CN104817155A - Method for immediate treatment of waste liquid generated in on-line detection of chemical oxygen demand through a dichromate method - Google Patents
Method for immediate treatment of waste liquid generated in on-line detection of chemical oxygen demand through a dichromate method Download PDFInfo
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- CN104817155A CN104817155A CN201410045278.0A CN201410045278A CN104817155A CN 104817155 A CN104817155 A CN 104817155A CN 201410045278 A CN201410045278 A CN 201410045278A CN 104817155 A CN104817155 A CN 104817155A
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- waste liquid
- reaction tank
- treatment process
- cod
- dichromate
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Abstract
The present invention discloses a method for immediate treatment of waste liquid generated in on-line detection of chemical oxygen demand through a dichromate method and pertains to the field of waste liquid treatment. In particular the method comprises the steps of: adding a reductant to a reaction cell after finishing detection and conducting reduction reaction in the reaction cell to reduce hexavalent chromium to trivalent chromium. The method disclosed by the present invention is simple in operation, realizes the immediate treatment of waste liquid and avoids causing secondary pollution.
Description
Technical field
The present invention relates to a kind of method for treating waste liquid, be specifically related to the instant treatment process of the waste liquid that dichromate titration on-line checkingi chemical oxygen demand (COD) produces, belong to field of waste liquid treatment.
Background technology
Dichromate titration detects the standard method that chemical oxygen demand (COD) (COD) is the consistent detection COD generally acknowledged both at home and abroad at present, current China generally adopts the dichromate titration on-line checkingi COD described in GB (HJ/T399-2007), but according to the detection method described in GB, some remaining potassium bichromate is understood in waste liquid, because potassium bichromate is strong oxidizer, very large to harm, if do not add process can cause serious pollution to environment with regard to direct discharge.But Most current import or domestic " COD on-line detector " all do not design the chromic treatment unit in waste liquid.As shown in Figure 1, COD on-line detector generally comprises reagent and water sample intake line, multiport valve, volume pump, reaction tank, detecting unit and waste liquid barrel, wherein, reagent and water sample are by injecting reaction tank after multiport valve and volume pump mixing, then to reaction tank heating and pressurizing, reagent and water sample react under the environment of High Temperature High Pressure, obtain COD value, finally reaction mixture is entered waste liquid barrel by detecting unit such as photometer.
The current process for these waste liquids also just first stores transfers to the liquid waste disposal company of specialty to process again, if store improper in storage process or have leakage, or the words occurring in transit to leak equally can cause secondary pollution to environment.Patent CN201010243373.3(patent documentation 1) disclose one upon completion of the assays, reaction mixture being transferred in waste liquid barrel, carrying out the method for reaction mixture by adding reductive agent (as sucrose) in described waste liquid barrel in advance.Patent CN201210019667.7(patent documentation 2) disclose a kind of method for treating waste liquid processing potassium dichromate process on-line checkingi COD and produce, be specially, the waste liquid that the detection of collecting produces is transferred in a reactor, then reductibility salt is joined in waste liquid and make hexavalent chromium be reduced into trivalent chromic ion.
Described in patent documentation 1, the shortcoming of method is, adds reductive agent in advance in waste liquid barrel, and reductive agent may be caused oxidized in put procedure, and this can waste reagent on the one hand, hexavalent chrome reduction may be caused insufficient on the other hand.
In addition, described in patent documentation 1 and patent documentation 2, the common drawback of method is, detecting the waste liquid produced is process after transferring to waste liquid barrel or collecting certain volume again, does not realize instant process, because sexavalent chrome is very large to harm, this easily causes secondary pollution to environment; Secondly, two kinds of methods all need a kind of reagent of the many preparations of testing staff (reductive agent/reductibility salt), bring inconvenience to liquid waste disposal work.
For the defect existed in prior art, problem to be solved by this invention is to provide the instant treatment process of the waste liquid that a kind of dichromate titration on-line checkingi COD produces.
Summary of the invention
The waste liquid that the invention provides a kind of dichromate titration on-line checkingi COD generation realizes the method for instant process in detector, it is characterized in that, upon completion of the assays, in reaction tank, add reductive agent, in reaction tank, carrying out reduction reaction by hexavalent chrome reduction is trivalent chromium.
Compared with prior art, the present invention can realize after COD has detected, process detecting the waste liquid produced immediately, without the need to being transferred in waste liquid barrel or processing again after collecting certain volume, achieve instant process, prevent the secondary pollution that may cause in transfer process or put procedure.
Secondly, the present invention, by disposing waste liquid in reaction tank, easily can realize interpolation reductive agent on the basis of existing COD detector, and can avoid the secondary pollution that may cause in transfer process, can also ensure that waste liquid is fully reduced.
In the further technical scheme of the present invention, described dichromate is potassium bichromate.Compare other dichromates, potassium bichromate stable in properties, the accuracy detected can be ensured.
In the further technical scheme of the present invention, described reductive agent is Potassium Hydrogen Phthalate.According to the method described in GB, Potassium Hydrogen Phthalate solution is the standardized solution detecting COD, testing staff needs to prepare Potassium Hydrogen Phthalate solution in advance for drawing working curve, therefore, a reagent intake line is generally had to connect Potassium Hydrogen Phthalate solution in existing COD detector.The present invention does not need testing staff to prepare a kind of reagent separately again by adopting Potassium Hydrogen Phthalate solution as reductive agent, and does not need to take a reagent port again, conveniently can realize the instant process of waste liquid on the basis of existing COD detector.
Compare other reductive agents, Potassium Hydrogen Phthalate stable in properties, and can be completely oxidized, be therefore easy to quantitative.The present invention is by adopting Potassium Hydrogen Phthalate solution as reductive agent, on the one hand, the Potassium Hydrogen Phthalate solution of preparation can use the long period, also accurately can calculate volume sexavalent chrome remaining in waste liquid being reduced to completely Potassium Hydrogen Phthalate solution needed for trivalent chromium on the other hand, and then ensure that waste liquid is fully processed.
In the further technical scheme of the present invention, first reaction tank is cooled to not higher than 95 DEG C before addition of the reducing agent.This by starting refrigerating unit, such as, can realizing with cooling fan, can preventing reagent from ejecting from the reaction tank of script High Temperature High Pressure after opening the valve of resistance to pressure valve higher than 95 DEG C by being cooled to.
In the further technical scheme of the present invention, described reduction reaction is at 165 DEG C to 180 DEG C, carries out under 6.5 to 10 atmospheric pressures.This by starting heating unit, such as, can realize with well heater, can ensure that reduction reaction fully makes sexavalent chrome all transfer harmless trivalent chromium in described temperature and pressure range.
In the further technical scheme of the present invention, after described reduction reaction completes, reaction tank is cooled to lower than 95 DEG C.This by starting refrigerating unit, such as, can realizing with cooling fan, can preventing reagent from ejecting from the reaction tank of script High Temperature High Pressure after opening the valve of resistance to pressure valve higher than 95 DEG C by being cooled to.
In the further technical scheme of the present invention, after processing is complete the not chromyl waste liquid after process is entered waste liquid barrel.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described.It should be noted that, accompanying drawing described below is only some embodiments of the present invention, its object is to help those skilled in the art better to understand the present invention, and should not it can be used as any limitation of the invention.
Fig. 1 is the structural representation of COD on-line detector in prior art;
Fig. 2 is the schema of the instant treatment process of waste liquid of the embodiment of the present invention 1.
Embodiment
In the present invention, " detection completes " is defined as: in the reaction tank of COD detector, reagent and water sample react, and obtains COD value by detecting.
In the present invention, " dichromate " is defined as: containing dichromic acid ion Cr
2o
7 2-salt, such as potassium bichromate and sodium dichromate 99 etc.
In the present invention, " reductive agent " is defined as: can make oxygenant, particularly dichromate, obtains electronics and the material reduced, such as COD standardized solution (i.e. Potassium Hydrogen Phthalate solution), sucrose, FeSO
4, FeCl
2, Fe
2(SO
3)
3, Na
2sO
3in a kind of or two or more arbitrarily combinations.
Reagent:
According to the Potassium Hydrogen Phthalate solution that the reagent of GB (HJ/T399-2007) and material component preparation COD concentration are 500mg/L, concentration is the potassium bichromate solution of 0.5mol/L, and density is the Sulfuric acid disilver salt-sulphuric acid soln of 10g/L and density is the sulphuric acid soln of 0.184g/ml.Wherein, Potassium Hydrogen Phthalate [C
6h
4(COOH) (COOK)] for reference level or top grade pure.
Equipment:
As shown in Figure 1, for the structural representation of COD on-line detector in prior art, comprise pure water intake line 1, dichromate solution intake line 2, sulphuric acid soln/Mercury bisulfate solution intake line 3, Sulfuric acid disilver salt-sulphuric acid soln intake line 4, COD standardized solution intake line 5, water sample intake line 6 to be measured, multiport valve 7, volume pump 8, reaction tank 9, detecting unit 10 and waste liquid barrel 11, wherein, detection reagent and water sample to be measured mix rear injection reaction tank 9 by multiport valve 7 and volume pump 8, then to reaction tank 9 heating and pressurizing, reagent and water sample react under the environment of High Temperature High Pressure, COD value is obtained by detecting unit 10 such as photometer, finally reaction mixture is entered waste liquid barrel 11.Described multiport valve comprises more than eight or eight reagent port.
COD detection method:
The water sample 1.3ml that COD concentration is 400mg/L is added to reaction tank, according to the known water sample added in reaction tank of GB: potassium bichromate: Sulfuric acid disilver salt-sulphuric acid soln: the ratio of the volume of sulphuric acid soln is 3:1:6:0.5, the volume namely needing above-mentioned potassium bichromate solution, Sulfuric acid disilver salt-sulphuric acid soln and the sulphuric acid soln added is 0.43ml, 2.6ml and 0.22ml respectively.To reaction tank temperature-pressure, reagent and water sample react under 165 DEG C and 6.5 atmospheric pressure conditions, and timing heating 15min, the organism now in water sample is completely oxidized.According to calculating, COD concentration is the COD containing 0.52mg in the water sample 1.3ml of 400mg/L, and need the potassium bichromate solution 0.13ml consuming 0.5mol/L, therefore in waste liquid, the potassium bichromate of remaining 0.5mol/L is 0.3ml.
According to GB, 1mol Potassium Hydrogen Phthalate [C
6h
4(COOH) (COOK)] can by 30mol potassium bichromate (1/6K
2cr
2o
7) complete oxidation, the oxygen (1/2O) of the suitable 30mol of its chemical oxygen demand (COD).Its chemical principle is as follows:
Wherein, " 6e " is added Potassium Hydrogen Phthalate solution.
Therefore remaining potassium bichromate in waste liquid of reducing completely needs to use the Potassium Hydrogen Phthalate solution 2.4ml that COD concentration is 500mg/L.Further, be reduced completely in order to ensure sexavalent chrome, increase by the surplus of 10%, the volume of the Potassium Hydrogen Phthalate solution namely added is 2.64ml.
The instant treatment process of waste liquid:
Embodiment 1:
As shown in Figure 2, be the schema of the instant treatment process of waste liquid of the present invention.Be specially, reaction tank naturally cools to 95 DEG C, then in reaction tank, add the Potassium Hydrogen Phthalate solution that 2.64mlCOD concentration is 500mg/L, starting well heater makes the environment in reaction tank arrive 180 DEG C and 10 atmospheric pressures, carries out reduction reaction, clock reaction 15 minutes, sexavalent chrome then now in water sample is reduced to trivalent chromium, reaction terminates, and reaction tank is cooled to 95 DEG C, and the waste liquid after process is entered waste liquid barrel.
Embodiment 2:
Reaction tank naturally cools to 70 DEG C, then in reaction tank, add the Potassium Hydrogen Phthalate solution that 2.64ml COD concentration is 500mg/L, starting well heater makes the environment in reaction tank arrive 165 DEG C and 6.5 atmospheric pressures, carry out reduction reaction, clock reaction 15 minutes, then the sexavalent chrome now in water sample is reduced to trivalent chromium, and reaction terminates, reaction tank is cooled to 70 DEG C, and the waste liquid after process is entered waste liquid barrel.
Embodiment 3:
In reagent and COD detection method part, detection reagent replaces with sodium dichromate solution by potassium bichromate solution, and other conditional parameters are identical, for detecting the waste liquid produced, takes following method to dispose waste liquid:
Reaction tank naturally cools to 95 DEG C, then in reaction tank, add the Potassium Hydrogen Phthalate solution that 2.64mlCOD concentration is 500mg/L, starting well heater makes the environment in reaction tank arrive 180 DEG C and 10 atmospheric pressures, carry out reduction reaction, clock reaction 15 minutes, then the sexavalent chrome now in water sample is reduced to trivalent chromium, and reaction terminates, reaction tank is cooled to 95 DEG C, and the waste liquid after process is entered waste liquid barrel.
Description above describe the preferred embodiments of the present invention, but be to be understood that the present invention is not limited to the form disclosed by this paper, should not regard the eliminating to other embodiments as, and can be used for other combinations various, amendment and environment, and can in invention contemplated scope as herein described, changed by the technology of above-mentioned instruction or association area or knowledge.The modifications and variations that those skilled in the art carry out without departing from the spirit and scope of the present invention, all should within the protection domain of claims of the present invention.
Claims (7)
1. the instant treatment process of the waste liquid of dichromate titration on-line checkingi chemical oxygen demand (COD) generation, it is characterized in that, upon completion of the assays, in reaction tank, add reductive agent, in reaction tank, carrying out reduction reaction by hexavalent chrome reduction is trivalent chromium.
2. treatment process as claimed in claim 1, it is characterized in that, described dichromate is potassium bichromate.
3. treatment process as claimed in claim 1, it is characterized in that, described reductive agent is Potassium Hydrogen Phthalate.
4. the treatment process as described in claim arbitrary in claim 1-3, is characterized in that, is first cooled to by reaction tank not higher than 95 DEG C before addition of the reducing agent.
5. the treatment process as described in claim arbitrary in claim 1-3, is characterized in that, described reduction reaction is at 165 DEG C to 180 DEG C, carries out under 6.5 to 10 atmospheric pressures.
6. the treatment process as described in claim arbitrary in claim 1-3, is characterized in that, is cooled to by reaction tank not higher than 95 DEG C after described reduction reaction completes.
7. the treatment process as described in claim arbitrary in claim 1-3, is characterized in that, after processing is complete the waste liquid after process is entered waste liquid barrel.
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| CN201410045278.0A CN104817155B (en) | 2014-01-30 | 2014-01-30 | The instant processing method for the waste liquid that dichromate titration on-line checking COD generates |
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| CN201410045278.0A CN104817155B (en) | 2014-01-30 | 2014-01-30 | The instant processing method for the waste liquid that dichromate titration on-line checking COD generates |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105588927A (en) * | 2014-11-14 | 2016-05-18 | 株式会社岛津制作所 | Treatment method for waste liquid in COD measurement apparatus |
| CN108956853A (en) * | 2018-07-16 | 2018-12-07 | 郑州市通标环境检测有限公司 | A kind of method that dichromate titration measures COD in water |
| CN109211892A (en) * | 2018-10-30 | 2019-01-15 | 九江天赐高新材料有限公司 | The detection method of EDTA content is remained in a kind of pair of lithium fluoride |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN202415297U (en) * | 2012-01-28 | 2012-09-05 | 马鞍山市桓泰环保设备有限公司 | Treatment equipment for waste liquor generated during online measuring COD (chemical oxygen demand) by potassium dichromate method |
-
2014
- 2014-01-30 CN CN201410045278.0A patent/CN104817155B/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105588927A (en) * | 2014-11-14 | 2016-05-18 | 株式会社岛津制作所 | Treatment method for waste liquid in COD measurement apparatus |
| CN108956853A (en) * | 2018-07-16 | 2018-12-07 | 郑州市通标环境检测有限公司 | A kind of method that dichromate titration measures COD in water |
| CN109211892A (en) * | 2018-10-30 | 2019-01-15 | 九江天赐高新材料有限公司 | The detection method of EDTA content is remained in a kind of pair of lithium fluoride |
| CN109211892B (en) * | 2018-10-30 | 2021-01-08 | 九江天赐高新材料有限公司 | Method for detecting content of residual EDTA in lithium fluoride |
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