CN101549925A - Method for electrolyzing and recovering hexavalent chrome in chromium-electroplating waste water - Google Patents
Method for electrolyzing and recovering hexavalent chrome in chromium-electroplating waste water Download PDFInfo
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- CN101549925A CN101549925A CNA2008100602301A CN200810060230A CN101549925A CN 101549925 A CN101549925 A CN 101549925A CN A2008100602301 A CNA2008100602301 A CN A2008100602301A CN 200810060230 A CN200810060230 A CN 200810060230A CN 101549925 A CN101549925 A CN 101549925A
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Abstract
The invention relates to a method for electrolyzing and recovering hexavalent chromium in chromium-electroplating waste water. Aiming at overcoming defects that chromium recovered from chromium waste water by the prior chromium-electroplating waste water treatment method cannot be reused for an electroplating tank, the invention provides the method for electrolyzing and recovering the hexavalent chromium in the chromium-electroplating waste water, which has simple operation and low recovering cost. The method comprises the following steps: sulfuric acid solution, sodium metabisulfite and sodium carbonate solution are sequentially added to the chromium-electroplating waste water; the reacted chromium-electroplating waste water flows into a precipitator for precipitation; through the precipitation, supernatant fluid flows into a neutralization pond for neutralization, the chromium-electroplating waste water is input a press filter for press filtering, and obtained chromic salts are washed with clear water; the chromium-electroplating waste water, the chromic salts and sulphuric acid are added in an electrolytic tank of a concentration purifier, and the sulphuric acid is added in a porous pot of the concentration purifier; when the concentration of the hexavalent chromium is larger than 20g/l and the concentration of trivalent chromium is smaller than 1g/l by electrolysis in the chromium-electroplating waste water in the electrolytic tank of the concentration purifier, the chromium-electroplating waste water can be used as a replenishing liquor for the electroplating chromium.
Description
Technical field
The invention belongs to the technical field of Industrial Wastewater Treatment, the method for electrolyzing and recovering hexavalent chrome in particularly a kind of chromium-electroplating waste water.
Background technology
Up to now, the method that the chromium-electroplating waste water processing is reclaimed has multiple, but is to reclaim to become the trivalent chromium form basically, makes chromic oxide, ferrite, leather treatment agent etc., also useful sexavalent chrome makes that chrome yellow, sodium dichromate 99 etc. reclaim, and does not see to have to be back to the electrodeposited chromium groove after the processing.The chrome waste water of existing most of Electroplate Factories generally all is to be reduced into chromic salt, waste water is flow in the comprehensive wastewater pond again, trivalent chromium is become electroplating sludge and discard, contain various heavy in the electroplating sludge, as copper, nickel, zinc, chromic salt etc., it is very difficult being recycled.
In plating, chromium is the extremely low metal of utilization ratio, usually the utilization ratio of chromium only 8～13% in the electroplated decorative chromium, and most of chromium is in waste water and waste gas, do not reclaim and abandon in mud, it is great waste, and be easy to generate secondary pollution, wherein sexavalent chrome is severe 1 pollutant, its strong toxicity, be carcinogens, the America and Europe is multinational all to forbid, is limiting chromic use.
Summary of the invention
The present invention is directed to and existing chromium-electroplating waste water is handled the weak point that the existing chromium that reclaims can not be back to plating tank from chrome waste water, the method for electrolyzing and recovering hexavalent chrome in a kind of simple to operate, chromium-electroplating waste water that cost recovery is low is provided.
The technical solution used in the present invention is finished in the following way: the method for electrolyzing and recovering hexavalent chrome in a kind of chromium-electroplating waste water, and it may further comprise the steps:
(1) add sulphuric acid soln under the stirring in chromium-electroplating waste water, the pH value that makes chromium-electroplating waste water is 1.0～1.3;
(2) add Sodium Pyrosulfite in chromium-electroplating waste water, the redox potential that makes chromium-electroplating waste water when chromic salt begins to precipitate, adds sodium carbonate solution again below 220mv, and the pH value that makes chromium-electroplating waste water is 8.0～8.5;
(3) flow into the settling vessel precipitation through reacted chromium-electroplating waste water;
(4) through precipitation, supernatant liquor flows into the neutralization tank neutralization, contains in the chromium-electroplating waste water input pressure filter of throw out chromic salt to carry out the chromic salts press filtration, and resulting throw out chromic salt repeatedly washs with clear water;
(5) in the electrolyzer of thickening-purification technology device, add chromium-electroplating waste water and chromic salt, and in containing the chromium-electroplating waste water of chromic salt, add sulfuric acid, the pH value that will contain the chromium-electroplating waste water of chromic salt is adjusted to 0.5～1.0, in the porous jar of thickening-purification technology device, add 5～20% sulphuric acid solns, in the electrolyzer of thickening-purification technology device, place the stereotype anode, in the porous jar of thickening-purification technology device, place the stereotype negative electrode, feed direct current; In the electrolytic process, the sulphuric acid soln in the porous jar of thickening-purification technology device can reduce gradually, should give to replenish sulphuric acid soln; In the electrolytic process, trivalent chromium amount in the chromium-electroplating waste water in the electrolyzer of thickening-purification technology device reduces gradually, hexavalent chromium amount increases gradually, can give to replenish chromic salt, when the hexavalent chromium concentration＞20g/l in the chromium-electroplating waste water in the electrolyzer of thickening-purification technology device, trivalent chromium concentration＜1g/L, just can be used as the additional liquid of electrodeposited chromium.
In the electrolytic process, iron in the chromium-electroplating waste water in the electrolyzer of thickening-purification technology device, copper, nickel, zinc plasma can be gradually tank skin by thickening-purification technology device porous jar enter in the porous jar, these foreign ions in the chromium-electroplating waste water in the electrolyzer of thickening-purification technology device reach purification by electrolysis.
In the electrolyzing and recovering hexavalent chrome method, can divide two sections to reclaim chromium in above-mentioned chromium-electroplating waste water, one section is to reclaim chromic salt in Electroplate Factory with Sodium Pyrosulfite, and another section is that chromic salt is fetched, and concentrated electrolytic recovery becomes the sexavalence strong solution.
In above-mentioned chromium-electroplating waste water, in the electrolyzing and recovering hexavalent chrome method, be aided with the chemical examination testing, guarantee specification of quality.
In above-mentioned chromium-electroplating waste water in the electrolyzing and recovering hexavalent chrome method, be used for detecting the pH value of chromium-electroplating waste water and the instrument of redox potential is to adopt potentiometer.
The method of electrolyzing and recovering hexavalent chrome in a kind of chromium-electroplating waste water of the present invention has following characteristics:
1, floor space is little, facility investment is few, process cost is low,
2, the operation simple and easy single, be easy to control, the organic efficiency height of chromium, good in economic efficiency,
3, solved the chrome waste water pollution problem, and made integrative electroplating waste owing to after having removed chromium, and easier to be processed.
Description of drawings
Fig. 1 is the process flow sheet of the method for electrolyzing and recovering hexavalent chrome in a kind of chromium-electroplating waste water of the present invention.
Embodiment
Contrast accompanying drawing below, the invention will be further described by embodiment.
With reference to accompanying drawing 1, the method for electrolyzing and recovering hexavalent chrome in a kind of chromium-electroplating waste water, it may further comprise the steps:
(1) chromium-electroplating waste water adds sulphuric acid soln by in liquid-inlet pipe 1 injecting reactor 4 under stirring in chromium-electroplating waste water, and the pH value that makes chromium-electroplating waste water is 1.0～1.3;
(2) in chromium-electroplating waste water, add Sodium Pyrosulfite, add Sodium Pyrosulfite amount be chromic 3.5～6 times, the redox potential that makes chromium-electroplating waste water is below 220mv, when chromic salt begins to precipitate, add sodium carbonate solution again, the pH value that makes chromium-electroplating waste water is 8.0～8.5;
(3) through opening inflow settling vessel 5 precipitations of reacted chromium-electroplating waste water by reactor 4 middle and lower parts;
(4) through precipitation, supernatant liquor in the settling vessel 5 flows into neutralization tank by drain pipe 6 and neutralizes, the chromium-electroplating waste water that contains the throw out chromic salt is by carrying out the chromic salts press filtration in the pipeline 7 input pressure filters 8, resulting throw out chromic salt repeatedly washs with clear water, can be stand-by by discharge nozzle 10 outputs;
(5) in the electrolyzer 11 of thickening-purification technology device, add chromium-electroplating waste water and chromic salt, and in containing the chromium-electroplating waste water of chromic salt, add sulfuric acid, the pH value that will contain the chromium-electroplating waste water of chromic salt is adjusted to 0.5～1.0, in the porous jar 14 of thickening-purification technology device, add 5～20% sulphuric acid solns, in the electrolyzer 11 of thickening-purification technology device, place stereotype anode 12, in the porous jar 14 of thickening-purification technology device, place stereotype negative electrode 13, feed direct current, galvanic voltage is 3～12 volts, 1.0～4.0 amperes/decimeter of current densities
2In the electrolytic process, the sulphuric acid soln in the porous jar 14 of thickening-purification technology device can reduce gradually, should give to replenish sulphuric acid soln; In the electrolytic process, trivalent chromium amount in the chromium-electroplating waste water in the electrolyzer 11 of thickening-purification technology device reduces gradually, hexavalent chromium amount increases gradually, can give to replenish chromic salt, when the hexavalent chromium concentration＞20g/l in the chromium-electroplating waste water in the electrolyzer of thickening-purification technology device, trivalent chromium concentration＜1g/L, just can be used as the additional liquid of electrodeposited chromium.
After testing, contain hexavalent chromium amount＜0.5mg/l the 6 effusive supernatant liquors of the drain pipe from settling vessel 5.
In above-mentioned chromium-electroplating waste water, in the electrolyzing and recovering hexavalent chrome method, be aided with the chemical examination testing, guarantee specification of quality.
In above-mentioned chromium-electroplating waste water, in the electrolyzing and recovering hexavalent chrome method, in reactor 4, be provided with the pH value that is used for detecting chromium-electroplating waste water, the potentiometer 2 and the agitator 3 of redox potential.
In the electrolyzing and recovering hexavalent chrome method, settling vessel 5 adopts tilted plate separator in above-mentioned chromium-electroplating waste water.
In the electrolyzing and recovering hexavalent chrome method, pressure filter 8 adopts the accurate pressure filter of micropore, is provided with the water inlet pipe 9 and the water pump that are used for carrying clear water on pressure filter 8 in above-mentioned chromium-electroplating waste water.
In above-mentioned chromium-electroplating waste water in the electrolyzing and recovering hexavalent chrome method, the thickening-purification technology device is made up of electrolyzer 11, porous jar 14, stereotype anode 12, stereotype negative electrode 13, wherein, the top tank skin 15 of porous jar 14 is made of plastics, the bottom tank skin 16 of porous jar 14 is made by porous ceramic film material, porous jar 14 is placed in the electrolyzer 11, is provided with drain pipe 17 in electrolyzer 11 cell walls bottom.
Claims (6)
1, the method for electrolyzing and recovering hexavalent chrome in a kind of chromium-electroplating waste water is characterized in that the method for electrolyzing and recovering hexavalent chrome in this chromium-electroplating waste water may further comprise the steps:
(1) add sulphuric acid soln under the stirring in chromium-electroplating waste water, the pH value that makes chromium-electroplating waste water is 1.0～1.3;
(2) add Sodium Pyrosulfite in chromium-electroplating waste water, the redox potential that makes chromium-electroplating waste water when chromic salt begins to precipitate, adds sodium carbonate solution again below 220mv, and the pH value that makes chromium-electroplating waste water is 8.0～8.5;
(3) flow into the settling vessel precipitation through reacted chromium-electroplating waste water;
(4) through precipitation, supernatant liquor flows into the neutralization tank neutralization, contains in the chromium-electroplating waste water input pressure filter of throw out chromic salt to carry out the chromic salts press filtration, and resulting throw out chromic salt repeatedly washs with clear water;
(5) in the electrolyzer of thickening-purification technology device, add chromium-electroplating waste water and chromic salt, and in containing the chromium-electroplating waste water of chromic salt, add sulfuric acid, the pH value that will contain the chromium-electroplating waste water of chromic salt is adjusted to 0.5～1.0, in the porous jar of thickening-purification technology device, add 5～20% sulphuric acid solns, in the electrolyzer of thickening-purification technology device, place the stereotype anode, in the porous jar of thickening-purification technology device, place the stereotype negative electrode, feed direct current; In the electrolytic process, the sulphuric acid soln in the porous jar of thickening-purification technology device can reduce gradually, should give to replenish sulphuric acid soln; In the electrolytic process, trivalent chromium amount in the chromium-electroplating waste water in the electrolyzer of thickening-purification technology device reduces gradually, hexavalent chromium amount increases gradually, can give to replenish chromic salt, when the hexavalent chromium concentration＞20g/l in the chromium-electroplating waste water in the electrolyzer of thickening-purification technology device, trivalent chromium concentration＜1g/L, just can be used as the additional liquid of electrodeposited chromium.
2, the method for electrolyzing and recovering hexavalent chrome in the chromium-electroplating waste water according to claim 1 is characterized in that being used for detecting the pH value of chromium-electroplating waste water and the instrument of redox potential is to adopt potentiometer.
3, the method for electrolyzing and recovering hexavalent chrome in the chromium-electroplating waste water according to claim 1 and 2 is characterized in that settling vessel adopts tilted plate separator.
4, the method for electrolyzing and recovering hexavalent chrome in the chromium-electroplating waste water according to claim 1 and 2 is characterized in that pressure filter adopts the accurate pressure filter of micropore.
5, the method for electrolyzing and recovering hexavalent chrome in the chromium-electroplating waste water according to claim 1 and 2, it is characterized in that the thickening-purification technology device is made up of electrolyzer, porous jar, stereotype anode, stereotype negative electrode, wherein, the top tank skin of porous jar is made of plastics, the bottom tank skin of porous jar is made by porous ceramic film material, the porous jar is placed in the electrolyzer, is provided with drain pipe in electrolyzer cell wall bottom.
6, the method for electrolyzing and recovering hexavalent chrome in the chromium-electroplating waste water according to claim 5, when it is characterized in that the chromium-electroplating waste water in the electrolyzer of thickening-purification technology device carried out electrolysis, galvanic voltage is 3～12 volts, 1.0～4.0 amperes/decimeter of current densities
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| CNA2008100602301A CN101549925A (en) | 2008-03-31 | 2008-03-31 | Method for electrolyzing and recovering hexavalent chrome in chromium-electroplating waste water |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249443A (en) * | 2011-04-27 | 2011-11-23 | 中信大锰矿业有限责任公司 | Method for recycling chromium from chromium passivation wastewater of electrolytic manganese factory |
| CN102383159A (en) * | 2011-08-09 | 2012-03-21 | 长春一汽富维高新汽车饰件有限公司 | Coarsening production and trivalent chromium electrolysis process incorporating device and method |
| CN104150651A (en) * | 2014-08-15 | 2014-11-19 | 中国科学院生态环境研究中心 | Method for removing hexavalent chromium in water through chemical reduction assisted electrochemical process |
| CN104310569A (en) * | 2014-11-10 | 2015-01-28 | 中国石油大学(华东) | Method for water treatment oxidation by using Cr (VI)/SO32 |
| CN105236639A (en) * | 2015-10-30 | 2016-01-13 | 太仓东能环保设备有限公司 | Chromium-containing wastewater treatment process |
| CN105568355A (en) * | 2014-11-05 | 2016-05-11 | 天津市津一电镀有限公司 | Method and device for purifying chromium plating solution and waste liquor thereof |
| CN105858991A (en) * | 2016-03-08 | 2016-08-17 | 侯绪华 | Chrome-containing wastewater treatment device |
| CN112850993A (en) * | 2020-12-25 | 2021-05-28 | 四川银河明宏环保科技有限公司 | Method for recovering chromium in chromium plating and zinc plating wastewater |
-
2008
- 2008-03-31 CN CNA2008100602301A patent/CN101549925A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249443A (en) * | 2011-04-27 | 2011-11-23 | 中信大锰矿业有限责任公司 | Method for recycling chromium from chromium passivation wastewater of electrolytic manganese factory |
| CN102249443B (en) * | 2011-04-27 | 2013-03-27 | 中信大锰矿业有限责任公司 | Method for recycling chromium from chromium passivation wastewater of electrolytic manganese factory |
| CN102383159A (en) * | 2011-08-09 | 2012-03-21 | 长春一汽富维高新汽车饰件有限公司 | Coarsening production and trivalent chromium electrolysis process incorporating device and method |
| CN104150651A (en) * | 2014-08-15 | 2014-11-19 | 中国科学院生态环境研究中心 | Method for removing hexavalent chromium in water through chemical reduction assisted electrochemical process |
| CN104150651B (en) * | 2014-08-15 | 2016-08-24 | 中国科学院生态环境研究中心 | A kind of electronation assisted electrochemical method removes chromic method in water |
| CN105568355A (en) * | 2014-11-05 | 2016-05-11 | 天津市津一电镀有限公司 | Method and device for purifying chromium plating solution and waste liquor thereof |
| CN104310569A (en) * | 2014-11-10 | 2015-01-28 | 中国石油大学(华东) | Method for water treatment oxidation by using Cr (VI)/SO32 |
| CN104310569B (en) * | 2014-11-10 | 2016-04-20 | 中国石油大学(华东) | Utilize Cr (VI)/SO 32-the method of water treatment oxidation |
| CN105236639A (en) * | 2015-10-30 | 2016-01-13 | 太仓东能环保设备有限公司 | Chromium-containing wastewater treatment process |
| CN105858991A (en) * | 2016-03-08 | 2016-08-17 | 侯绪华 | Chrome-containing wastewater treatment device |
| CN112850993A (en) * | 2020-12-25 | 2021-05-28 | 四川银河明宏环保科技有限公司 | Method for recovering chromium in chromium plating and zinc plating wastewater |
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Application publication date: 20091007 |