CN105181688A - Method for measuring COD (Chemical Oxygen Demand) in water sample containing high-concentration Cl<-> by acidification chloride removal method - Google Patents

Method for measuring COD (Chemical Oxygen Demand) in water sample containing high-concentration Cl<-> by acidification chloride removal method Download PDF

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Publication number
CN105181688A
CN105181688A CN201510564098.8A CN201510564098A CN105181688A CN 105181688 A CN105181688 A CN 105181688A CN 201510564098 A CN201510564098 A CN 201510564098A CN 105181688 A CN105181688 A CN 105181688A
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water sample
cod
concentration
water
sample containing
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王吉德
王立志
高云
寿培峰
王丰
陈廷祥
谢洪涛
唐湘军
王雅玲
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Xinjiang University
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Xinjiang University
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Abstract

The invention discloses a method for measuring the COD (Chemical Oxygen Demand) in a water sample containing high-concentration Cl<-> (greater than 1,000 mg.L<-1>) by an acidification chloride removal method. According to the method, HCl can be generated by Cl<-> after H<+> is added into a sample solution; the Cl<-> is discharged from a sample system in the form of the HCl under the conditions of heating, shaking and vibrating, so that the influence on the measurement of the COD in the water sample caused by the high-concentration Cl<-> can be eliminated. Therefore, excessive high-concentration strong acid is added before measurement, and the COD in the water sample is measured after the Cl<-> is separated from the solution system in the form of the HCl. The invention provides a simple, accurate and green measurement method for the COD in the water sample containing the high-concentration Cl<->.

Description

Acidifying is driven chlorine method and is measured the method containing COD in high concentration Cl-water sample
Technical field
The present invention relates to a kind of acidifying and drive chlorine method mensuration containing high concentration Cl -the method of COD in water sample.
Background technology
Chemical oxygen demand (COD) (COD) reflects in water by the degree that reducing substances pollutes.In water, reducing substances comprises organism, NO 2 -, Fe 2+, S 2-deng.Water is very general by Organic Pollution, and therefore chemical oxygen demand (COD) is one of important indicator measuring organism relative content at present.
China is Polyvinylchloride (PVC) production capacity first big country, can produce a large amount of containing high concentration Cl in its production run -water sample, very large to environmental hazard.Current mensuration chemical oxygen demand (COD) mainly adopts potassium dichromate method (GB11914-89), but the Cl existed in water sample -cOD will be measured to potassium dichromate method and produce interference.Measure in the process of COD at potassium dichromate method, the Cl in water sample -can oxidized dose of oxidation, can also react with catalyst sulfuric acid silver, make catalyst deactivation, drastically influence the accuracy of measurement result.For eliminating the Cl in water body -potassium dichromate method is measured to the interference of COD generation, adopt in potassium dichromate method and add mercuric sulfate, generate complex compound to eliminate concentration lower than 1000mgL -1cl -interference, work as Cl -content is higher than 1000mgL -1time, first do quantitatively dilution, make content lower than 1000mgL -1below row measures again.But potassium dichromate method is pointed out, as Cl in water sample -more than 1000mgL -1time, the Minimum Acceptable Value of COD is 250mgL -1, lower than this value, the accuracy of result is just unreliable.
Therefore, for elimination high concentration Cl -water sample in Cl -interference, improve and measure the accuracy of its COD and do a lot of work, propose many methods, mainly contain chlorine correction method, precipitating method of silver nitrate, calibration curve method etc.But these methods have certain limitation: mercuric sulfate masking method can cause secondary pollution, and Cl -concentration is at 5000mgL -1above time error is larger; Chlorine correction method needs to measure Cl in water sample in advance -concentration, measures process complicated, and employs a large amount of mercuric sulfate; The cost of determination of precipitating method of silver nitrate is higher, when there being suspension in water sample, in the process of AgCl precipitation, the effects such as flocculation and co-precipitation can occur thus make measured value less than normal; Standard curve method, due to the difference of operating conditions, makes must first draw corresponding typical curve before each mensuration, adds workload.Current methods is for Cl -concentration is greater than 10000mgL -1water sample in the mensuration of COD have obvious deviation.The basic potassium permanganate method (HJ/T132-2003) implemented for 2004 is although can be used for high concentration Cl -the mensuration of COD in water sample, but measurement result COD oHKIwith the result COD of current methods crbetween conversion relation comparatively complicated, and the sensing range of method is less.Therefore be necessary that setting up one meets existing chlor-alkali and relevant industries high concentration Cl -cOD method for measuring in discharge water.
The inventive method has volatility according to HCl, and when higher temperature and shake, volatility is stronger.Therefore, can by adding excessive H in sample solution +, make a large amount of Cl -discharge outside sample system with the form of HCl, eliminate the Cl of high concentration -on the impact that COD in water sample measures.Oxygenant K 2cr 2o 7or KMnO 4to react under strong acidic environment, during reaction, excessive acid will be added.Therefore, the present invention proposes and add excessive strong acid to eliminate the Cl of high concentration -with the suitable condition measuring COD, propose simple, a Fast Measurement height Cl -concentration (1000-100000mgL -1) assay method of COD in discharge water.
Summary of the invention
The invention provides a kind of acidifying and drive chlorine method mensuration containing high concentration Cl -the method of COD in water sample.As following step:
1) get water sample 10.00mL to be measured in reaction bulb, and in reaction bulb, add 3 anti-bumping beaded glasses;
2) in water sample, add the dense H of 10-30mL 2sO 4or HNO 3, move to water bath with thermostatic control oscillator;
3) in fuming cupboard, set water temperature is 40-73 DEG C, rotating speed is 200rmin -1lower vibration 0.5-2h;
4) Cl is being driven -after water sample in add 0.15gAg 2sO 4and 5.00mLK 2cr 2o 7or KMnO 4solution, mixes, and is placed in constent temperature heater, is warming up to 180 DEG C, and reflux 2h from solution comes to life;
5), after backflow terminates, be transferred to by solution in conical flask, after being cooled to room temperature, add 2 phenanthroline indicator, with the titration of iron ammonium sulfate standard solution, the color from yellow of solution becomes bronzing through blue-green and is terminal;
6) write down the volume that iron ammonium sulfate standard solution consumes, draw COD value as calculated;
7) water sample is replaced to carry out blank assay by same steps with 10.00mL distilled water.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this.
Embodiment 1:
Get water sample 10.00mL to be measured in reaction bulb, add 3 anti-bumping beaded glasses; The H of 15mL98% is added in water sample 2sO 4, move to water bath with thermostatic control oscillator; In fuming cupboard, 70 DEG C, rotating speed is 200rmin -1lower vibration 1h.Measure with potassium dichromate method.
Embodiment 2:
Get water sample 10.00mL to be measured in reaction bulb, add 3 anti-bumping beaded glasses; The H of 20mL98% is added in water sample 2sO 4, move to water bath with thermostatic control oscillator; In fuming cupboard, 65 DEG C, rotating speed is 150rmin -1lower vibration 1.5h.Measure with potassium dichromate method.
Embodiment 3:
Get water sample 10.00mL to be measured in reaction bulb, add 3 anti-bumping beaded glasses; The H of 25mL98% is added in water sample 2sO 4, move to water bath with thermostatic control oscillator; In fuming cupboard, 45 DEG C, rotating speed is 180rmin -1lower vibration 2h.Measure with potassium dichromate method.
Embodiment 4:
Get water sample 10.00mL to be measured in reaction bulb, add 3 anti-bumping beaded glasses; The HNO of 25mL65% is added in water sample 3, move to water bath with thermostatic control oscillator; In fuming cupboard, 60 DEG C, rotating speed is 150rmin -1lower vibration 1.5h.Measure with potassium dichromate method.
Embodiment 5:
Get water sample 10.00mL to be measured in reaction bulb, add 3 anti-bumping beaded glasses; The HNO of 30mL65% is added in water sample 3, move to water bath with thermostatic control oscillator; In fuming cupboard, 65 DEG C, rotating speed is 120rmin -1lower vibration 2h.Measure by permanganimetric method.
Embodiment 6:
Get water sample 10.00mL to be measured in reaction bulb, add 3 anti-bumping beaded glasses; The H of 25mL98% is added in water sample 2sO 4, move to water bath with thermostatic control oscillator; In fuming cupboard, 55 DEG C, rotating speed is 200rmin -1lower vibration 2h.Measure by permanganimetric method.
Embodiment 7:
Get water sample 10.00mL to be measured in reaction bulb, add 3 anti-bumping beaded glasses; The H of 12mL98% is added in water sample 2sO 4, move to water bath with thermostatic control oscillator; In fuming cupboard, 70 DEG C, rotating speed is 150rmin -1lower vibration 2h.Measure by permanganimetric method.
Embodiment 8:
Get water sample 10.00mL to be measured in reaction bulb, add 3 anti-bumping beaded glasses; The HNO of 15mL65% is added in water sample 3, move to water bath with thermostatic control oscillator; In fuming cupboard, 70 DEG C, rotating speed is 150rmin -1lower vibration 2h.Measure by permanganimetric method.
Embodiment 9:
Get water sample 10.00mL to be measured in reaction bulb, add 3 anti-bumping beaded glasses; The H of 25mL98% is added in water sample 2sO 4, move to water bath with thermostatic control oscillator; In fuming cupboard, 68 DEG C, rotating speed is 200rmin -1lower vibration 0.5h.Measure with potassium dichromate method.
Embodiment 10:
Get water sample 10.00mL to be measured in reaction bulb, add 3 anti-bumping beaded glasses; The H of 18mL98% is added in water sample 2sO 4, move to water bath with thermostatic control oscillator; In fuming cupboard, 72 DEG C, rotating speed is 200rmin -1lower vibration 0.5h.Measure with potassium dichromate method.

Claims (2)

1. an acidifying drives chlorine method mensuration containing high concentration Cl -the method of COD in water sample, is characterized in that: the strong acid first adding excessive high concentration, and jolting makes Cl at relatively high temperatures -after driving away with the form of HCl, then add oxygenant K 2cr 2o 7or KMnO 4measure.
2. chlorine method is driven for acidifying according to claim 1, it is characterized in that:
1) strong acid of the present invention is H 2sO 4and HNO 3;
2) when water sampling amount is 10.00mL, the dense H of 98% is added 2sO 410-25mL or 65% dense HNO 310-30mL;
3) shake carries out in water bath with thermostatic control oscillator, and water temperature controls at 40-73 DEG C, and oscillation frequency is 50-250rmin -1, duration of oscillation is 0.5-2h.
CN201510564098.8A 2015-09-08 2015-09-08 Method for measuring COD (Chemical Oxygen Demand) in water sample containing high-concentration Cl<-> by acidification chloride removal method Pending CN105181688A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106525832A (en) * 2016-10-27 2017-03-22 新疆大学 Manganese-chromium two-stage oxidation method for determining COD in high chlorine-containing wastewater
CN107643206A (en) * 2017-09-11 2018-01-30 浙江海洋大学 Preprocess method and its application before a kind of high chlorine water COD measure
CN109061041A (en) * 2018-06-15 2018-12-21 深圳市深投环保科技有限公司 The measuring method of the COD of waste water

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104535567A (en) * 2015-01-14 2015-04-22 成都海兰天澄科技有限公司 Automatic COD metering method

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CN104535567A (en) * 2015-01-14 2015-04-22 成都海兰天澄科技有限公司 Automatic COD metering method

Non-Patent Citations (4)

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WAGNER ET AL.: "Elimination of the chloride interference in the deternation of the COD", 《Z .WASSER ABWASSER FORSCH》 *
孙冬月等: "重铬酸钾法测定COD中的干扰及消除", 《环境科学与管理》 *
张红进等: "高氯离子水样COD测定方法的研究进展", 《中国环境管理干部学院学报》 *
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106525832A (en) * 2016-10-27 2017-03-22 新疆大学 Manganese-chromium two-stage oxidation method for determining COD in high chlorine-containing wastewater
CN107643206A (en) * 2017-09-11 2018-01-30 浙江海洋大学 Preprocess method and its application before a kind of high chlorine water COD measure
CN107643206B (en) * 2017-09-11 2021-01-05 浙江海洋大学 Pretreatment method for high-chlorine water before COD (chemical oxygen demand) determination and application thereof
CN109061041A (en) * 2018-06-15 2018-12-21 深圳市深投环保科技有限公司 The measuring method of the COD of waste water

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Application publication date: 20151223