national standard method, has guaranteed simultaneously real-time and the accuracy measured.Even detected water sample is not very stable, also can carry out instant correction to data.As the water sample of phasic Chang, do not need manually to do the control experiment of UV method and National Standard Method yet, be to have realized online detection and automatic comparison experiment.The present invention is applicable to the on-line determination of any water quality except the waste water of sugaring and liquor industry, because alcohol and glucide are the straight chain hydrocarbon organism, do not absorb at ultraviolet 254nm, so CODcr or TOC on-line monitoring method are directly used in sugaring and brewing wastewater suggestion.
Embodiment disclosed herein is exemplary, and it only is for explanation that the present invention is made an explanation, and is not limitation of the present invention, and improvement and the expansion that those skilled in the art will envision that are included within protection scope of the present invention.
Claims (8)
1. the on-line monitoring method for double module linkage water quality that combines of a UV method and chemical method may further comprise the steps:
(1) demarcation of instrument, wherein the UV method is carried out Zero calibration, measures the UV value of distilled water; Then detect same time water sample with chemical detection module and UV detection module respectively, two groups of data are carried out linear regression processing, calculate dependent equation:
COD or TOC=k UV+b
In the formula, UV represents the ultraviolet absorptivity value, and dimensionless or dimension are 1/m; COD represents the chemical oxygen demand value, and dimension is mg/L; TOC represents the total organic carbon value, and dimension is mg/L; K represents the slope of linear equation; B represents the intercept of linear equation;
(2) dependent equation that calculates is input to the UV detection module, aqueous sample stream is through the UV detection module, and the UV detection module carries out the real time measure, and every 3-30 measures once second, utilizes the K and the b value that obtain after demarcating to calculate COD or TOC content;
(3) demarcate according to the time that sets, recomputate dependent equation.
2. on-line monitoring method for double module linkage water quality as claimed in claim 1, wherein:
If the water quality of measuring is sewage, the chemical detection module can adopt the detection module of potassium dichromate oxidation.
3. on-line monitoring method for double module linkage water quality as claimed in claim 1, wherein:
If the water quality of measuring is clean water or surface water, the chemical detection module can adopt the detection module of permanganate index.
4. on-line monitoring method for double module linkage water quality as claimed in claim 1, wherein:
If the index that water quality need to be monitored is TOC, the chemical detection module can adopt the detection module of TOC.
5. such as the described on-line monitoring method for double module linkage water quality of above-mentioned arbitrary claim, wherein:
Measure the chemical detection module of same index, can adopt the chemical detection method of different national standards.
6. on-line monitoring method for double module linkage water quality as claimed in claim 1, wherein:
Time in the step (3) can be set as 0.5 hour-30 days.
7. on-line monitoring method for double module linkage water quality as claimed in claim 1, wherein:
Time in the step (3) can be set according to the situation of change of water quality.
8. on-line monitoring method for double module linkage water quality as claimed in claim 1, wherein:
In the step (3), when the UV value is undergone mutation N time the time, N＞3 wherein, instrument also can automatic Calibration, recomputates dependent equation.
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| CN102156183B (en) * | 2011-05-23 | 2013-08-07 | 浙江工大盈码科技发展有限公司 | Multi-parameter integrated COD (Chemical Oxygen Demand) water quality monitoring method |
| CN102323234A (en) * | 2011-08-09 | 2012-01-18 | 上海广照光电科技有限公司 | Self-adaption type on-line chemical oxygen demand (COD) monitoring method and instrument |
| CN108254521A (en) * | 2018-01-23 | 2018-07-06 | 苏州卫水环保科技有限公司 | A kind of combined type COD water quality in-line analyzer and its detecting system and method |
| CN109975221A (en) * | 2019-04-17 | 2019-07-05 | 四川万江一泓环境科技有限责任公司 | A kind of spectral water quality analyzer calibration system and method based on machine learning |
| CN115060867B (en) * | 2022-06-27 | 2023-07-21 | 广州喜露宝科技有限公司 | High-precision water quality monitoring method capable of realizing continuous calibration |
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| US3535044A (en) * | 1969-10-22 | 1970-10-20 | Harold H Seward | Total organic carbon colorimeter |
| GB2312278A (en) * | 1996-04-19 | 1997-10-22 | Boghos Awanes Manook | Organic and/or biological pollution monitor |
| CN101105448A (en) * | 2007-08-01 | 2008-01-16 | 山东省科学院海洋仪器仪表研究所 | Method for measuring total organic carbon by ozone oxidation and ultraviolet scanning spectrum integral way |
| CN101271062A (en) * | 2008-05-09 | 2008-09-24 | 哈尔滨天朗清科技有限公司 | On-line monitoring instrument for measuring COD concentration by ultraviolet light absorption method |
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| CN201051071Y (en) * | 2007-06-18 | 2008-04-23 | 北京鸿海清科技有限公司 | Chemical oxygen demand and biologic oxygen demand detection device |
| CN201047827Y (en) * | 2007-06-18 | 2008-04-16 | 北京鸿海清科技有限公司 | Chemical oxygen demand testing apparatus |
| CN101221145B (en) * | 2008-01-25 | 2012-01-04 | 大连理工大学 | Subaqueous chemical oxygen demand measuring apparatus and method and method based on flow injection sampling |
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Patent Citations (4)
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|---|---|---|---|---|
| US3535044A (en) * | 1969-10-22 | 1970-10-20 | Harold H Seward | Total organic carbon colorimeter |
| GB2312278A (en) * | 1996-04-19 | 1997-10-22 | Boghos Awanes Manook | Organic and/or biological pollution monitor |
| CN101105448A (en) * | 2007-08-01 | 2008-01-16 | 山东省科学院海洋仪器仪表研究所 | Method for measuring total organic carbon by ozone oxidation and ultraviolet scanning spectrum integral way |
| CN101271062A (en) * | 2008-05-09 | 2008-09-24 | 哈尔滨天朗清科技有限公司 | On-line monitoring instrument for measuring COD concentration by ultraviolet light absorption method |
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| JP特开2005-106668A 2005.04.21 |
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