CN108588439A - A kind of method of cyanide in removal cyanide residue - Google Patents
A kind of method of cyanide in removal cyanide residue Download PDFInfo
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Abstract
The invention discloses a kind of methods of cyanide in removal cyanide residue, include the following steps：Thiobacillus thioxidans is tamed, the Thiobacillus thioxidans tamed, the Thiobacillus thioxidans of domestication is added in cyanide residue and is reacted, the oxygen sulfur compound transition state generated during the lower valency sulphur in cyanide residue is oxidized to high-valence state sulphur using the Thiobacillus thioxidans of domestication aoxidizes the cyanide in cyanide residue, realize the removal of cyanide, wherein, pyrite or magnetic iron ore are contained in the cyanide residue.This method has many advantages, such as that technological process is simple, removal effect is good, pollution-free, and by cyanide residue pyrite or magnetic iron ore resource turn waste into wealth, greatly reduce SO2Usage amount, greatly reduce cost.This method solve SO during existing INCO methods removal cyanide2Consumption is big, the high problem of processing cost.
Description
Technical field
The present invention relates to cyanide Treatment process fields, and in particular to a method of cyanide in removal cyanide residue.
Background technology
Cyanide is extremely toxic substance.50 milligrams of the oral lethal dose average out to of HCN people, about 100 milligrams of Cymag, potassium cyanide
About 120 milligrams.Harm of the cyanide to human body and the influence to health are very big, and cyanide is to fish and other aquatic organisms
Harm is also larger.Cyanide content is converted into cryanide ion (CN in water-) a concentration of 0.04-0.1 mg/litres when, fish can be made
It is lethal.To the CN of planktonic organism and crustaceans-Maximum acceptable concentration is 0.01 mg/litre.Cyanide is in water to fish
Toxicity also with the pH value of water, dissolved oxygen and other metal ions there are related.Cyanide wastewater can also cause the agriculture underproduction, domestic animal
Poultry is dead.Gold extraction need to carry out leaching process with cyanide to ore, therefore a large amount of cyanides can be remained in its leached mud.It is right
Human health and surrounding enviroment cause significant damage.
Continuous improvement with national environmental protection policy requirements and Developing Circulation Economy establish gold Cyanide Leaching tailings
Exhaust emission constraint is imperative with administrative mechanism.Currently, the restructuring bankrupt of cyanide mainly has chemical oxidation, biological oxidation and other
Physical and chemical adsorption method.But for the cyanide in processing ore pulp, INCO methods (SO2/ air oxidation process) be it is the most cheap and
One of reliable method, and applied in many enterprises.But INCO methods are in use, need to use SO2。SO2Purchase
It is extremely inconvenient and of high cost to buy, transport and preserve.Some barghs can utilize pyrite oneself the production SO that mine is rich in2,
But there is also production examination ＆ approval are difficult, the problems such as found the factory costly.Cause the processing cost of cyanide in ore pulp high.
Invention content
The main purpose of the present invention is to provide a kind of methods of cyanide in removal cyanide residue, to solve the prior art
Cyanide process SO is removed in INCO methods2Consumption is big, the high problem of processing cost.
To achieve the goals above, the present invention provides a kind of methods of cyanide in removal cyanide residue, including following step
Suddenly：Thiobacillus thioxidans is tamed, the Thiobacillus thioxidans tamed, the Thiobacillus thioxidans of domestication is added to cyanogen
It is reacted in slugging, the lower valency sulphur in cyanide residue is oxidized to the process of high-valence state sulphur using the Thiobacillus thioxidans of domestication
The oxygen sulfur compound transition state of middle generation aoxidizes the cyanide in cyanide residue, that is, realizes the removal of cyanide, wherein institute
It states and contains pyrite or magnetic iron ore in cyanide residue, the total mass fraction of pyrite or magnetic iron ore is more than 5% in cyanide residue.
In the present invention, it includes following two modes that the Thiobacillus thioxidans of domestication, which is added in cyanide residue, and carries out reaction.
First way is：The Thiobacillus thioxidans of domestication is added under stirring into cyanide residue and its leachate, cyanogen is added
The CuSO of slugging and its leachate gross mass 0%-0.02%4·5H2O, and air is blasted, regulation system pH is 10-11, reaction
4-32 hours, wherein speed of agitator 90r/min-120r/min, air velocity 50mL/min-200mL/min, reaction temperature
Degree is 5 DEG C -45 DEG C.
Further, the addition volume and the mass ratio of cyanide residue and its leachate of the Thiobacillus thioxidans of domestication are
0.8mL/kg-1.2mL/kg。
Further, Cu in system2+A concentration of 10mg/L-50mg/L.
Further, sulfur dioxide is also passed through into system in reaction process.
Another way is：Cyanide residue is deposited in antiseepage film, the CuSO of cyanide residue quality 0%-0.02% is added4·
5H2The Thiobacillus thioxidans of domestication is dissolved in the aqueous slkali that pH is 10-11, then sprays cyaniding slag muck, spray with aqueous slkali by O
The pH of control cyaniding slag muck is 10-11 in the process, is sprayed 1-4 weeks.
Further, the addition volume and the mass ratio of cyanide residue and its leachate of the Thiobacillus thioxidans of domestication are
0.8mL/kg-1.2mL/kg。
Further, in the present invention, by Thiobacillus thioxidans tame the specific steps are：
Separation and concentration obtains Thiobacillus thioxidans bacterium solution from the alkaline leaching liquid of cyanide residue, and culture is added in taming bottle
The pH of cyanide residue at liquid and Thiobacillus thioxidans bacterium solution acquisition and its alkaline leaching liquid, regulation system is 9-11, and oxygen is added
Change sulphur Thiobacillus bacterium solution, concussion is cultivated 3-5 days, and then low-speed centrifugal obtains supernatant liquor, then is centrifuged from supernatant liquor high speed
The bacterium solution that separation and concentration is activated；
It repeats the above steps and the bacterium solution of activation is repeatedly tamed, culture solution is gradually decreased during multiple domestication
Additive amount, gradually increases the concentration of cyanide in cyanide residue and its alkaline leaching liquid, and is gradually added copper sulphate, until no longer adding
Bacterium solution can obtain inorganic matter from cyanide residue and its alkaline leaching liquid when adding culture solution.
Further, in the present invention, culture solution is by 0.1g/L KCl, 0.5g/L K3PO4、3g/L NH4SO4With
0.05g/L KNO3Composition.
Further, in the present invention, oxygen sulfur compound transition state includes S2O5 2-、SO3 2-。
It applies the technical scheme of the present invention, the sulphur in pyrite or magnetic iron ore in cyanide residue ore pulp is dexterously utilized to make
For sulphur source, using the Thiobacillus thioxidans of domestication by lower valency sulphur (S2-) it is oxidized to high-valence state sulphur (S6+) during generate sulphur
Oxygen compound transition state (S2O5 2-、SO3 2-) instead of the SO in INCO methods2Reduction-oxidation cyanide, this method have technological process letter
Single, the advantages that removal effect is good, pollution-free, and by cyanide residue pyrite or magnetic iron ore resource turn waste into wealth, subtract significantly
SO is lacked2Usage amount, greatly reduce cost.This method solve SO during existing INCO methods removal cyanide2Consumption
Greatly, the high problem of processing cost.
Specific implementation mode
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.Below in conjunction with embodiment, the present invention will be described in detail.
As recorded in background technology, the cyanide generally use INCO methods in ore pulp are handled, existing INCO methods are using
It needs to use a large amount of SO in the process2, cause the processing cost of cyanide in ore pulp high.To solve the above-mentioned problems, originally
Application provides a kind of method removing cyanide in cyanide residue.
In a kind of typical embodiment of the application, a kind of method removing cyanide in cyanide residue, the party are provided
Method includes the following steps：Thiobacillus thioxidans is tamed, the Thiobacillus thioxidans tamed, by the sulfur oxide sulphur of domestication
Bacillus, which is added in cyanide residue, to be reacted, and the lower valency sulphur in cyanide residue is oxidized to height using the Thiobacillus thioxidans of domestication
The oxygen sulfur compound transition state generated during valence state sulphur aoxidizes the cyanide in cyanide residue, that is, realizes cyanide
Removal, wherein in the cyanide residue contain pyrite or magnetic iron ore, and in cyanide residue pyrite or magnetic iron ore gross mass
Score should be more than 5%.
By verification experimental verification, the application dexterously using the sulphur in the pyrite or magnetic iron ore in cyanide residue ore pulp as
Sulphur source, using the Thiobacillus thioxidans of domestication by lower valency sulphur (S2-) it is oxidized to high-valence state sulphur (S6+) during generate sulphur oxygen
Compound transition state (S2O5 2-、SO3 2-) instead of the SO in INCO methods2Reduction-oxidation cyanide.This method has technological process letter
Single, the advantages that removal effect is good, pollution-free, and by cyanide residue pyrite or magnetic iron ore resource turn waste into wealth, subtract significantly
SO is lacked2Usage amount, greatly reduce cost.This method solve SO during existing INCO methods removal cyanide2Consumption
Greatly, the high problem of processing cost.The application removes the principle of cyanide as shown in following reaction 1 and reaction 2.It is existing
INCO methods remove the principle of cyanide as shown in following reaction 3.
Reaction 1：
Reaction 2：
Reaction 3：
Specifically, in the application by the Thiobacillus thioxidans of domestication be added to the mode reacted in cyanide residue have it is following
Two kinds.Wherein, first way is：The Thiobacillus thioxidans of domestication is added under stirring into cyanide residue and its leachate, is added
The CuSO of cyanide residue and its leachate gross mass 0%-0.02%4·5H2O, and air is blasted, regulation system pH is 10-11, instead
It answers 4-32 hours, wherein speed of agitator 90r/min-120r/min, air velocity 50mL/min-200mL/min, reaction
Temperature is 5 DEG C -45 DEG C.
This mode is that cyanide residue is mixed into its leachate, and the sulfur oxide sulphur bar of domestication is added in suspension system
Bacterium removes the cyanide in cyanide residue.By controlling during the reaction blasting air velocity, and to the pH of system into
Row regulation and control, control bacterium pyrite or Surface of Pyrrhotite oxidation rate, to utilize S2-It is oxidized to S6+Sulphur aoxidizes in the process
Close object transition state (S2O5 2-、SO3 2-) generation, and orderly carried out and comprehensive each control parameter by control each step
Cooperation, finally realizes the innoxious removal to cyanide, greatly reduces SO2Usage amount, reduce cost.
Further, the addition volume and the mass ratio of cyanide residue and its leachate of the Thiobacillus thioxidans of domestication are
0.8mL/kg-1.2mL/kg, preferably 1mL/kg can obtain better cyanide removal effect with this condition.
(reaction 2) needs Cu during oxygen sulfur compound transition state is reacted with cyanide2+Catalytic action is played, preferably will
Cu in system2+Concentration control in 10mg/L-50mg/L, better cyanide removal effect can be obtained.Cu2+Concentration
CuSO can be added into system by being adjusted in reaction4·5H2The amount of O is adjusted, if ore pulp Central Plains is originally contained
Cu2+And Cu2+Concentration reach the demand and can not then add CuSO4·5H2O, if being free of Cu in ore pulp originally2+It then can be with
The CuSO within cyanide residue and its leachate gross mass 0.02% is added4·5H2O provides enough Cu2+。
It is possible to further be passed through a certain amount of sulfur dioxide into system during the reaction, sulfur dioxide is passed through
Flow velocity can determine according to the amount of handled cyanide residue or cyanating solution, can be with 0mL/min- when such as handling 2kg cyanide residues
The rate of 5mL/min is passed through sulfur dioxide.Also, it is specific whether need to be passed through sulfur dioxide and sulfur dioxide be passed through flow velocity
It is codetermined by the amount containing cyanogen of cyanide residue, sulfur content and institute processing speed to be achieved.Speed up processing is such as thought, at shortening
The reason time can then be passed through a small amount of SO2To promote reaction speed；If do not required processing time, without being passed through SO2。
In the present invention, the Thiobacillus thioxidans of domestication, which is added to the second way reacted in cyanide residue, is：
Cyanide residue is deposited in antiseepage film, the CuSO of cyanide residue quality 0%-0.02% is added4·5H2O, by domestication
Thiobacillus thioxidans is dissolved in the aqueous slkali that pH is 10-11, then sprays cyaniding slag muck with aqueous slkali, and spray liquid is received in antiseepage film
Collect and spray repeatedly, persistently spray a small amount of limewash, the pH that cyaniding slag muck is controlled during spray is 10-11, is sprayed 1-4 weeks.
This mode is individually to handle solid cyanide residue, the method for the Thiobacillus thioxidans liquid by spraying domestication repeatedly
Remove the cyanide in cyanide residue.Likewise, by regulating and controlling during the reaction to each parameters such as pH to system, control
Bacterium pyrite or Surface of Pyrrhotite oxidation rate, to utilize S2-It is oxidized to S6+Oxygen sulfur compound transition state in the process
(S2O5 2-、SO3 2-) generation, finally realize the innoxious removal to cyanide, greatly reduce SO2Usage amount, reduce
Cost.
Specifically, the addition volume of the Thiobacillus thioxidans of domestication exists with the control of the mass ratio of cyanide residue and its leachate
0.8mL/kg-1.2mL/kg, preferably 1mL/kg can obtain better cyanide removal effect with this condition.
Specifically, the present invention in, by Thiobacillus thioxidans tame the specific steps are：
Separation and concentration obtains Thiobacillus thioxidans bacterium solution from the alkaline leaching liquid of cyanide residue, and culture is added in taming bottle
The pH of cyanide residue at liquid and Thiobacillus thioxidans bacterium solution acquisition and its alkaline leaching liquid, regulation system is 9-11, and oxygen is added
Change sulphur Thiobacillus bacterium solution, concussion cultivates 3-5 days, then low-speed centrifugal (800r/min) acquisition supernatant liquor, then from supernatant liquor
The bacterium solution that high speed centrifugation (20000r/min) separation and concentration is activated；
It repeats the above steps and the bacterium solution of activation is repeatedly tamed, culture solution is gradually decreased during multiple domestication
Additive amount, gradually increases the concentration of cyanide in cyanide residue and its alkaline leaching liquid, and is gradually added copper sulphate, until no longer adding
Bacterium solution can obtain inorganic matter from cyanide residue and its alkaline leaching liquid when adding culture solution, tame latter stage, and total cyanogen amount is promoted to
1000mg/L, Cu in solution2+Concentration reaches 50mg/L, and maintains 4 days.
The Thiobacillus thioxidans of required domestication of the invention can be obtained by the above method.
Further, culture solution is minimal media liquid, and the minimal media liquid is by 0.1g/L KCl, 0.5g/L K3PO4、3g/L
NH4SO4With 0.05g/L KNO3Composition.
Below in conjunction with specific embodiment, the invention will be further described, but should not be construed as protecting the present invention
The limitation of range.
Embodiment 1：
Utilize the methods Laboratory processing Shandong enterprise gold Cyanide Leaching slag of the present invention, total cyanogen root amount 552mg/L, pH
For 10.5-11.
By 2kg cyanide residues and its leachate (solid-liquid mass ratio 1:3) it is added in 15L reaction kettles, mixing speed 90-120r/
200-250mg CuSO are added in min4·5H2O is added 2ml and tames bacterium, and blasts air and (or be passed through SO simultaneously2), air stream
Fast 50-200ml/min；Lime water management pH to 10-11 is added, reaction temperature is 25-30 DEG C, reaction time 12-72 hour.It removes
After the completion of cyanogen, slurry filtration is separated by solid-liquid separation, measures its cyanide content respectively.Leached mud containing cyanogen removes cyanogen test result such as table 1
It is shown.
1 leached mud containing cyanogen of table removes cyanogen test result
By table 1 as it can be seen that method using the present invention, is not passed through SO2In the case of, react the cyanide removal effect of 48h
With existing INCO methods SO2Flow 2mL/min, the cyanide removal effect for reacting 12h are suitable；It is being passed through SO2Flow is identical, reacts
In the case of time is identical, the removal effect of method cyanide using the present invention is substantially better than existing INCO methods.Illustrate this hair
Bright method can substitute existing INCO methods and be effectively removed to the cyanide in cyanide residue.
Embodiment 2：
Utilize the methods Laboratory processing Hunan enterprise gold Cyanide Leaching slag of the present invention, total cyanogen root amount 732mg/L, pH
For 10-10.5.
By 2kg cyanide residues and its leachate (solid-liquid mass ratio 1:3) it is added in 15L reaction kettles, mixing speed 90-120r/
200-250mg CuSO are added in min4·5H2O is added 2.5ml and tames bacterium, and blasts air and (or be passed through SO simultaneously2), air
Flow velocity 50-200mL/min；Lime water management pH to 10-11 is added, reaction temperature is 25-30 DEG C of room temperature, reaction time 18-84
Hour.After the completion of cyanogen, slurry filtration is separated by solid-liquid separation, it is measured respectively and contains cyanide content.Leached mud containing cyanogen is tested except cyanogen
The results are shown in Table 2.
2 leached mud containing cyanogen of table removes cyanogen test result
As can be seen from Table 2, method using the present invention, is not passed through SO2In the case of, react the cyanide removal effect of 60h
With existing INCO methods SO2Flow 2mL/min, the cyanide removal effect for reacting 18h are suitable；It is being passed through SO2Flow is identical, reacts
In the case of time is identical, the removal effect of method cyanide using the present invention is substantially better than existing INCO methods.Illustrate this hair
Bright method can substitute existing INCO methods and be effectively removed to the cyanide in cyanide residue.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, any made by repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of method of cyanide in removal cyanide residue, which is characterized in that include the following steps：Thiobacillus thioxidans is carried out
Domestication, the Thiobacillus thioxidans of domestication is added in cyanide residue and reacts by the Thiobacillus thioxidans tamed, using taming and dociling
The oxygen sulfur compound mistake that the Thiobacillus thioxidans of change generates during the lower valency sulphur in cyanide residue is oxidized to high-valence state sulphur
It crosses state to aoxidize the cyanide in cyanide residue, that is, realizes the removal of cyanide, wherein contain pyrite in the cyanide residue
Or magnetic iron ore, and the total mass fraction of pyrite or magnetic iron ore is more than 5% in cyanide residue.
2. according to the method described in claim 1, it is characterized in that, described be added to cyanide residue by the Thiobacillus thioxidans of domestication
In carry out reaction specifically refer to：
The Thiobacillus thioxidans of domestication is added under stirring into cyanide residue and its leachate, cyanide residue and its total matter of leachate is added
Measure the CuSO of 0%-0.02%4·5H2O, and air is blasted, regulation system pH is 10-11, is reacted 4-32 hours, wherein stirring
Rotating speed is 90r/min-120r/min, and air velocity 50mL/min-200mL/min, reaction temperature is 5 DEG C -45 DEG C.
3. according to the method described in claim 2, it is characterized in that, addition volume and the institute of the Thiobacillus thioxidans of the domestication
The mass ratio for stating cyanide residue and its leachate is 0.8mL/kg-1.2mL/kg.
4. according to the method described in claim 2, it is characterized in that, Cu in the system2+A concentration of 10mg/L-50mg/L.
5. according to the method described in claim 2, it is characterized in that, sulfur dioxide is also passed through in reaction process into system.
6. according to the method described in claim 1, it is characterized in that, described be added to cyanide residue by the Thiobacillus thioxidans of domestication
In carry out reaction specifically refer to：
Cyanide residue is deposited in antiseepage film, the CuSO of cyanide residue quality 0%-0.02% is added4·5H2O, by the oxidation of domestication
Sulphur Thiobacillus is dissolved in the aqueous slkali that pH is 10-11, then sprays cyaniding slag muck with aqueous slkali, cyaniding slag muck is controlled during spray
PH be 10-11, spray 1-4 weeks.
7. according to the method described in claim 6, it is characterized in that, addition volume and the institute of the Thiobacillus thioxidans of the domestication
The mass ratio for stating cyanide residue and its leachate is 0.8mL/kg-1.2mL/kg.
8. according to the method described in claim 1, it is characterized in that, the specific steps that Thiobacillus thioxidans is tamed
For：
Separation and concentration obtains Thiobacillus thioxidans bacterium solution from the alkaline leaching liquid of cyanide residue, in taming bottle be added culture solution with
And the cyanide residue at bacterium solution acquisition and its alkaline leaching liquid, the pH of regulation system is 9-11, and Thiobacillus thioxidans bacterium solution, shake is added
Cultivation 3-5 days is swung, then low-speed centrifugal obtains supernatant liquor, then centrifuges what enrichment was activated from supernatant liquor high speed
Bacterium solution；
It repeats the above steps and the bacterium solution of activation is repeatedly tamed, the addition of culture solution is gradually decreased during multiple domestication
Amount, gradually increases the concentration of cyanide in cyanide residue and its alkaline leaching liquid, and be gradually added copper sulphate, until no longer addition training
Bacterium solution can obtain inorganic matter from cyanide residue and its alkaline leaching liquid when nutrient solution.
9. according to the method described in claim 8, it is characterized in that, the culture solution is by 0.1g/L KCl, 0.5g/L K3PO4、
3g/L NH4SO4With 0.05g/L KNO3Composition.
10. according to the method described in claim 1, it is characterized in that, the oxygen sulfur compound transition state includes S2O5 2-、SO3 2-。
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