CN1141583C - Automatic analysis method for chemical total oxygen demand - Google Patents
Automatic analysis method for chemical total oxygen demand Download PDFInfo
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- CN1141583C CN1141583C CNB021134820A CN02113482A CN1141583C CN 1141583 C CN1141583 C CN 1141583C CN B021134820 A CNB021134820 A CN B021134820A CN 02113482 A CN02113482 A CN 02113482A CN 1141583 C CN1141583 C CN 1141583C
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Abstract
The present invention relates to an automatic analysis method for chemical oxygen demand, which comprises the steps: test analysis of a standard sample and test analysis of a test sample. The test analysis of a standard sample and the test analysis of a test sample both comprise base line plotting and spectrogram plotting. A solution for generating a base line is a push solution, and the base line formed through an analysis flow path of a test analysis instrument under the push of the push solution is plotted; after a standard sample or a test sample is mixed with an oxidation solution in a sample inlet flow path of the test analysis instrument, the mixture enters the analysis flow path, and a spectrogram is formed by the analysis flow path under the push of the push solution is plotted. The push solution and the oxidation solution are both water solutions compounded from potassium permanganate (KMnO4) and sulphuric acid. The method thoroughly solves the problem of base line fluctuation of a KMnO4 system, the noise of the base line is greatly reduced, and the required amount of chemical reagents is only equivalent to 1 to 2% of the amount of chemical reagents of a conventional standard method.
Description
One, technical field
The invention belongs to water quality monitoring method, the automatic analysis method of chemical oxygen demand (COD) (COD) in particularly a kind of mensuration water.
Two, background technology
Chemical oxygen demand (COD) (COD) is one of leading indicator of water pollution, also is an important parameter of water quality monitoring.Therefore, in order to grasp the water pollution situation, must the chemical oxygen demand (COD) in the water be detected.About detection method, China's accepted standard method has two kinds at present: a kind of is the permanganate index method, be applicable to the chemical oxygen demand component analysis in underground water, potable water and the cleaner surface water, another kind is a potassium dichromate oxidation, is applicable to the chemical oxygen demand component analysis in industrial waste water and the sanitary sewage.Above-mentioned two kinds of methods are manual chemical analysis, owing to adopt manual operations, have following shortcoming: 1, consuming time, potassium dichromate oxidation was once analyzed common need more than two hours, and the permanganate index method is once analyzed common need 40 minutes～60 minutes; 2, complex operation, labour intensity are big, easily introduce personal error, thereby influence accuracy of detection; 3, sample collection will be returned analysis again after the testing laboratory usually, in the transportation, sample often changes easily, causes the result of detection not conform to the actual conditions; 4, expend chemical reagent.In addition, potassium dichromate oxidation must use silver salt to make catalyzer, eliminate the interference of chlorion with mercury salt, thereby increases analysis cost greatly, and causes new severe contamination.Some countries of external Japan and Europe detect chemical oxygen demand (COD) and adopt permanganimetric method usually, and the characteristics of this kind method are: the solution that produces baseline is for promoting liquid---the oxidation liquid that water and potassium permanganate and dilute sulfuric acid are formed; Sample mixes with oxidation liquid after sampling valve enters the analysis stream again, and the oxidation liquid phase of this oxidation liquid and generation baseline together.The shortcoming of this kind method mainly is that the baseline noise is big, influences accuracy of detection.
Three, summary of the invention
The present invention is directed to the deficiency that prior art exists, a kind of automatic analysis method of chemical oxygen demand (COD) is provided, this kind method not only analysis speed is fast, the energy online automatic detection, and can reduce the baseline noise effectively, improve accuracy of detection.
Method provided by the invention is the improvement to permanganimetric method, and its technical scheme is: the solution that produces baseline is for promoting liquid, and this promotion liquid is surveyed and drawn by the analysis stream formation baseline of test analytical instrument; Standard specimen or sample the sample introduction stream of test analytical instrument with enter the analysis stream road after oxidation liquid mixes, under the promotion that promotes liquid, form spectrogram and surveyed and drawn, the sample spectrogram acquisition testing result of comparing with the standard specimen spectrogram by analyzing stream.
Promotion liquid that said method uses and oxidation liquid are the aqueous solution of potassium permanganate and sulfuric acid formation.Promote in the liquid, the concentration of potassium permanganate is 0.25～2.5 * 10
-3Mol/L, the concentration of sulfuric acid is 0.25～1mol/L; In the oxidation liquid, the concentration of potassium permanganate is 0.5～5 * 10
-3Mol/L, the concentration of sulfuric acid is 0.5～2mol/L.
Stable in order to guarantee detection system, the technical measures that the present invention takes are: in the analysis stream of test analytical instrument chromatographic column is set, makes sample add thermal response in analyzing stream and carry out check and analysis again after remove precipitation.
Method provided by the invention, when sample introduction, the ratio of sample or standard specimen and oxidation liquid is 1～2: 1.
Method provided by the invention both can be used for the chemical oxygen demand component analysis of underground water, river mouth water, surface water, can be used for the chemical oxygen demand component analysis of industrial waste water, sanitary sewage again, when being used for the analysis of industrial waste water and sanitary sewage, need sample dilution, sample: water=1: 5～20.
The present invention has the following advantages and beneficial effect:
1, produces the improvement of baseline solution and the improvement of technological process, fundamentally solved the baseline fluctuation problem that adopts the potassium permanganate system, reduced the baseline noise greatly, help improving analysis precision.
2, save chemical reagent, required reagent only is 1～2% of conventional criteria method.
3, can design the instrument with online automatic detection function according to this method, finishing once only to analyze needs 4～6 minutes.
Four, description of drawings
Fig. 1 is a kind of process chart according to the automatic analysis method of chemical oxygen demand (COD) provided by the present invention;
Fig. 2 is another process chart according to the automatic analysis method of chemical oxygen demand (COD) provided by the present invention;
Fig. 3 is the third process chart according to the automatic analysis method of chemical oxygen demand (COD) provided by the present invention;
Fig. 4 is the 4th a kind of process chart according to the automatic analysis method of chemical oxygen demand (COD) provided by the present invention.
Five, embodiment
Embodiment 1:
Present embodiment is the detection to the chemical oxygen demand (COD) in the surface water, and its step is as follows:
1, the preparation of standard specimen
(1) takes by weighing oxalic acid and be made into the standard water solution of 1000mg/L as mother liquor;
(2) with mother liquor dilution, be mixed with a series of standard specimens, the concentration of each standard specimen is respectively 0,1.00mg/L, 2.00mg/L, 4.00mg/L, 8.00mg/L, 10.00mg/L, 20.00mg/L.
2, the preparation of oxidation liquid
Raw material: potassium permanganate, the concentrated sulphuric acid and water.
Method: the concentrated sulphuric acid slowly poured in the water stir evenly, be made into the sulfuric acid solution of 0.5mol/L, add potassium permanganate then, the concentration that makes potassium permanganate in the solution is 0.5 * 10
-3/ mol/L.
3, promote the preparation of liquid
Get above-mentioned oxidation liquid 500ml and pour in the water of 500ml, promptly be mixed with promotion liquid.
4, the testing and drawing of sample spectrogram
Employing is tested by the automatic analyzer of technical flow design shown in Figure 1, and the optical flow cell in the instrument is the 20mm light path, and the detection wavelength is 530nm.
At first carry out the baseline mapping, promote liquid C under the driving of low-lift pump 3, enter the analysis stream of forming by heated at constant temperature reactor 5, optical flow cell 6 and waste fluid container through sampling valve 4, by fluorescence detector 7 signal is transferred to computer processing system 8 and promptly on computer display, draws a baseline.After the baseline mapping is finished, 1: 1 sample S is delivered to mixer 2 with oxidation liquid R by low-lift pump 1 to be mixed, enter the analysis stream through sampling valve 4 then, meanwhile, promote liquid C under the driving of low-lift pump 3, also enter the analysis stream through sampling valve, the mixed liquor of sample S and oxidation liquid R is pushed heated at constant temperature reactor 5, the temperature of heated at constant temperature reactor is controlled at 95 ℃, oxidation reaction at high temperature takes place in the organism in the sample, potassium permanganate is consumed, and causes the color of the solution that flows through optical flow cell 6 to go down, thus on computer display, the obtain chemical oxygen demand (COD) spectrogram of (COD).
5, the testing and drawing of standard specimen spectrogram
The used instrument of testing and drawing standard specimen spectrogram, promote the used instrument of liquid, oxidation liquid and testing and drawing sample spectrogram, promote liquid, the oxidation liquid phase is same, method of testing is also identical.The standard specimen of being prepared is analyzed from thin to thick successively, promptly got the series of standards spectrogram.
6, the sample testing result calculates
Sample spectrogram and the standard spectrogram drawn are compared, then can calculate the chemical oxygen demand (COD) in the sample.
Embodiment 2:
Present embodiment is the detection to the chemical oxygen demand (COD) in the industrial waste water, and its step is as follows:
1, the preparation of standard specimen;
(1) takes by weighing glucose and be made into the standard water solution of 1000mg/L as mother liquor;
(2) with mother liquor dilution, be mixed with a series of standard specimens, the concentration of each standard specimen is respectively 0,10.00mg/L, 20.00mg/L, 40.00mg/L, 80.00mg/L, 100.00mg/L, 200.00mg/L.
2, the preparation of oxidation liquid
Raw material: potassium permanganate, the concentrated sulphuric acid and water
Method: the concentrated sulphuric acid slowly poured in the water stir evenly, be made into the sulfuric acid solution of 1.0mol/L, add potassium permanganate then, the concentration that makes the potassium permanganate in the solution is 3 * 10
-3Mol/L.
3, promote the preparation of liquid
Get above-mentioned oxidation liquid 500ml and pour in the water of 500ml, promptly be mixed with promotion liquid.
4, dilution sample
With the sample dilute with water, sample: water=1: 10.
5, the testing and drawing of sample spectrogram
Employing is tested by the automatic analyzer of technical flow design shown in Figure 4, and optical flow cell is the 5mm light path in the instrument, and the detection wavelength is 530nm.
Method of testing is identical with embodiment 1, and difference from Example 1 is: in (1) technological process shown in Figure 4, sample S and oxidation liquid R are sent into by low-lift pump 1 and also will enter reactor 10 after mixer 2 mixes and further mix just and enter the analysis stream through sampling valve 4; (2) sample solution after heated at constant temperature reactor 5 oxidation reactions is removed post precipitation through chromatographic column 9 and is entered optical flow cell 6 again.
6, the testing and drawing of standard spectrogram
The used instrument of surveying and mapping standard spectrogram, promote the used instrument of liquid, oxidation liquid and mapping sample spectrogram, promote liquid, the oxidation liquid phase with, method of testing is also identical.The standard specimen of being prepared is analyzed from thin to thick successively, promptly got the series of standards spectrogram.
7, the sample testing result calculates
Sample spectrogram and the standard spectrogram surveyed and drawn are compared, then can calculate the chemical oxygen demand (COD) in the sample.
Embodiment 3:
Present embodiment is the detection to the chemical oxygen demand (COD) in the river mouth water, and its step is as follows:
1, the preparation of standard specimen
The raw material of preparation standard specimen is identical with embodiment 1 with method.
2, the preparation of oxidation liquid
The raw material of preparation oxidation liquid is identical with embodiment 1 with method, and the concentration of potassium permanganate is 0.5 * 10
-3Mol/L, the concentration of sulfuric acid is 1.0mol/L.
3, promote the preparation of liquid
The raw material that preparation promotes liquid is identical with embodiment 1 with method.
4, the testing and drawing of sample spectrogram
Employing is tested by the automatic analyzer of technical flow design shown in Figure 3, and the optical flow cell in the instrument is the 20mm light path, and the detection wavelength is 530nm.
Method of testing is identical with embodiment 1, and difference from Example 1 is in the technological process shown in Figure 3, and sample S and oxidation liquid R are sent into by low-lift pump 1 and also will enter reactor 10 after mixer 2 mixes and further mix just and enter the analysis stream through sampling valve 4.
5, the testing and drawing of standard spectrogram
The used instrument of surveying and mapping standard spectrogram, promote the used instrument of liquid, oxidation liquid and mapping sample spectrogram, promote liquid, the oxidation liquid phase with, method of testing is also identical.The standard specimen of being prepared is analyzed from thin to thick successively, promptly got the series of standards spectrogram.
6, the sample testing result calculates
The sample testing result calculates identical with embodiment 1.
Embodiment 4:
Present embodiment is the detection to the chemical oxygen demand (COD) in the sanitary sewage, and its step is as follows:
1, the preparation of standard specimen
The raw material of preparation standard specimen is identical with embodiment 2 with method.
2, the preparation of oxidation liquid
The raw material of preparation oxidation liquid is identical with embodiment 1 with method, and the concentration of potassium permanganate is 2 * 10
-3Mol/L, the concentration of sulfuric acid is 1.0mol/L.
3, promote the preparation of liquid
The raw material that preparation promotes liquid is identical with embodiment 1 with method.
4, dilution sample
With the sample dilute with water, sample: water=1: 5.
5, the testing and drawing of sample spectrogram
Employing is tested by the automatic analyzer of technical flow design shown in Figure 2, and optical flow cell is the 5mm light path in the instrument, and the detection wavelength is 530nm.
Method of testing is identical with embodiment 1, and difference from Example 1 is: in the technological process shown in Figure 2, the sample solution after heated at constant temperature reactor 5 oxidation reactions is removed post precipitation through chromatographic column 9 and is entered optical flow cell 6 again.
6, the testing and drawing of standard spectrogram
The used instrument of surveying and mapping standard spectrogram, promote the used instrument of liquid, oxidation liquid and mapping sample spectrogram, promote liquid, the oxidation liquid phase with, method of testing is also identical.The standard specimen of being prepared is analyzed from thin to thick successively, promptly got the series of standards spectrogram.
7, the sample testing result calculates
The sample testing result calculates identical with embodiment 2.
Claims (2)
1, a kind of automatic analysis method of chemical oxygen demand (COD), comprise the test analysis of standard specimen and the test analysis of sample, the test analysis of standard specimen and sample includes the mapping of baseline and the mapping of measured matter spectrogram, used promotion liquid and oxidation liquid are the aqueous solution that potassium permanganate and sulfuric acid form during test analysis, promote liquid and surveyed and drawn, it is characterized in that by the analysis stream formation baseline of test analytical instrument:
(1) the promotion liquid of generation baseline is formed by the dilution of oxidation liquid,
(2) standard specimen or sample the sample introduction stream of test analytical instrument with enter the analysis stream road after oxidation liquid mixes, under the promotion that promotes liquid, form spectrogram and surveyed and drawn by analyzing stream.
2, the automatic analysis method of chemical oxygen demand (COD) according to claim 1 is characterized in that sample adds thermal response and carries out check and analysis again after remove precipitation in analyzing stream.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021134820A CN1141583C (en) | 2002-03-20 | 2002-03-20 | Automatic analysis method for chemical total oxygen demand |
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|---|---|---|---|
| CNB021134820A CN1141583C (en) | 2002-03-20 | 2002-03-20 | Automatic analysis method for chemical total oxygen demand |
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| CN101187637B (en) * | 2007-12-18 | 2010-05-19 | 四川大学 | Automatic analysis method for seawater phenols compounds |
| CN101387651B (en) * | 2008-10-08 | 2012-05-16 | 中国科学院南海海洋研究所 | Automatic sample handling system and control method thereof |
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