CN104550205B - Clean conversion and comprehensive utilization method for cyanided tailings - Google Patents
Clean conversion and comprehensive utilization method for cyanided tailings Download PDFInfo
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- CN104550205B CN104550205B CN201510023812.2A CN201510023812A CN104550205B CN 104550205 B CN104550205 B CN 104550205B CN 201510023812 A CN201510023812 A CN 201510023812A CN 104550205 B CN104550205 B CN 104550205B
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Abstract
The invention discloses a clean conversion and comprehensive utilization method for cyanided tailings. The method comprises the following steps: hydrolyzing cyanides in the cyanided tailings with a high-pressure steaming method, closing an autoclave, vacuumizing for 0.4-1h, introducing steam, keeping the pressure for 1.5-4h after the temperature is raised to 170-200 DEG C, then reducing the pressure, discharging ammonia containing steam water, wherein secondary resource-cyanided tailings are remained in the autoclave; treating the ammonia nitrogen containing steam water with a magnesium ammonium phosphate precipitation method; and finally, carrying out flotation on the secondary resource-cyanided tailings to obtain sulfur concentrate with more than 48% of sulfur. The method has a good cyanogen removal effect and can achieve the one-time cyanogen removal rate up to more than 99.5%, and high-quality sulfur concentrate with more than 48% of sulfur and more than 5g/t of alloy can be obtained through floatation; and besides, the method is simple and convenient, can achieve clean production, and has cyanided tailing treatment cost of not higher than 80 yuan per ton.
Description
Technical field
The invention belongs to metallurgical slag application technology as the second resource field, and in particular to a kind of cyanidation tailings clean conversion synthesis
The method for utilizing.
Background technology
Gold recovery is high because it is carried for Cyanide Process, and the strong adaptability, technological operation to ore is simple, cost is relatively low
The advantages of, in numerous methods and technique of gold smelting, Cyanide Leaching extraction of gold process can not be substituted always.
Since 1887 apply, extensively applied all over the world, to 2005, newly-built solution of gold smelting plant in the world
More than 80% remains and adopts Cyanide Process.
But the cyanide used during cyanide gold-leaching, it possesses the toxicity being bound to arouse fear.
Cyanide gold-leaching process can produce substantial amounts of cyanidation tailings.
Contain substantial amounts of cyanide in cyanidation tailings, if these cyanides are not processed, cyanidation tailings may become danger
It is strategically secure useless.
According to country and place environmental protection laws and regulations regulation：Producing hazardous waste unit must be concentrated hazardous waste
Process, arrange special messenger to be responsible for collecting and management work, as ready hazardous waste will arrange dedicated container storage, and hazardous waste must be handed over
There is the unit with corresponding qualification to be collected, transport and process.
Dangerous solid waste generally requires depth landfill disposal.Depth landfill further relates to that dirt can or can not be produced to underground water
Dye.
These cyanidation tailings are dealt with improperly and are polluted the environment, but wherein containing some valuable elements such as：Sulphur, iron etc. are again
Less than recycling.
Therefore how to process these cyanidation tailings has very great meaning to the environmental protection of China and the comprehensive utilization of resource.
The content of the invention
The technical problem to be solved in the present invention is the defect for overcoming prior art, there is provided a kind of cyanidation tailings clean conversion is comprehensive
The method that conjunction is utilized, comprises the following steps：
1）, using steam pressure method hydrolysis cyanidation tailings in cyanide
To be installed with trolley after cyanidation tailings press filtration, then trolley put into into still kettle, it is closed after vacuumize 0.4～1
Hour, steam is then passed to, after temperature rises to 180～200 DEG C, start 1.5～4 hours of pressurize, then it is depressured, discharge contains
Ammonia steam water, remaining secondary resource cyanidation tailings in still kettle.Even if cyanide also can slowly hydrolyze at normal temperatures generation ammonium salt
And formates, when temperature reaches 65 DEG C, reaction speed is accelerated, when temperature reaches more than 170 DEG C, the hydrolysis speed of cyanide
Degree is quickly.Using this principle carry out containing cyanogen waste disposal method cry pressurizing hydrolysis, also known as add pyrohydrolytic method.Heat resolve is anti-
Answer mechanism as follows：CN-+ 2H2O= HCOO- + NH3
The method also referred to as destruction of the pyrohydrolysis containing cyanogen material method, its advantage is not consume other any medicaments,
Simultaneously free cyanide not only can be processed, can also process the fluor-complex containing cyanogen;The scope that concentration containing cyanogen in waste material is adapted to
Extensively, it is simple to operate, it is stable.
Under this condition, free CN- can not only hydrolyzed, moreover it is possible to make some water containing cyano complex such as ferrocyanide
Solution.Heating hydrolysis principle mechanism is as follows：
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
2）, to 1）Sodium dihydrogen phosphate and magnesium chloride are added in the water of steam containing ammonia of middle gained, it is 8.5～9.5 to adjust pH, is adopted
With magnesium ammonium phosphate sediment method steam water of the process containing ammonia nitrogen, then the water sedimentation of steam containing ammonia is filtered, be precipitated as rich in ammonium phosphate
The slow release fertilizer of magnesium, supernatant then reflowable recycling.Due to NH4+Typically will not generate with anion and precipitate, and it some
Double salt is water insoluble in the basic conditions.Therefore, phosphate anion is added in waste water and specific metal ion can be with height
The ammonia nitrogen of concentration is combined and generates sediment, so as to remove it.Relative to other metals, of many uses, the low price of magnesium, and
And be difficult to cause secondary pollution, therefore magnesium salts and phosphate are added, the ammonia nitrogen in water is made with magnesium ammonium phosphate sediment (MAP) form quilt
Remove, so as to realize the effective process of high-concentration ammonia nitrogenous wastewater.Product MgNH4PO46H2O is commonly called as guanite, is a kind of good
Slow-release fertilizer, realize the recycling of ammonia nitrogen.The main process of MAP methods can be represented with following ion-reaction equation：
Mg2++PO4 3-+NH4 ++6H20→MgNH4PO4·6H2O
Mg2++HP04 2-+NH4 ++6H20→+MgNH4PO4·6H2O+H+
Mg2++H2PO4 -+NH4 ++6H20→MgNH4PO4·6H2O+2H+
3）, flotation secondary resource cyanidation tailings
Using butylamine black powder and butyl xanthate combined capturing and collecting agent, the one thick two single-minded flow process swept, closed circuit energy are passed through
Obtain sulfur grade>48% iron concentrate, sulfur recovery rate up to 80.65%, iron concentrate 6.12g/t containing gold, gold recovery up to 63.13%, tail
It is mining to do construction material.
Further, the step 2）In in steam containing ammonia plus NH4+、Mg2+And PO4-3Mol ratio be n (NH4+)：n
(Mg2+)：n(PO4-3)=1:1.1:1。
Preferably, the step 1）In, 0.5 hour is vacuumized after still kettle is closed, steam is passed through, rise in temperature
After 190 DEG C, 2 hours of pressurize
Further, the step 3）In, the consumption of butylamine black powder is 15～35 grams per ton, and the consumption of butyl xanthate is 60
～120 grams per ton.
The beneficial effect that reached of the present invention is：
First, the method for cyanidation tailings clean conversion of the invention comprehensive utilization, except cyanogen effect is good, disposable Hydrolysis rate reaches
More than 99.5%, steam pressure is unrelated with the initial concentration of cyanogen except cyanogen, is temperature dependent with the time, the cyanidation tailings energy after steam pressure process
The requirement of environmentally friendly common solid waste is reached, slag ph is not required to be processed again for 7-8 after process, can be directly as the secondary money of iron concentrate
Source recycles.Sulfur-bearing more than 48% can be obtained after flotation, the iron concentrate containing high-quality of the gold more than 5g/t.
2nd, the method for cyanidation tailings clean conversion of the invention comprehensive utilization, simple and convenient, technique clean manufacturing is not dirty
Dye environment, without any medicament, cost of investment and operating cost are low, process cyanidation tailings cost per ton and are not higher than 80
Yuan/ton, thoroughly solve the problems, such as that cyanidation tailings overstock and secondary pollution, realize clean manufacturing, the useless row of nothing that gold cyaniding is smelted
The target for put, comprehensively utilize, turning waste into wealth.
Description of the drawings
Accompanying drawing is used for providing a further understanding of the present invention, and constitutes a part for specification, the reality with the present invention
Applying example is used to explain the present invention together, is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the schematic flow sheet of the present invention.
Specific embodiment
Below in conjunction with illustrating to the preferred embodiments of the present invention, it will be appreciated that preferred embodiment described herein
The present invention is merely to illustrate and is explained, is not intended to limit the present invention.
Embodiment 1
A kind of method of cyanidation tailings clean conversion comprehensive utilization, comprises the following steps：
1）, using steam pressure method hydrolysis cyanidation tailings in cyanide
To be installed with trolley after cyanidation tailings press filtration, then trolley put into into still kettle, it is closed after vacuumize 0.4 it is little
When, steam is then passed to, after temperature rises to 170 DEG C, start 4 hours of pressurize, then it is depressured, the water of steam containing ammonia is discharged, steam
Remaining secondary resource cyanidation tailings in pressure kettle；
2）, to 1）Sodium dihydrogen phosphate and magnesium chloride are added in the water of steam containing ammonia of middle gained so that NH4+、Mg2+And PO4-3
Mol ratio be n (NH4+)：n(Mg2+)：n(PO4-3)=1:1.1:1, it is 8.5 to adjust pH, is contained using the process of magnesium ammonium phosphate sediment method
The steam water of ammonia nitrogen, then filters to the water sedimentation of steam containing ammonia, is precipitated as the slow release fertilizer rich in ammonium magnesium phosphate, and supernatant then may be used
Backflow is recycled；
3）, flotation secondary resource cyanidation tailings
Using butylamine black powder and butyl xanthate combined capturing and collecting agent, the one thick two single-minded flow process swept is passed through, can obtain
Sulphur>48% iron concentrate, mine tailing is used as construction material, and the wherein consumption of butylamine black powder is 15 grams per ton, and the consumption of butyl xanthate is
120 grams per ton.
Embodiment 2
A kind of method of cyanidation tailings clean conversion comprehensive utilization, comprises the following steps：
1）, using steam pressure method hydrolysis cyanidation tailings in cyanide
To be installed with trolley after cyanidation tailings press filtration, then trolley put into into still kettle, it is closed after vacuumize 0.5 it is little
When, steam is then passed to, after temperature rises to 190 DEG C, start 2 hours of pressurize, then it is depressured, the water of steam containing ammonia is discharged, steam
Remaining secondary resource cyanidation tailings in pressure kettle；
2）, to 1）Sodium dihydrogen phosphate and magnesium chloride are added in the water of steam containing ammonia of middle gained so that NH4+、Mg2+And PO4-3
Mol ratio be n (NH4+)：n(Mg2+)：n(PO4-3)=1:1.1:1, it is 9 to adjust pH, and using the process of magnesium ammonium phosphate sediment method ammonia is contained
The steam water of nitrogen, then filters to the water sedimentation of steam containing ammonia, is precipitated as the slow release fertilizer rich in ammonium magnesium phosphate, and supernatant then can be returned
Stream is recycled；
3）, flotation secondary resource cyanidation tailings
Using butylamine black powder and butyl xanthate combined capturing and collecting agent, the one thick two single-minded flow process swept is passed through, can obtain
Sulphur>48% iron concentrate, mine tailing is used as construction material, and the wherein consumption of butylamine black powder is 20 grams per ton, and the consumption of butyl xanthate is
60 grams per ton.
Embodiment 3
A kind of method of cyanidation tailings clean conversion comprehensive utilization, comprises the following steps：
1）, using steam pressure method hydrolysis cyanidation tailings in cyanide
To be installed with trolley after cyanidation tailings press filtration, then trolley put into into still kettle, it is closed after vacuumize 1 hour,
Steam is then passed to, after temperature rises to 200 DEG C, starts 1.5 hours of pressurize, be then depressured, discharge the water of steam containing ammonia, steam pressure
Remaining secondary resource cyanidation tailings in kettle；
2）, to 1）Sodium dihydrogen phosphate and magnesium chloride are added in the water of steam containing ammonia of middle gained so that NH4+、Mg2+And PO4-3
Mol ratio be n (NH4+)：n(Mg2+)：n(PO4-3)=1:1.1:1, it is 9.5 to adjust pH, is contained using the process of magnesium ammonium phosphate sediment method
The steam water of ammonia nitrogen, then filters to the water sedimentation of steam containing ammonia, is precipitated as the slow release fertilizer rich in ammonium magnesium phosphate, and supernatant then may be used
Backflow is recycled；
3）, flotation secondary resource cyanidation tailings
Using butylamine black powder and butyl xanthate combined capturing and collecting agent, the one thick two single-minded flow process swept is passed through, can obtain
Sulphur>48% iron concentrate, mine tailing is used as construction material, and the wherein consumption of butylamine black powder is 35 grams per ton, and the consumption of butyl xanthate is
80 grams per ton.
Finally it should be noted that：The preferred embodiments of the present invention are the foregoing is only, the present invention is not limited to,
Although being described in detail to the present invention with reference to the foregoing embodiments, for a person skilled in the art, it still may be used
To modify to the technical scheme described in foregoing embodiments, or equivalent is carried out to which part technical characteristic.
All any modification, equivalent substitution and improvements within the spirit and principles in the present invention, made etc., should be included in
Within protection scope of the present invention.
Claims (7)
1. a kind of method that cyanidation tailings clean conversion is comprehensively utilized, it is characterised in that comprise the following steps：
1）, using steam pressure method hydrolysis cyanidation tailings in cyanide
To be installed with trolley after cyanidation tailings press filtration, then trolley put into into still kettle, it is closed after vacuumize 0.4～1 hour,
Steam is then passed to, after temperature rises to 170～200 DEG C, starts 1.5～4 hours of pressurize, be then depressured, discharged and steamed containing ammonia
Carbonated drink, remaining secondary resource cyanidation tailings in still kettle；
2）, to 1）Sodium dihydrogen phosphate and magnesium chloride are added in the water of steam containing ammonia of middle gained, it is 8.5～9.5 to adjust pH, using phosphorus
Sour ammonium magnesium precipitate method processes the water of steam containing ammonia, and then the water sedimentation of steam containing ammonia is filtered, and is precipitated as the sustained release rich in ammonium magnesium phosphate
Fertilizer, supernatant then reflowable recycling；
3）, flotation secondary resource cyanidation tailings
Using butylamine black powder and butyl xanthate combined capturing and collecting agent, the one thick two single-minded flow process swept is passed through, sulphur can have been obtained>
48% iron concentrate, mine tailing is used as construction material.
2. the method that a kind of cyanidation tailings clean conversion as claimed in claim 1 is comprehensively utilized, it is characterised in that the step
2）In in steam containing ammonia plus NH4+、Mg2+And PO4-3Mol ratio be n (NH4+)：n(Mg2+)：n(PO4-3)=1:1.1:1。
3. the method that a kind of cyanidation tailings clean conversion as claimed in claim 1 is comprehensively utilized, it is characterised in that the step
1）In, 0.5 hour is vacuumized after still kettle is closed.
4. the method that a kind of cyanidation tailings clean conversion as claimed in claim 1 is comprehensively utilized, it is characterised in that the step
1）In, steam is passed through, after temperature rises to 190 DEG C, start pressurize.
5. the method that a kind of cyanidation tailings clean conversion as claimed in claim 1 is comprehensively utilized, it is characterised in that the step
1）In, after temperature rises to 180～200 DEG C, 2 hours of pressurize.
6. the method that a kind of cyanidation tailings clean conversion as claimed in claim 1 is comprehensively utilized, it is characterised in that the step
3）In, the consumption of butylamine black powder is 15～35 grams per ton.
7. the method that a kind of cyanidation tailings clean conversion as claimed in claim 1 is comprehensively utilized, it is characterised in that the step
3）In, the consumption of butyl xanthate is 60～120 grams per ton.
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| CN104889134B (en) * | 2015-05-13 | 2017-03-01 | 长春黄金研究院 | A kind of gold mine cyanogen-containing tailing Slag treatment method |
| CN107812342A (en) * | 2017-10-20 | 2018-03-20 | 福建省双旗山矿业有限责任公司 | The method of cyanidation tailings cyanide complex degraded |
| CN107890622A (en) * | 2017-10-20 | 2018-04-10 | 福建省双旗山矿业有限责任公司 | The method of cyanidation tailings cyanide oxidation degraded |
| CN108043587A (en) * | 2017-10-20 | 2018-05-18 | 福建省双旗山矿业有限责任公司 | Extraction process containing ferrous sulfide in golden cyaniding tailing |
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| JP2001121132A (en) * | 1999-10-28 | 2001-05-08 | Eco-Techno Corp | Insolubilizing method of soil and industrial waste containing cyan compound and soluble heavy metals |
| RU2291909C1 (en) * | 2005-06-08 | 2007-01-20 | Хазрет Меджидович Совмен | Method for extracting of gold from rebellious auriferous-arsenical ores |
| CA2619529A1 (en) * | 2005-08-19 | 2007-03-01 | Barrick Gold Corporation | Treatment of reclaim water for use in metals recovery |
| JP2007105669A (en) * | 2005-10-14 | 2007-04-26 | Kurita Water Ind Ltd | Method for insolubilizing and treating cyanide-contaminated system |
| CN104107761A (en) * | 2014-04-28 | 2014-10-22 | 云南黄金矿业集团股份有限公司 | Method for recycling valuable metals from cyanidation slag containing gold |
| CN104073645B (en) * | 2014-06-30 | 2016-01-20 | 东北大学 | A kind of method reclaiming valuable metal in ultra-fine cyanidation tailings with high cyanogen backwater to float |
| CN104195349B (en) * | 2014-08-28 | 2016-09-14 | 福建省双旗山矿业有限责任公司 | A kind of cyanidation tailings waste residue degradation treatment technique |
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