CN1255327C - Hexa valence chromium in industriel waste water electrolysis treatment method - Google Patents
Hexa valence chromium in industriel waste water electrolysis treatment method Download PDFInfo
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- CN1255327C CN1255327C CN 200410010007 CN200410010007A CN1255327C CN 1255327 C CN1255327 C CN 1255327C CN 200410010007 CN200410010007 CN 200410010007 CN 200410010007 A CN200410010007 A CN 200410010007A CN 1255327 C CN1255327 C CN 1255327C
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Abstract
The present invention provides an economically feasible electrolysis treatment method for hexavalence chromium in industrial waste water. In the method, electrolysis is directly carried out under an alkaline condition, non-soluble lead-antimony alloy is used as an anode, a cathode is an iron plate, or the non-soluble lead-antimony alloy and a soluble iron plate are together used as the anode, and the cathode is still as the iron plate; direct current is supplied to an open type no-diaphragm electrolytic tank, and then hexavalence chromium is directly reduced to trivalent chromium at the cathode; when the content of the hexavalent chromium in an electrolytic solution is less than 5 mg. L<-1>, the electrolysis is stopped. The economically feasible electrolysis treatment method can directly carry out electrolytic treatment to chromate waste water flowing into a water collecting well, and a pole plate can be inserted in the waste water then supplied with low voltage and low current to carry out electrolysis for a long time so that the hexavalent chromium is reduced for removal. Because the electrodes adopt the lead-antimony alloy and the waste iron plate, the economically feasible electrolysis treatment method has the advantages of convenient material acquirement, low cost and investment cost saving; acid and alkali do not need to be added for regulating the pH value of the solution before electrolysis and after electrolysis so that the economically feasible electrolysis treatment method has the advantages of process simplification, reduction of acid and alkali consumption, corresponding reduction of running cost and operation simplification.
Description
Technical field: the present invention relates to a kind of treatment process of the three wastes, relate in particular to a kind of chromic method of lower concentration in the electrolysis treatment waste water that in alkaline medium, adopts.
Background technology: the chromium slag is the main waste residue that chromium salt production is discharged, these chromium slags mostly are air storage, basically do not process, owing to contain the sexavalent chrome of water-soluble attitude and sour molten attitude in the slag, these soluble state sexavalent chromes can lose the soil of severe contamination surrounding environment, river and underground water source with the molten seepage flow of rainwater.
Chromate waste water has multiple treatment process, and the ferrous salt reduction precipitation method is a classic methods., running expense simple because of its technical maturity, equipment is low to be that many producers adopt.But also there are many shortcomings in this technology.At first add acid for adjusting pH in waste water, reduction of hexavalent chromium when pH=2-3, and then add alkali and regulate pH to 8-9 forms trivalent chromium and other heavy metal ion to precipitate and separates.The pH value of general chromate waste water does not reach above-mentioned requirements, and the process that adds acid for adjusting pH is all arranged, and therefore makes troubles to operation, and it is many to produce sediment, and power consumption is also big.At these problems,, will make work simplification, soda acid consumption reduce the corresponding reduction of running expense so if the precipitation of hexavalent chrome reduction and metal ion is all carried out under alkaline condition.
Generally speaking, the chrome liquor body that contains that rainwater pouring wash rice goes out is weakly alkaline, therefore, directly adopts electrolytic reduction Cr in weak alkaline medium
6+Handle chromium slag leach liquor, do not need chromium slag leach liquor is remake pre-treatment, can make like this and operate simple, the processing costs reduction that becomes.
Summary of the invention:
In order to solve, the invention provides that a kind of treatment process is simple, expense is low, sexavalent chrome electrolytic processing method in the trade effluent of processing ease to containing the problem that chromium (VI) waste water can not directly be handled.
Technical scheme of the present invention realizes in the following manner: sexavalent chrome electrolytic processing method in a kind of trade effluent, this method comprises the following steps:
Preparation electrolytic solution;
Choose anode, cathode material, energising electrolysis: sampling analysis;
Sediment is handled.
Wherein: (1) preparation electrolytic solution is to contain in alkalescence to add additive sulfuric acid potassium in chromium (VI) waste water, the vitriolate of tartar add-on: every liter of waste water adds 1.2g～3.5g vitriolate of tartar; Alkalescence contains chromium (VI) waste water pH value: 7.01≤PH≤12.91 (2) are anode with the lead antimony alloy or are anode with the iron plate, with the iron plate is negative electrode, in the open type undivided cell, logical direct current, sexavalent chrome directly is reduced to trivalent chromium or is reduced to trivalent chromium with the ferrous ion reaction of anodic stripping in solution at negative electrode, since in alkaline medium, the Cr of generation
3+Form Cr (OH)
3Precipitation, thus reach the purpose of dechromisation; Electrolysis temperature≤318.15K.(3) sampling analysis: content of 6-valence Cr ions is less than 5mg.L in electrolytic solution
-1The time, stop electrolysis.
During electrolysis, bath voltage: 1.8～3V, cathode area: annode area=3～8: 1, polar plate spacing: 2～8mm, electrolysis temperature: 283.15K～318.15K.
Sediment after the electrolysis adopts centrifuge dripping for using, and electrolytic solution recycles or discharges.
Can adopt the scrap iron plate to make negative electrode during electrolysis.
When adopting the lead antimony alloy of non-dissolubility to make anode, the precipitation that generates in the solution mainly is blue gray chromium hydroxide precipitation.
Inventive point of the present invention is that in alkaline medium direct electrolytic reduction handles the sexavalent chrome in the waste water, and its electrolysis principle is as follows:
With the lead antimony alloy is anode, and iron plate is a negative electrode, in the open type undivided cell, and logical direct current, electrolysis while stirring makes hexavalent chromium be reduced into trivalent chromic ion, because solution is alkalescence, the Cr of generation
3+Form Cr (OH)
3Precipitation, thus reach the purpose of dechromisation.The principal reaction formula is as follows:
Anodic process:
Or
Cathodic process:
Sampling analysis, content of 6-valence Cr ions is less than 5mg.L in electrolytic solution
-1The time, waste water promptly reaches discharging standards, stops electrolysis.
The sediment centrifuge dripping is for using, and electrolytic solution can be recycled or discharges.
Electrolysis temperature should not be higher than 318.15K, but in the limiting temperature scope, helps the carrying out of electrolytic reaction when temperature is higher.
Positively effect of the present invention is:
1, the present invention can insert pole plate to flowing into the direct electrolysis treatment of chromate waste water in the pump well in waste water, and logical low voltage and low current long period are carried out electrolysis, sexavalent chrome is reduced and removes.Because electrode adopts lead antimony alloy and scrap iron plate, to draw materials conveniently, cost is lower, can save a large amount of costs of investment.
2, all need not add the potential of hydrogen that soda acid comes regulator solution before the electrolysis and after the electrolysis, thereby work simplification, soda acid consumption are reduced, the corresponding reduction of running expense, operation also becomes simple.
Embodiment:
Embodiment 1
Getting the sexavalent chrome starting point concentration is 6mgL
-1Electrolytic solution 320ml to place volume be the electrolyzer of 650ml, add 0.8gK
2SO
4, stir with agitator then and heat energising and carry out electrolysis, electrolysis while stirring.Anode adopts the lead antimony alloy mesh electrode, evenly bores empty iron plate above negative electrode adopts, and ratio of cathodic to anodic area is 7: 1.
In the electrolytic process, sexavalent chrome is reduced to trivalent chromium at negative electrode:
Hydroxide ion reaction in trivalent chromium and the electrolytic solution generates precipitation:
This electrolytic reaction is carried out under alkaline condition, and electrolysis voltage is about 2.2V, and the electrolytic solution initial pH value is 11, and along with the carrying out of electrolytic process, the pH value is more and more little, and when electrolysis finished, the pH value of measuring solution approached neutrality.Electrolysis time is 6～12 hours.The time of the big more then electrolysis of sexavalent chrome starting point concentration is many more.Because electrolysis voltage and Faradaic current are all very little, logical low voltage of insertion battery lead plate long period, low current carry out electrolysis in the pond so can accumulate at waste water, and making hexavalent chrome reduction is trivalent chromium, and trivalent chromium is removed with sedimentary form.Be about at electrolysis voltage under the situation of 2.2V, polar plate spacing is chosen as 4mm, and the vitriolate of tartar add-on is 1.5gL
-1During electrolytic solution, when middling speed stirred, chromic rate of reduction was the highest.
The different initial pH value of table 1 are to Cr
6+The influence of reduction rate
| The pH value | 9.01 | 11.00 | 12.91 |
| Cr 6+Starting point concentration/mgL -1 Cr 6+Stop concentration/mgL -1Electrolysis time/min Cr 6*Reduction ratio/% | 5.36 0.31 125 94.22 | 5.36 0.22 166 95.90 | 7.33 0.78 720 89.36 |
Experiment condition: polar plate spacing is 4mm, K
2SO
4Add-on is 0.8g, and temperature is that 294.15K electrolysis certain hour is measured chromic content in the electrolytic solution, and content of 6-valence Cr ions is less than 0.5mgL in solution
-1The time, stop electrolysis.The pH value of measuring solution approaches 7.Electrolysis after finishing separates sedimentation and filtration.
Above-mentioned experiment has been carried out three times altogether, but the initial pH value difference of each electrolytic solution, experimental result is listed in the table 1.
Experimental result: waste water meets discharging standards after the electrolysis, and content of 6-valence Cr ions is less than 0.5mgL
-1
Embodiment 2
Getting the sexavalent chrome starting point concentration is 25mgL
-1Electrolytic solution 320ml to place volume be the electrolyzer of 650ml, add 0.8gK
2SO
4, above all adopting, anode, negative electrode evenly bore empty iron plate, and ratio of cathodic to anodic area is 1: 1.Stir with agitator then and heat energising and carry out electrolysis, electrolysis while stirring.In the electrolytic process, the chemical reaction of generation is as follows:
Anodic process:
Cathodic process:
Trivalent chromium and ferric iron are separated out precipitation of hydroxide in basic solution
In addition, trivalent chromium also can be non-dissolubility chromous acid molysite deposition
Hydroxide ion reaction in trivalent chromium and the electrolytic solution generates precipitation:
This electrolytic reaction is carried out under alkaline condition, and the electrolytic solution initial pH value is 9, and along with the carrying out of electrolytic process, the pH value is more and more little, and when electrolysis finished, the pH value of measuring solution approached neutrality.Electrolysis time is approximately 10 minutes.The big more then electrolysis of sexavalent chrome starting point concentration required time is many more.Electrolysis voltage is about 2V, and electrolysis temperature is a normal temperature, and polar plate spacing is chosen as 4mm, and the vitriolate of tartar add-on is 1.5gL
-1Electrolytic solution, middling speed stirs, and at this moment chromic rate of reduction is the highest.
The electrolysis certain hour is measured chromic content in the electrolytic solution, and content of 6-valence Cr ions is less than 0.5mgL in solution
-1The time, stop electrolysis.The pH value of measuring solution approaches 7.Electrolysis after finishing separates sedimentation and filtration.
Above-mentioned experiment has been carried out three times altogether, but the initial pH value difference of each electrolytic solution, experimental result is listed in the table 2.
The electrolytic solution electrolysis effectiveness of the different initial pH value of table 2 relatively
| The pH value | 7.01 | 9.04 | 11.00 |
| Cr 6+Starting point concentration/mgL -1 Cr 6+Stop concentration/mgL -1Reduction ratio/% | 25.07 0.97 96.64 | 25.05 0.80 96.82 | 25.10 0.41 98.72 |
Electrolytic condition: the electrolytic solution volume is 320ml, K
2SO
4Add-on is 0.8g, and temperature is 293.15K, and bath voltage is 2V, and polar plate spacing is 4mm
Experimental result: waste water meets discharging standards after the electrolysis, and content of 6-valence Cr ions is less than 0.5mgL
-1
Claims (3)
1, sexavalent chrome electrolytic processing method in a kind of trade effluent, this method comprises the following steps:
Preparation electrolytic solution; Choose anode, cathode material, the energising electrolysis; Sampling analysis; Sediment is handled; It is characterized in that: (1) contains in alkalescence and adds additive sulfuric acid potassium, vitriolate of tartar add-on: add 1.2g～3.5g vitriolate of tartar in every liter of waste water in chromium (VI) waste water; Alkalescence contains chromium (VI) waste water pH value: 7.01≤PH≤12.91; (2) be anode with the lead antimony alloy or be anode with the iron plate, with the iron plate is negative electrode, in the open type undivided cell, and logical direct current, sexavalent chrome directly is reduced to trivalent chromium or is reduced to trivalent chromium, the Cr of generation with the ferrous ion reaction of anodic stripping in solution at negative electrode
3+Form Cr (OH)
3Precipitation; Electrolysis temperature≤318.15K; (3) sampling analysis: content of 6-valence Cr ions is less than 5mg.L in electrolytic solution
-1The time, stop electrolysis;
Bath voltage: 1.8～3V; Cathode area: annode area=3～8: 1; Polar plate spacing: 2～8mm; Electrolysis temperature: 283.15K～318.15K.
2, sexavalent chrome electrolytic processing method in the trade effluent according to claim 1 is characterized in that: sediment adopts centrifuge dripping for using, and electrolytic solution discharges or recycles.
3, according to sexavalent chrome electrolytic processing method in claim 1 or the described trade effluent, it is characterized in that: the scrap iron plate is made negative electrode.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ITMI20052297A1 (en) * | 2005-11-30 | 2007-06-01 | De Nora Elettrodi Spa | ELECTROCHEMICAL TREATMENT OF SOLUTIONS WITH HEXAVALENT CHROME |
| CN100381370C (en) * | 2006-06-14 | 2008-04-16 | 浙江大学 | System for removing and retrieving hexavalent chrome from wastewater |
| CN101723490A (en) * | 2009-11-17 | 2010-06-09 | 中国环境科学研究院 | Pulse electro-flocculation treatment process and device of berberine waste water |
| JP5652293B2 (en) * | 2011-03-29 | 2015-01-14 | 栗田工業株式会社 | Method for processing heavy metal-containing solids |
| CN102887559B (en) * | 2011-07-21 | 2014-03-19 | 中国科学院生态环境研究中心 | Electrochemical reduction assistance-based biosorption integrated reactor and treatment method of hexavalent chromium-containing wastewater |
| CN105858991A (en) * | 2016-03-08 | 2016-08-17 | 侯绪华 | Chrome-containing wastewater treatment device |
| CN107720891A (en) * | 2017-11-21 | 2018-02-23 | 中国石油大学(华东) | A kind of method for promoting the reduction of heavy metal chromium ion electrochemical |
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Assignee: Luxi Xinxing Chemical Industry Co., Ltd. Assignor: Zhengzhou University Contract fulfillment period: 2009.7.28 to 2022.7.28 contract change Contract record no.: 2009430000213 Denomination of invention: Hexa valence chromium in industriel waste water electrolysis treatment method Granted publication date: 20060510 License type: Exclusive license Record date: 2009.12.1 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2009.7.28 TO 2022.7.28; CHANGE OF CONTRACT Name of requester: LUXI COUNTY XINXING METALLURGICAL CO., LTD. Effective date: 20091201 |