CN104261624B - One gold cyaniding enterprise Treatment of cyanogen-contained wastewater - Google Patents
One gold cyaniding enterprise Treatment of cyanogen-contained wastewater Download PDFInfo
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- CN104261624B CN104261624B CN201410514179.2A CN201410514179A CN104261624B CN 104261624 B CN104261624 B CN 104261624B CN 201410514179 A CN201410514179 A CN 201410514179A CN 104261624 B CN104261624 B CN 104261624B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/18—Cyanides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/10—Packings; Fillings; Grids
- C02F3/105—Characterized by the chemical composition
- C02F3/106—Carbonaceous materials
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- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention discloses a kind of gold cyaniding enterprise Treatment of cyanogen-contained wastewater, the method is by electrochemical treatments, chemical oxidation treatment, coagulating sedimentation is processed and biological activated carbon is processed four step compositions, first cyanide wastewater adopts electrochemical process for treating to carry out electrolytic treatments to cyanide in the time processing, then carry out coagulating sedimentation by adding coagulated agent, remove the heavy metal contaminants in waste water, waste water after precipitation adds chemical reagent and carries out oxidation processes, the pollutant that finally by biological activated carbon treatment system, chemical method in waste water is difficult to remove is got rid of by the method for biological and physical absorption. the present invention is according to containing pollutant complexity, unmanageable feature in gold manufacturing enterprise cyanide wastewater, four steps are combined, work in coordination with gold manufacturing enterprise cyanide wastewater is carried out to advanced treating, have advantages of that treatment effect is good, treatment effeciency is high, system run all right, technological process are simple, be convenient to realize commercial Application, waste water after treatment can return to the technological process of production and use or qualified discharge as recycled water.
Description
Technical field
The present invention relates to field of Environment Protection pollutant processing method, particularly a kind of gold cyaniding enterprise is containing cyanogenThe processing method of waste water.
Background technology
Gold cyaniding enterprise owing to using Cyanide Process, can produce a large amount of in the ore dressing process of goldCyanide wastewater, this part cyanide wastewater not only contains a certain amount of hypertoxic cyanide, but also contains sulphurThe heavy metal ion of cyanate and copper, zinc, lead and so on, if can not get effective processing, will produceGreat environmental protection hidden danger. At present, the method for conventional Treatment of Cyanide-containing Wastewater has acidifying absorption method, alkali both at home and abroadChlorine method, Yin Kefa, sulfur dioxide method etc., although adopt acidifying absorption method can reclaim a certain amount of cyanidingThing, but because recovery of cyanide is not thorough, can remaining a certain amount of cyanide, simultaneously thiocyanic acid in waste waterRoot and some heavy metal ion are not all effectively removed. More than can be remaining a large amount of after Pomolio-Celdecor process processingChlorine, produces ClCN product, causes secondary pollution problem, simultaneously the heavy metal such as the copper in waste water, zinc, leadIon fails effectively to be administered. Although Yin Kefa and sulfur dioxide method can make cyanid up to standard,But the rhodanate in waste water fails to be processed, in addition, the waste residue producing in processing heavy metal process alsoMore, easily cause secondary pollution. Therefore, aspect cyanide wastewater processing, also still lack more satisfactoryMethod, if resolve this problem, the sustainable development to China's gold industry and gold mineEnvironmental protection will have important meaning.
Summary of the invention
Object of the present invention is exactly the problems referred to above that exist for existing processing method, and a kind of technique is providedThe Treatment of cyanogen-contained wastewater that flow process is simple, treatment effect good, treatment effeciency is high, stable. ThisBright according to containing the multiple pollutants such as cyanide, rhodanate and heavy metal in gold mine cyanide wastewaterFeature, adopts electrochemical process for treating first cyanide to be carried out to electrolytic treatments, then by adding coagulationMedicament carries out coagulating sedimentation, removes the heavy metal contaminants in waste water, and the waste water after precipitation adds chemistry examinationOxidation processes is carried out in agent, finally by biological activated carbon treatment system, chemical method in waste water is difficult to removePollutant get rid of by the method for biological and physical absorption. Concrete technology step is as follows:
(1) adopt acid-base reagent to regulate the pH value of waste water between 8～11, add and add mass fraction and be5%～50% sodium chloride solution, makes waste water homogeneous;
(2) waste water after adjusting enters into electrolytic cell, under the effect of dc source harmonizing yinyang battery lead plate, entersRow electrochemical treatments, the processing time is 30min～360min;
(3) waste water after electrochemical treatments is moved in tank diameter, under stirring, add oxidant andCatalyst carries out oxidation processes, processing time 10min～60min;
(4) waste water after oxidation processes adds successively flocculating agent and flocculant carries out coagulation under stirringPrecipitation, after coagulation, waste water enters sedimentation basin and staticly settles 15min～120min;
(5) supernatant after precipitation enters biological activated carbon treatment system, active carbon filler, biofilm bacteriumUnder the condition of kind and air aeration, carry out biological activated carbon processing, the processing time is 30min～120min;
(6) supernatant after treatment returns in the technological process of production or qualified discharge.
In described step (1), sour reagent is sulfuric acid or hydrochloric acid, and base reagent is sodium hydroxide solution or limeBreast.
In described step (2), the positive plate in electrolytic cell is graphite cake, iron plate or scribbles metal oxideMetallic plate, minus plate is iron plate, corrosion resistant plate, other metal or alloy plates.
In described step (3), stirring linear velocity is 0.01m/s～10m/s, and oxidant is hydrogen peroxide solution,Catalyst is copper-bath.
In described step (4), stirring linear velocity is 0.01m/s～10m/s, and flocculating agent is for adding mass fraction10%～30% macromolecule inorganic salt solution, flocculant is the polyacrylamide of mass fraction 0.3 ‰～0.5 ‰Solution.
In described step (5), biological activated carbon treatment system is up flow type or downflow system reaction tank, at the bottom of pondBe provided with water-distributing device and aerator, aerator top is active carbon filler layer, and active carbon is coconut husk charcoalOr ature of coal charcoal, dress charcoal amount accounts for 1/5～4/5 of reactor volume, and biofilm bacterial classification, for falling cyanogen flora, falls cyanogen floraFor in Pseudomonas fluorescens, pseudomonas putida, Pseudomonas stutzeri, Nocard's bacillus and bacillusThe combination of one or more, falls cyanogen flora and is collected near the topsoil of Tailings Dam, bacterial classification biofilm modeTake manually to add bacterial classification biofilm or Biofilmculturing, gas liquid ratio is set as 1～15:1.
Beneficial effect of the present invention:
The present invention, will according to containing pollutant complexity, unmanageable feature in gold manufacturing enterprise cyanide wastewaterElectrochemical treatments technology, chemical oxidation treatment technology, coagulating sedimentation technology and biological activated carbon treatment technologyCombine, collaborative gold manufacturing enterprise cyanide wastewater carried out to advanced treating, have treatment effect good,Treatment effeciency is high, system run all right, technological process simple, be convenient to realize the advantage of commercial Application, locatesWaste water after reason can return to the technological process of production and use or qualified discharge as recycled water.
Detailed description of the invention
The present invention includes following steps:
(1) adopt acid-base reagent to regulate the pH value of waste water between 8～11, add and add mass fraction and be5%～50% sodium chloride solution, makes waste water homogeneous;
(2) waste water after adjusting enters into electrolytic cell, under the effect of dc source harmonizing yinyang battery lead plate, entersRow electrochemical treatments, the processing time is 30min～360min;
(3) waste water after electrochemical treatments is moved in tank diameter, under stirring, add oxidant andCatalyst carries out oxidation processes, processing time 10min～60min;
(4) waste water after oxidation processes adds successively flocculating agent and flocculant carries out coagulation under stirringPrecipitation, after coagulation, waste water enters sedimentation basin and staticly settles 15min～120min;
(5) supernatant after precipitation enters biological activated carbon treatment system, active carbon filler, biofilm bacteriumUnder the condition of kind and air aeration, carry out biological activated carbon processing, the processing time is 30min～120min;
(6) supernatant after treatment returns in the technological process of production or qualified discharge.
In described step (1), sour reagent is sulfuric acid or hydrochloric acid, and base reagent is sodium hydroxide solution or limeBreast.
In described step (2), the positive plate in electrolytic cell is graphite cake, iron plate or scribbles metal oxideMetallic plate, minus plate is iron plate or corrosion resistant plate or other metallic plates or alloy sheets.
In described step (3), stirring linear velocity is 0.01m/s～10m/s, and oxidant is hydrogen peroxide solution,Catalyst is copper-bath.
In described step (4), stirring linear velocity is 0.01m/s～10m/s, and flocculating agent is for adding mass fraction10%～30% macromolecule inorganic salt solution, flocculant is the polyacrylamide of mass fraction 0.3 ‰～0.5 ‰Solution.
In described step (5), biological activated carbon treatment system is up flow type or downflow system reaction tank, at the bottom of pondBe provided with water-distributing device and aerator, aerator top is active carbon filler layer, and active carbon is coconut husk charcoalOr ature of coal charcoal, dress charcoal amount accounts for 1/5～4/5 of reactor volume, and biofilm bacterial classification, for falling cyanogen flora, falls cyanogen floraFor in Pseudomonas fluorescens, pseudomonas putida, Pseudomonas stutzeri, Nocard's bacillus and bacillusThe combination of one or more, falls cyanogen flora and is collected near the topsoil of Tailings Dam, bacterial classification biofilm modeTake manually to add bacterial classification biofilm or Biofilmculturing, gas liquid ratio is set as 1～15:1.
Instantiation 1:
Certain gold mine cyanide wastewater, pH is 9.6, CNTFor 226.25mg/L, SCN—For 78.24mg/L,Cu2+For 65.86mg/L, Fe3+For 7.26mg/L, COD is 214.28mg/L, contains in addition its of traceIts heavy metal ion. Get 3L waste water and be placed in tank diameter, add mass fraction and be 30% NaCl solution 5mL,Open agitating device, after stirring, waste water is placed in electrolytic cell and carries out electrolytic treatments, electrolytic cell is squareShape groove, parallel three blocks of graphite anode plates and three stainless steel cathode plates of being provided with in the inside, positive plate is connected to directlyThe positive pole of stream power supply, positive plate is connected to the positive pole of dc source, after electrolytic treatments 120min, will give upWater moves in tank diameter, and open and stir, be under 0.8m/s condition stirring linear velocity, add mass fraction 30%Hydrogen peroxide solution 10mL, the copper-bath 0.5mL of mass fraction 5%, reaction 30min, then addThe polymeric aluminum chlorides solution 30mL of 10g/L stirs 5min, then adds mass fraction 0.5 ‰ anion pp acylsAmine aqueous solution 5mL, continues to regulate stirring linear velocity 0.1m/s to stir 5min after stirring 2min, stops stirring, quietPut 30min, supernatant is pumped in biological activated carbon reactor and is processed, biological activated carbon with peristaltic pumpReactor is up flow type bioreactor, and active carbon adopts column ature of coal charcoal, and amount of fill is 5kg, and air adoptsTi-alloyed filter element micro-pore aeration, is placed in reactor bottom, and gas liquid ratio is set as 3:1, and bacterial classification adopts and manually addsBiofilm, reaction time is 60min. Waste water through system water outlet after treatment through assay pH 8～9Between, CNT＜0.1mg/L，SCN—＜0.5mg/L，Cu2+< 0.5mg/L, COD < 20mg/L, firstPollutant is all within the highest permission concentration of emission limit value, and after processing, water quality can reach reuse or discharge standard.
Instantiation 2:
Certain gold mine cyanide wastewater, pH is 10.5, CNTFor 365.54mg/L, SCN—For 43.65mg/L,Cu2+For 26.62mg/L, Pb2+For 8.37mg/L, COD is 135.45mg/L, contains in addition its of traceIts heavy metal ion. Get 3L waste water and be placed in tank diameter, add the NaCl solution 5mL of mass fraction 30%,Open agitating device, after stirring, waste water is placed in electrolytic cell and carries out electrolytic treatments, electrolytic cell is squareShape groove, parallel three blocks of graphite anode plates and three stainless steel cathode plates of being provided with in the inside, positive plate is connected to directlyThe positive pole of stream power supply, positive plate is connected to the positive pole of dc source, after electrolytic treatments 120min, will give upWater moves in tank diameter, and open and stir, be under 0.8m/s condition stirring linear velocity, add mass fraction 30%Hydrogen peroxide solution 15mL, the copper-bath 0.8mL of mass fraction 5%, reaction 30min, then addThe polymeric aluminum chlorides solution 22mL of 10g/L stirs 5min, then adds mass fraction 0.5 ‰ anion pp acylsAmine aqueous solution 4mL, continues to regulate stirring linear velocity 0.1m/s to stir 5min after stirring 2min, stops stirring, quietPut 30min, supernatant is pumped in biological activated carbon reactor and is processed, biological activated carbon with peristaltic pumpReactor is up flow type bioreactor, and active carbon adopts column ature of coal charcoal, and amount of fill is 5kg, and air adoptsTi-alloyed filter element micro-pore aeration, is placed in reactor bottom, and gas liquid ratio is set as 3:1, and bacterial classification adopts and manually addsBiofilm, reaction time is 60min. Waste water through system water outlet after treatment through assay pH 8～9Between, CNT＜0.1mg/L，SCN—＜0.5mg/L，Cu2+< 0.5mg/L, COD < 20mg/L, firstPollutant is all within the highest permission concentration of emission limit value, and after processing, water quality can reach reuse or discharge standard.
Claims (9)
1. a gold cyaniding enterprise Treatment of cyanogen-contained wastewater, the step of the method is as follows:
(1) adopt acid-base reagent to regulate the pH value of waste water between 8 ~ 11, adding mass fraction is 5% ~ 50% sodium chloride solution, makes waste water homogeneous;
(2) waste water after adjusting enters into electrolytic cell, under the effect of dc source harmonizing yinyang battery lead plate, carries out electrochemical treatments, and the processing time is 30min ~ 360min;
(3) waste water after electrochemical treatments is moved in tank diameter, under stirring, add oxidant and catalyst to carry out oxidation processes, processing time 10min ~ 60min;
(4) waste water after oxidation processes adds successively flocculating agent and flocculant carries out coagulating sedimentation under stirring, and after coagulation, waste water enters sedimentation basin and staticly settles 15min ~ 120min;
(5) supernatant after precipitation enters biological activated carbon treatment system, under the condition of active carbon filler, biofilm bacterial classification and air aeration, carries out biological activated carbon processing, and the processing time is 30min ~ 120min;
(6) supernatant after treatment returns in the technological process of production or qualified discharge.
2. a kind of gold cyaniding according to claim 1 enterprise Treatment of cyanogen-contained wastewater, is characterized in that: in described step (1), sour reagent is sulfuric acid or hydrochloric acid, and base reagent is sodium hydroxide solution or milk of lime.
3. a kind of gold cyaniding according to claim 1 enterprise Treatment of cyanogen-contained wastewater, it is characterized in that: in described step (2), positive plate in electrolytic cell is graphite cake, iron plate or the metallic plate that scribbles metal oxide, and minus plate is iron plate or corrosion resistant plate.
4. a kind of gold cyaniding according to claim 1 enterprise Treatment of cyanogen-contained wastewater, is characterized in that: in described step (3), stirring linear velocity is 0.01m/s ~ 10m/s.
5. a kind of gold cyaniding according to claim 1 enterprise Treatment of cyanogen-contained wastewater, is characterized in that: in described step (3), oxidant is hydrogen peroxide solution, and catalyst is copper-bath.
6. a kind of gold cyaniding according to claim 1 enterprise Treatment of cyanogen-contained wastewater, is characterized in that: in described step (4), stirring linear velocity is 0.01m/s ~ 10m/s.
7. a kind of gold cyaniding according to claim 1 enterprise Treatment of cyanogen-contained wastewater, it is characterized in that: in described step (4), flocculating agent is the macromolecule inorganic salt solution of mass fraction 10% ~ 30%, and flocculant is the polyacrylamide solution of mass fraction 0.3 ‰ ~ 0.5 ‰.
8. a kind of gold cyaniding according to claim 1 enterprise Treatment of cyanogen-contained wastewater, it is characterized in that: in described step (5), biofilm bacterial classification is for falling cyanogen flora, one or more the combination in Pseudomonas fluorescens, pseudomonas putida, Pseudomonas stutzeri, Nocard's bacillus and bacillus cyanogen flora falls is, fall cyanogen flora and be collected near the topsoil of Tailings Dam, bacterial classification biofilm mode takes manually to add bacterial classification biofilm or Biofilmculturing.
9. a kind of gold cyaniding according to claim 1 enterprise Treatment of cyanogen-contained wastewater, is characterized in that: in described step (5), biological activated carbon treatment system gas liquid ratio is set as 1 ~ 15:1.
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| CN109626678A (en) * | 2019-02-25 | 2019-04-16 | 湖南馨湘碧浪环保科技有限公司 | A kind of method of the harmless processing of cyaniding tailing slurry |
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| CN105198120A (en) * | 2015-10-15 | 2015-12-30 | 桂林市春晓环保科技有限公司 | Method for removing cyanide in tailing wastewater |
| CN106396205B (en) * | 2016-08-30 | 2019-06-14 | 盛隆资源再生（无锡）有限公司 | A kind of method of high concentration cyanide wastewater broken cyanide removing heavy metals |
| CN107176760A (en) * | 2017-06-26 | 2017-09-19 | 中电环保股份有限公司 | A kind of high salt advance for the treatment of process of cyanide-bearing effluent and processing system |
| CN112093947B (en) * | 2020-09-21 | 2022-08-23 | 招金矿业股份有限公司 | Method for removing heavy metals by cyanogen breaking of high-concentration cyanide-containing wastewater in gold production |
| CN112939322B (en) * | 2021-02-07 | 2022-12-23 | 郑州航空工业管理学院 | Water treatment method for sudden oil pollution of drinking water |
| CN112980723B (en) * | 2021-02-22 | 2022-07-12 | 中南大学 | High-arsenic-resistant thiocyanide degradation strain and application thereof |
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| WO2005082788A1 (en) * | 2004-03-01 | 2005-09-09 | Aquenox Pty Ltd | Fluoride species removal process |
| CN102515401B (en) * | 2011-12-31 | 2013-09-11 | 长沙华时捷环保科技发展有限公司 | Cyanide wastewater degradation system and cyanide wastewater degradation method thereof |
| CN103253834A (en) * | 2013-06-04 | 2013-08-21 | 长春黄金研究院 | Deep treatment method for cyanide-containing waste water of tailings pond in gold industry |
| CN103253796B (en) * | 2013-06-04 | 2014-07-16 | 长春黄金研究院 | Method for processing waste water containing cyanide, thiocyanogen and heavy metal |
| CN103922524B (en) * | 2014-05-14 | 2015-03-11 | 山东盛阳集团有限公司 | Advanced treatment method for coking wastewater |
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| CN109626678A (en) * | 2019-02-25 | 2019-04-16 | 湖南馨湘碧浪环保科技有限公司 | A kind of method of the harmless processing of cyaniding tailing slurry |
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