CN104193121B - A kind of cyanide wastewater treatment process - Google Patents
A kind of cyanide wastewater treatment process Download PDFInfo
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- CN104193121B CN104193121B CN201410509831.1A CN201410509831A CN104193121B CN 104193121 B CN104193121 B CN 104193121B CN 201410509831 A CN201410509831 A CN 201410509831A CN 104193121 B CN104193121 B CN 104193121B
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Abstract
The invention discloses a kind of cyanide wastewater treatment process, the method is made up of electrochemical treatment, coagulating kinetics and biological activated carbon process three steps, electrochemical process for treating is adopted first to be removed by tractable prussiate, then by adding solution of zinc sulfate and coagulated agent carries out coagulating sedimentation, remove the metal top cradle in waste water and heavy metal ion, pollutent chemical process in waste water being difficult to remove finally by biological activated carbon treatment system is got rid of by method that is biological and physical adsorption.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 and advanced treatment is carried out to gold mine cyanide wastewater, 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 process can return the technological process of production and use or qualified discharge as reuse water.
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, a large amount of cyanide wastewaters can be produced, this part cyanide wastewater is not only containing a certain amount of hypertoxic prussiate, but also the heavy metal ion containing thiocyanate-, COD and copper, zinc, lead and so on, if can not get effective process, great environmental protection hidden danger will be produced.At present, the method of conventional process 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 process, produces ClCN product, causes secondary pollution problem, and the heavy metal ion such as copper, zinc, lead simultaneously in waste water fails 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, the waste residue produced in process heavy metal process is also more, easily causes secondary pollution.Therefore, also still lacking more satisfactory method in cyanide wastewater process, if resolve this problem, will important meaning had to development China's golden production and environmental protection development.
Summary of the invention
Object of the present invention is exactly the problems referred to above existed for existing treatment process, and provides the cyanide wastewater treatment process that a kind of technical process is simple, treatment effect good, processing efficiency is high, stable.The present invention is according to the feature containing multiple pollutants such as prussiate, thiocyanate-, COD and heavy metals in gold mine cyanide wastewater, particularly also comprise various unmanageable metal top cradle etc. in prussiate, electrochemical process for treating is adopted first to be removed by tractable prussiate, then by adding solution of zinc sulfate and coagulated agent carries out coagulating sedimentation, remove the metal top cradle in waste water and heavy metal ion, pollutent chemical process in waste water being difficult to remove finally by biological activated carbon treatment system is got rid of by method that is 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 the sodium chloride solution that mass percentage concentration is 5% ~ 50%, make waste water homogeneous;
(2) waste water after regulating enters into electrolyzer, and under the effect of direct supply regulating YIN and YANG battery lead plate, carry out electrochemical treatment, the treatment time is 30min ~ 360min;
(3) it is that 5% ~ 30% solution of zinc sulfate, flocculation agent and flocculation agent carry out coagulating sedimentation that the waste water after process adds mass percentage concentration successively under whipped state, and after coagulation, waste water enters settling tank and staticly settles 15min ~ 120min;
(4) supernatant liquor after precipitation enters biological activated carbon treatment system, and under the condition of active carbon filler, biofilm bacterial classification and air aeration, carry out biological activated carbon process, the treatment time is 30min ~ 120min;
(5) supernatant liquor after process 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 scribbling 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, flocculation agent to be mass percentage concentration be 10% ~ 30% polymer inorganic salt solution, flocculation agent to be mass percentage concentration be 0.3 ‰ ~ 0.5 ‰ polyacrylamide solution.
In described step (4), biological activated carbon treatment system is upflowing or downflow system reaction tank, water-distributing device and aerating apparatus is provided with at the bottom of pond, it is active carbon filler layer above aerating apparatus, 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 for manually gathering containing in cyanogen topsoil near Tailings Dam, be separated, what domestication was cultivated falls cyanogen flora, comprise bacillus pumilus to belong to, genera cryptococcus, pseudomonas etc., bacterial classification biofilm mode is taked 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 and advanced treatment is carried out to gold mine cyanide wastewater, 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 process can return 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 the sodium chloride solution that mass percentage concentration is 5% ~ 50%, make waste water homogeneous;
(2) waste water after regulating enters into electrolyzer, and under the effect of direct supply regulating YIN and YANG battery lead plate, carry out electrochemical treatment, the treatment time is 30min ~ 360min;
(3) waste water after process add successively under whipped state mass percentage concentration be 5% ~ 30% solution of zinc sulfate, flocculation agent and flocculation agent carry out coagulating sedimentation, after coagulation, waste water enters settling tank and staticly settles 15min ~ 120min;
(4) supernatant liquor after precipitation enters biological activated carbon treatment system, and under the condition of active carbon filler, biofilm bacterial classification and air aeration, carry out biological activated carbon process, the treatment time is 30min ~ 120min;
(5) supernatant liquor after process 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 scribbling 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, flocculation agent to be mass percentage concentration be 10% ~ 30% polymer inorganic salt solution, flocculation agent to be mass percentage concentration be 0.3 ‰ ~ 0.5 ‰ polyacrylamide solution.
In described step (4), biological activated carbon treatment system is upflowing or downflow system reaction tank, water-distributing device and aerating apparatus is provided with at the bottom of pond, it is active carbon filler layer above aerating apparatus, 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 for manually gathering containing in cyanogen topsoil near Tailings Dam, be separated, what domestication was cultivated falls cyanogen flora, comprise bacillus pumilus to belong to, genera cryptococcus, pseudomonas etc., bacterial classification biofilm mode is taked 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 are 204.25mg/L, other heavy metal ion in addition containing trace.Getting 3L waste water is placed in steel basin, add the NaCl solution 5mL of 30%, open whipping appts, after stirring, waste water is placed in electrolyzer and carries out electrolysis treatment, electrolyzer is rectangular tank, the inside is parallel is provided with three blocks of graphite anode plates and three pieces of stainless steel cathode plates, 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, the solution of zinc sulfate 3mL that mass percentage concentration is 10% is slowly added under stirring linear velocity is 0.8m/s condition, reaction 5min, the polymeric aluminum chlorides solution 8mL adding 10g/L stirs 5min, then the anionic polyacrylamide solution 4mL that mass percentage concentration is 0.5 ‰ is added, regulate after continuing to stir 2min and stir linear velocity 0.1m/s stirring 5min, stop stirring, leave standstill 15min, with peristaltic pump supernatant liquor is pumped in biological activated carbon reactor and processes, 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 process 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 process, 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 are 119.65mg/L, other heavy metal ion in addition containing trace.Getting 3L waste water is placed in steel basin, add the NaCl solution 5mL that mass percentage concentration is 30%, open whipping appts, after stirring, waste water is placed in electrolyzer and carries out electrolysis treatment, electrolyzer is rectangular tank, the inside is parallel is provided with three blocks of graphite anode plates and three pieces of stainless steel cathode plates, 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, the solution of zinc sulfate 2mL that mass percentage concentration is 10% is slowly added under stirring linear velocity is 0.8m/s condition, reaction 5min, the polymeric aluminum chlorides solution 8mL adding 10g/L stirs 5min, then adding mass percentage concentration is 0.5 ‰ anionic polyacrylamide solution 4mL, regulate after continuing to stir 2min and stir linear velocity 0.1m/s stirring 5min, stop stirring, leave standstill 15min, with peristaltic pump supernatant liquor is pumped in biological activated carbon reactor and processes, 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 process 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 process, 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 the sodium chloride solution that mass percentage concentration is 5% ~ 50%, make waste water homogeneous;
(2) waste water after regulating enters into electrolyzer, and under the effect of direct supply regulating YIN and YANG battery lead plate, carry out electrochemical treatment, the treatment time is 30min ~ 360min;
(3) waste water after process add successively under whipped state mass percentage concentration be 5% ~ 30% solution of zinc sulfate, flocculation agent and flocculation agent carry out coagulating sedimentation, after coagulation, waste water enters settling tank and staticly settles 15min ~ 120min;
(4) supernatant liquor after precipitation enters biological activated carbon treatment system, and under the condition of active carbon filler, biofilm bacterial classification and air aeration, carry out biological activated carbon process, the treatment time is 30min ~ 120min;
(5) supernatant liquor after process returns in the technological process of production or qualified discharge.
2. a kind of cyanide wastewater treatment process according to claim 1, it 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 scribbling 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, it 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. a kind of cyanide wastewater treatment process according to claims 1, it is characterized in that: in described step (4), biological activated carbon treatment system is upflowing or downflow system reaction tank, water-distributing device and aerating apparatus is provided with at the bottom of pond, it is active carbon filler layer above aerating apparatus, 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 is fall cyanogen flora containing what manually gather, be separated, tame cultivation in cyanogen topsoil near Tailings Dam, comprise bacillus pumilus genus, genera cryptococcus, pseudomonas, bacterial classification biofilm mode is taked manually to add bacterial classification biofilm or Biofilmculturing.
8. a kind of cyanide wastewater treatment process according to claim 1, it 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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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 |
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 |
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 |