CN106583025A - Tailing heavy metal pollutant electrokimtic and precipitated combined remediation method - Google Patents
Tailing heavy metal pollutant electrokimtic and precipitated combined remediation method Download PDFInfo
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- CN106583025A CN106583025A CN201710015281.1A CN201710015281A CN106583025A CN 106583025 A CN106583025 A CN 106583025A CN 201710015281 A CN201710015281 A CN 201710015281A CN 106583025 A CN106583025 A CN 106583025A
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- heavy metal
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- liquor
- sulfide
- mine tailing
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000005067 remediation Methods 0.000 title abstract 7
- 239000003344 environmental pollutant Substances 0.000 title abstract 4
- 231100000719 pollutant Toxicity 0.000 title abstract 4
- 239000000243 solution Substances 0.000 claims abstract description 57
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003513 alkali Substances 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims description 61
- 230000008439 repair process Effects 0.000 claims description 31
- 238000001556 precipitation Methods 0.000 claims description 27
- 239000000356 contaminant Substances 0.000 claims description 26
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- 150000002500 ions Chemical class 0.000 claims description 15
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- FANSKVBLGRZAQA-UHFFFAOYSA-M dipotassium;sulfanide Chemical compound [SH-].[K+].[K+] FANSKVBLGRZAQA-UHFFFAOYSA-M 0.000 claims description 5
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000009393 electroremediation Methods 0.000 abstract 4
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 239000011701 zinc Substances 0.000 description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 15
- 229910052802 copper Inorganic materials 0.000 description 11
- 239000010949 copper Substances 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 7
- 239000011780 sodium chloride Substances 0.000 description 7
- 229910001629 magnesium chloride Inorganic materials 0.000 description 5
- 230000005611 electricity Effects 0.000 description 4
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- JNVCSEDACVAATK-UHFFFAOYSA-L [Ca+2].[S-]SSS[S-] Chemical compound [Ca+2].[S-]SSS[S-] JNVCSEDACVAATK-UHFFFAOYSA-L 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 229940051851 sulfurated lime Drugs 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- -1 sodium sulfide sulfides Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B7/00—Combinations of wet processes or apparatus with other processes or apparatus, e.g. for dressing ores or garbage
Landscapes
- Processing Of Solid Wastes (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention relates to a tailing heavy metal pollutant electrokinetic and precipitated combined remediation method and belongs to the technical field of tailing heavy metal remediation environmental protection. According to the method, heavy metal pollutant electrokinetic remediation is conducted in a remediation tank; the middle of the remediation tank is provided with a tailing heavy metal remediation groove; the pH of cathode liquor or anode liquor is maintained to be 6-7 through a replenisher; cathode and anode overflow liquor is collected; alkali liquor is added into the obtained cathode overflow liquor, and the pH is controlled to be 7-8; sulfide is added, the liquor is subjected to stirring, standing and filtering to obtain a purified solution, the purified solution is used as the anode liquor replenisher in the remediation process, and the obtained anode overflow liquor is used as cathode liquor replenisher until electrokinetic remediation is completed; and after electrokinetic remediation is completed, the cathode liquor and the overflow liquor are mixed to obtain a mixed solution, alkali liquor is added into the mixed solution to enable the pH of the mixed solution to be controlled within 7-8, sulfide is added, the solutions is subjected to precipitating, stirring, standing and filtering, and finally the solution becomes the purified solution. Through the method, cathode liquor heavy metal secondary pollutants after electrokinetic remediation can be effectively purified.
Description
Technical field
The present invention relates to a kind of electronic method with precipitation combine d bioremediation mine tailing heavy metal contaminants, belongs to mine tailing heavy metal
Repair environmental technology field.
Background technology
With the utilization of continually developing of mineral resources, a large amount of mine tailings, debris dump are abandoned in ecological environment, contained in mine tailing
Heavy metal element can cause high risks to Soil Surrounding, river, agricultural production etc., and mine tailing is into important source of heavy metal pollution
Head.For this purpose, becoming important topic to heavy metal reparation in mine tailing.
Heavy metal restorative procedure has a lot, including plant method, stabilizing method, Physical etc., wherein, electric repairing technique tool
Many advantages, such as effective property is strong, effect is good, removal is thorough, because anode and cathode electrode reaction easily causes the moon during electro reclamation
Pole liquid pH is raised, and anolyte pH is reduced, and catholyte pH is raised can cause heavy metal ion to precipitate in advance, is repaired index and is deteriorated, control
Negative electrode pH processed becomes lifting and repairs index key factor, repairs in the overflowing liquid for producing and contains heavy metal ion, meanwhile, it is electronic to repair
Heavy metal ion great majority are still resided in catholyte after multiple, and catholyte and overflowing liquid become pollution source, and it is carried out only
Change the application for processing not having been reported that.
The content of the invention
The problem existed for above-mentioned prior art and deficiency, the present invention provides a kind of electronic and precipitation combine d bioremediation mine tailing
The method of heavy metal contaminants.This method can effectively purify negative electrode liquid heavy metal secondary pollution after electro reclamation, realize electronic repairing
Multiple catholyte purification is used again, and the present invention is achieved through the following technical solutions.
A kind of electronic method with precipitation combine d bioremediation mine tailing heavy metal contaminants, it includes step in detail below：
（1）Electro reclamation operation：Heavy metal electro reclamation is carried out repairing in groove（As shown in Figure 1）, it is mine tailing to repair in the middle of groove
Heavy metal repairs groove（Mine tailing is repaired area 2 and is being repaired in the middle of groove）, anodic-cathodic is placed respectively at two ends（4 points of anode region 3, cathode chamber
Groove two ends Wei Yu not be repaired, in anode region 3, cathode chamber 4 anolyte and catholyte are separately added into）, being powered carries out electro reclamation, uses
It is 6～7 that replenisher maintains the moon or anolyte pH, and collects anode and cathode overflowing liquid；
（2）Negative electrode overflowing liquid heavy metal precipitation：By step（1）It is 7～8 that the negative electrode overflowing liquid for obtaining adds alkali liquor to control pH, so
After add sulfide solution, sulfide solution addition be sulphion with heavy metal ion mol ratio in negative electrode overflowing liquid be 1～
1.5：1, purified solution is obtained after stirring, standing, filtration, purified solution is used as repair process Anodic liquid replenisher, same to time step
Suddenly（1）The anode overflowing liquid for obtaining is used as catholyte replenisher, until electro reclamation is completed；
（3）After the completion of electro reclamation, catholyte and overflowing liquid are mixed to get into mixed solution, it is 7～8 to add alkali liquor to control pH,
Be subsequently adding sulfide solution, sulfide solution addition be sulphion with heavy metal ion mol ratio in mixed solution be 1～
1.5：1, after precipitation, stirring, standing, filtration, filtrate is purified solution, can be used as the catholyte in next electro reclamation test.
The step（1）Middle catholyte is combined for organic acid with chlorate, and organic acid is citric acid, tartaric acid or Fructus Mali pumilae
Acid, chlorate is Sodium Chloride, potassium chloride or magnesium chloride solution, and organic acid is 0.1 ~ 0.2 with chlorate mol ratio：0.1 ~ 0.2, sun
Pole liquid is chlorination saline solution, is Sodium Chloride, potassium chloride, one or more arbitrary proportion mixture solution of magnesium chloride, and chlorate is molten
0.1 ~ 0.3mol/L of chlorine ion concentration in liquid.
The step（1）Middle heavy metal electro reclamation voltage gradient is 0.5～2.0V/cm.
The step（2）And step（3）Middle alkali liquor is sodium hydroxide, potassium hydroxide or calcium oxide.
The step（2）And step（3）Middle sulfide is one or more in sodium sulfide, ammonium sulfide, Potassium monosulfide., calcium sulfide
Arbitrary proportion mixture.
Above-mentioned steps（1）It is 0.3～0.4m that middle mine tailing repairs the slot length of area 2.
The invention has the beneficial effects as follows：
1st, strong applicability.This it is electronic with precipitation integrated processes have the suitability to mine tailing various heavy, can be used for Zn, Cu, Pb,
The mine tailing of the big number heavy metal pollution absolutely such as Fe.
2nd, green is circulated.Purified solution used in repair process, realizes the Recycling of water, and reparation is completed, catholyte etc.
Can purify standby.
3rd, raw material is cheap.Precipitant selects sodium sulfide sulfides, and raw material is easy to get, cheaply.
4th, it is simple to operation.Standing, filter pressing or centrifugation is only needed just to be capable of achieving catholyte or overflow liquid heavy metal purifying regeneration,
Equipment is simply ripe, it is easy to Technique Popularizing application.
Description of the drawings
Fig. 1 is the electronic method schematic diagram with precipitation combine d bioremediation mine tailing heavy metal contaminants of the present invention.
In figure：1- current detectings, 2- mine tailings repair area, and 3- anode regions, 4- cathode chambers, 5- graphite electrode plates, 6- anodes overflow
Flow liquid, 7- negative electrode overflowing liquids, catholyte after 8- remove impurity, 9- is filtered, 10- negative electrode replenishers, 11- anode replenishers, and 12- negative electrodes are mended
Topping up is standby, and 13- anode replenishers are standby.
Specific embodiment
With reference to the accompanying drawings and detailed description, the invention will be further described.
Embodiment 1
The electronic and precipitation combine d bioremediation mine tailing heavy metal contaminants（Mine tailing heavy metal contaminants sample is from Dali City, yunnan Province
Certain bargh, heavy metal zinc content overproof in sample）Method, it includes step in detail below：
（1）Electro reclamation operation：Heavy metal electro reclamation is carried out repairing in groove（As shown in Figure 1）, it is mine tailing to repair in the middle of groove
Heavy metal repairs groove（Mine tailing is repaired area 2 and is being repaired in the middle of groove, and it is 0.3m that mine tailing repairs the slot length of area 2）, the moon is placed respectively at two ends
Anelectrode（Anode region 3, cathode chamber 4 are located at repair groove two ends respectively, and in anode region 3, cathode chamber 4 anolyte and the moon are separately added into
Pole liquid, anolyte is combined for citric acid solution with sodium chloride solution, and content is respectively 0.2mol/L, 0.1mol/L, and catholyte is
Sodium Chloride is combined with potassium chloride, and consumption is 0.1mol/L, 0.1mol/L, and anode region 3, the Anodic of cathode chamber 4 and negative electrode are stone
Ink）, it is that 1.0V/cm energizations carry out electro reclamation in voltage gradient, it is 6～7 to maintain the moon or anolyte pH with replenisher, and is collected
Anode and cathode overflowing liquid；
（2）Negative electrode overflowing liquid heavy metal precipitation：The step of receiving in 12h（1）The negative electrode overflowing liquid for obtaining adds alkali liquor
（0.01mol/LNaOH solution）It is 8 to control pH, is subsequently adding sulfide（0.01mol/LNa2S solution）, sulfide addition is
Sulphion is 1 with heavy metal ion mol ratio in negative electrode overflowing liquid：1, purified solution is obtained after stirring, standing, filtration, purify molten
Liquid is used as repair process Anodic liquid replenisher, while step（1）The anode overflowing liquid for obtaining is used as catholyte replenisher, until
Electro reclamation is completed（The electro reclamation time is 12d）；
（3）After the completion of electro reclamation, catholyte and overflowing liquid are mixed to get into mixed solution, add alkali liquor（0.01mol/LNaOH
Solution）It is 8 to control pH, is subsequently adding sulfide（0.01mol/LNa2S solution）, sulfide addition be sulphion with mix molten
Heavy metal ion mol ratio is 1 in liquid：1, after precipitation, stirring, standing, filtration, filtrate is purified solution, can be used as next time electronic
Catholyte in repairing test.
Zn content and step in heavy metal contaminants after the completion of Zn content, Jing electro reclamations in heavy metal contaminants（2）、
（3）In in the purified solution that obtains Zn content it is as shown in table 1.
Table 1
。
Embodiment 2
The electronic and precipitation combine d bioremediation mine tailing heavy metal contaminants（Mine tailing heavy metal contaminants sample is from Hunan Province mine
Enterprise, heavy metal copper, Zn content are exceeded in sample）Method, it includes step in detail below：
（1）Electro reclamation operation：Heavy metal electro reclamation is carried out repairing in groove（As shown in Figure 1）, it is mine tailing to repair in the middle of groove
Heavy metal repairs groove（Mine tailing is repaired area 2 and is being repaired in the middle of groove, and it is 0.35m that mine tailing repairs the slot length of area 2）, the moon is placed respectively at two ends
Anelectrode（Anode region 3, cathode chamber 4 are located at repair groove two ends respectively, and in anode region 3, cathode chamber 4 anolyte and the moon are separately added into
Pole liquid, anolyte is combined for tartaric acid with magnesium chloride solution, and content is respectively 0.2mol/L, 0.2mol/L, and catholyte is chlorination
Magnesium is combined with Klorvess Liquid, and consumption is 0.1mol/L, 0.1mol/L, and anode region 3, the Anodic of cathode chamber 4 and negative electrode are stone
Ink）, it is that 1.5V/cm energizations carry out electro reclamation in voltage gradient, it is 6～7 to maintain the moon or anolyte pH with replenisher, and is collected
Anode and cathode overflowing liquid；
（2）Negative electrode overflowing liquid heavy metal precipitation：The step of receiving in 6h（1）The negative electrode overflowing liquid for obtaining adds alkali liquor
（0.01mol/LKOH solution）It is 8 to control pH, is subsequently adding sulfide（0.02mol/LNa2S solution）, sulfide addition is
Sulphion is 1.5 with heavy metal ion mol ratio in negative electrode overflowing liquid：1, purified solution is obtained after stirring, standing, filtration, purify
Solution is used as repair process Anodic liquid replenisher, while step（1）The anode overflowing liquid for obtaining is used as catholyte replenisher, directly
Complete to electro reclamation（The electro reclamation time is 15d）；
（3）After the completion of electro reclamation, catholyte and overflowing liquid are mixed to get into mixed solution, add alkali liquor（0.01mol/LKOH
Solution）It is 8 to control pH, is subsequently adding sulfide（0.02mol/LNa2S solution）, sulfide addition be sulphion with mix molten
Heavy metal ion mol ratio is 1.5 in liquid：1, after precipitation, stirring, standing, filtration, filtrate is purified solution, can be used as next electricity
Catholyte in dynamic repairing test.
Copper, Zn content in heavy metal contaminants, copper, Zn content and step in heavy metal contaminants after the completion of Jing electro reclamations
Suddenly（2）、（3）In in the purified solution that obtains copper, Zn content it is as shown in table 2.
Table 2
。
Embodiment 3
The electronic and precipitation combine d bioremediation mine tailing heavy metal contaminants（Mine tailing heavy metal contaminants sample is from mountain of papers city of Yunnan Province
Certain bargh, heavy metal content of Pb＆Zn is exceeded in sample）Method, it includes step in detail below：
（1）Electro reclamation operation：Heavy metal electro reclamation is carried out repairing in groove（As shown in Figure 1）, it is mine tailing to repair in the middle of groove
Heavy metal repairs groove（Mine tailing is repaired area 2 and is being repaired in the middle of groove, and it is 0.4m that mine tailing repairs the slot length of area 2）, the moon is placed respectively at two ends
Anelectrode（Anode region 3, cathode chamber 4 are located at repair groove two ends respectively, and in anode region 3, cathode chamber 4 anolyte and the moon are separately added into
Pole liquid, anolyte is combined for malic acid with magnesium chloride, and content is respectively 0.2mol/L, 0.1mol/L, catholyte be magnesium chloride with
Sodium Chloride is combined, and consumption is 0.1mol/L, 0.2mol/L, and anode region 3, the Anodic of cathode chamber 4 and negative electrode are graphite）, in electricity
Pressure gradient is that 2V/cm energizations carry out electro reclamation, and it is 6～7 to maintain the moon or anolyte pH with replenisher, and collects anode and cathode overflow
Liquid；
（2）Negative electrode overflowing liquid heavy metal precipitation：The step of receiving in 10h（1）The negative electrode overflowing liquid for obtaining adds alkali liquor
（0.01mol/LKOH solution）It is 8 to control pH, is subsequently adding sulfide（0.04mol/LNa2S solution）, sulfide addition is
Sulphion is 1.2 with heavy metal ion mol ratio in negative electrode overflowing liquid：1, purified solution is obtained after stirring, standing, filtration, purify
Solution is used as repair process Anodic liquid replenisher, while step（1）The anode overflowing liquid for obtaining is used as catholyte replenisher, directly
Complete to electro reclamation（The electro reclamation time is 20d）；
（3）After the completion of electro reclamation, catholyte and overflowing liquid are mixed to get into mixed solution, add alkali liquor（0.01mol/LKOH
Solution）It is 7 to control pH, is subsequently adding sulfide（0.04mol/LNa2S solution）, sulfide addition be sulphion with mix molten
Heavy metal ion mol ratio is 1.2 in liquid：1, after precipitation, stirring, standing, filtration, filtrate is purified solution, can be used as next electricity
Catholyte in dynamic repairing test.
Copper, Zn content in heavy metal contaminants, copper, Zn content and step in heavy metal contaminants after the completion of Jing electro reclamations
Suddenly（2）、（3）In in the purified solution that obtains copper, Zn content it is as shown in table 3.
Table 3
。
Embodiment 4
The electronic and precipitation combine d bioremediation mine tailing heavy metal contaminants（Mine tailing heavy metal contaminants sample is from mountain of papers city of Yunnan Province
Certain bargh, heavy metal content of Pb＆Zn is exceeded in sample）Method, it includes step in detail below：
（1）Electro reclamation operation：Heavy metal electro reclamation is carried out repairing in groove（As shown in Figure 1）, it is mine tailing to repair in the middle of groove
Heavy metal repairs groove（Mine tailing is repaired area 2 and is being repaired in the middle of groove, and it is 0.4m that mine tailing repairs the slot length of area 2）, the moon is placed respectively at two ends
Anelectrode（Anode region 3, cathode chamber 4 are located at repair groove two ends respectively, and in anode region 3, cathode chamber 4 anolyte and the moon are separately added into
Pole liquid, anolyte is combined for citric acid with Sodium Chloride, and content is respectively 0.1mol/L, 0.2mol/L, and catholyte is that Sodium Chloride is molten
Liquid, consumption is 0.3mol/L, and anode region 3, the Anodic of cathode chamber 4 and negative electrode are graphite）, it is logical for 0.5V/cm in voltage gradient
Electricity carries out electro reclamation, and it is 6～7 to maintain the moon or anolyte pH with replenisher, and collects anode and cathode overflowing liquid；
（2）Negative electrode overflowing liquid heavy metal precipitation：The step of receiving in 10h（1）The negative electrode overflowing liquid for obtaining adds alkali liquor
（0.01mol/LKOH solution）It is 7 to control pH, is subsequently adding sulfide（0.04mol/L Potassium monosulfide .s and sulfurated lime solution, wherein sulfur
The mass ratio for changing potassium and calcium sulfide is 1:1）, sulfide addition is sulphion and heavy metal ion mol ratio in negative electrode overflowing liquid
For 1.4：1, purified solution is obtained after stirring, standing, filtration, purified solution is used as repair process Anodic liquid replenisher, while
Step（1）The anode overflowing liquid for obtaining is used as catholyte replenisher, until electro reclamation is completed（The electro reclamation time is 20d）；
（3）After the completion of electro reclamation, catholyte and overflowing liquid are mixed to get into mixed solution, add alkali liquor（0.01mol/LKOH
Solution）It is 7 to control pH, is subsequently adding sulfide（0.04mol/L Potassium monosulfide .s and sulfurated lime solution, wherein Potassium monosulfide. and calcium sulfide
Mass ratio be 1:1）, sulfide addition is that heavy metal ion mol ratio is 1.4 in sulphion and mixed solution：1, precipitation,
After stirring, standing, filtration, filtrate is purified solution, can be used as the catholyte in next electro reclamation test.
Copper, Zn content in heavy metal contaminants, copper, Zn content and step in heavy metal contaminants after the completion of Jing electro reclamations
Suddenly（2）、（3）In in the purified solution that obtains copper, Zn content it is as shown in table 4.
Table 4
The specific embodiment of the present invention is explained in detail above in association with accompanying drawing, but the present invention is not limited to above-mentioned enforcement
Mode, in the ken that those of ordinary skill in the art possess, can be with the premise of without departing from present inventive concept
Various changes can be made.
Claims (5)
1. a kind of electronic methods with precipitation combine d bioremediation mine tailing heavy metal contaminants, it is characterised in that including walking in detail below
Suddenly：
（1）Electro reclamation operation：Heavy metal electro reclamation is carried out in groove repairing, is repaired in the middle of groove as the reparation of mine tailing heavy metal
Anodic-cathodic is placed respectively at groove, two ends, and energization carries out electro reclamation, and it is 6～7 to maintain the moon or anolyte pH with replenisher, and is received
Collection anode and cathode overflowing liquid；
（2）Negative electrode overflowing liquid heavy metal precipitation：By step（1）It is 7～8 that the negative electrode overflowing liquid for obtaining adds alkali liquor to control pH, so
After add sulfide solution, sulfide solution addition be sulphion with heavy metal ion mol ratio in negative electrode overflowing liquid be 1～
1.5：1, purified solution is obtained after stirring, standing, filtration, purified solution is used as repair process Anodic liquid replenisher, same to time step
Suddenly（1）The anode overflowing liquid for obtaining is used as catholyte replenisher, until electro reclamation is completed；
（3）After the completion of electro reclamation, catholyte and overflowing liquid are mixed to get into mixed solution, it is 7～8 to add alkali liquor to control pH,
Be subsequently adding sulfide solution, sulfide solution addition be sulphion with heavy metal ion mol ratio in mixed solution be 1～
1.5：1, after precipitation, stirring, standing, filtration, filtrate is purified solution, can be used as the catholyte in next electro reclamation test.
2. according to claim 1 electronic and precipitation combine d bioremediation mine tailing heavy metal contaminants methods, it is characterised in that：
The step（1）Middle catholyte is combined for organic acid with chlorate；Anolyte is chlorate.
3. according to claim 1 electronic and precipitation combine d bioremediation mine tailing heavy metal contaminants methods, it is characterised in that：
The step（1）Middle heavy metal electro reclamation voltage gradient is 0.5～2.0V/cm.
4. according to claim 1 electronic and precipitation combine d bioremediation mine tailing heavy metal contaminants methods, it is characterised in that：
The step（2）And step（3）Middle alkali liquor is sodium hydroxide, potassium hydroxide or calcium oxide.
5. according to claim 1 electronic and precipitation combine d bioremediation mine tailing heavy metal contaminants methods, it is characterised in that：
The step（2）And step（3）Middle sulfide is one or more arbitrary proportions in sodium sulfide, ammonium sulfide, Potassium monosulfide., calcium sulfide
Mixture.
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