CN103253834A - Deep treatment method for cyanide-containing waste water of tailings pond in gold industry - Google Patents
Deep treatment method for cyanide-containing waste water of tailings pond in gold industry Download PDFInfo
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Abstract
The invention discloses a deep treatment method for cyanide-containing waste water of a tailings pond in the gold industry. The process adopts an ozone oxidation method, a catalytic oxidation method and a biological treatment method to collectively deeply treat the cyanide-containing waste water of the tailings pond in the gold industry. Through the combination of the three methods, a good treatment effect on the cyanide, thiocyanate, arsenic and heavy metals is good, the content of the cyanide after being treated is less than or equal to 0.05mg/L, the content of ammonia and nitrogen after being treated is less than 1mg/L, and other pollutants after being treated can meet the requirement of the ground surface water grade-B water quality standard. The method is used for treating the cyanide-containing waste water of the tailings pond in the gold industry, the treatment effect on the cyanide, the COD, As and heavy metals is good, the heavy metals such as the gold and silver as well as other metal resource can be recovered, and the secondary pollution caused by the ammonia and nitrogen can be avoided. By adopting the deep treatment method for the cyanide-containing waste water of the tailings pond, a good environment, a good economic benefit and a good social benefit can be achieved.
Description
Technical field
The invention belongs to Mining Environment Conservation and process for comprehensively treating field; relate to a kind of gold industry mine tailing storehouse cyanide wastewater advanced treatment process method, this process using ozone oxidation method, catalytic oxidation and bioremediation are united gold industry mine tailing storehouse cyanide wastewater are carried out advanced treatment.Gold industry mine tailing storehouse cyanide wastewater by present method processing, prussiate, COD, As, heavy metal treatment effect are good, prussiate is after treatment smaller or equal to 0.05mg/L, ammonia nitrogen is after treatment less than 1mg/L, other pollutents all can reach surface water two class water quality standard requirements after treatment, can reclaim precious metal and other metals resources such as gold and silver, can avoid ammonia nitrogen to cause secondary pollution.Adopt method of the present invention to handle mine tailing storehouse cyanide wastewater and have good environment, economic and social benefit.
Background technology
In the tailings reservoir for piling process, meet the rainwater leaching through dried mine tailing after the press filtration in the gold industry mine tailing storehouse and still can discharge prussiate, thiocyanate-, arsenic, heavy metal, cause prussiate, thiocyanate-, arsenic, heavy metals exceeding standard in the exterior liquid of mine tailing storehouse, make the mine tailing stock in potential safety hazard, rainy season this potential safety hazard especially serious.At present, state includes the cyanogen treatment technology and mainly contains natural degradation method, Pomolio-Celdecor process, Yin Kefa, ozone oxidation method etc.Mainly to destroy prussiate, thiocyanide, these methods produce the secondary pollutant ammonia nitrogen when pollutent destroys, and relatively poor to Pollutant Treatment effects such as heavy metal and arsenic for natural degradation method, Pomolio-Celdecor process, Yin Kefa, ozone method.The precious metals such as gold and silver that contain in the mine tailing storehouse waste water efflux with waste water and have also caused the wasting of resources simultaneously.
Progressively raising along with the Environmental Protection in China requirement; gold industry press for a kind of simultaneously to prussiate, thiocyanate-, arsenic, the heavy metal treatment effect is good and can not cause secondary pollution, the advance for the treatment of process of cyanide-bearing effluent that can reclaim simultaneously gold and silver in the mine tailing storehouse waste water satisfies the gold industry environmental protection requirement of increasingly stringent.
Method of the present invention adopts ozone oxidation method, catalytic oxidation and bioremediation to unite gold industry mine tailing storehouse cyanide wastewater to be carried out advanced treatment, overcome the shortcoming that above method exists, be a kind of new method and technology.
Summary of the invention
The purpose of this invention is to provide a kind of gold industry mine tailing storehouse cyanide wastewater deep treatment method, this method adopts ozone oxidation method, catalytic oxidation and bioremediation to unite gold industry mine tailing storehouse cyanide wastewater is carried out advanced treatment.Its innovative point one is to unite by three kinds of methods prussiate, thiocyanate-, arsenic, heavy metal are all had treatment effect preferably, prussiate is after treatment smaller or equal to 0.05mg/L, ammonia nitrogen is after treatment less than 1mg/L, and other pollutents all can reach surface water two class water quality standard requirements after treatment; The 2nd, can reclaim precious metal gold and silver of containing in the gold industry mine tailing storehouse waste water etc., the rate of recovery is more than or equal to 90%; The 3rd, the ozone effective rate of utilization is higher, and the ozone tail gas of handling the waste water generation through the ozone oxidation method can be utilized again by catalytic oxidation, improves the treatment effect of prussiate and COD; Ozone can reach the emission standard requirement in the tail gas simultaneously.The 4th, this processing method is to the Pollutant Treatment effect stability, and capacity of resisting impact load is strong.Three kinds of methods all have good treatment effect to pollutents such as prussiate, COD, heavy metals, can guarantee that Pollutant levels progressively reduce to reach processing requirements, and treatment effect is stable.The 5th, handle the secondary pollutant ammonia nitrogen by biological process, avoid causing secondary pollution.By the gold industry mine tailing storehouse cyanide wastewater that present method is handled, prussiate, COD, As, heavy metal treatment effect are good, can reclaim precious metal and other metals resources such as gold and silver, can avoid ammonia nitrogen to cause secondary pollution.Therefore adopt method of the present invention to handle mine tailing storehouse cyanide wastewater and have good environment, economic and social benefit.
This invention is undertaken by following five steps:
(1) pharmacy response is prepared: adopt and contain sodium hydroxide or unslaked lime or sodium bicarbonate liquid as ozone oxidation, catalyzed oxidation and biological treatment pH value conditioning agent, need and react the pH value adjusting dosage that required pH value is determined required interpolation according to the original pH value of waste water; Need add the liquid that contains flocculation agent and flocculation agent in the solid-liquid separation process in case of necessity and improve solid-liquid separation effect, additive amount of medicament needs to determine according to flocculation agent and flocculation agent kind and solid-liquid separation effect flocculation agent and the cohesion dosage of required interpolation; Need in the biological treatment process to add the nutrition medicament according to waste water quality and biological metabolic requirement.The pH regulator agent can be adopted sodium hydroxide, unslaked lime, yellow soda ash, sodium bicarbonate and sulfuric acid.The coagulating agent that adds in the solid-liquid separation comprises that mineral-type iron system, aluminium are coagulating agent and organic class coagulating agent.
(2) ozone Oxidation Treatment: waste water enters into oxidation reactor after regulating pH, ozone fully contacts in the ozone oxidation reaction device with waste water redox reaction takes place, reducing substanceses such as prussiate, thiocyanide, COD in the waste water are destroyed decomposition, may have the secondary pollutant ammonia nitrogen to produce in this process.The metal of while prussiate destruction decomposition course and prussiate complexing is converted into sedimentable matter and separates from waste water.The ozone tail gas that contains that ozone oxidation produces feeds the catalyst oxidation reactor recycling.The ozone addition needs to determine according to reducing substances concentration in the waste water.Ozone Oxidation Treatment is disposed most reducing substances, makes most of heavy metal with the prussiate complexing generate throw out simultaneously.The generation of ozone can adopt air to reach the ozone that produces with additive method as raw material gap discharge generation ozone as raw material and with liquid oxygen.Ozone oxidation reaction equipment matter is necessary for the material of ability ozone corrosion, comprises 316,304 stainless steels, Resins, epoxy, tetrafluoroethylene.The ozone oxidation reaction device can guarantee that ozone fully contacts with waste water, and closure is good, and ozone can not leak.Can adopt gas-liquid counter current or smooth contact, in the ozone oxidation reaction device water-distributing device and distribution device will be arranged simultaneously.Water-distributing device comprises water-distributing devices such as perforated pipe, shower nozzle.Distribution device comprises aeration head, aeration tube and perforated pipe gas distribution.The pH of ozone and waste water reaction can not overflow with the form of prussic acid to guarantee prussiate between 7～11, guarantees that simultaneously redox reaction normally carries out.Waste water in oxidation reactor hydraulic detention time more than or equal to 0.5h.
(3) solid-liquid separation: the throw out that oxide treatment produces need carry out solid-liquid separation to be separated from treatment solution, prevents from causing catalytic oxidation treatment stage filler to stop up, and recyclable metal values material of while is as copper.Solid-liquid separating method can adopt the associating of methods such as settling tank precipitation, filtration and flocculation sediment or several method.Turbidity is smaller or equal to 10NTU behind the solid-liquid separation side.The throw out recoverable metal resource that produces after the solid-liquid separation.
(4) catalytic oxidation treatment: waste water clear liquid after solid-liquid separation enters into catalyst oxidation reactor, active carbon filler is housed in the catalyst oxidation reactor, while bubbling air and ozone oxidation tail gas, waste water is at activated carbon surface and oxygen and ozone generation catalytic oxidation, it is destroyed that redox reaction further takes place reducing substances in the waste water, simultaneously remains heavy metal in the waste water, precious metal is adsorbed on activated carbon surface and removes from waste water.Ozone is lower than emission standard and air emptying together after catalytic oxidation treatment.The bubbling air amount is determined according to waste water quality and wastewater flow rate.
The catalyst oxidation reactor material is the material of ability ozone corrosion, can guarantee that ozone fully contacts with waste water simultaneously.The material of ability ozone corrosion comprises 316,304 stainless steels, Resins, epoxy, tetrafluoroethylene.Abundant for guaranteeing gas-to-liquid contact, in the catalyst oxidation reactor water-distributing device and distribution device to be arranged.Water-distributing device sprays waste water above active carbon layer, distribution device is gas distribution below active carbon layer, and aqueous vapor only contacts at activated carbon surface.Water-distributing device comprises water-distributing devices such as perforated pipe, shower nozzle.Distribution device comprises aeration head, aeration tube and perforated pipe gas distribution.The waste water spraying intensity is smaller or equal to 4m
3/ m
2H, gas-liquid volume ratio are 100～800, and the pH of catalytic oxidation guarantees that prussiate can not overflow with the form of prussic acid between 7～11, guarantee that simultaneously redox reaction normally carries out.The filler of catalytic oxidation is active carbon filler.The gac material is coconut palm nuclear charcoal, almond charcoal or ature of coal charcoal.Gac is shaped as column, granular, powdery, cellular or other shapes.
(5) biological treatment: biological treatment utilizes nitrococcus, nitrifier that ammonia nitrogen is converted into nitrate, can utilize denitrifying bacterium that nitrate is converted into nitrogen if need.Comprise active sludge, biomembrance process, wetland processing.Waste water enters into bio-reactor after catalytic oxidation treatment, waste water fully contacts with aerobic nitrosification and nitrifier in the bio-reactor, the ammonia nitrogen that ozone oxidation produces is converted into nitrate by bacterial metabolism, pollutents such as COD and heavy metal further reductions through carrying out a biological disposal upon after in the waste water simultaneously efflux after reaching the processing standard.
Beneficial effect of the present invention:
The present invention adopts ozone oxidation method, catalytic oxidation and bioremediation to unite gold industry mine tailing storehouse cyanide wastewater is carried out advanced treatment and compares former method and have the following advantages:
1, can handle multiple pollutent simultaneously, can remove the heavy metal cyano complex, treatment effect is good;
2, the precious metal gold and silver that contains in the gold industry mine tailing storehouse waste water etc. is reclaimed, the rate of recovery is more than or equal to 90%, has recovery value and also can reclaim if metal contents such as waste water copper are higher;
3, the ozone effective rate of utilization is higher, and the ozone tail gas of handling the waste water generation through the ozone oxidation method can be utilized again by catalytic oxidation, can save professional tail gas breaking plant, and ozone can reach the emission standard requirement in the tail gas;
4, it is few to add reaction reagent, and ozone oxidation method, catalytic oxidation, the required main agents of biological treatment are oxygen and can obtain from air, and the biological process desired microorganisms mainly obtains from nature, is environment-friendly type reagent, also is conducive to reduce processing cost;
5, this processing method is to the Pollutant Treatment effect stability, and capacity of resisting impact load is strong.；
6, handle the secondary pollutant ammonia nitrogen by biological process, avoid causing secondary pollution.
Description of drawings
Fig. 1 is certain 3000m of company
3The process flow sheet of/d mine tailing leaching liquor advanced treatment engineering.
Embodiment
Embodiment 1-small-scale test
Get certain gold mine tailing storehouse waste water as the test water sample, its water quality is composed as follows:
The cyanide wastewater principal pollutant are formed
| Sequence number | Analysis project | Chemical symbol | Concentration value (mg/L) |
| 1 | Total cyanogen | CN T | 87.17 |
| 2 | Free cyanogen | CN f | 17.69 |
| 3 | Thiocyanate- | SCN - | 20.51 |
| 4 | Chemical oxygen demand (COD) | COD | 89 |
| 5 | Ammonia nitrogen | NH 4-N | 0.13 |
| 6 | Copper | Cu | 83.63 |
(1) ozone oxidation test
Test conditions
Reaction vessel: Φ 100mm * H1000mm synthetic glass post; Processing mode: handle continuously; PH:8～9; Ozone addition: 0.33g/L waste water; Tolerance: 0.15m
3/ h; Wastewater treatment capacity: 1L/h; Hydraulic detention time: 1h.
Test-results
The ozone oxidation test-results
| Analysis project | CN T | NH 3-N? | Cu | SCN - | COD |
| Concentration (mg/L) | 0.12-0.21 | 12.30-14.56 | 0.20-0.99 | 0.34-0.78 | 19.8-45.91 |
(2) catalyzed oxidation test
Test conditions
Reaction vessel: Φ 40mm * H500mm synthetic glass post; Processing mode: handle continuously; PH:8～9; Ozone addition (tail gas after the ozone oxidation): 0.03g/L waste water; Tolerance: 0.10m
3/ h; Wastewater treatment capacity (waste water after the ozone oxidation): 1.0L/h; Hydraulic detention time: 0.5h, gac: coconut palm nuclear activity charcoal
Test-results
The catalyzed oxidation test result
| Analysis project | CN T | NH 3-N? | Cu | SCN - | COD |
| Concentration (mg/L) | 0.01-0.05 | 10.10-12.70 | 0.05-0.20 | 0.14-0.38 | 5.8-15.91 |
(3) BAF
Test conditions
Reaction vessel: Φ 50mm * H1000mm synthetic glass post; Processing mode: handle continuously; PH:8～9; Tolerance: 10L/h; Wastewater treatment capacity (waste water behind the catalyzed oxidation): 1.0L/h; Hydraulic detention time: 2h, filler: coal mass active carbon
Test-results
The BAF test-results
| Analysis project | CN T | NH 3-N? | Cu | SCN - | COD |
| Concentration (mg/L) | 0.01-0.05 | 0.11-0.89 | 0.05-0.19 | 0.12-0.43 | 8.9-17.91 |
Embodiment 2-commerical test
Certain 3000m of company
3The technology of/d mine tailing leaching liquor advanced treatment engineering as shown in Figure 1,
This project ozone oxidation workshop section main technique condition is as follows:
Wastewater treatment capacity: 125m
3/ h; Ozone generating capacity: 40kg/h; Tolerance: 280 m
3/ h; Reaction pH:8～9; Hydraulic detention time 1h; Oxidation reactor: 4, φ 2600 * 9000
Catalyzed oxidation workshop section main technique condition is as follows:
Wastewater treatment capacity: 125m
3/ h; Tolerance: 14000 m
3/ h; Waste water spraying intensity: 3-4m
3/ m
2H; Hydraulic detention time: 0.5h; Reaction pH:8～9; Filler: coconut palm nuclear activity charcoal 36t; Ozone oxidation tail gas: 280 m
3/ h; Ozone amount: 2.0kg/h; Catalyst oxidation reactor: 8, φ 2600 * 9000
BAF workshop section main technique condition is as follows:
Wastewater treatment capacity: 125m
3/ h; Tolerance: 500 m
3/ h; Hydraulic detention time: 5.0h; Reaction pH:8～9; Filler: coal mass active carbon 50t, zeolite 200t; The BAF reactor: 4, φ 5100 * 6400, and 2 fillers are coal mass active carbon, and 2 is zeolite.
Each workshop section's treatment effect is as follows:
This project has reached following technic index
Engineering main technique index
| Project | Unit | Value |
| Throughput | m 3/d | 3000 |
| Handle back CN - | mg/L | ≤0.05 |
| Copper | mg/L | ≤1.0 |
| Handle back COD | mg/L | ≤20 |
| Handle the back ammonia nitrogen | mg/L | ≤1.0 |
| Copper recovery | % | ≥90 |
| Gold recovery | % | ≥90 |
| Silver raising recovery rate | % | ≥90 |
| HCN gas in the workshop | mg/m 3 | ≤1 |
| Ozone gas in the workshop | mg/m 3 | ≤0.1 |
Claims (9)
1. gold industry mine tailing storehouse cyanide wastewater deep treatment method, this method adopt ozone oxidation method, catalytic oxidation and bioremediation to unite pollutents such as prussiate, thiocyanate-, arsenic, heavy metal, ammonia nitrogen in the cyanide wastewater of gold industry mine tailing storehouse are carried out advanced treatment; The step of this method is as follows:
(1) pharmacy response is prepared: this method adopts and contains sodium hydroxide or unslaked lime or sodium bicarbonate liquid as ozone oxidation, catalyzed oxidation and biological treatment pH value conditioning agent, need and react the pH value adjusting dosage that required pH value is determined required interpolation according to the original pH value of waste water; Need add the liquid that contains flocculation agent and flocculation agent in the solid-liquid separation process in case of necessity and improve solid-liquid separation effect, additive amount of medicament needs to determine according to flocculation agent and flocculation agent kind and solid-liquid separation effect flocculation agent and the cohesion dosage of required interpolation; Need in the biological treatment process to add the nutrition medicament according to waste water quality and biological metabolic requirement;
(2) ozone Oxidation Treatment: waste water enters into oxidation reactor after regulating pH, ozone fully contacts in the ozone oxidation reaction device with waste water redox reaction takes place, reducing substanceses such as prussiate, thiocyanide, COD in the waste water are destroyed decomposition, may have the secondary pollutant ammonia nitrogen to produce in this process.The metal of while prussiate destruction decomposition course and prussiate complexing is converted into sedimentable matter and separates from waste water.The ozone tail gas that contains that ozone oxidation produces feeds the catalyst oxidation reactor recycling; The ozone addition needs to determine according to reducing substances concentration in the waste water; Ozone Oxidation Treatment is disposed most reducing substances, makes most of heavy metal with the prussiate complexing generate throw out simultaneously;
(3) solid-liquid separation: the throw out that oxide treatment produces need carry out solid-liquid separation to be separated from treatment solution, prevents from causing catalytic oxidation treatment stage filler to stop up, and recyclable metal values material of while is as copper; Solid-liquid separating method can adopt the associating of methods such as settling tank precipitation, filtration and flocculation sediment or several method;
(4) catalytic oxidation treatment: waste water clear liquid after solid-liquid separation enters into catalyst oxidation reactor, active carbon filler is housed in the catalyst oxidation reactor, while bubbling air and ozone oxidation tail gas, waste water is at activated carbon surface and oxygen and ozone generation catalytic oxidation, it is destroyed that redox reaction further takes place reducing substances in the waste water, simultaneously remains heavy metal in the waste water, precious metal is adsorbed on activated carbon surface and removes from waste water.Ozone is lower than emission standard and air emptying together after catalytic oxidation treatment; The bubbling air amount is determined according to waste water quality and wastewater flow rate;
(5) biological treatment: waste water enters into bio-reactor after catalytic oxidation treatment, waste water fully contacts with aerobic nitrosification and nitrifier in the bio-reactor, the ammonia nitrogen that ozone oxidation produces is converted into nitrate by bacterial metabolism, pollutents such as COD and heavy metal further reductions through carrying out a biological disposal upon after in the waste water simultaneously efflux after reaching the processing standard.
2. a kind of gold industry mine tailing according to claim 1 storehouse cyanide wastewater deep treatment method, it is characterized in that: described pH regulator agent is sodium hydroxide or unslaked lime or yellow soda ash or sour hydrogen sodium or sulfuric acid.
3. a kind of gold industry mine tailing according to claim 1 storehouse cyanide wastewater deep treatment method, it is characterized in that: the coagulating agent that adds in the described solid-liquid separation is that mineral-type iron system or aluminium are coagulating agent or organic class coagulating agent.
4. a kind of gold industry mine tailing according to claim 1 storehouse cyanide wastewater deep treatment method is characterized in that: in described ozone oxidation reaction device and the catalyst oxidation reactor water-distributing device and distribution device will be arranged; Described water-distributing device has perforated pipe and shower nozzle; Described distribution device has aeration head, aeration tube and perforated pipe gas distribution.
5. a kind of gold industry mine tailing according to claim 1 storehouse cyanide wastewater deep treatment method, it is characterized in that: the pH of described ozone oxidation reaction and catalyzed oxidation reaction is between 7～11, guarantee that prussiate can not overflow with the form of prussic acid, guarantee that simultaneously redox reaction normally carries out.
6. a kind of gold industry mine tailing according to claim 1 storehouse cyanide wastewater deep treatment method is characterized in that: described waste water answers in device and the catalyst oxidation reactor hydraulic detention time more than or equal to 0.5h in ozone oxidation.
7. a kind of gold industry mine tailing according to claim 1 storehouse cyanide wastewater deep treatment method, it is characterized in that: described solid-liquid separating method adopts the settling tank precipitation, filters the goods flocculation sediment, or the associating of several method; Turbidity is smaller or equal to 10NTU after the solid-liquid separation; The throw out recoverable metal resource that produces after the solid-liquid separation.
8. a kind of gold industry mine tailing according to claim 1 storehouse cyanide wastewater deep treatment method, it is characterized in that: the water-distributing device of described catalyst oxidation reactor sprays waste water above active carbon layer, distribution device is gas distribution below active carbon layer, and aqueous vapor only contacts at activated carbon surface; Waste water spraying intensity 3-4m
3/ m
2H, gas-liquid volume ratio are 100～800.
9. a kind of gold industry mine tailing according to claim 1 storehouse cyanide wastewater deep treatment method, it is characterized in that: the filler of described catalytic oxidation is active carbon filler; Described gac be shaped as column or granular or powdery or cellular.
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