CN107890622A - The method of cyanidation tailings cyanide oxidation degraded - Google Patents
The method of cyanidation tailings cyanide oxidation degraded Download PDFInfo
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- CN107890622A CN107890622A CN201710985601.6A CN201710985601A CN107890622A CN 107890622 A CN107890622 A CN 107890622A CN 201710985601 A CN201710985601 A CN 201710985601A CN 107890622 A CN107890622 A CN 107890622A
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- cyanidation tailings
- tailings
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/35—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by hydrolysis
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/40—Inorganic substances
- A62D2101/45—Inorganic substances containing nitrogen or phosphorus
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- Removal Of Specific Substances (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The present invention relates to a kind of method of cyanidation tailings cyanide oxidation degraded, it is by the cyanidation tailings after press filtration, aqueous mass percent is controlled between 20~30%, stirring adds cement, aluminium powder, Cosan, sodium perborate, the three kinds or more of sodium chloride, and medicament addition is the 2.2~7.7% of cyanidation tailings dry weight percentage；Above-mentioned material is installed with trolley, then trolley is put into autoclave, after material vacuumizes in autoclave, it is passed through steam, after being warming up to 180~200 DEG C, 4.5~10 hours of pressurize, decompression, the water of steam containing ammonia is discharged, remaining cyanidation tailings can be converted into general another solid waste by the discriminating of hazardous waste toxicity in autoclave.The biodegrading process of the present invention, except cyanogen effect is good, except cyanogen is unrelated with the initial concentration of cyanogen, it is temperature dependent, the cyanidation tailings energy meet the requirement of environmental protection after processing, can be recycled directly as secondary resource with the time, leached by hazardous waste toxicity and differentiate that pH value is 7~9, total cyanide is less than 2mg/L.
Description
Technical field
The present invention relates to a kind of cyanide degradation method, particularly relates to a kind of side of cyanidation tailings cyanide oxidation degraded
Method.
Background technology
Cyanidation tailings are gold caused waste residues after being leached in Cyanide Process.Often produce 1 ton of gold to discharge 2.5~
30000 tons of cyaniding waste residues.And iron contained in cyanidation tailings is resource reutilization chief value.But remained in cyanidation tailings certain
The cyanide of amount has strong inhibitory action to pyrite.As CN in solution-When concentration is low, CN-In troilite Surface Creation parent
The Fe (CN) of water-based indissoluble2, with CN-Concentration increases, the Fe (CN) of indissoluble2It can be changed into and stablize readily soluble and hydrophilic Fe
(CN)64-, and the Fe that mineral surfaces are free2+Concentration drastically declines, Fe (CN)2、Fe(CN)6 4-Presence also make mineral and xanthate
The adsorbance of class collecting agent declines, and reduces the floatability of troilite.Therefore in order to fully activate troilite, it is necessary first to abolish
The cyanide wherein remained.
At present, mainly there is the comprehensive utilization of resources that following three kinds of methods realize cyanidation tailings：（ 1）Magnetizing roast method：Will
Cyanidation tailings and coal mix by a certain percentage, are calcined under the conditions of 800 DEG C, then carry out magnetic separation, and products obtained therefrom is more than 60%
Iron ore concentrate, the rate of recovery reaches more than 88%.(2) chloride-chlorate process：Using the Coordinate property of chlorion and gold, in chloric acid
In the presence of salt, the gold in cyanidation tailings is complexed into liquid phase, then reclaims the gold in cyanidation tailings with adsorption method.(3) make
Take iron salt method：It is that precipitating reagent has produced nanometer iron oxide red or bodied ferric sulfate using ammoniacal liquor with sulfuric acid to leach cyanidation tailings.
Although the valuable metal that the above method can be in partially recycled tailings, there is also utilization rate it is not high, produce secondary pollution
The drawbacks of.
The content of the invention
The present invention provides a kind of method of cyanidation tailings cyanide oxidation degraded, to overcome existing cyanidation tailings to recycle
Utilization rate existing for technique is not high, produces the problem of secondary pollution.
The present invention adopts the following technical scheme that：
Cyanidation tailings cyanide oxidation degraded method be：By the cyanidation tailings after press filtration, aqueous mass percent is controlled to exist
Between 20~30%, stirring adds cement, aluminium powder, Cosan, sodium perborate, the three kinds or more of sodium chloride, medicament
Addition is the 2.2~7.7% of cyanidation tailings dry weight percentage, and cement, which is bonded in tailings surface formation micropore, can increase place
The gas permeability of material is managed, aluminium powder can react with water produces hydrogen formation micropore, so as to increase the gas permeability of processing material and heat conduction
Property；Installed with trolley, trolley then put into autoclave, 0.4~1 hour is vacuumized after closed, then passes to steam,
After temperature rises to 180~200 DEG C, start 4.5~10 hours of pressurize, be then depressured, discharge the water of steam containing ammonia, steam containing ammonia
Water collects otherwise processed, and remaining cyanidation tailings can be converted into general another solid by the discriminating of hazardous waste toxicity in autoclave
Waste.
Cyanide even if also can slowly hydrolyze generation ammonium salt and formates at normal temperatures, and when temperature reaches 120 DEG C, reaction is fast
Degree is accelerated, and when temperature reaches more than 170 DEG C, the hydrolysis speed of cyanide is quickly.Waste material containing cyanogen is carried out using this principle
The method of processing also known as heats Hydrolyze method pressurizing hydrolysis.Heat resolve reaction mechanism is：CN-+ 2H2O= HCOO- +
NH3。
The pyrohydrolysis that this method is also referred to as the material containing cyanogen destroys method, and it can not only handle free cyanide, can also locate
Manage the fluor-complex containing cyanogen；The scope adapted to concentration containing cyanogen in waste material is wide, simple to operate, stable.
Under this condition, free CN can not only be made-Hydrolysis, moreover it is possible to make some water containing cyano complex such as ferrocyanide
Solution.It is as follows to heat hydrolysis principle mechanism：
Fe(CN)6 4-→ Fe(CN)2+4CN-
Fe(CN)2+ 2OH-→Fe(OH)2+2CN-
Zn(CN)4 2-+ 2OH-→ZnO+ 4CN-
Cu(CN)4 2- +2OH-→CuO+ 4CN-
CN-+S=SCN-
SCN-+H2O=HSCN+OH-
2CN-+5BO3 -+H2O=5BO2 -+2CO2+N2+2OH-
CN-+ 2H2O= HCOO-+ NH3
Oxidant used in this application can consume CN well-, generate nontoxic SCN-, promote CN-Release is decomposed, then will
CN-Carry out oxidative degradation and hydrolytic degradation, SCN-Easily complex is formed with metal ion.Sodium chloride plays enhancing infiltration and made
With.
From the above-mentioned description of this invention, compared to the prior art, the invention has the advantages that：
First, the method for cyanidation tailings cyanide oxidation of the invention degraded, disposable Hydrolysis rate is up to more than 99.5%, except cyanogen effect
Good, steam pressure is unrelated with the initial concentration of cyanogen except cyanogen, is temperature dependent with the time, and the cyanidation tailings after steam pressure processing can reach environmental protection
The requirement of common solid waste, slag can recycle directly as secondary resource after processing, leached by hazardous waste toxicity and differentiate PH
It is worth for 7~9, total cyanide is less than 2mg/L.
2nd, the method for cyanidation tailings cyanide oxidation of the invention degraded, it is simple and convenient, technique clean manufacturing, do not pollute
Environment, by adding oxidant, pore creating material accelerates the decomposition of cyanide, shortens the reaction time, thoroughly solves cyanidation tailings product
Pressure and secondary pollution problem, realize clean manufacturing, non-waste-emission, the target for comprehensively utilizing, turning waste into wealth that gold cyaniding is smelted.
Embodiment
Embodiment one
Present embodiment cyanidation tailings cyanide oxidation degraded method be：By the cyanidation tailings after press filtration, control aqueous
For mass percent between 20~30%, stirring adds cement, Cosan and sodium chloride, the addition of cement, Cosan and sodium chloride
Amount is followed successively by 1.5%, 3% and the 0.5% of cyanidation tailings dry weight percentage, and cement, which is bonded in tailings surface formation micropore, to be increased
Add the gas permeability of processing material, so as to increase the gas permeability and thermal conductivity of processing material；Then material is installed with trolley, then will
Trolley puts into autoclave, and 0.6~0.8 hour is vacuumized after closed, then passes to steam, 180~200 are risen in temperature
After DEG C, start 2.5~6 hours of pressurize, be then depressured, discharge the water of steam containing ammonia, the water of steam containing ammonia collects otherwise processed, high pressure
Remaining cyanidation tailings are differentiated by hazardous waste toxicity in reactor can be converted into general another solid waste.The cyanogen of present embodiment
Change the method for tailings cyanide oxidation degraded, except cyanogen effect is good, steam pressure is unrelated with the initial concentration of cyanogen except cyanogen, with time and temperature
Correlation, the cyanidation tailings after steam pressure processing can reach the requirement of environmentally friendly common solid waste, and slag can be directly as secondary money after processing
Source recycles, and is leached by hazardous waste toxicity and differentiates that pH value is 7~9, total cyanide is less than 1.5mg/L.Present embodiment
Cyanidation tailings cyanide oxidation degraded method, simple and convenient, technique clean manufacturing is free from environmental pollution, by add oxidant,
Pore creating material accelerate cyanide decomposition, shorten the reaction time, thoroughly solve the problems, such as cyanidation tailings overstock and secondary pollution, realization
Clean manufacturing, non-waste-emission, the target for comprehensively utilizing, turning waste into wealth of gold cyaniding smelting.
Embodiment two
Present embodiment cyanidation tailings cyanide oxidation degraded method be：By the cyanidation tailings after press filtration, control aqueous
For mass percent between 20~30%, stirring adds cement, aluminium powder, Cosan, sodium perborate and sodium chloride, cement, aluminium powder,
The addition of Cosan, sodium perborate and sodium chloride be followed successively by cyanidation tailings dry weight percentage 0.5%, 0.5%, 0.5%,
0.5% and 0.2%, aluminium powder can react with water produces hydrogen formation micropore, so as to increase the gas permeability and thermal conductivity of processing material；So
Material is installed with trolley afterwards, and trolley then is put into autoclave, and 0.8~1.0 hour is vacuumized after closed, is then passed to
Steam, after temperature rises to 180~200 DEG C, start 3~6 hours of pressurize, be then depressured, discharge the water of steam containing ammonia, steamed containing ammonia
Carbonated drink collects otherwise processed, in autoclave remaining cyanidation tailings differentiated by hazardous waste toxicity can be converted into it is general another solid
Body waste.The method of the cyanidation tailings cyanide oxidation degraded of present embodiment, except cyanogen effect is good, steam pressure is initial except cyanogen and cyanogen
Concentration is unrelated, is temperature dependent with the time, and the cyanidation tailings after steam pressure processing can reach the requirement of environmentally friendly common solid waste, after processing
Slag can recycle directly as secondary resource, leached by hazardous waste toxicity and differentiate that pH value is 7~9, total cyanide is less than
2mg/L.The method of the cyanidation tailings cyanide oxidation degraded of present embodiment, it is simple and convenient, technique clean manufacturing, do not pollute ring
Border, by adding oxidant, pore creating material accelerates the decomposition of cyanide, shortens the reaction time, thoroughly solves cyanidation tailings and overstock
With secondary pollution problem, clean manufacturing, non-waste-emission, the target for comprehensively utilizing, turning waste into wealth that gold cyaniding is smelted are realized.
Embodiment three
Present embodiment cyanidation tailings cyanide oxidation degraded method be：By the cyanidation tailings after press filtration, control aqueous
For mass percent between 20~30%, stirring adds aluminium powder, sodium perborate and sodium chloride, aluminium powder, sodium perborate and sodium chloride
Addition is followed successively by 2%, 5% and the 0.7% of cyanidation tailings dry weight percentage, and aluminium powder can form micro- with water reaction generation hydrogen
Hole, so as to increase the gas permeability and thermal conductivity of processing material；Then material is installed with trolley, and trolley then is put into reaction under high pressure
Kettle, 0.4~0.6 hour is vacuumized after closed, then passes to steam, after temperature rises to 180~200 DEG C, start pressurize 3.5
~5.5 hours, then it is depressured, the discharge water of steam containing ammonia, the water of steam containing ammonia collection otherwise processed, remaining cyanogen in autoclave
General another solid waste can be converted into by the discriminating of hazardous waste toxicity by changing tailings.The cyanidation tailings cyanide oxygen of present embodiment
Change the method for degraded, except cyanogen effect is good, steam pressure is unrelated with the initial concentration of cyanogen except cyanogen, is temperature dependent with the time, steam pressure processing
Cyanidation tailings afterwards can reach the requirement of environmentally friendly common solid waste, and slag can recycle directly as secondary resource after processing, pass through
Hazardous waste toxicity, which leaches, differentiates that pH value is 7~9, and total cyanide is less than 1.5mg/L.The cyanidation tailings cyanide of present embodiment
The method of oxidative degradation, simple and convenient, technique clean manufacturing is free from environmental pollution, and by adding oxidant, pore creating material accelerates cyaniding
The decomposition of thing, shorten the reaction time, thoroughly solve the problems, such as cyanidation tailings overstock and secondary pollution, realize gold cyaniding smelting
Clean manufacturing, non-waste-emission, the target for comprehensively utilizing, turning waste into wealth.
The embodiment of the present invention is above are only, but the design concept of the present invention is not limited thereto, it is all to utilize this
Conceive the change that unsubstantiality is carried out to the present invention, the behavior for invading the scope of the present invention all should be belonged to.
Claims (2)
1. the method for cyanidation tailings cyanide oxidation degraded, it is characterised in that including the following step carried out successively：
A. by the cyanidation tailings after press filtration, aqueous mass percent is controlled between 20~30%；Add oxidant, pore creating material
Stirred mixing with bleeding agent, wherein, pore creating material is cement and/or aluminium powder, and oxidant is Cosan and/or sodium perborate,
Bleeding agent is sodium chloride, and the addition total amount of oxidant and pore creating material is the 2.2~7.7% of cyanidation tailings dry weight percentage；
B. mixed tailings is transferred to autoclave, 0.4~1 hour is vacuumized after closed；
C. steam is then passed to, after temperature rises to 180~200 DEG C, starts 4.5~10 hours of pressurize；
D. and then it is depressured, the discharge water of steam containing ammonia, the water of steam containing ammonia collection otherwise processed, remaining cyaniding tail in autoclave
Slag is differentiated by hazardous waste toxicity can be converted into general another solid waste.
2. the method for cyanidation tailings cyanide oxidation degraded as claimed in claim 1, it is characterised in that：The oxidant adds
It is 1~2% to enter amount, and the addition of the pore creating material is 1~5%, and the bleeding agent is 0.2~0.7%.
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| CN201710985601.6A CN107890622A (en) | 2017-10-20 | 2017-10-20 | The method of cyanidation tailings cyanide oxidation degraded |
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| CN201710985601.6A CN107890622A (en) | 2017-10-20 | 2017-10-20 | The method of cyanidation tailings cyanide oxidation degraded |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112028309A (en) * | 2020-08-22 | 2020-12-04 | 长春黄金研究院有限公司 | Method for resource recovery of high-concentration cyanide-containing wastewater and treatment of intermediate product |
| CN113185265A (en) * | 2021-07-01 | 2021-07-30 | 北京矿冶研究总院 | Cyanide sludge sintering cyanogen removal process, cyanide-free brick, cyanide sludge sintering cyanogen removal system and application |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112028309A (en) * | 2020-08-22 | 2020-12-04 | 长春黄金研究院有限公司 | Method for resource recovery of high-concentration cyanide-containing wastewater and treatment of intermediate product |
| CN113185265A (en) * | 2021-07-01 | 2021-07-30 | 北京矿冶研究总院 | Cyanide sludge sintering cyanogen removal process, cyanide-free brick, cyanide sludge sintering cyanogen removal system and application |
| CN113185265B (en) * | 2021-07-01 | 2021-11-05 | 北京矿冶研究总院 | Cyanide sludge sintering cyanogen removal process, cyanide-free brick, cyanide sludge sintering cyanogen removal system and application |
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Application publication date: 20180410 |