CN105174524A - Pretreatment device and method before coking wastewater chemical oxygen demand detection - Google Patents
Pretreatment device and method before coking wastewater chemical oxygen demand detection Download PDFInfo
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- CN105174524A CN105174524A CN201410252838.XA CN201410252838A CN105174524A CN 105174524 A CN105174524 A CN 105174524A CN 201410252838 A CN201410252838 A CN 201410252838A CN 105174524 A CN105174524 A CN 105174524A
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Abstract
The invention relates to a pretreatment device and method before coking wastewater COD (Chemical Oxygen Demand) detection. The pretreatment device comprises a constant-temperature heating rod, a liquid level display pipe, a reaction box, a pH determinator, a stirrer and illumination plates; the stirrer, the pH determinator and the constant-temperature heating rod are arranged on the reaction box, and a charging opening is formed in the reaction box; the liquid level display pipe is mounted outside the reaction box, and the illumination plates are respectively arranged before and behind the reaction box. The pretreatment method comprises the following steps: injecting coking wastewater after fenton treatment into the reaction box, adding a sodium hydroxide solution firstly, and controlling the pH of the solution to be 9-10; then adding a sodium bisulfite solution, opening the constant-temperature heating rod after carrying out a reaction for 2-4 h, controlling the temperature of the solution to be 45-55 DEG C, and opening the illumination plates; then, after carrying out a reaction for 4-6 h, adding concentrated sulfuric acid, and carrying out a reaction for 1-2 h when the pH value is 2-3; and closing the stirrer, the constant-temperature heating rod and the illumination plates, injecting deionized water, and after the liquid level is restored, and taking a sample and carrying out COD[cr] determination. The pretreatment device and method can remove residual oxidants and reducing agents in the coking wastewater, eliminate interference factors for affecting coking wastewater COD detection, and help improve the accuracy of COD[cr] detection results.
Description
Technical field
The invention belongs to water-treatment technology field, particularly relate to a kind of to the coking chemical waste water after Fenton process carry out chemical oxygen demand (COD) (COD) detect before pretreatment unit and pretreatment process.
Background technology
Coking industry can produce a large amount of coking chemical waste waters, its water quality poisonous and harmful, and water yield fluctuation is very large, and COD index wherein enjoys the concern of people.Chemical oxygen demand (COD) (COD) refers under certain condition, and by the amount of strong oxidizer process water sample time institute oxygen consumed agent, result is converted to the content (in mg/l) of oxygen.It characterizes the composite target that in water body, reducing substances pollutes, and usually adopts potassium dichromate process to measure chemical oxygen demand (COD) (COD
cr).
Adopt chemical oxidation process Treatment of Wastewater in Coking to develop in recent years very fast, the selection of oxygenant is also varied.Hydrogen peroxide (H
2o
2) be a kind of oxidizing species, be used widely with the field such as advanced treatment and high concentration hard-degraded organic waste water process of the form of Fenton (Fenton) oxidation system at waste water.Although H
2o
2have powerful oxidation capacity, but in the reaction as run into stronger oxidizing substance as potassium permanganate, it is oxidized that it then can serve as reducing substance.So in National Standard Method, the potassium bichromate as oxygenant can be reacted with the hydrogen peroxide of remnants, thus has a strong impact on the accuracy of its measurement result.
For the chemical plant of certain iron and steel enterprise in Liaoning Province, adopt the coking chemical waste water after Fenton oxidation technique advanced treatment, the COD result adopting existing measurement standard to detect but always does not reach design requirements." Liaoning Province's provincial standard " (DB21/1627-2008) is 50mg/L to the highest permission emission concentration of the COD in waste water; therefore the true COD numerical value of waste discharge is detected; for production run and the protection ecotope around of enterprise, all have important practical significance.
Summary of the invention
The present invention aims to provide a kind of oxygenant that can reduce in coking chemical waste water to be detected, and reductive agent is fully decomposed, thus the interference factor that after Fenton process of eliminating the effects of the act, coking chemical waste water COD detects, improve COD
crdetected result accuracy, pretreatment unit and method before the coking chemical waste water chemical oxygen demand detection of true reflection water treatment effect.
For this reason, this invention takes following technical solution:
Pretreatment unit before a kind of coking chemical waste water chemical oxygen demand detection, it is characterized in that, comprise thermostatically heating rod, liquid level charactron, reaction box, pH determinator, agitator and illumination plate, reaction box is one with the rectangular box of case lid, case lid center is provided with rabbling door, in rabbling door, agitator is installed, flabellum is stirred at the bottom of reaction box in the agitator arm lower end of agitator, rabbling door side is provided with and measures hole, opposite side is outwards provided with charging opening and bottoming hole successively, measure in hole and bottoming hole and be respectively equipped with pH determinator and thermostatically heating rod, the liquid level charactron lower end be located at outside reaction box is communicated with on the reaction box sidewall mid-way of pH determinator side, two blocks of illumination plates are separately positioned on the front and back of reaction box.
Pretreatment process before a kind of coking chemical waste water chemical oxygen demand detection, its concrete treatment process and process are:
Coking chemical waste water after Fenton oxidation process is injected in reaction box by charging opening, shows liquid level position and constant volume by liquid level charactron scale.Under whipped state, in the coking chemical waste water in reaction box, add sodium hydroxide solution by charging opening, make coking chemical waste water pH value remain between 9.0-10.0; Then, add sodium sulfite solution by charging opening, the dosage of sodium sulfite solution is identical with the dosage of hydrogen peroxide in Fenton treating processes, and the reaction times controls at 2-4 hour, sodium bisulfite and hydrogen peroxide is made fully to carry out redox reaction, by hydrogen peroxide Restore All; Reaction terminates rear unlatching thermostatically heating rod, makes solution temperature remain on 45-55 DEG C, opens illumination plate simultaneously, reacts 4-6 hour more with this understanding, promotes the decomposition of sodium bisulfite; After secondary reaction terminates, add the vitriol oil by charging opening, make solution ph be between 2-3, continue reaction 1-2 hour, get rid of the sulfurous gas and sulphur trioxide that dissolve in water; In above-mentioned interpolation solution and reaction process, under being in whipped state all the time.After third-order reaction terminates, close agitator, thermostatically heating rod and illumination plate, inject deionized water by charging opening, after making liquid level return to the initial constant volume scale of liquid level charactron, namely sampling carries out potassium dichromate process chemical oxygen demand (COD) and COD
crmensuration.
Beneficial effect of the present invention is:
After above-mentioned pre-treatment, both the oxygenants such as hydrogen peroxide remaining in coking chemical waste water in reaction box can have been consumed, also can decompose reductive agents such as removing sodium bisulfite, and can ensure that the original organism class material in coking chemical waste water does not change, and the existence of the vitriol oil is for COD
crdetected result have no effect, thus after Fenton process of eliminating the effects of the act coking chemical waste water COD detect interference factor, improve COD
crthe accuracy of detected result, reflects the actual processing effect of sewage work objective reality, for Optimizing Process Parameters provides reliable data basis.
Accompanying drawing explanation
Fig. 1 is pretreatment unit front view;
Fig. 2 is pretreatment unit vertical view;
Fig. 3 is pretreatment technology schema.
In figure: reaction box 1, liquid level charactron 2, case lid 3, pH determinator 4, agitator 5, charging opening 6, thermostatically heating rod 7, illumination plate 8, stirring flabellum 9.
Embodiment
From Fig. 1,2, before coking chemical waste water chemical oxygen demand detection of the present invention, pretreatment unit is mainly made up of reaction box 1, liquid level charactron 2, pH determinator 4, agitator 5, thermostatically heating rod 7 and illumination plate 8.Agitator 4 comprises motor, agitator arm and stirs flabellum 8, and motor speed can regulate.Reaction box 2 is one with the rectangular box of case lid 3, the central position of case lid 3 has a rabbling door, the agitator arm of agitator 5 stretches in rabbling door, and the stirring flabellum 9 of agitator arm lower end is positioned at central position at the bottom of the case of reaction box 1, complete to ensure the mixing of materials in reaction box 1.Be provided with a mensuration hole in the left side of case lid 3 rabbling door, measure in hole and be installed on pH determinator 4; The right side of rabbling door, the mid-way between rabbling door medullary ray and reaction box 1 right side wall are provided with a charging opening 6, for coking chemical waste water and the solution of annotating.On the right side of rabbling door, have bottoming hole on the position of reaction box 1 right side wall, bottoming hole internal fixtion has constant temperature heating rod 7.Liquid level charactron 2 is arranged on outside the left side wall of reaction box 1, the lower end of liquid level charactron 2 is communicated with on the mid-way of reaction box 1 left side wall, upper end level is concordant with case lid 3 upper surface, liquid level charactron 2 not only can record the liquid level before reaction, and mark effect can be played to reacted liquor capacity constant volume, thus guarantee that the liquor capacity reacting front and back is consistent.Two blocks of illumination plates 8 are separately positioned on the front and back of reaction box 1, to provide another thermal source for coking chemical waste water, make the temperature that the waste water of reaction box 1 inside and solution keep fixing.
Before coking chemical waste water chemical oxygen demand detection of the present invention, pretreated concrete grammar and process (see Fig. 3) are:
Coking chemical waste water after Fenton oxidation process is injected in reaction box 1 by charging opening 6, shows liquid level position and constant volume by liquid level charactron 2 scale.Under whipped state, add sodium hydroxide solution by charging opening 6, make coking chemical waste water pH value remain between 9.0-10.0; Then, add sodium sulfite solution by charging opening 6, the dosage of sodium sulfite solution is identical with the dosage of hydrogen peroxide in Fenton treating processes, and the reaction times controls at 2-4 hour, sodium bisulfite and hydrogen peroxide is made fully to carry out redox reaction, by hydrogen peroxide Restore All; Reaction terminates rear unlatching thermostatically heating rod 7, makes solution temperature remain on 45-55 DEG C, opens illumination plate 8 simultaneously, reacts 4-6 hour more with this understanding, promotes the decomposition of sodium bisulfite; After secondary reaction terminates, add the vitriol oil by charging opening 6, make solution ph be between 2-3, continue reaction 1-2 hour, get rid of the sulfurous gas and sulphur trioxide that dissolve in water; In above-mentioned interpolation solution and reaction process, under being in whipped state all the time.After third-order reaction terminates, close agitator 5, thermostatically heating rod 7 and illumination plate 8, inject deionized water by charging opening 6, after making liquid level return to the initial constant volume scale of liquid level charactron 2, namely sampling carries out potassium dichromate process chemical oxygen demand (COD) and COD
crmensuration.
Below in conjunction with embodiment, treatment process of the present invention is described in detail.
Embodiment 1
First, in reaction box 1, inject the coking chemical waste water water sample after the process of 2000mL Fenton, under the state stirred, drop into sodium hydroxide solution, make coking chemical waste water pH be 9.0.Thereafter, be 7.5mmol/L according to concentration after hydrogen peroxide is added to coking chemical waste water in Fenton technology, after therefore adding sodium bisulfite, make coking chemical waste water concentration be similarly 7.5mmol/L, under the state stirred, react 2h.Then under the state making water sample be in illumination, and keep the constant temperature of 45 DEG C, under the state stirred, react 4h.Finally adopt the vitriol oil to regulate water sample pH to be 2.0, under the state of stirring, react 1h.
Embodiment 2
In reaction box 1, inject the coking chemical waste water water sample after the process of 2000mL Fenton, under the state stirred, drop into sodium hydroxide solution, make its pH be 9.5; Thereafter be 7.5mmol/L according to concentration after hydrogen peroxide being added to coking chemical waste water in Fenton technology, make its concentration be similarly 7.5mmol/L after therefore adding sodium bisulfite, under the state stirred, react 3h; Then under the state making water sample be in illumination, and keep the constant temperature of 50 DEG C, under the state stirred, react 5h; Finally adopt the vitriol oil to regulate water sample pH to be 2.5, under the state of stirring, react 1.5h.
Embodiment 3
In reaction box 1, inject the coking chemical waste water water sample after the process of 2000mL Fenton, under the state stirred, drop into sodium hydroxide solution, make its pH be 10.0; Thereafter be 7.5mmol/L according to concentration after hydrogen peroxide being added to coking chemical waste water in Fenton technology, make its concentration be similarly 7.5mmol/L after therefore adding sodium bisulfite, under the state stirred, react 4h; Then under the state making water sample be in illumination, and keep the constant temperature of 45 DEG C, under the state stirred, react 6h; Finally adopt the vitriol oil to regulate water sample pH to be 3.0, under the state of stirring, react 2h.
2000mL is settled to the water sample after above-mentioned process, then sampling and measuring COD
cr, concrete outcome is as shown in table 1.
The detected result of each embodiment of table 1 and contrast
Result shows, the oxygenant that the present invention can be effectively residual in shield water is for COD
crimpact during detection, obtains real numerical value.
Claims (2)
1. pretreatment unit before a coking chemical waste water chemical oxygen demand detection, it is characterized in that, comprise thermostatically heating rod, liquid level charactron, reaction box, pH determinator, agitator and illumination plate, reaction box is one with the rectangular box of case lid, case lid center is provided with rabbling door, in rabbling door, agitator is installed, flabellum is stirred at the bottom of reaction box in the agitator arm lower end of agitator, rabbling door side is provided with and measures hole, opposite side is outwards provided with charging opening and bottoming hole successively, measure in hole and bottoming hole and be respectively equipped with pH determinator and thermostatically heating rod, the liquid level charactron lower end be located at outside reaction box is communicated with on the reaction box sidewall mid-way of pH determinator side, two blocks of illumination plates are separately positioned on the front and back of reaction box.
2. the method for pretreatment unit before coking chemical waste water chemical oxygen demand detection as claimed in claim 1, it is characterized in that, concrete treatment process and process are:
Coking chemical waste water after Fenton oxidation process is injected in reaction box by charging opening, shows liquid level position and constant volume by liquid level charactron scale; Under whipped state, in the coking chemical waste water in reaction box, add sodium hydroxide solution by charging opening, make coking chemical waste water pH value remain between 9.0-10.0; Then, add sodium sulfite solution by charging opening, the dosage of sodium sulfite solution is identical with the dosage of hydrogen peroxide in Fenton treating processes, and the reaction times controls at 2-4 hour, sodium bisulfite and hydrogen peroxide is made fully to carry out redox reaction, by hydrogen peroxide Restore All; Reaction terminates rear unlatching thermostatically heating rod, makes solution temperature remain on 45-55 DEG C, opens illumination plate simultaneously, reacts 4-6 hour more with this understanding, promotes the decomposition of sodium bisulfite; After secondary reaction terminates, add the vitriol oil by charging opening, make solution ph be between 2-3, continue reaction 1-2 hour, get rid of the sulfurous gas and sulphur trioxide that dissolve in water; In above-mentioned interpolation solution and reaction process, under being in whipped state all the time; After third-order reaction terminates, close agitator, thermostatically heating rod and illumination plate, inject deionized water by charging opening, after making liquid level return to the initial constant volume scale of liquid level charactron, namely sampling carries out potassium dichromate process chemical oxygen demand (COD) and COD
crmensuration.
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|---|---|---|---|
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| CN105174524B CN105174524B (en) | 2017-08-11 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110104845A (en) * | 2019-06-11 | 2019-08-09 | 武汉深能环保新沟垃圾发电有限公司 | A kind of percolation liquid membrane processing method reducing concentration output of fluid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992001223A1 (en) * | 1990-07-04 | 1992-01-23 | Commonwealth Scientific And Industrial Research Organisation | Continuous rbcod measurement |
| CN1374520A (en) * | 2001-02-02 | 2002-10-16 | 饭岛电子工业株式会社 | Method for measuring chemical oxygen requirement and its apparatus |
| CN101694471A (en) * | 2009-10-15 | 2010-04-14 | 承慰才 | Drinking water COD online automatic detection method and detection instrument |
| CN203922898U (en) * | 2014-06-09 | 2014-11-05 | 鞍钢股份有限公司 | Pretreatment unit before a kind of coking chemical waste water chemical oxygen demand detection |
-
2014
- 2014-06-09 CN CN201410252838.XA patent/CN105174524B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992001223A1 (en) * | 1990-07-04 | 1992-01-23 | Commonwealth Scientific And Industrial Research Organisation | Continuous rbcod measurement |
| CN1374520A (en) * | 2001-02-02 | 2002-10-16 | 饭岛电子工业株式会社 | Method for measuring chemical oxygen requirement and its apparatus |
| CN101694471A (en) * | 2009-10-15 | 2010-04-14 | 承慰才 | Drinking water COD online automatic detection method and detection instrument |
| CN203922898U (en) * | 2014-06-09 | 2014-11-05 | 鞍钢股份有限公司 | Pretreatment unit before a kind of coking chemical waste water chemical oxygen demand detection |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110104845A (en) * | 2019-06-11 | 2019-08-09 | 武汉深能环保新沟垃圾发电有限公司 | A kind of percolation liquid membrane processing method reducing concentration output of fluid |
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