CN104193121A - Treating method for cyanide waste water - Google Patents
Treating method for cyanide waste water Download PDFInfo
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- CN104193121A CN104193121A CN201410509831.1A CN201410509831A CN104193121A CN 104193121 A CN104193121 A CN 104193121A CN 201410509831 A CN201410509831 A CN 201410509831A CN 104193121 A CN104193121 A CN 104193121A
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- waste water
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- cyanide wastewater
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Abstract
The invention discloses a treating method for cyanide waste water. The method comprises three steps of electrochemical treatment, coagulating sedimentation treatment and bioactive carbon treatment; cyanide which is easy to treat is removed through the electrochemical treatment method first; coagulating sedimentation is conducted by adding a zinc sulfate solution and a coagulating agent to remove metal cyanogen complex compounds and heavy metal ions in the waste water; pollutants which are difficult to remove by the chemical methods in the waste water are removed according to a biological and physical adsorption method in the bioactive carbon treating system finally. According to the characteristic that the pollutants in gold mine cyanide waste water are complex and difficult to treat, the method integrates the electrochemical treatment technique, the coagulating sedimentation technique and the bioactive carbon treatment technique together to synergistically conduct advanced treatment on the gold mine cyanide waste water, and is good in treating effect, high in treating efficiency, stable in operation of the system, simple in technological process and convenient to realize industrial application; the treated waste water can be returned to a manufacturing technology process to be used as reused water or discharged after reaching the standard.
Description
Technical field
The present invention relates to field of Environment Protection Pollutant Treatment method, particularly a kind for the treatment of process of gold mine cyanide wastewater.
Background technology
Gold mine is in process of production owing to using Cyanide Process, can produce a large amount of cyanide wastewaters, this part cyanide wastewater not only contains a certain amount of hypertoxic prussiate, but also the heavy metal ion that contains thiocyanate-, COD and copper, zinc, lead and so on, if can not get effective processing, will produce great environmental protection hidden danger.At present, the conventional method of processing cyanide wastewater has acidifying absorption method, Pomolio-Celdecor process, Yin Kefa, sulfurous gas method etc. both at home and abroad, although adopt acidifying absorption method can reclaim a certain amount of prussiate, but because recovery of cyanide is not thorough, the remaining a certain amount of prussiate of meeting in waste water, thiocyanate ion and some heavy metal ion are not all effectively removed simultaneously.Chlorine residue that can be remaining a large amount of after Pomolio-Celdecor process processing, produces ClCN product, causes secondary pollution problem, and the heavy metal ion such as the copper in while waste water, zinc, lead fail effectively to be administered.Although Yin Kefa and sulfurous gas method can make cyanid up to standard, the thiocyanate-in waste water fails to be processed, and in addition, processes the waste residue producing in heavy metal process also more, easily causes secondary pollution.Therefore, aspect cyanide wastewater processing, also still lacking more satisfactory method, if resolve this problem, the gold production of development China and environmental protection development will had to important meaning.
Summary of the invention
Object of the present invention is exactly the problems referred to above that exist for existing treatment process, and the cyanide wastewater that a kind of technical process is simple, treatment effect good, processing efficiency is high, stable treatment process is provided.The present invention is according to the feature that contains the multiple pollutants such as prussiate, thiocyanate-, COD and heavy metal in gold mine cyanide wastewater, particularly in prussiate, also comprise various unmanageable metal cyano complexs etc., adopt electrochemical process for treating first tractable prussiate to be removed, then by adding solution of zinc sulfate and coagulated agent, carry out coagulating sedimentation, remove metal cyano complex and heavy metal ion in waste water, the pollutent that finally by biological activated carbon treatment system, chemical process in waste water is difficult to remove is got rid of by the method for biological and physical adsorption.Concrete technology step is as follows:
(1) adopt acid-base reagent to regulate the pH value of waste water between 8～10, add mass percentage concentration and be 5%～50% sodium chloride solution, make waste water homogeneous;
(2) waste water after adjusting enters into electrolyzer, under the effect of direct supply regulating YIN and YANG battery lead plate, carries out electrochemical treatment, and the treatment time is 30min～360min;
(3) under whipped state, to add successively mass percentage concentration be that 5%～30% solution of zinc sulfate, flocculation agent and flocculation agent carry out coagulating sedimentation to the waste water after processing, and after coagulation, waste water enters settling tank and staticly settles 15min～120min;
(4) supernatant liquor 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 treatment time is 30min～120min;
(5) supernatant liquor after processing returns in the technological process of production or qualified discharge.
In described step (1), acid-base reagent is sulfuric acid, hydrochloric acid, sodium hydroxide solution or milk of lime.
In described step (2), the positive plate in electrolyzer is graphite cake, iron plate or the metal sheet that scribbles metal oxide, and negative plate is iron plate, stainless steel plate, other metal or alloy plates.
In described step (3), stirring linear velocity is 0.01m/s～10m/s, and flocculation agent is that mass percentage concentration is 10%～30% polymer inorganic salt solution, and flocculation agent is that mass percentage concentration is 0.3 ‰～0.5 ‰ polyacrylamide solution.
In described step (4), biological activated carbon treatment system is upflowing or downflow system reaction tank, at the bottom of pond, be provided with water-distributing device and aerating apparatus, aerating apparatus top is active carbon filler layer, gac is coconut husk charcoal or ature of coal charcoal, dress charcoal amount accounts for 1/5～4/5 of reactor volume, biofilm bacterial classification is containing manually gathering in cyanogen topsoil near Tailings Dam, separated, domestication is cultivated falls cyanogen flora, comprise that bacillus pumilus belongs to, genera cryptococcus, pseudomonas etc., bacterial classification biofilm mode takes manually to add bacterial classification biofilm or Biofilmculturing, vapour-liquid ratio is set as 1～15:1.
Beneficial effect of the present invention:
The present invention is according to, unmanageable feature complicated containing pollutent in gold mine cyanide wastewater, electrochemical treatment technology, coagulating sedimentation technology and biological activated carbon treatment technology are combined, work in coordination with gold mine cyanide wastewater is carried out to advanced treatment, treatment effect is good, processing efficiency is high, system run all right, technical process is simple, is convenient to realize industrial application, and the waste water after processing can return to the technological process of production and use or qualified discharge as reuse water.
Embodiment
The present invention includes following steps:
(1) adopt acid-base reagent to regulate the pH value of waste water between 8～10, add mass percentage concentration and be 5%～50% sodium chloride solution, make waste water homogeneous;
(2) waste water after adjusting enters into electrolyzer, under the effect of direct supply regulating YIN and YANG battery lead plate, carries out electrochemical treatment, and the treatment time is 30min～360min;
(3) under whipped state, to add successively mass percentage concentration be that 5%～30% solution of zinc sulfate, flocculation agent and flocculation agent carry out coagulating sedimentation to the waste water after processing, and after coagulation, waste water enters settling tank and staticly settles 15min～120min;
(4) supernatant liquor 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 treatment time is 30min～120min;
(5) supernatant liquor after processing returns in the technological process of production or qualified discharge.
In described step (1), acid-base reagent is sulfuric acid, hydrochloric acid, sodium hydroxide solution or milk of lime.
In described step (2), the positive plate in electrolyzer is graphite cake, iron plate or the metal sheet that scribbles metal oxide, and negative plate is iron plate, stainless steel plate, other metal or alloy plates.
In described step (3), stirring linear velocity is 0.01m/s～10m/s, and flocculation agent is that mass percentage concentration is 10%～30% polymer inorganic salt solution, and flocculation agent is that mass percentage concentration is 0.3 ‰～0.5 ‰ polyacrylamide solution.
In described step (4), biological activated carbon treatment system is upflowing or downflow system reaction tank, at the bottom of pond, be provided with water-distributing device and aerating apparatus, aerating apparatus top is active carbon filler layer, gac is coconut husk charcoal or ature of coal charcoal, dress charcoal amount accounts for 1/5～4/5 of reactor volume, biofilm bacterial classification is containing manually gathering in cyanogen topsoil near Tailings Dam, separated, domestication is cultivated falls cyanogen flora, comprise that bacillus pumilus belongs to, genera cryptococcus, pseudomonas etc., bacterial classification biofilm mode takes manually to add bacterial classification biofilm or Biofilmculturing, vapour-liquid ratio is set as 1～15:1.
Specific examples 1:
Certain gold mine cyanide wastewater, pH is 9.6, CN
tfor 526.57mg/L, SCN
-for 15.35mg/L, Cu
2+for 112.72mg/L, COD is 204.25mg/L, contains in addition other heavy metal ion of trace.Getting 3L waste water is placed in steel basin, add 30% NaCl solution 5mL, open whipping appts, after stirring, waste water is placed in and in electrolyzer, carries out electrolysis treatment, electrolyzer is rectangular tank, 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 the positive pole of direct supply, positive plate is connected to the positive pole of direct supply, after electrolysis treatment 120min, waste water is moved in steel basin, open and stir, stirring linear velocity, be that under 0.8m/s condition, slowly to add mass percentage concentration be 10% solution of zinc sulfate 3mL, reaction 5min, the polymeric aluminum chlorides solution 8mL that adds 10g/L stirs 5min, then add mass percentage concentration and be 0.5 ‰ anionic polyacrylamide solution 4mL, after continuing to stir 2min, regulate stirring linear velocity 0.1m/s to stir 5min, stop stirring, standing 15min, with peristaltic pump, supernatant liquor is pumped in biological activated carbon reactor and is processed, biological activated carbon reactor is upflowing bio-reactor, gac adopts column ature of coal charcoal, amount of fill is 2kg, air adopts Ti-alloyed filter element micro-pore aeration, be placed in reactor bottom, vapour-liquid ratio is set as 5:1, bacterial classification adopts and manually adds biofilm, reaction time is 60min.The water outlet of waste water after system is processed through assay pH between 8～9, CN
t< 0.1mg/L, SCN
-< 0.5mg/L, Cu
2+< 0.5mg/L, COD < 20mg/L, first kind pollutent is all within the highest permission emission concentration limit value, and after processing, water quality can reach reuse or emission standard.
Specific examples 2:
Certain gold mine cyanide wastewater, pH is 9.2, CN
tfor 445.23mg/L, SCN
-for 16.69mg/L, Cu
2+for 48.55mg/L, Pb
2+for 8.75mg/L, COD is 119.65mg/L, contains in addition other heavy metal ion of trace.Getting 3L waste water is placed in steel basin, add mass percentage concentration and be 30% NaCl solution 5mL, open whipping appts, after stirring, waste water is placed in and in electrolyzer, carries out electrolysis treatment, electrolyzer is rectangular tank, 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 the positive pole of direct supply, positive plate is connected to the positive pole of direct supply, after electrolysis treatment 120min, waste water is moved in steel basin, open and stir, stirring linear velocity, be that under 0.8m/s condition, slowly to add mass percentage concentration be 10% solution of zinc sulfate 2mL, reaction 5min, the polymeric aluminum chlorides solution 8mL that adds 10g/L stirs 5min, then adding mass percentage concentration is 0.5 ‰ anionic polyacrylamide solution 4mL, after continuing to stir 2min, regulate stirring linear velocity 0.1m/s to stir 5min, stop stirring, standing 15min, with peristaltic pump, supernatant liquor is pumped in biological activated carbon reactor and is processed, biological activated carbon reactor is upflowing bio-reactor, gac adopts column ature of coal charcoal, amount of fill is 2kg, air adopts Ti-alloyed filter element micro-pore aeration, be placed in reactor bottom, vapour-liquid ratio is set as 5:1, bacterial classification adopts and manually adds biofilm, reaction time is 60min.The water outlet of waste water after system is processed through assay pH between 8～9, CN
t< 0.1mg/L, SCN
-< 0.5mg/L, Cu
2+< 0.5mg/L, COD < 20mg/L, first kind pollutent is all within the highest permission emission concentration limit value, and after processing, water quality can reach reuse or emission standard.
Claims (8)
1. a cyanide wastewater treatment process, the step of the method is as follows:
(1) adopt acid-base reagent to regulate the pH value of waste water between 8～10, add mass percentage concentration and be 5%～50% sodium chloride solution, make waste water homogeneous;
(2) waste water after adjusting enters into electrolyzer, under the effect of direct supply regulating YIN and YANG battery lead plate, carries out electrochemical treatment, and the treatment time is 30min～360min;
(3) under whipped state, to add successively mass percentage concentration be that 5%～30% solution of zinc sulfate, flocculation agent and flocculation agent carry out coagulating sedimentation to the waste water after processing, and after coagulation, waste water enters settling tank and staticly settles 15min～120min;
(4) supernatant liquor 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 treatment time is 30min～120min;
(5) supernatant liquor after processing returns in the technological process of production or qualified discharge.
2. a kind of cyanide wastewater treatment process according to claim 1, is characterized in that: in described step (1), acid-base reagent is sulfuric acid, hydrochloric acid, sodium hydroxide solution or milk of lime.
3. a kind of cyanide wastewater treatment process according to claim 1, it is characterized in that: in described step (2), positive plate in electrolyzer is graphite cake, iron plate or the metal sheet that scribbles metal oxide, and negative plate is iron plate, stainless steel plate, other metal or alloy plates.
4. a kind of cyanide wastewater treatment process according to claim 1, is characterized in that: in described step (3), stirring linear velocity is 0.01m/s～10m/s.
5. a kind of cyanide wastewater treatment process according to claim 1, it is characterized in that: in described step (3), flocculation agent is the polymer inorganic salt solution of mass percentage concentration 10%～30%, and flocculation agent is the polyacrylamide solution of mass percentage concentration 0.3 ‰～0.5 ‰.
6. according to a kind of cyanide wastewater treatment process described in claims 1, it is characterized in that: in described step (4), biological activated carbon treatment system is upflowing or downflow system reaction tank, at the bottom of pond, be provided with water-distributing device and aerating apparatus, aerating apparatus top is active carbon filler layer, gac is coconut husk charcoal or ature of coal charcoal, and dress charcoal amount accounts for 1/5～4/5 of reactor volume.
7. a kind of cyanide wastewater treatment process according to claim 1, it is characterized in that: in described step (4), biofilm bacterial classification near Tailings Dam containing manually gathering in cyanogen topsoil, separated, domestication is cultivated falls cyanogen flora, comprise bacillus pumilus genus, genera cryptococcus, pseudomonas etc., bacterial classification biofilm mode takes manually to add bacterial classification biofilm or Biofilmculturing.
8. a kind of cyanide wastewater treatment process according to claim 1, is characterized in that: in described step (4), biological activated carbon treatment system vapour-liquid ratio is set as 1～15:1.
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Cited By (5)
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| CN106315943A (en) * | 2015-06-30 | 2017-01-11 | 铜仁市万山区盛和矿业有限责任公司 | Method for processing gold mine wastewater |
| CN108220197A (en) * | 2018-01-10 | 2018-06-29 | 南京林业大学 | A kind of gold tailings slag microorganism combined processing and application process |
| CN109809650A (en) * | 2019-03-29 | 2019-05-28 | 江苏京源环保股份有限公司 | A kind of cyanide wastewater electrocatalytic oxidation processing method and system |
| CN113415959A (en) * | 2021-08-25 | 2021-09-21 | 湖南江山春锦科技有限公司 | Modular acid mine wastewater treatment equipment |
| CN115043475A (en) * | 2022-05-31 | 2022-09-13 | 广东邦普循环科技有限公司 | Treatment method of wastewater containing iron-cyanogen complex and oxalate |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108220197A (en) * | 2018-01-10 | 2018-06-29 | 南京林业大学 | A kind of gold tailings slag microorganism combined processing and application process |
| CN109809650A (en) * | 2019-03-29 | 2019-05-28 | 江苏京源环保股份有限公司 | A kind of cyanide wastewater electrocatalytic oxidation processing method and system |
| CN113415959A (en) * | 2021-08-25 | 2021-09-21 | 湖南江山春锦科技有限公司 | Modular acid mine wastewater treatment equipment |
| CN113415959B (en) * | 2021-08-25 | 2021-12-31 | 湖南江山春锦科技有限公司 | Modular acid mine wastewater treatment equipment |
| CN115043475A (en) * | 2022-05-31 | 2022-09-13 | 广东邦普循环科技有限公司 | Treatment method of wastewater containing iron-cyanogen complex and oxalate |
| CN115043475B (en) * | 2022-05-31 | 2023-06-13 | 广东邦普循环科技有限公司 | Treatment method of wastewater containing iron-cyanide complex and oxalate |
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Address after: 130012 nanhu road, Jilin, Changchun, No. 6760 Patentee after: Changchun Gold Research Institute Co., Ltd. Address before: 130012 nanhu road, Jilin, Changchun, No. 6760 Patentee before: Changchun Gold Research Institute |
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