CN104176888B - A kind of gold manufacturing enterprises Treatment of cyanogen-contained wastewater - Google Patents
A kind of gold manufacturing enterprises Treatment of cyanogen-contained wastewater Download PDFInfo
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- CN104176888B CN104176888B CN201410456557.6A CN201410456557A CN104176888B CN 104176888 B CN104176888 B CN 104176888B CN 201410456557 A CN201410456557 A CN 201410456557A CN 104176888 B CN104176888 B CN 104176888B
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Abstract
The invention discloses a kind of gold manufacturing enterprises Treatment of cyanogen-contained wastewater, the method is made up of electrochemical treatment, coagulating kinetics, ozone Oxidation Treatment and biological activated carbon process four steps; First tractable prussiate is removed with electrochemical treatment when processing by cyanide wastewater, waste water after process is by adding solution of zinc sulfate and coagulating agent carries out coagulating sedimentation, remove the metal top cradle in waste water and heavy metal ion, then get supernatant liquor to pass into ozone and be oxidized, fallen by the pollutant removal such as difficult prussiate, thiocyanate-of waste water remnants, 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 carries out advanced treatment to cyanide wastewater, and treatment effect is good, processing efficiency is high, and technical process is simple, 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 manufacturing enterprises cyanide wastewater.
Background technology
Gold manufacturing enterprises in the exploitation and smelting process of gold due to use prussiate, a large amount of cyanide wastewater can be produced, this part cyanide wastewater is not only containing a certain amount of hypertoxic prussiate, but also contain the heavy metal ion of thiocyanate-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 Treatment of Cyanide-containing 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 Treatment of cyanogen-contained wastewater that a kind of technical process is simple, treatment effect good, processing efficiency is high, stable.The present invention contains prussiate according in gold mine cyanide wastewater, the feature of the multiple pollutant such as thiocyanate-and heavy metal, particularly also comprise 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, waste water after precipitation passes into ozone and is oxidized, by the difficult prussiate of waste water remnants, the pollutant removals such as thiocyanate-fall, 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 5% ~ 50% sodium chloride solution, 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 adds 5% ~ 30% solution of zinc sulfate, flocculation agent and flocculation agent successively and carries out coagulating sedimentation under whipped state, and after coagulation, waste water enters settling tank and staticly settles 15min ~ 120min;
(4) supernatant liquor after precipitation passes into ozone and carries out ozone oxidation reaction, and the reaction times is 15min ~ 120min;
(5) reacted waste water 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;
(6) 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, and flocculation agent is the polymer inorganic salt solution of 10% ~ 30%, and flocculation agent is the polyacrylamide solution of 0.3 ‰ ~ 0.5 ‰.
In described step (4), ozone intake is determined according to the number of the remaining prussiate in influent quality and COD content and processing requirements, prussiate and COD content is high, process index request tight, the intake of ozone is corresponding to be increased, otherwise, prussiate and COD content is low, process index request pine, the corresponding minimizing of intake of ozone.
In described step (5), 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, be 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, biofilm bacterial classification is nitrococcus and nitrobacteria, be collected near Tailings Dam in topsoil, bacterial classification biofilm mode is taked manually to add bacterial classification biofilm or Biofilmculturing, and 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 manufacturing enterprises cyanide wastewater, electrochemical treatment technology, coagulating sedimentation technology, ozonation technology and biological activated carbon treatment technology are combined, work in coordination with and advanced treatment is carried out to gold manufacturing enterprises 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 5% ~ 50% sodium chloride solution, 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 adds 5% ~ 30% solution of zinc sulfate, flocculation agent and flocculation agent successively and carries out coagulating sedimentation under whipped state, and after coagulation, waste water enters settling tank and staticly settles 15min ~ 120min;
(4) supernatant liquor after precipitation passes into ozone and carries out ozone oxidation reaction, and the reaction times is 15min ~ 120min;
(5) reacted waste water 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;
(6) 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, and flocculation agent is the polymer inorganic salt solution of 10% ~ 30%, and flocculation agent is the polyacrylamide solution of 0.3 ‰ ~ 0.5 ‰.
In described step (4), ozone intake is determined according to the number of the remaining prussiate in influent quality and COD content and processing requirements, prussiate and COD content is high, process index request tight, the intake of ozone is corresponding to be increased, otherwise, prussiate and COD content is low, process index request pine, the corresponding minimizing of intake of ozone.
In described step (5), 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, be 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, biofilm bacterial classification is nitrococcus and nitrobacteria, be collected near Tailings Dam in topsoil, bacterial classification biofilm mode is taked manually to add bacterial classification biofilm or Biofilmculturing, and vapour-liquid ratio is set as 1 ~ 15:1.
Specific examples 1:
Certain gold manufacturing enterprises cyanide wastewater, pH is 9.8, CN
tfor 627.38mg/L, SCN
-for 69.36mg/L, Cu
2+for 136.47mg/L, COD are 207.46mg/L, NH
3-N is 48.95mg/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 3 blocks of graphite anode plates and 3 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 of 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 0.5 ‰ anionic polyacrylamide solution 4mL are 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 the reactor that ozonation aerated device is housed, ozonation aerated device adopts titanium alloy micro-hole aerator, be placed in the bottom in reactor, ozone reaction 30min is passed into after reaction starts, ozone intake is 250mg, reaction terminates rear stopping and passing into ozone, with peristaltic pump the waste water after ozone oxidation 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, NH
3-N < 1.0mg/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 manufacturing enterprises cyanide wastewater, pH is 9.5, CN
tfor 539.66mg/L, SCN
-for 78.58mg/L, Cu
2+for 65.35mg/L, COD are 258.48mg/L, NH
3-N is 35.24mg/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 3 blocks of graphite anode plates and 3 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 of 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 0.5 ‰ anionic polyacrylamide solution 4mL are 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 the reactor that ozonation aerated device is housed, ozonation aerated device adopts titanium alloy micro-hole aerator, be placed in the bottom in reactor, ozone reaction 30min is passed into after reaction starts, ozone intake is 210mg, reaction terminates rear stopping and passing into ozone, with peristaltic pump the waste water after ozone oxidation 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, NH
3-N < 1.0mg/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 (7)
1. a gold manufacturing enterprises 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 ~ 10, add 5% ~ 50% sodium chloride solution, 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 adds 5% ~ 30% solution of zinc sulfate, flocculation agent and flocculation agent successively and carries out coagulating sedimentation under whipped state, and after coagulation, waste water enters settling tank and staticly settles 15min ~ 120min;
(4) supernatant liquor after precipitation passes into ozone and carries out ozone oxidation reaction, and the reaction times is 15min ~ 120min;
(5) reacted waste water 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;
(6) supernatant liquor after process returns in the technological process of production or qualified discharge.
2. a kind of gold manufacturing enterprises Treatment of cyanogen-contained wastewater 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 gold manufacturing enterprises Treatment of cyanogen-contained wastewater 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 or stainless steel plate.
4. a kind of gold manufacturing enterprises Treatment of cyanogen-contained wastewater 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 gold manufacturing enterprises Treatment of cyanogen-contained wastewater according to claim 1, it is characterized in that: in described step (3), flocculation agent is the polymer inorganic salt solution of 10% ~ 30%, and flocculation agent is the polyacrylamide solution of 0.3 ‰ ~ 0.5 ‰.
6. a kind of gold manufacturing enterprises Treatment of cyanogen-contained wastewater according to claim 1, it is characterized in that: in described step (5), 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 gold manufacturing enterprises Treatment of cyanogen-contained wastewater according to claim 1, it is characterized in that: in described step (5), biofilm bacterial classification is nitrococcus and nitrobacteria, to be collected near Tailings Dam in topsoil, bacterial classification biofilm mode is taked manually to add bacterial classification biofilm or Biofilmculturing, and vapour-liquid ratio is set as 1 ~ 15:1.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10141318A1 (en) * | 2001-08-28 | 2003-03-27 | Friedrich Binder Gmbh & Co Kg | Treatment of cyanide-containing waste water comprises at least two oxidation steps performed at acidic pH separated by a decomposition step performed at alkaline pH |
| CN1430581A (en) * | 2000-05-25 | 2003-07-16 | 日本科技股份有限公司 | Method and device for continuous electrolytic disposal of waste liquid |
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| WO2012019243A1 (en) * | 2010-08-13 | 2012-02-16 | The University Of Melbourne | Process for treating thiocyanate containing aqueous solutions |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1430581A (en) * | 2000-05-25 | 2003-07-16 | 日本科技股份有限公司 | Method and device for continuous electrolytic disposal of waste liquid |
| DE10141318A1 (en) * | 2001-08-28 | 2003-03-27 | Friedrich Binder Gmbh & Co Kg | Treatment of cyanide-containing waste water comprises at least two oxidation steps performed at acidic pH separated by a decomposition step performed at alkaline pH |
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