CN107812342A - The method of cyanidation tailings cyanide complex degraded - Google Patents
The method of cyanidation tailings cyanide complex degraded Download PDFInfo
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- CN107812342A CN107812342A CN201710984068.1A CN201710984068A CN107812342A CN 107812342 A CN107812342 A CN 107812342A CN 201710984068 A CN201710984068 A CN 201710984068A CN 107812342 A CN107812342 A CN 107812342A
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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
- A62D3/33—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by chemical fixing the harmful substance, e.g. by chelation or complexation
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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
- A62D3/20—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by hydropyrolysis or destructive steam gasification, e.g. using water and heat or supercritical water, to effect chemical change
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
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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
- A62D2101/43—Inorganic substances containing heavy metals, in the bonded or free state
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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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Abstract
The present invention relates to a kind of method of cyanidation tailings cyanide complex degraded, it is by the cyanidation tailings after press filtration, aqueous mass percent is controlled between 20~30%, stirring adds cement, aluminium powder, EDTA, sodium humate, fulvic acid, the one or more of ulmic acid, and medicament addition is the 2~7% 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 7~8, 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 complex 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 complex 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 complex degraded method be：By the cyanidation tailings after press filtration, aqueous mass percent is controlled to exist
Between 20~30%, add complexing agent and pore creating material and stir mixing, wherein, pore creating material is cement and/or aluminium powder, and cement glues
The gas permeability of processing material can be increased in tailings surface formation micropore by tying, and aluminium powder can react generation hydrogen with water and form micropore, from
And increase the gas permeability and thermal conductivity of processing material；Complexing agent is EDTA, sodium humate, fulvic acid, one kind of ulmic acid or one
More than kind, the addition total amount of complexing agent and pore creating material is the 2~7% of cyanidation tailings dry weight percentage；Installed with trolley, so
Trolley is put into autoclave afterwards, 0.4~1 hour is vacuumized after closed, then passes to steam, 180 are risen in temperature~
After 200 DEG C, starting 4.5~10 hours of pressurize, be then depressured, discharge the water of steam containing ammonia, the water of steam containing ammonia collects otherwise processed,
Remaining cyanidation tailings are differentiated by hazardous waste toxicity in autoclave can be converted into general another solid 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 handle and contain
The fluor-complex of 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-+ 2H2O= HCOO-+ NH3
Complexing agent used in this application can deprive metal ion well, promote CN-Release is decomposed, then by CN-Enter water-filling
Solution degraded.
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 complex 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 7~8, total cyanide is less than 2mg/L.
2nd, the method for cyanidation tailings cyanide complex of the invention degraded, it is simple and convenient, technique clean manufacturing, do not pollute
Environment, by adding complexing agent, 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 complex degraded method be：By the cyanidation tailings after press filtration, control aqueous
Mass percent is between 20~30%, stirring addition cement and EDTA, and cement and EDTA addition are respectively that cyanidation tailings are done
The 1.5% of weight mass percent and 3.5%；Cement, which is bonded in tailings surface formation micropore, can increase the gas permeability of processing material, from
And increase the gas permeability and thermal conductivity of processing material；Then material is installed with trolley, and trolley then is put into autoclave, close
0.6~0.8 hour is vacuumized after closing, then passes to steam, after temperature rises to 180~200 DEG C, starts pressurize 2.5~6
Hour, then it is depressured, the discharge water of steam containing ammonia, the water of steam containing ammonia collection otherwise processed, remaining cyanidation tailings in autoclave
General another solid waste can be converted into by being differentiated by hazardous waste toxicity.The cyanidation tailings cyanide complex degraded of present embodiment
Method, except cyanogen effect is good, steam pressure except cyanogen it is unrelated with the initial concentration of cyanogen, be temperature dependent with the time, steam pressure processing after cyanogen
The requirement of environmentally friendly common solid waste can be reached by changing tailings, and slag can recycle directly as secondary resource after processing, useless by danger
Thing toxicity, which leaches, differentiates that pH value is 7~8, and total cyanide is less than 1.5mg/L.The cyanidation tailings cyanide complex drop of present embodiment
The method of solution, simple and convenient, technique clean manufacturing is free from environmental pollution, by point for adding complexing agent, pore creating material quickening cyanide
Solution, shorten the reaction time, thoroughly solve the problems, such as cyanidation tailings overstock and secondary pollution, realize gold cyaniding smelt cleaning give birth to
Production, non-waste-emission, the target for comprehensively utilizing, turning waste into wealth.
Embodiment two
Present embodiment cyanidation tailings cyanide complex degraded method be：By the cyanidation tailings after press filtration, control aqueous
For mass percent between 20~30%, stirring adds cement, aluminium powder, EDTA, fulvic acid, cement, aluminium powder, EDTA, fulvic acid
Addition is followed successively by 0.5%, 0.5%, 0.3%, the 0.7% of cyanidation tailings dry weight percentage；Cement is bonded in tailings surface shape
The gas permeability of processing material can be increased into micropore, aluminium powder can react with water produces hydrogen formation micropore, so as to increase processing material
Gas permeability and thermal conductivity；Then material is installed with trolley, and trolley then is put into autoclave, 0.8 is vacuumized after closed
~1.0 hours, steam is then passed to, after temperature rises to 180~200 DEG C, starts 3~6 hours of pressurize, be then depressured,
The water of steam containing ammonia is discharged, the water of steam containing ammonia collects otherwise processed, and remaining cyanidation tailings pass through hazardous waste poison in autoclave
Property differentiate and can be converted into general another solid waste.The method of the cyanidation tailings cyanide complex degraded of present embodiment, except cyanogen is imitated
Fruit is good, and 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 ring
The requirement of common solid waste is protected, slag can recycle directly as secondary resource after processing, leach and differentiate by hazardous waste toxicity
PH value is 7~8, and total cyanide is less than 2mg/L.The method of the cyanidation tailings cyanide complex degraded of present embodiment, simple side
Just, technique clean manufacturing, free from environmental pollution, by adding complexing agent, pore creating material accelerates the decomposition of cyanide, when shortening reaction
Between, thoroughly solve the problems, such as cyanidation tailings overstock and secondary pollution, realize gold cyaniding smelting clean manufacturing, non-waste-emission,
The target comprehensively utilize, to turn waste into wealth.
Embodiment three
Present embodiment cyanidation tailings cyanide complex degraded method be：By the cyanidation tailings after press filtration, control aqueous
For mass percent between 20~30%, stirring adds aluminium powder, sodium humate, fulvic acid, ulmic acid, aluminium powder, sodium humate, Huang
Rotten acid, the addition of ulmic acid are followed successively by 2%, 1%, 1%, the 3% of cyanidation tailings dry weight percentage；Aluminium powder can react with water to be produced
Raw hydrogen forms micropore, so as to increase the gas permeability and thermal conductivity of processing material；Then material is installed with trolley, then by trolley
Autoclave is put into, 0.4~0.6 hour is vacuumized after closed, then passes to steam, 180~200 DEG C are risen in temperature
Afterwards, start 1.5~5.5 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 complex 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 7~8, total cyanide is less than 1.5mg/L.Present embodiment
Cyanidation tailings cyanide complex degraded method, simple and convenient, technique clean manufacturing is free from environmental pollution, by add complexing agent,
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.
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 complex 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 complexing agent and pore creating material
Stir mixing, wherein, pore creating material is cement and/or aluminium powder, complexing agent EDTA, sodium humate, fulvic acid, ulmic acid
The addition total amount of one or more, complexing agent and pore creating material is the 2~7% 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 complex degraded as claimed in claim 1, it is characterised in that：The complexing agent adds
It is 1~2% to enter amount, and the addition of the pore creating material is 1~5%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113105067A (en) * | 2021-03-22 | 2021-07-13 | 内蒙古金中矿业有限公司 | Method for removing cyanogen and recovering copper by mixing bacterial liquid and copper-containing cyanogen-containing wastewater |
| CN115647004A (en) * | 2022-11-04 | 2023-01-31 | 中国科学院过程工程研究所 | Harmless treatment method for cyanide tailings |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113105067A (en) * | 2021-03-22 | 2021-07-13 | 内蒙古金中矿业有限公司 | Method for removing cyanogen and recovering copper by mixing bacterial liquid and copper-containing cyanogen-containing wastewater |
| CN113105067B (en) * | 2021-03-22 | 2022-10-18 | 内蒙古金中矿业有限公司 | Method for removing cyanogen and recovering copper by mixing bacterial liquid and copper-containing cyanide-containing wastewater |
| CN115647004A (en) * | 2022-11-04 | 2023-01-31 | 中国科学院过程工程研究所 | Harmless treatment method for cyanide tailings |
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Application publication date: 20180320 |