CN103526044B - Zinc hydrometallurgy process favorable for floatation silver and adopted precipitating silver mixture - Google Patents
Zinc hydrometallurgy process favorable for floatation silver and adopted precipitating silver mixture Download PDFInfo
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- CN103526044B CN103526044B CN201310431759.0A CN201310431759A CN103526044B CN 103526044 B CN103526044 B CN 103526044B CN 201310431759 A CN201310431759 A CN 201310431759A CN 103526044 B CN103526044 B CN 103526044B
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Abstract
The invention discloses a zinc hydrometallurgy process favorable for floatation silver. The process comprises five steps: zinc concentrate roasting, leaching, liquid purifying, electrodepositing and obtaining an electric zinc product. Zinc sulfate and active carbon powder are added in the leaching step depending on the total amount of zinc calcine in the entire process, wherein 0.3-0.6kg of zinc sulfate and 0.6-1.5kg of active carbon powder are added in each ton of the zinc calcine. The zinc sulfate and the active carbon powder added in the leaching step can reduce silver contents in various leaching solutions, and reduce silver entering into the liquid purifying and alum precipitating steps, so that the silver is precipitated in the leaching step and enters into acid leaching residue or high leaching residue, thus avoiding dispersing loss of the silver. The zinc sulfate can reduce formation of argentojarosite, so as to reduce silver loss and improve silver recovery rate. And the active carbon powder can not only absorb the silver but also absorb organic matters to reduce the organic matters entering into a zinc electrolyte solution, which is favorable for improving electrolysis efficiency and saving electric energy.
Description
Technical field
The invention belongs to non-ferrous metal metallurgy technical field, be specifically related to a kind ofly be conducive to the Zinc hydrometallurgy process of silver floatation and heavy silver-colored mixture used.
Background technology
Zinc hydrometallurgy is the topmost zinc metallurgy method in the world today, and its output accounts for more than 85% of the total zinc output in the world.Recent world throughput that is newly-built and enlarging all adopts Zinc hydrometallurgy process.The normal process of wet method smelting process is sulfuric acid → leaching → clean liquid → electrodeposition → electric zinc product.Condition wherein because leaching operation is different with link is divided into again conventional extract technology and high acidic oils technique two kinds.The leaching link of conventional extract technology comprises meutral innersion and Weak-acid leaching step; This technique produces acid leaching residue and clear liquid dreg; The leaching link of high acidic oils technique comprises meutral innersion, Weak-acid leaching, high acidic oils, and it also comprises heavy alum step in addition; This technique produces high leaching slag, clear liquid dreg and iron vitriol slag.
The various slags that two kinds of Zinc hydrometallurgy process produce, only have the silver in acid leaching residue and high leaching slag to have flotation and are worth.Silver a large amount of in existing Zinc hydrometallurgy process all disperses to enter in clear liquid dreg and iron vitriol slag, and the ratio of optional silver reduces, and is unfavorable for the floatation recovery of silver.
Patent of invention " a kind of low pollution vanadium settling iron-removing wet zinc smelting method " ZL200610101223.2 disclosed in Chifeng Hongye Zinc Smelting Co., Ltd, the method belongs to high temperature high acidic oils technique, mainly comprise meutral innersion, pre-neutralization (Weak-acid leaching), high acidic oils and heavy alum four processing steps, also comprise clean liquid processing step in actual applications.This processing method produces high leaching slag, iron vitriol slag and clear liquid dreg, and the silver that the anode sludge produced with calcining and zinc electrolysis brings wet zinc-making system into mainly enters into this three kinds of slags, discharges wet zinc-making system.Chifeng Hongye Zinc Smelting Co., Ltd checked the weight to the classification of height leaching slag, iron vitriol slag and clear liquid dreg over the past two years and added up and year chemical composition average analysis result statistics, and result is as following table 1.
Table 1 classification is checked the weight and is added up and year chemical composition average analysis result statistics
Added up and year chemical composition average analysis interpretation of result by checking the weight to the classification of height leaching slag, iron vitriol slag and clear liquid dreg over the past two years, in high acidic oils-low pollution vanadium settling Leaching Technology of Zinc Hydrometallurgy process, due to silver dissolving and participate in the chemical reaction of various complexity, the silver major part that the form of the anode sludge of calcining and the zinc electrolysis generation produced by roasting is entered in wet zinc-making system enters high leaching slag through enrichment, partly disperses to enter iron vitriol slag and clear liquid dreg, in high leaching slag, the enriching and recovering rate of silver is in 76.7 ~ 78.3% scopes, and average 77.5%; Enter the ratio of silver in iron vitriol slag 10.9 ~ 14.3%, average 12.6%; Enter the ratio of silver in one, two section of clear liquid dreg 9 ~ 10.8%, average 9.9%.
Because the silver content in iron vitriol slag and clear liquid dreg is lower, silver particularly in iron vitriol slag forms complicated argentojarosite double salt structure, be difficult to reclaim economically, cause the spread loss of silver in high acidic oils-low pollution vanadium settling Leaching Technology of Zinc Hydrometallurgy process thus, silver is reduced in height leaching slag enriching and recovering rate.By the analysis to high acidic oils-low pollution vanadium settling Leaching Technology of Zinc Hydrometallurgy process, silver in iron vitriol slag derives from the Weak-acid leaching liquid of Weak-acid leaching operation, silver in clear liquid dreg derives from meutral innersion overflowing liquid, therefore, only has the silver content by controlling Weak-acid leaching liquid and meutral innersion overflowing liquid, make the deposition of silver in solution in respective leached mud, be finally deposited in high leaching slag, reach the target improving high leaching slag silver enriching and recovering rate.
Summary of the invention
The object of this invention is to provide a kind of Zinc hydrometallurgy process being conducive to silver floatation, the method reduces the spread loss of silver, is conducive to silver-colored flotation, thus improves the rate of recovery of silver.
Another object of the present invention is also to provide a kind of heavy silver-colored mixture, and this design of mixture is reasonable, easy to use, adds in the leaching step of Zinc hydrometallurgy process, can reduce the spread loss of silver.
Technical scheme of the present invention is: a kind of Zinc hydrometallurgy process being conducive to silver floatation, it comprises sulfuric acid → leaching → clean liquid → electrodeposition → electric zinc product five process procedures, it is characterized in that: in the leaching step leaching link, add zinc sulphide and active carbon powder, the add-on of zinc sulphide and active carbon powder is with whole technological process zinc baking sand total amount for foundation, and every 1 ton of zinc baking sand adds 0.3 ~ 0.6 kilogram of zinc sulphide and 0.6 ~ 1.5 kilogram of active carbon powder.
Described Zinc hydrometallurgy process is a kind of conventional extract technology, leaches link and comprises meutral innersion and Weak-acid leaching step; In meutral innersion step, every 1 ton of zinc baking sand adds 0.3 ~ 0.6 kilogram of zinc sulphide and 0.6 ~ 1.5 kilogram of active carbon powder.
Described Zinc hydrometallurgy process is a kind of conventional extract technology, leaches link and comprises meutral innersion and Weak-acid leaching step; In meutral innersion step, every 1 ton of zinc baking sand adds 0.15 ~ 0.3 kilogram of zinc sulphide and 0.3 ~ 0.75 kilogram of active carbon powder; In Weak-acid leaching step, every 1 ton of zinc baking sand adds 0.15 ~ 0.3 kilogram of zinc sulphide and 0.3 ~ 0.75 kilogram of active carbon powder.
Described Zinc hydrometallurgy process is a kind of high acidic oils technique, leaches link and comprises meutral innersion, Weak-acid leaching, high acidic oils and heavy alum step, and it produces high leaching slag, clear liquid dreg and iron vitriol slag; In meutral innersion step, every 1 ton of zinc baking sand adds 0.3 ~ 0.6 kilogram of zinc sulphide and 0.6 ~ 1.5 kilogram of active carbon powder.
Described Zinc hydrometallurgy process is a kind of high acidic oils technique, leaches link and comprises meutral innersion, Weak-acid leaching, high acidic oils and heavy alum step; In meutral innersion step, every 1 ton of zinc baking sand adds 0.1 ~ 0.2 kilogram of zinc sulphide and 0.2 ~ 0.5 kilogram of active carbon powder; In Weak-acid leaching step, every 1 ton of zinc baking sand adds 0.1 ~ 0.2 kilogram of zinc sulphide and 0.2 ~ 0.5 kilogram of active carbon powder; In high acidic oils step, every 1 ton of zinc baking sand adds 0.1 ~ 0.2 kilogram of zinc sulphide and 0.2 ~ 0.5 kilogram of active carbon powder.
The conveniently realization of above-mentioned Technology, the present invention makes heavy silver-colored mixture in proportion zinc sulphide and active carbon powder, is packaged into pouch, can facilitate production application.This technical scheme is: a kind of for the heavy silver-colored mixture described in above-mentioned technique, it comprises zinc sulphide and active carbon powder, and the part by weight of zinc sulphide and active carbon powder is: 1:2 ~ 5, active carbon powder fineness 200 ~ 400 order.
Advantage of the present invention is:
1) in order to verify effect of the present invention, We conducted simultaneous test, comparing the difference adding heavy silver-colored mixture and do not add between heavy silver-colored mixture.For high acidic oils technique, all add the heavy silver-colored mixture of 1.5 kilograms according to every 1 ton of zinc baking sand in three steps of meutral innersion, Weak-acid leaching and high acidic oils, the part by weight of zinc sulphide and active carbon powder is: 1:3.5, active carbon powder fineness 300 order.In zinc leaching process, add heavy silver-colored mixture and do not add heavy silver-colored mixture test-results as table 2,
Table 2 production system solution on-site sampling test chemical composition average analysis result
Illustrated in the leaching step of Zinc hydrometallurgy process by comparison test, add zinc sulphide and active carbon powder and have the content reducing silver in leach liquor significantly, reduction ratio reaches more than 80, effect highly significant.
2) clear liquid dreg argentiferous ratio is little does not have flotation to be worth, and iron vitriol slag silver silver can not flotation.Add the content that zinc sulphide and active carbon powder can reduce silver in various leach liquor leaching in step, reduce silver and enter clean pendular ring joint and alum link of sinking.
3) in leaching process, the Sulfuric acid disilver salt in calcining, silver suboxide dissolve or reaction enters in solution, and zinc sulphide reaction, main reflection is as follows: 2Ag
++ ZnS=Ag
2s+Zn
2+silver is just precipitated in leaching link, enters in acid leaching residue or high leaching slag, avoid the spread loss of silver.
4) add the formation that zinc sulphide can reduce argentojarosite, argentojarosite is the non-optional silver of flotation technology, thus reduces the loss of silver, improves silver raising recovery rate.
5) add active carbon powder, the silver that can adsorb in leach liquor makes it to enter into acid leaching residue or high leaching slag through filtering.Gac can also adsorb organism a large amount of in leach liquor in addition, reduces organism and enters in zinc electrolyte, is conducive to improving electrolytic efficiency, saves electric energy, avoid organic adhering on electrolytic zinc-coated steel sheet.
Accompanying drawing explanation
Fig. 1 is the conventional extract technology schema that the present invention is conducive to the Zinc hydrometallurgy process of silver floatation.
Fig. 2 is the high acidic oils process flow sheet that the present invention is conducive to the Zinc hydrometallurgy process of silver floatation.
Embodiment
Below to be described in further detail the present invention by test and embodiment:
Embodiment 1: as shown in Figure 1, it belongs to the conventional extract technology method in zinc hydrometallurgy: a kind of Zinc hydrometallurgy process being conducive to silver floatation, it comprises following several step: it comprises following several step: (1) meutral innersion: will add zinc baking sand in waste electrolyte and Weak-acid leaching overflowing liquid and Manganse Dioxide carries out meutral innersion, produces meutral innersion overflowing liquid and meutral innersion underflow liquid; (2) clean liquid: carrying out clean liquid by adding zinc powder in meutral innersion overflowing liquid, producing scavenging solution and clear liquid dreg, scavenging solution electrodeposition extracts zinc and produces waste electrolyte; (3) Weak-acid leaching: will add waste electrolyte in meutral innersion underflow liquid and dilute sulphuric acid carries out Weak-acid leaching, produces Weak-acid leaching overflowing liquid and acid leaching residue.Zinc sulphide and active carbon powder is added in meutral innersion is rapid, the add-on of zinc sulphide and active carbon powder with whole technological process zinc baking sand total amount for foundation, every 1 ton of zinc baking sand adds 0.5 kilogram of zinc sulphide and 1 kilogram of active carbon powder, and active carbon powder fineness is 250 orders.
Embodiment 2: other scheme is with embodiment 1, difference all adds zinc sulphide and active carbon powder in meutral innersion and Weak-acid leaching step, the add-on of zinc sulphide and active carbon powder is with whole technological process zinc baking sand total amount for foundation, and in meutral innersion step, every 1 ton of zinc baking sand adds 0.2 kilogram of zinc sulphide and 0.6 kilogram of active carbon powder; In Weak-acid leaching step, every 1 ton of zinc baking sand adds 0.2 kilogram of zinc sulphide and 0.6 kilogram of active carbon powder, and active carbon powder fineness is 200 orders.
Embodiment 3: other scheme is with embodiment 1, difference all adds zinc sulphide and active carbon powder in meutral innersion and Weak-acid leaching step, the add-on of zinc sulphide and active carbon powder is with whole technological process zinc baking sand total amount for foundation, and in meutral innersion step, every 1 ton of zinc baking sand adds 0.25 kilogram of zinc sulphide and 0.7 kilogram of active carbon powder; In Weak-acid leaching step, every 1 ton of zinc baking sand adds 0.25 kilogram of zinc sulphide and 0.7 kilogram of active carbon powder, and active carbon powder fineness is 400 orders.
Embodiment 4: as shown in Figure 2, it belongs to the high acidic oils processing method in zinc hydrometallurgy: a kind of Zinc hydrometallurgy process being conducive to silver floatation, it comprises following several step: (1) meutral innersion: will add zinc baking sand in waste electrolyte and heavy alum overflowing liquid and Manganse Dioxide carries out meutral innersion, produces meutral innersion overflowing liquid and meutral innersion underflow liquid; (2) clean liquid: carrying out clean liquid by adding zinc powder in meutral innersion overflowing liquid, producing scavenging solution and clear liquid dreg, scavenging solution electrodeposition extracts zinc and produces waste electrolyte; (3) Weak-acid leaching: carry out Weak-acid leaching by adding Manganse Dioxide in meutral innersion underflow liquid and high acidic oils overflowing liquid, when whole acid can not meet processing requirement, adds the neutralization of appropriate zinc baking sand, produces Weak-acid leaching overflowing liquid and Weak-acid leaching underflow liquid; (4) high acidic oils: carry out high acidic oils by adding sulfuric acid in Weak-acid leaching underflow liquid and waste electrolyte, high acidic oils overflowing liquid returns Weak-acid leaching, and high acidic oils slag muck is deposited; (5) heavy alum: will add bicarbonate of ammonia in Weak-acid leaching overflowing liquid and sodium bicarbonate carries out heavy alum, the heavy alum overflowing liquid produced by heavy alum returns meutral innersion groove and carries out meutral innersion, and low pollution vanadium settling slag muck is deposited.Zinc sulphide and active carbon powder is added in meutral innersion is rapid, the add-on of zinc sulphide and active carbon powder with whole technological process zinc baking sand total amount for foundation, every 1 ton of zinc baking sand adds 0.4 kilogram of zinc sulphide and 1.2 kilograms of active carbon powders, and active carbon powder fineness is 300 orders.
Embodiment 5: other scheme is with embodiment 4, difference all adds zinc sulphide and active carbon powder in meutral innersion, Weak-acid leaching and high acidic oils step, the add-on of zinc sulphide and active carbon powder is with whole technological process zinc baking sand total amount for foundation, and in meutral innersion step, every 1 ton of zinc baking sand adds 0.15 kilogram of zinc sulphide and 0.4 kilogram of active carbon powder; In Weak-acid leaching step, every 1 ton of zinc baking sand adds 0.15 kilogram of zinc sulphide and 0.4 kilogram of active carbon powder; In high acidic oils step, every 1 ton of zinc baking sand adds 0.15 kilogram of zinc sulphide and 0.4 kilogram of active carbon powder, and active carbon powder fineness is 280 orders.
Embodiment 6: other scheme is with embodiment 4, difference all adds zinc sulphide and active carbon powder in meutral innersion, Weak-acid leaching and high acidic oils step, the add-on of zinc sulphide and active carbon powder is with whole technological process zinc baking sand total amount for foundation, and in meutral innersion step, every 1 ton of zinc baking sand adds 0.12 kilogram of zinc sulphide and 0.48 kilogram of active carbon powder; In Weak-acid leaching step, every 1 ton of zinc baking sand adds 0.12 kilogram of zinc sulphide and 0.48 kilogram of active carbon powder; In high acidic oils step, every 1 ton of zinc baking sand adds 0.12 kilogram of zinc sulphide and 0.48 kilogram of active carbon powder, and active carbon powder fineness is 350 orders.
Embodiment 7: a kind of heavy silver-colored mixture for technique described in embodiment 1, it comprises zinc sulphide and active carbon powder, and the part by weight of zinc sulphide and active carbon powder is: 1:2, active carbon powder fineness 250 order.
Embodiment 8: a kind of heavy silver-colored mixture for technique described in embodiment 4, it comprises zinc sulphide and active carbon powder, and the part by weight of zinc sulphide and active carbon powder is: 1:3, active carbon powder fineness 300 order.
Embodiment 9: a kind of heavy silver-colored mixture for technique described in embodiment 6, it comprises zinc sulphide and active carbon powder, and the part by weight of zinc sulphide and active carbon powder is: 1:4, active carbon powder fineness 350 order.
Claims (5)
1. one kind is conducive to the Zinc hydrometallurgy process of silver floatation, it comprises sulfuric acid → leaching → clean liquid → electrodeposition → electric zinc product five process procedures, it is characterized in that: in the leaching step leaching link, add zinc sulphide and active carbon powder, the add-on of zinc sulphide and active carbon powder is with whole technological process zinc baking sand total amount for foundation, and every 1 ton of zinc baking sand adds 0.3 ~ 0.6 kilogram of zinc sulphide and 0.6 ~ 1.5 kilogram of active carbon powder.
2. the Zinc hydrometallurgy process being conducive to silver floatation according to claim 1, is characterized in that: described Zinc hydrometallurgy process is a kind of conventional extract technology, leaches link and comprises meutral innersion and Weak-acid leaching step; In meutral innersion step, every 1 ton of zinc baking sand adds 0.3 ~ 0.6 kilogram of zinc sulphide and 0.6 ~ 1.5 kilogram of active carbon powder.
3. the Zinc hydrometallurgy process being conducive to silver floatation according to claim 1, is characterized in that: described Zinc hydrometallurgy process is a kind of conventional extract technology, leaches link and comprises meutral innersion and Weak-acid leaching step; In meutral innersion step, every 1 ton of zinc baking sand adds 0.15 ~ 0.3 kilogram of zinc sulphide and 0.3 ~ 0.75 kilogram of active carbon powder; In Weak-acid leaching step, every 1 ton of zinc baking sand adds 0.15 ~ 0.3 kilogram of zinc sulphide and 0.3 ~ 0.75 kilogram of active carbon powder.
4. the Zinc hydrometallurgy process being conducive to silver floatation according to claim 1, it is characterized in that: described Zinc hydrometallurgy process is a kind of high acidic oils technique, leach link and comprise meutral innersion, Weak-acid leaching, high acidic oils and heavy alum step, it produces high leaching slag, clear liquid dreg and iron vitriol slag; In meutral innersion step, every 1 ton of zinc baking sand adds 0.3 ~ 0.6 kilogram of zinc sulphide and 0.6 ~ 1.5 kilogram of active carbon powder.
5. the Zinc hydrometallurgy process being conducive to silver floatation according to claim 1, is characterized in that: described Zinc hydrometallurgy process is a kind of high acidic oils technique, leaches link and comprises meutral innersion, Weak-acid leaching, high acidic oils and heavy alum step; In meutral innersion step, every 1 ton of zinc baking sand adds 0.1 ~ 0.2 kilogram of zinc sulphide and 0.2 ~ 0.5 kilogram of active carbon powder; In Weak-acid leaching step, every 1 ton of zinc baking sand adds 0.1 ~ 0.2 kilogram of zinc sulphide and 0.2 ~ 0.5 kilogram of active carbon powder; In high acidic oils step, every 1 ton of zinc baking sand adds 0.1 ~ 0.2 kilogram of zinc sulphide and 0.2 ~ 0.5 kilogram of active carbon powder.
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| CN104498728A (en) * | 2014-12-13 | 2015-04-08 | 株洲冶炼集团股份有限公司 | Technique for enhancing silver recovery rate in silver-containing zinc concentrate |
| CN104962755B (en) * | 2015-06-08 | 2017-09-12 | 长沙矿冶研究院有限责任公司 | Flotation of Zinc Oxide concentrate pre-processes extract technology |
| CN106191456A (en) * | 2016-08-19 | 2016-12-07 | 黄婧 | The technique that silver is reclaimed in a kind of zinc leaching residue flotation |
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| CN102205279B (en) * | 2011-05-05 | 2012-12-19 | 赤峰中色库博红烨锌业有限公司 | Collective floatation method for recycling silvers from high leaching residues |
| CN102876888A (en) * | 2012-10-18 | 2013-01-16 | 广西华锡集团股份有限公司 | Zinc hydrometallurgy production process |
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