CN103523965A - Two-section innocent treatment technology for cyanogens-containing tailing pulp - Google Patents
Two-section innocent treatment technology for cyanogens-containing tailing pulp Download PDFInfo
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- CN103523965A CN103523965A CN201310507299.5A CN201310507299A CN103523965A CN 103523965 A CN103523965 A CN 103523965A CN 201310507299 A CN201310507299 A CN 201310507299A CN 103523965 A CN103523965 A CN 103523965A
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Abstract
The invention discloses a two-section innocent treatment technology for cyanogens-containing tailing pulp. The technology comprises a pulp concentration step and an oxidization step, wherein in the pulp concentration step, thickening equipment is used for improving the concentration of the pulp to 50-55 percent; thickened supernate is returned to a site selection technology; high-concentration pulp enters the next treatment procedure; a thickening theory is that solid-liquid separation is performed through gravity sedimentation; in the oxidization step, oxidization is divided into two stages by an OOT oxidization method; in the first stage, sulfuric acid is added to control the pH of the pulp to be 9 to 10, and most releasable cyanides, thiocyanate ions and reductive substances can be removed through oxidization, so that the concentration of the releasable cyanides is smaller than 30 mg/L, and the concentration of the thiocyanate ions is smaller than 10 mg/L; in the second stage, the sulfuric acid is added to adjust the pH of the pulp to be 7 to 8; active carbon is fed in the second oxidization stage to enhance the oxidization effect; due to the adsorption effect of the carbon, gold in part of the tailing pulp can be recycled.
Description
Technical field
Gold mine is generally applied sodium cyanide and is soaked gold, and the sludge containing cyanogens of its generation has hazardness to physical environment in stacking process, need to carry out harmless treatment to it, and the present invention will solve qualified discharge and the safe stacking problem of sludge containing cyanogens.
Background technology
1, sludge containing cyanogens innoxious process for treating present situation and development trend
The harmless treatment research of sludge containing cyanogens is taken seriously in recent years gradually, and its processing approach has two classes, and a class is to Tailings Slurry press filtration, the dry heap of filter residue, and filtrate is carried out comprehensive treating process, reuse or qualified discharge after processing; Another kind of is that Tailings Slurry is directly processed, and method is to destroy prussiate substantially, and method has Yin Kefa, alkaline chlorination process, Ozonation etc.The former is due to mud-water separation, and prussiate is easily processed, and technology maturation is controlled simple and easyly, but because press filtration cost is high, is difficult to apply at large-scale mine.The development trend of gold industry is that correspondingly, the development trend of sludge containing cyanogens harmless treatment is towards the direction progress of direct processing towards extensive treatment capacity development.
2, sludge containing cyanogens treatment technology relative merits
Sludge containing cyanogens is because its concentration of cyanide belongs to low strength range, and general tree prussiate wherein reclaims, but directly carries out Oxidative demage.Research application is more Yin Kefa, oxychlorination method, Ozonation etc.
(1) Yin Kefa
Yin Kefa is the technology of a ripe processing prussiate, the method has processing cost low, easy to operate and the good feature for the treatment of effect, its except cyanogen process be that Sodium Pyrosulfite or sulfurous gas and air are quantitatively filled with in sludge containing cyanogens by a certain percentage, with cupric, make catalyzer, control reaction pH between 7.5～10, reaction product is cyanate and sulfuric acid, and cyanate is converted into carbonate and ammonia under certain condition.
The advantage of Yin Kefa:
1. can be total cyanide (CN in waste water
t -) be reduced to 0.5mg/L.
2. the effect of removing heavy metal in waste water is better, and outside workshop discharge outlet copper removal exceeds standard sometimes, other heavy metal is all up to standard.
3. technological process is fairly simple, can Artificial Control, also can automatically control, and all can obtain satisfied treatment effect.
4. when catalyzer is appropriate, speed of response is very fast, can in 0.5～1.0 hour, complete reaction.
5. processed waste water forms simply, on being received water system, affects littlely, to waste water circulation, uses the condition of having created.
6. sulfur oxide prussiate, medicine consumption is not low, from the viewpoint of processing cost, and an also advantage at last.
The shortcoming of Yin Kefa:
If 1. reaction process pH value is too low, HCN and SO can overflow
2, and residual cyanogen is high; When pH value is too high, residual cyanogen is also high, therefore the control of pH value in reaction is required strict; While having iron cyanogen in cyanide pulp and waste water, be difficult to be oxidized up to standard.
2. discharge outlet cupric ion in workshop exceeds standard sometimes, but Tailings Dam overflow water copper can not exceed standard.
3. the Zassol hydrolysis producing is slow, and waste water need be grown in the Tailings Dam residence time, otherwise waste water still has certain toxicity.
4. may need the non-ferrous metal that adds catalyzer mantoquita-preciousness to be consumed.
5. power consumption is high, is generally 3～5 times of oxychlorination method.
6. the factor that affects treatment effect is many, pH value in reaction, catalyzer dosage, sulfurous gas dosage, aeration quantity and air-dispersion degree etc.
While 7. using liquid, gaseous sulfur dioxide, the etching problem of equipment can not be ignored, and catalyst sulfuric acid copper solutions is very big to the corrosion of iron, should be specifically noted that.
8. when waste water contains arsenic, because sulfurous gas is reduced to arsenic at a low price, cause the clearance of arsenic to decline, draining arsenic may exceed standard.
9. belong to the method for destroying prussiate, without economic benefit, in waste water, precious metal, heavy metal can not reclaim.
(2) oxychlorination method
The technique that Treatment of Cyanide-containing Wastewater is the most traditional is oxychlorination method, also be the method for applying at home the earliest, the method also has application in sludge containing cyanogens process field, it removes cyanogen process is to be that oxygenant quantitatively drops in sludge containing cyanogens by chlorine, control reaction pH between 10-11, speed of response is very fast, and product is cyanate, and cyanate is converted into carbonate and ammonia under certain condition.
The advantage of oxychlorination method:
1. be a kind of method of maturation, at aspects such as processing units, all accumulated rich experience.
2. can be reduced to 0.5mg/L even lower for prussiate.
3. poisonous heavy metal generates indissoluble throw out, and draining reaches containing heavy metal concentration the emission standard that meets national regulation.
If 4. in waste water containing arsenic, chlorine is oxidized to pentavalent arsenic trivalent arsenic, and then forms the Tricalcium arsenate of indissoluble more and remove, arsenic can be up to standard.
The shortcoming of oxychlorination method:
If the equipment of 1. processing in waste water process is airtight bad, CNCl escapes in air, operating environment of pollution.
2. can not destroy the prussiate in ferrous cyanogen network thing and iron cyanogen network thing, can not make it form throw out and remove, therefore total cyanogen is sometimes higher, while especially processing refined gold ore cyaniding factory lean solution, because lean solution iron content is high, can discharge prussiate and be difficult to be reduced to below 0.5mg/L.Total cyanide content is higher.
3. when processing high cyanide containing wastewater with chlorinated lime or high test bleaching powder, because consumption is large, in waste water, chlorine ion concentration is high, forms complex compound with copper, and copper is exceeded standard.
4. draining chlorine ion concentration is high, makes surface water and soil salinization, water conservancy projects corrosion.
When 5. chlorine ion concentration is high, make calcium, magnesium dissolve in a large number, waste water is from Tailings Dam leaks out, and polluted underground water, greatly increases calcium in underground water, magnesium, cl concn, seriously affects the function of water, can not drink, can not irrigated farmland when serious.
6. chlorine be oxygenant especially transportation and the use of liquid chlorine have certain danger, because chlorine leaks accident person poultry poisoning, farmland and the fish pond cause being endangered, in other industry, happen occasionally.
7. chlorine products price increase in recent years, processing cost is high.
Due to oxychlorination method, have the toxic gases such as high, the easy release chlorine of processing costs and mauguinite, can bring Potential environmental risk, the national gold extracting shop of this technique that adopts of external main pan significantly reduces.
(3) Ozonation
Ozone is a kind of clean oxygenant, has extremely strong oxidation susceptibility, can easily poisonous cyanide oxidation be become to the cyanate of low toxicity.In recent years, along with development and the maturation of ozone technology, the generation expense of the manufacturing cost of ozone generating apparatus and unit ozone has been reduced to can economic utilization level.At present, in Treatment of Cyanide-containing Wastewater field, had successful Application, it removes cyanogen process is that ozonize gasometry is passed in cyanide wastewater, control reaction pH between 10-11, speed of response is very fast, and product is cyanate, and cyanate is converted into carbonate and ammonia under certain condition.
Ozonation Treatment of Cyanide-containing Wastewater, technically mainly utilizes air to make it change into ozone to be filled in cyanide wastewater, meanwhile, to make full use of jet Aeration Technology and Its, realize ozone oxidation reaction, thereby reach the object except cyanogen.
The advantage of Ozonation:
1. raw material is easy to get, particularly favourable for the cyanide plant of outlying mountain area.
2. use clean oxygenant, in waste water, do not introduce other ion, be conducive to waste water circulation.
3. processing its cost of every cubic metre of cyanide wastewater is only 1/3 of Pomolio-Celdecor process.
By Ozone shortcoming:
1. bad adaptability, By Ozone is only suitable for processing the clear liquor that CN-content is less than 30mg/L, and gold cyanide plant waste water is mostly ore pulp, and also CN-content is more than 80mg/L, therefore this method can only be as second-stage treatment method.
2. investment is large, and ozonizer and air cleaning, the subset price that dewaters are higher.
3. power consumption is large, every production 1kg ozone power consumption 15～20kwh, and 50t/d all sliming cyanidation factory needs ozone more than 100 kilograms every day, is equivalent to increase electrical capacity 100kw.Compare with current wastewater treatment electrical capacity 15kw, electricity consumption is excessive, and because Electricity Investment is large, electricity charge valency is high, and processing cost is inevitable high, and difficulty and sulfurous gas-air oxidation process and oxychlorination method are competed mutually.
4. oxidising process non-selectivity, in waste water, reducing substances is as SCN
-, SO
3 2-deng time, ozone consumption is larger.5. ozonizer equipment is complicated, and maintenance difficult, requires high to operator.
Summary of the invention
The object of this invention is to provide that a kind for the treatment of effect is good, expense is low, stable, reliable sludge containing cyanogens two-stage method harmless treatment process, the derivative that the present invention is directed to dissimilar prussiate and prussiate is taked staging treating, make to have reached " integrated wastewater discharge standard " primary standard (GB8978-1996) through indexs such as the prussiate in the sludge containing cyanogens of its processing and heavy metals, and are the II class solid wastes in Ordinary solid waste through this art breading mine tailings up to standard.
The present invention consists of slurry concentrating step and oxidation step;
Slurry concentrating step is to utilize thickening equipment to promote ore pulp mass percent concentration to 50%～55%, the supernatant fluid reuse Yu Xuan factory technique after dense, and high-concentration ore slurry enters next step treatment scheme, and dense principle is to utilize gravity settling to carry out solid-liquid separation.
Oxidation step is to adopt OOT oxidation style, oxidation minute two stages, first stage adds sulfuric acid and controls pH values of pulp between 9～10, by oxide treatment, fall most prussiate, thiocyanate ion and the reducing substances of discharging, make to discharge concentration of cyanide lower than 30mg/L, thiocyanate ionic concn is lower than 10mg/L; Subordinate phase adds sulfuric acid and adjusts pH values of pulp between 7～8, add medicament zinc sulfate and the copper sulfate of assisting oxidation, continue to use OOT oxidative treatment to fall remaining prussiate, make the total concn that remains prussiate lower than 0.5mg/L, simultaneously, at the second oxidation stage, add gac and strengthen oxidation effectiveness, charcoal also has adsorption, can reclaim the gold in a part of Tailings Slurry.OOT oxidation style oxygenant used is ozone.
The meaning of OOT is Ozonation.
Beneficial effect of the present invention:
1, concentration technique feature
Sludge containing cyanogens is after concentration, and by the useful prussiate of reuse approximately 30%, meanwhile, pending prussiate load will cut down approximately 30%, kill two birds with one stone.
2, oxidation technology feature
Oxidation minute two stages, two topmost differences of stage are the pH difference of ore pulp, and first stage pH is between 9～10, and subordinate phase pH is between 7～8, first stage is disposed most prussiate, and second section is up to standard by remaining prussiate and other reduction class mass treatment; The medicament copper sulfate and the zinc sulfate that during subordinate phase oxidation, also need to add a small amount of assisted oxidation.
3 gac assisted oxidation technology
At oxidation stage, add gac, charcoal has certain assisted oxidation effect, the oxidation effectiveness of energy oxidation method, and meanwhile, charcoal also has adsorption, can reclaim the gold in a part of Tailings Slurry.
Embodiment
The present invention consists of slurry concentrating step and oxidation step;
Described slurry concentrating step utilizes ore pulp thickening equipment to promote ore pulp mass percent concentration to 50%～55%, the supernatant fluid reuse Yu Xuan factory technique after dense, and high-concentration ore slurry enters next step treatment scheme.
Oxidation step is to adopt OOT oxidation style, in oxidation minute two stages, the first stage is to add the vitriol oil in the ore pulp after concentrated, adjusts its pH 9～10, then add OOT oxidation medicament, OOT oxidation pharmaceutical quantities and prussiate and other reduction class amount of substance match.
Subordinate phase is, ore pulp after one section of oxidation, add again a small amount of zinc sulfate, copper sulfate, oxygenant and gac, the pharmaceutical quantities of assisted oxidation medicament copper sulfate and zinc sulfate is all less than 0.25g/L ore pulp, OOT oxidation pharmaceutical quantities is less than 0.2g/L ore pulp, activated carbon dosage is at 10～25g/L ore pulp, and fully reaction, can make prussiate and heavy metal reach " integrated wastewater discharge standard " primary standard (GB8978-1996).
Through above-mentioned steps, processing gold concentrator tailings slag up to standard is the II class solid waste in Ordinary solid waste.
Example
Adopt technical process of the present invention to carry out " slurry concentrating+OOT two-stage method " Processing Test to the sludge containing cyanogens of output in certain gold mine actual production process, treatment capacity 10L/h, sludge containing cyanogens result is in Table 1, and sludge containing cyanogens toxicity leaches and the results are shown in Table 2, table 3.
Water quality result unit: mg/L after the processing of table 1 sludge containing cyanogens
Table 2 upset succusion unit: mg/L
The horizontal succusion unit of table 3: mg/L
Claims (1)
1. a sludge containing cyanogens two-stage method harmless treatment process, this technique is to consist of slurry concentrating step and oxidation step;
Described slurry concentrating step is to utilize thickening equipment to promote pulp density to 50%～55%, the supernatant fluid reuse Yu Xuan factory technique after dense, and high-concentration ore slurry enters next step treatment scheme, and dense principle is to utilize gravity settling to carry out solid-liquid separation;
Described oxidation step is to adopt OOT oxidation style, oxidation minute two stages, first stage adds sulfuric acid and controls pH values of pulp between 9～10, by oxide treatment, fall most prussiate, thiocyanate ion and the reducing substances of discharging, make to discharge concentration of cyanide lower than 30mg/L, thiocyanate ionic concn is lower than 10mg/L; Subordinate phase adds sulfuric acid and adjusts pH values of pulp between 7～8, add medicament zinc sulfate and the copper sulfate of assisting oxidation, continue to use OOT oxidative treatment to fall remaining prussiate, make the total concn that remains prussiate lower than 0.5mg/L, simultaneously, at the second oxidation stage, add gac and strengthen oxidation effectiveness, charcoal also has adsorption, can reclaim the gold in a part of Tailings Slurry.
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Cited By (3)
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| CN104909498A (en) * | 2015-06-07 | 2015-09-16 | 长春黄金研究院 | Comprehensive treatment method for flotation wastewater of gold industry |
| CN104944639A (en) * | 2015-06-09 | 2015-09-30 | 长春黄金研究院 | Comprehensive utilization method for cyanogen-containing tailing slurry |
| CN105032918A (en) * | 2015-06-16 | 2015-11-11 | 长春黄金研究院 | Restorative method for soil polluted by cyanide |
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| CN105032918A (en) * | 2015-06-16 | 2015-11-11 | 长春黄金研究院 | Restorative method for soil polluted by cyanide |
| CN105032918B (en) * | 2015-06-16 | 2017-05-03 | 长春黄金研究院 | Restorative method for soil polluted by cyanide |
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Application publication date: 20140122 |