CN103301929A - Selective zinc oxide leaching and weak acidic zinc sulfide flotation smelting and selection combining process - Google Patents
Selective zinc oxide leaching and weak acidic zinc sulfide flotation smelting and selection combining process Download PDFInfo
- Publication number
- CN103301929A CN103301929A CN2013101061402A CN201310106140A CN103301929A CN 103301929 A CN103301929 A CN 103301929A CN 2013101061402 A CN2013101061402 A CN 2013101061402A CN 201310106140 A CN201310106140 A CN 201310106140A CN 103301929 A CN103301929 A CN 103301929A
- Authority
- CN
- China
- Prior art keywords
- zinc
- flotation
- ore
- smelting
- zinc oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention discloses a selective zinc oxide leaching and weak acidic zinc sulfide flotation smelting and selection combining process. For oxygen and sulfide mixed lead zinc ore, a zinc wet-method smelting process and a zinc flotation process are combined, zinc oxide in the ore is partially and selectively leached out by the first wet-method smelting process, and then zinc sulfide in the ore is floated out by the flotation process. In order to overcome the difficulty in treating the oxygen and sulfide mixed lead zinc ore, the invention provides the smelting and selection combining process which is short in process flow, reliable in technology, easy to operate and control, relatively low in material consumption and energy consumption for production, high in metal reclaiming efficiency, relatively good in economic benefit and high in practicability, the recovery of lead and zinc in the low-grade complex difficultly-selected oxygen and sulfide mixed lead zinc ore can be greatly improved, and the total recovery of lead and zinc can be up to over 90 percent.
Description
Technical field
The present invention relates to plumbous zinc ore hydrometallurgy and flotation technology field.
Background technology
China is zinc metal the first big producing country and consumption big country, and zinc resource problem in short supply shows especially day by day, approximately has every year 1/3rd zinc raw material to need import, and the resource provisioning deficiency has become the key factor of restriction social sustainable development.Yet the processing treatment technology is not rationally utilized again the zinc ore of the especially low-grade high impurity of China's zinc resource owing to lacking effectively.
At present, China has at least the low-grade refractory more than 5,000 ten thousand tons to select the plumbous zinc ore of complicated oxysulphied, particularly there are 4,000 ten thousand tons of such ores of surpassing in the Lan Ping mining area of China the western regions of the Yunnan Province, potential economic worth surpasses 30,000,000,000 RMB, because its ore properties is extremely complicated, has oxygenation efficiency high, the characteristics such as clay content is large and poor, thin, assorted, never have effective technology extraction zinc wherein, these ores can only be passed into disuse, not only cause the significant wastage of resource, formed huge pressure also for simultaneously the mine safety environmental protection.Therefore, select the new technology of complicated oxysulphied Development of lead-zinc mine for low-grade refractory, become very urgent and the problem of reality.
The method of traditional processing oxysulphied lead-zinc ore is to adopt first the enrichment of flotation means and improve plumbous zinc metal content, then adopts pyrogenic process or wet process smelting technique to produce zinc ingot metal and lead pig.The technique of smelting is extensive single after this first choosing, only can develop part and contain zinc greater than the lead-zinc more than 15%, and a large amount of grades are lower than 10% plumbous Zinc oxide and the plumbous zinc ore of oxysulphied, are difficult to effectively develop with conventional method.In addition, prior art is in the zinc sulphide flotation, oxysulphied lead-zinc ore segmentation associating flotation, in the lead-zinc pyrogenic process preliminary treatment floatation process, first flotation vulcanized lead, rear flotation zinc sulphide, last Flotation of Zinc Oxide again, above three kinds of floatation process all exist the accommodation of raw material and granularity little, technological process is long, the multiplex amount of medicament kind is large, the tail gas hazard-free intractability that produces is large, it is higher that the PbS concentrate contains zinc, ZnO concentrate and ZnS concentrate grade are low, it is high that mine tailing contains zinc, lead and zinc recovery are low, the ZnO concentrate contains the amine organic matter and is difficult to the conventional problems such as hydrometallurgy production electrolytic zinc.
Select the character characteristics of the plumbous zinc ore of complicated oxysulphied for above-mentioned low-grade refractory, from 2000 to 2012, the associating of many scientific research institutions such as Kunming Inst. of Metallurgy, Beijing Mine and Metallurgy General Inst, Changsha Mining ﹠ Metallurgy Inst, Guangzhou Research Institute of Nonferrous Metals, Kunming University of Science and Technology and Central South University and colleges and universities and applicant and relevant unit thereof is successively arranged, carried out a large amount of research, research of technique and engineer testing.The various processes such as development test " ore preliminary treatment-flotation " technique, " diffeential floatation " technique, " ore deposit dense media-flotation acidleach associating " technique, " first Flotation of Sulfide Ores desliming-zinc oxide flotation " technique, plumbous zinc ore hot pressing conversion technology, " preliminary treatment-flotation of plumbous zinc ore pyrogenic process " technique.These processes have more or less all obtained respectively some interim scientific achievements.Technological process is long, installations and facilities are many but all also exist, and tail gas and mine tailings harmless environmental protection intractability are larger, is not easy to operation and control, coal-fired energy consumption is high, the deficiencies such as metal recovery rate is lower, and production cost is relatively high, and economic benefit, environmental benefit and social benefit are relatively low.Especially, PROCESS FOR TREATMENT low-grade refractory with routine existing " first flotation-rear the smelting " selects the plumbous zinc ore of complicated oxysulphied, through repeatedly small-scale test and half industrial production test, zinc oxide ore floatation process production target is relatively relatively poor, the zinc oxide concentrate grade of flotation is lower, Zn content only can reach 17.85～26.47%, zinc recovery only is 53.02～68.86%, also contain a large amount of lauryl amines and octadecylamine organic matter foaming agent in the concentrate, these organic matters can cause serious bubbling in the zinc leaching process, have a strong impact on the zinc electrolysis and separate out, cause the zinc hydrometallurgy to be difficult to normally produce.The Flotation of Zinc Oxide concentrate is smelting operation and the production that is difficult to carry out direct acidleach-electrolysis, after generally must processing through " pyrogenic process roasting reagent removal ", just can enter the hydrometallurgy production of leaching and electrolysis.This is just so that zinc smelting process flow process is longer, and installations and facilities are more, and heat material and the energy consumption of production are excessive, the tail gas hazard-free difficult treatment, and the production technology difficulty is large, not easy to operate and control, cost is higher, this not only uneconomical but also not environmental protection.The lot of domestic and international expert unanimously thinks for many years, and this class low-grade refractory selects the ore-dressing technique technology of oxidase complex zinc ore and the plumbous zinc ore of oxysulphied to be not only a domestic difficult problem, also is the difficult problem in the world.Prior art also has a kind of process integration that adopts organic solvent extracting zinc and zinc hydrometallurgy, and such as Chinese patent 200610010938.7, the strip liquor in its technique after the zinc back extraction also will be transmitted back to the leaching operation of flowsheet of wet zinc smelting, adopts this technique, contains H in the back washing agent
2SO
4Usually up to 150～200 grams per liters, not only acid consumption is high, and further purified treatment also in the actual production increases cleaning procedure, has prolonged production procedure, has increased fire coal, cleanser etc. and has produced consumption, has raised production cost.In addition, the flotation of prior art is normally carried out the lead-zinc sulfide ore flotation under the pH values of pulp value is 8～11 weak basic condition, and the flotation under weak basic condition, not only equipment investment is larger, available floating agent kind is few, consumption is large, water, electric consumption are high, and the zinc sulfide concentrates that obtains and the grade of concentrate of lead sulfide ore and the rate of recovery are also lower.
For a long time, fail always all both at home and abroad to develop that a kind of technological process is short, technology reliable, be easy to operate and control, production material consumption and energy consumption is lower, metal recovery rate is high, better economic benefit, processing low-grade refractory with better industrialization prospect are selected the plumbous zinc ore of complicated oxysulphied technology.
Summary of the invention
Purpose of the present invention is just in order to solve the deficiency that exists on the above-mentioned prior art, for the difficulty in treatment of the plumbous zinc ore of oxysulphied, provide that a kind of technological process is short, technology reliable, be easy to operate and control, production material consumption and energy consumption is lower, metal recovery rate is high, process integration is selected in the selective leaching zinc oxide of flotation after the better economic benefit, practical first hydrometallurgy and the smelting of Weak-acid flotation zinc sulphide.
The objective of the invention is to be achieved through the following technical solutions.
Process integration is selected in selective smelting of leaching zinc oxide and Weak-acid flotation zinc sulphide, this technique is for the oxysulphied lead-zinc ore, the zinc wet method smelting process is combined with the zinc floatation process, adopt first wet method smelting process with the selective leaching of the part of the zinc oxide in the ore, with floatation process the zinc sulphide in the ore is partly flotated again.
Zinc wet method smelting process of the present invention is to use sulfuric acid as solvent, sulfuric acid is added in the ore pulp of oxysulphied lead-zinc ore, and the zinc oxide in the ore pulp and other oxide dissolution are entered ZnSO
4In the solution, the leached mud of output Containing Sulfur zinc and other sulfide is realized the selective zinc oxide that leaches simultaneously.In the oxysulphied lead-zinc ore ore pulp that grinds, the weight that grinding particle size is not more than the breeze of 0.0018mm accounts for more than 80% of total breeze amount, and the weight percent concentration of ore pulp is 35～50%.The present invention will selectively leach the ZnSO that zinc oxide obtains
4Solution obtains zinc product by zinc extraction, zinc back extraction, zinc electrodeposition.The present invention also is transmitted back to the waste liquid that produces behind the zinc electrodeposition zinc back extraction operation and again carries out the zinc electrodeposition after the back extraction.Zinc back extraction of the present invention is 3～6 grades of continuous back extractions, and back washing agent is electrolysis waste solution, H2SO in the back washing agent
4Content is 120～150 grams per liters, and Zn content is 50～70 grams per liters.The present invention can will selectively leach the ZnSO of zinc oxide acquisition
4Solution carries out first Ca, Mg and separates out processing, and then by zinc extraction, zinc back extraction, zinc electrodeposition, obtains zinc product.Described to ZnSO
4Solution carries out Ca, Mg and separates out processing, is with ZnSO
4Solution cools to 20 ℃～40 ℃, adds CaSO in the cooling procedure
42H
2O crystal seed and active additive, crystallization CaSO
4And MgSO
4, form calcium magnesium slag.
The leached mud that contains zinc sulphide that the present invention will form in the time of will selectively leaching zinc oxide partly carries out flotation with floatation process with the zinc sulphide in the ore, floatation process is leached mud to be carried out ore grinding size mixing, make the pH value and be 1～7 faintly acid ore pulp, then carry out full flotation of ore pulp, obtain the ZnS concentrate.The moisture content of leached mud is not more than 28% during flotation of the present invention, and the zinc oxygenation efficiency is not more than 30% in the leached mud.The present invention obtains the poor zinc mine tailing flotation PbS that produces behind the ZnS concentrate with full flotation of ore pulp, and the poor plumbous mine tailing that obtains producing behind the PbS concentrate carries out again flotation FeS
2, obtain FeS
2Concentrate.The present invention adopts isoamyl xanthate as the collecting agent of flotation zinc sulphide.
The present invention has the following advantages at least:
(1) the present invention has broken the technique of smelting after traditional first flotation, proposes innovatively the technique of flotation behind the first hydrometallurgy, realized the smelting choosing in conjunction with, closely help each other, create mutually technical conditions.Adopt acid leaching process selectively to leach zinc oxide, can when fully reclaiming the zinc oxide mineral, take in advance basic gangue away for follow-up flotation, reduced the flotation difficulty, also reduced the calcium concentration that contains of flotation backwater, be beneficial to the recycling of flotation backwater.Floatation process is after fully reclaiming zinc sulfide mineral, and its flotation leached mud itself has just finally reduced the volume of cargo in storage of leached mud, has reduced the harm to environment.
(2) the present invention is for the leached mud of Containing Sulfur zinc, in the pH value is to carry out full flotation of ore pulp under 1～7 the solutions of weak acidity, leaches intensity and created process conditions for improving acidleach, is convenient to improve leaching rate.It is lead-zinc sulfide ore flotation mode under 8～11 weak basic conditions that the present invention has broken conventional pH value fully.The Weak-acid flotation process need not broken and roughly grinds, need not to regulate slurry pH with lime, compare the alkalescent flotation and reduced equipment investment and floating agent dosage, also reduced the consumption of water, electricity, energy conservation and consumption reduction effects is remarkable, can significantly improve percentage of product and the rate of recovery of zinc sulfide concentrates and concentrate of lead sulfide ore simultaneously.Owing under solutions of weak acidity, carrying out full flotation of ore pulp, solved under weak basic condition isoamyl xanthate should not as the collecting agent of flotation zinc sulphide, only should be as the technical barrier of the collecting agent of flotation lead oxide, take full advantage of that isoamyl xanthate is the strongest in xanthate collectors to the collecting rate of zinc sulphide, consumption minimum outstanding advantage again, successfully adopt first isoamyl xanthate as the collecting agent of flotation zinc sulphide.
(3) solution of zinc sulfate sulfur acid calcium, the magnesium sulfate for selective leaching zinc oxide output is higher, obtain in the technological process of zinc product and can bring the problem of harm by continuous crystallization in subsequent production, also in order to reduce production costs, this technique takes to cool, add CaSO
42H
2The O crystal seed, add polyethylene glycol, sodium polyphosphate, (NH
4)
2SO
4The methods such as isoreactivity additive allow CaSO
4And MgSO
4Crystallization, the calcium magnesium slag that obtains also can be used as product and sell.
(4) the present invention has simplified the zinc extraction procedure, has optimized technique.The strip liquor of the present invention after with the zinc back extraction directly carries out electrodeposition, and electrolysis waste solution is all for the back extraction operation, and strip liquor, electrolysis waste solution no longer return the leaching operation of flowsheet of wet zinc smelting, compares existing Zinc hydrometallurgy process and reduced cleaning procedure.By increasing back extraction progression, adopt the multistage continuous back extraction more than three grades, will be mainly the H of the back washing agent of electrolysis waste solution
2SO
4Content to 120～150 grams per liters, Zn content is increased to 50～70 grams per liters, has both guaranteed that back extraction ratio and strip liquor contain Zn 〉=75 grams per liters, reach again the purpose of Reduction of acid consumption and cost.
(5) because extraction process itself selectively stronger, the ZnSO that the present invention obtains
4Co, Ni, As, Sb, the impurity such as F, Cl contained in the solution can not be extracted in follow-up extraction process and cut off with strip liquor, Cd, Cu impurity by trace extraction or extractant mechanical entrapment then also can be removed by adding a small amount of zinc powder under the normal temperature before extraction process, all dirt need not through removing the purification and impurity removal matter operations such as NI-G except cobalt, high low temperature, can greatly shorten production procedure, reduce consumption coal-fired, cleanser, effectively reduce production costs.And tradition ZnSO
4Solution is produced the technique of electrolytic zinc must remove first ZnSO by the operation that adds a large amount of auxiliary materials such as zinc powder and employing complexity
4Could electrolysis obtain zinc behind contained Co, Ni, As, Sb, the impurity such as F, Cl in the solution.
(6) during the sulfuration phase metal of the present invention in flotation of ores, floatingly select first zinc sulphide, and then flotation vulcanized lead and sulphur concentrate, have raw material and granularity wide accommodation, technological process short, be easy to operate and control, medicament kind and consumption is few, do not produce the advantages such as newborn waste gas and harmful dangerous waste residue in the process, realized the utilization of resources and environmental friendliness doulbe-sides' victory.
The present invention can significantly improve the rate of recovery that the low-grade complex difficulty is selected plumbous zinc metal in the plumbous zinc ore of oxysulphied, and plumbous zinc overall recovery can be up to more than 90%, and the plumbous zinc metal overall recovery of comparing conventional " first flotation-rear the smelting " process integration has improved 20～30%.This technique forms three class solution closed circuit circulatory systems, and the one, leachate, the 2nd, strip liquor, the 3rd, flotation fluid, whole flow process produces without waste water.Technological process continuity of the present invention is good, production procedure is short, operation control easily, be conducive to select promotion and application in the large-scale industrial production of the plumbous zinc ore of oxysulphied at complicated difficult.
Description of drawings
Fig. 1 is process flow diagram of the present invention.
The specific embodiment
As shown in the figure, it is for the oxysulphied lead-zinc ore that process integration is selected in the smelting of selective leaching zinc oxide of the present invention and Weak-acid flotation zinc sulphide, the zinc wet method smelting process is combined with the zinc floatation process, adopt first wet method smelting process with the selective leaching of the part of the zinc oxide in the ore, with floatation process the zinc sulphide in the ore is partly flotated again.
Zinc wet method smelting process of the present invention is as solvent, with the oxide in the selective technology processing raw ore that leaches with sulfuric acid.Be specially sulfuric acid is added in the ore pulp of oxysulphied lead-zinc ore, ore pulp dissolves the oxides such as the zinc oxide in the ore pulp and cupric oxide, cadmium oxide fully and to enter ZnSO under the condition of acidity, high temperature, stirring
4In the solution, the leached mud of while output Containing Sulfur zinc and sulfide.ZnSO
4Solution obtains zinc metal sheet by zinc extraction, zinc back extraction, zinc electrodeposition, and zinc metal sheet obtains the zinc ingot metal product through founding production.
In selective leaching process, when ore grinding slurrying, the weight of the breeze of control mill ore particle degree＜=0.0018mm accounts for more than 80% of total breeze amount, and the weight percent concentration of ore pulp is controlled at 35～50%, uses as far as possible ZnSO during modulation ore pulp solution
4Raffinate is sized mixing.Selective extract technology comprises neutral leaching, acidic leaching and three process sections of pulp washing, and leaching agent is sulfuric acid and raffinate.The concentration that at first will grind is that 35～50% ore pulp carries out neutrality and leaches, neutral leaching starting point acid pH value is 1.5～2.5, terminal point acid pH value is 4.5～5.2, Leaching way can adopt the interruption Leaching way, also can adopt continuous Leaching way, neutrality is leached the ore pulp of ending be pumped into the concentrator natural subsidence and concentrate to realize liquid-solid the separation, the supernatant that overflows namely contains Zn SO
4Solution.In selective leaching process, Zn SO
4It is low that solution contains zinc ion concentration, needs to adopt zinc extraction and zinc back extraction with ZnSO
4The enrichment of solution zinc ion concentration is increased to more than the 75g/L, obtains electrolytic zinc plate through the zinc electrodeposition again, and zinc metal sheet obtains the zinc ingot metal product through founding production.ZnSO
4Solution preferably carries out first Ca, Mg and separates out processing, elder generation's crystallization calcium sulfate, magnesium sulfate wherein, prevent from obtaining in subsequent production that the continuous crystallization of Ca, Mg brings adverse effect to obtaining zinc product in the technological process of zinc product, the calcium magnesium slag that obtains can be used as product and sells, and is enterprise's create beneficial result.To ZnSO
4Solution carries out Ca, Mg and separates out processing, is ZnSO4 solution is cooled to 20 ℃～40 ℃, adds CaSO in the cooling procedure
42H
2O crystal seed and active additive, crystallization calcium sulfate and magnesium sulfate form calcium magnesium slag.Described active additive can adopt polyethylene glycol, sodium polyphosphate, (NH
4)
2SO
4In one or more, also can adopt other that active additive of same purpose is arranged.ZnSO
4Solution obtains zinc metal sheet by zinc extraction, zinc back extraction, zinc electrodeposition again after Ca, Mg separate out processing, further founding obtains qualified zinc ingot metal product up to standard.Thickener underflow carries out acidic leaching, further dissolves other oxide in the leached mud fully, and other oxide is entered in the solution with sulphate form, in order to reclaim and extract other valuable metal in the ore.The sour pH value of acidic leaching process section starting point is 0.5～1.5, terminal point acid pH value is 2.0～3.5, and the pressing filtering liquid behind the acidic leaching turns back to neutral extracting stage.Filter-press residues behind the acidic leaching is with again pulp washing of raffinate, and with the oxide in the reduction acid leaching residue, the pressing filtering liquid after the pulp washing returns the acidic leaching process section, and filter-press residues is that leached mud enters flotation.Leached mud after the press filtration contains H
2O≤28%, zinc oxygenation efficiency≤30% in the leached mud is thought the full flotation of ore pulp production of follow-up faintly acid, creates necessary operating condition.The main P204 that adopts of zinc extraction as diluent, is mixed with organic extraction agent of P204 content 30% with 260# kerosene as extractant, comes extracting and enriching and improves ZnSO
4Zinc ion concentration in the solution.The zinc back extraction is to use to contain Zn50～70 grams per liters, H
2SO
4The zinc electrolysis waste solution of 120～150 grams per liters is as back washing agent, back extraction zinc load organic phases, and strip liquor is directly delivered to the zinc electrowinning process.ZnSO of the present invention
4Neutral supernatant need not to remove Cu, Cd, the impurity such as Co, Ni with process high temperature zinc powder cleaning process technology and the means of prior art, can reduce coal-fired consumption and the zinc powder consumption, but Effective Raise zinc metal recovery rate and reduction consumption and production cost.The present invention can be transmitted back to the waste liquid that produces behind the zinc electrodeposition zinc back extraction operation and again carry out the zinc electrodeposition after the back extraction.3～6 grades of continuous back extractions are adopted in zinc back extraction of the present invention, with the H of back washing agent
2SO
4Content to 120～150 grams per liters, Zn content is increased to 50～70 grams per liters, has both guaranteed that back extraction ratio and strip liquor contain Zn 〉=75 grams per liters, reach again the purpose of Reduction of acid consumption and cost.Used back washing agent is mainly electrolysis waste solution.Because extraction process itself is selectively stronger, ZnSO
4Co, Ni, As, Sb, the impurity such as F, Cl contained in the solution can not be extracted in follow-up extraction process and cut off with strip liquor, Cd, Cu impurity by trace extraction or extractant mechanical entrapment then also can be removed by adding a small amount of zinc powder under the normal temperature before extraction process, all dirt need not through removing the purification and impurity removal matter operations such as NI-G except cobalt, high low temperature, can greatly shorten production procedure, reduce consumption coal-fired, cleanser, effectively reduce production costs.Zinc extraction of the present invention, zinc back extraction, zinc electrolysis, founding zinc ingot metal, separate out Ca, Mg and all can adopt prior art.
What form when selectively leaching zinc oxide contains ZnS, also contains PbS, FeS
2Leached mud with floatation process the zinc sulphide in the ore is partly carried out flotation, floatation process is leached mud to be carried out ore grinding size mixing, and makes the pH value and be 1～7 faintly acid ore pulp, carries out full flotation of ore pulp, obtains the ZnS concentrate.The poor cadmia that full flotation of ore pulp is obtained producing behind the ZnS concentrate carries out flotation again, obtains PbS concentrate and sulphur concentrate.The pulp density of the full flotation of ore pulp of faintly acid is 25～35%.The main medicament of flotation has waterglass, calgon, pine tar, copper sulphate, vulcanized sodium, isoamyl xanthate, butyl xanthate, all can directly purchase from market.With isoamyl xanthate or butyl xanthate as collecting agent, with pine tar as foaming agent, with copper sulphate, vulcanized sodium, dilute sulfuric acid as activator, with waterglass, calgon as the sludge dispersant.Collecting agent preferably uses isoamyl xanthate, and addition is 85～120g/t ore deposit, and comparable prior art reduces the collector dosage of 25～35 %.The addition of calgon is 150～200g/t ore deposit, and the waterglass consumption is 50～100g/t ore deposit, and the pine tar consumption is 10～20g/t ore deposit, and the copper sulphate consumption is 50～80g/t ore deposit, and amount of sodium sulfide is 500～1500g/t ore deposit.Owing under solutions of weak acidity, carrying out full flotation of ore pulp, having solved under weak basic condition isoamyl xanthate should not be as the collecting agent of flotation vulcanized lead, zinc, only should as the technical barrier of the collecting agent of flotation lead oxide, zinc, successfully adopt first isoamyl xanthate as the collecting agent of flotation vulcanized lead zinc.Having solved simultaneously under the meta-alkalescence condition calgon should not be as the inhibitor of impurity and gangue, only should as the technical barrier of the inhibitor of flotation lead oxide zinc, successfully adopt first calgon as the inhibitor of flotation vulcanized lead zinc.Flotation adopt diffeential floatation ZnS, again select PbS, select FeS at last
2Three sections flotation flowsheets, three sections flotation all adopt one roughing, scan for twice, the triple cleaning flow process, and the sulfide ore pulp that floatingly selects becomes ZnS, PbS, FeS after press filtration
2The concentrate product, flotation tailing is sent into tailings reservoir for piling.In process of production, because leached mud granularity≤80 purposes have accounted for 92.31%, need not to use broken and corase grind equipment, only need a rod mill to stir and size mixing.Corresponding equipment investment and the energy consumption of fragmentation with two sections of corase grind that reduced, in operation process, also need not to add pulverized limestone and regulate slurry pH to 8～11, can effectively reduce floating agent kind and consumption, flow process power consumption and the new water yield are less, reach energy-saving and cost-reducing purpose, but grade and the rate of recovery of while Effective Raise zinc sulphide and concentrate of lead sulfide ore.Grade can reach Zn＞=30%, and the rate of recovery can be increased to 93～98%; The grade of concentrate of lead sulfide ore can reach Pb＞=30%, and the rate of recovery can be increased to 90～95%.Among the present invention, ore grinding sizes mixing, roughly selects, scans, the method such as selected all can adopt prior art.
The applicant adopts technique of the present invention to select the plumbous zinc ore of oxysulphied to carry out the industrialness trial production by 100 tons of/day blue level ground low-grade refractories.
Trial production uses the blue level ground existing low-grade refractory of plumbous zinc ore to select the raw ore main component of the plumbous zinc ore of oxysulphied as follows:
| Element | Zn | Fe | Pb | CaO | MgO | SiO 2 | S | Oxygenation efficiency |
| Content (%) | 7.72 | 4.13 | 1.97 | 13.65 | 1.55 | 39.91 | 2.90 | 75.97 |
Raw ore is in selective leaching process, and neutrality leaches the ZnSO of output
4The solution zinc ion concentration is lower, only reaches Zn ion 13～27 grams per liters, does not reach the electrolyte Zn ion of zinc hydrometallurgy zinc 〉=75 grams per liter requirements, needs to adopt zinc extraction and multistage zinc back extraction means to come enrichment raising ZnSO
4The zinc ion concentration of solution is to reach the required zinc ion concentration requirement of zinc electrolyte.After 3～5 grades of back extractions, zinc ion concentration obtains enrichment, realizes that strip liquor contains Zn 〉=75 grams per liters, and strip liquor is directly sent into zinc electrodeposition operation and obtained negative electrode zinc metal sheet and electrolysis waste solution, electrolysis waste solution is all for the back extraction operation, and zinc metal sheet is produced the standard zinc ingot metal product that contains zinc 〉=99.99% through founding.ZnSO
4Solution is after extraction, and raffinate turns back to the leaching operation, recycles.Raffinate contains Zn5.5～13.7 grams per liters, H
2SO
412.7～23.68 grams per liters.
The leached mud main component of sulfur compound is as follows:
| Element | H 2O | Zn | Zn Water | Pb | CaO | MgO | SiO 2 | S | Oxygenation efficiency |
| Content (%) | 26.98 | 2.80 | 0.83 | 1.87 | 15.11 | 0.55 | 33.26 | 2.90 | 30.27 |
Leached mud is in the full flotation of ore pulp process of faintly acid, the zinc sulfide concentrates of output contains Zn 〉=27.3%, Pb≤4.29%, S 〉=26.75%, zinc flotation recovery rate and reaches 93～98%, the concentrate of lead sulfide ore of output contains Pb 〉=31.76%, Zn≤5.37%, S 〉=29.79%, and the sulphur concentrate of output contains S 〉=48.54%, Fe 〉=35.62%.
In the industrialness trial production, the overall recovery that hydrometallurgy of the present invention leaches zinc oxide and flotation zinc sulphide reaches 91～93%.
By the experimental production preliminary proof, technique of the present invention has realized that the smelting choosing organically combines, maximize favourable factors and minimize unfavourable ones, both bring into play acidleach and can fully reclaim the advantage of zinc oxide mineral, bring into play again flotation and can fully reclaim the zinc sulfide mineral advantage, can realize on the whole taking full advantage of low-grade refractory and select the plumbous zinc ore of complicated oxysulphied, expansion can utilize zinc resource, not increase process gas, waste water simultaneously, reach efficient utilization of resource and eco-friendly double goal.
Claims (12)
1. selectively leach the smelting of zinc oxide and Weak-acid flotation zinc sulphide and select process integration, it is characterized in that, this technique is for the oxysulphied lead-zinc ore, the zinc wet method smelting process is combined with the zinc floatation process, adopt first wet method smelting process with the selective leaching of the part of the zinc oxide in the ore, with floatation process the zinc sulphide in the ore is partly flotated again.
2. process integration is selected in the smelting of selective leaching zinc oxide according to claim 1 and Weak-acid flotation zinc sulphide, it is characterized in that, described zinc wet method smelting process is as solvent with sulfuric acid, sulfuric acid is added in the ore pulp of oxysulphied lead-zinc ore, the zinc oxide in the ore pulp and other oxide dissolution are entered ZnSO
4In the solution, the leached mud of output Containing Sulfur zinc and other sulfide is realized the selective zinc oxide that leaches simultaneously.
3. process integration is selected in the smelting of selective leaching zinc oxide according to claim 2 and Weak-acid flotation zinc sulphide, it is characterized in that, in the oxysulphied lead-zinc ore ore pulp that grinds, the weight that grinding particle size is not more than the breeze of 0.0018mm accounts for more than 80% of total breeze amount, and the weight percent concentration of ore pulp is 35～50%.
According to claim 1 and 2 or the smelting of 3 described selective leaching zinc oxide and Weak-acid flotation zinc sulphide select process integration, it is characterized in that, will selectively leach the ZnSO that obtains of zinc oxide
4Solution obtains zinc product by zinc extraction, zinc back extraction, zinc electrodeposition.
5. process integration is selected in the smelting of selective leaching zinc oxide according to claim 4 and Weak-acid flotation zinc sulphide, it is characterized in that, the waste liquid that produces behind the zinc electrodeposition is transmitted back to zinc back extraction operation again carries out the zinc electrodeposition after the back extraction.
6. process integration is selected in the smelting of selective leaching zinc oxide according to claim 4 and Weak-acid flotation zinc sulphide, it is characterized in that, described zinc back extraction is 3～6 grades of continuous back extractions, and back washing agent is electrolysis waste solution, H in the back washing agent
2SO
4Content is 120～150 grams per liters, and Zn content is 50～70 grams per liters.
7. process integration is selected in the smelting of selective leaching zinc oxide according to claim 4 and Weak-acid flotation zinc sulphide, it is characterized in that, will selectively leach the ZnSO of zinc oxide acquisition
4Solution carries out first Ca, Mg and separates out processing, and then by zinc extraction, zinc back extraction, zinc electrodeposition, obtains zinc product.
8. process integration is selected in the smelting of selective leaching zinc oxide according to claim 7 and Weak-acid flotation zinc sulphide, it is characterized in that, and is described to ZnSO
4Solution carries out Ca, Mg and separates out processing, is with ZnSO
4Solution cools to 20 ℃～40 ℃, adds CaSO in the cooling procedure
42H
2O crystal seed and active additive, crystallization CaSO
4And MgSO
4, form calcium magnesium slag.
According to claim 1 and 2 or the smelting of 3 described selective leaching zinc oxide and Weak-acid flotation zinc sulphide select process integration, it is characterized in that, the leached mud that contains zinc sulphide that forms when selectively leaching zinc oxide partly carries out flotation with floatation process with the zinc sulphide in the ore, floatation process is leached mud to be carried out ore grinding size mixing, make the pH value and be 1～7 faintly acid ore pulp, then carry out full flotation of ore pulp, obtain the ZnS concentrate.
10. process integration is selected in the smelting of selective leaching zinc oxide according to claim 9 and Weak-acid flotation zinc sulphide, it is characterized in that, the moisture content of leached mud is not more than 28%, and the zinc oxygenation efficiency is not more than 30% in the leached mud.
11. process integration is selected in the smelting of selective leaching zinc oxide according to claim 9 and Weak-acid flotation zinc sulphide, it is characterized in that, the poor zinc mine tailing that full flotation of ore pulp is obtained producing behind the ZnS concentrate carries out flotation PbS again, and the poor plumbous mine tailing that obtains producing behind the PbS concentrate carries out again flotation FeS
2, obtain FeS
2Concentrate.
12. process integration is selected in the smelting of selective leaching zinc oxide according to claim 9 and Weak-acid flotation zinc sulphide, it is characterized in that, adopts isoamyl xanthate as the collecting agent of flotation zinc sulphide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310106140.2A CN103301929B (en) | 2013-03-29 | 2013-03-29 | Smelting and selection combined process of selective zinc oxide leaching and weak acidic zinc sulfide flotation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310106140.2A CN103301929B (en) | 2013-03-29 | 2013-03-29 | Smelting and selection combined process of selective zinc oxide leaching and weak acidic zinc sulfide flotation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103301929A true CN103301929A (en) | 2013-09-18 |
| CN103301929B CN103301929B (en) | 2015-03-25 |
Family
ID=49127904
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310106140.2A Active CN103301929B (en) | 2013-03-29 | 2013-03-29 | Smelting and selection combined process of selective zinc oxide leaching and weak acidic zinc sulfide flotation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103301929B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103480495A (en) * | 2013-09-27 | 2014-01-01 | 浙江华友钴业股份有限公司 | Method for recycling copper and cobalt from copper-cobalt pickling and smelting slags in beneficiating-smelting combined manner |
| CN103613116A (en) * | 2013-12-09 | 2014-03-05 | 衡阳师范学院 | Method for simultaneously and comprehensively recycling zinc ash and high-arsenic zinc oxide in iron and steel plant |
| CN103752416A (en) * | 2014-01-14 | 2014-04-30 | 兰坪金利达矿业有限责任公司 | Zinc oxide mineral collector and use method thereof |
| CN104475265A (en) * | 2014-11-21 | 2015-04-01 | 广西大学 | Method for flotation removal of coronadite out of manganic concerntrate |
| CN105170339A (en) * | 2015-09-30 | 2015-12-23 | 广西大学 | Floating method for recycling sulfur oxygen mixed minerals in tailings |
| CN109663663A (en) * | 2019-01-22 | 2019-04-23 | 昆明理工大学 | A kind of extracting method of the minal vulcanization after cure product of heavy metal oxidation mineral |
| CN110052327A (en) * | 2018-04-28 | 2019-07-26 | 巴彦淖尔紫金有色金属有限公司 | A kind of Zinc Ore with High Copper Content method for separating of high-sulfur containing zinc oxide |
| CN110142144A (en) * | 2019-06-03 | 2019-08-20 | 云南金鼎锌业有限公司 | The method that low-grade difficulty selects Flotation of Zinc Oxide in oxysulphied lead-zinc ore tailings |
| CN111118286A (en) * | 2020-01-16 | 2020-05-08 | 尤灵革 | Comprehensive recovery process for copper-lead-zinc bulk concentrates difficult to separate |
| CN111349794A (en) * | 2019-12-06 | 2020-06-30 | 中国船舶重工集团公司七五0试验场 | Automatic control method for lead-zinc ore smelting and selecting combined process |
| CN114950712A (en) * | 2022-05-27 | 2022-08-30 | 华刚矿业股份有限公司 | Combined treatment process for comprehensively recovering copper and cobalt |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101690910A (en) * | 2009-10-16 | 2010-04-07 | 株洲市湘麒科技开发有限公司 | Method for separating lead and silver from manganese in anode sludge |
| CN102527497A (en) * | 2011-12-29 | 2012-07-04 | 中南大学 | Beneficiation method for separating zinc sulfide ores from sulphur in wet-method zinc smelting slag |
| CN102583598A (en) * | 2012-03-19 | 2012-07-18 | 赤峰中色锌业有限公司 | Cycle production method for recovering zinc from beneficiation wastewater of high leaching slag |
| CN102899491A (en) * | 2012-10-12 | 2013-01-30 | 中南大学 | Method for floating and separating high-concentration iron ions from zinc sulfate leachate |
| CN102994747A (en) * | 2011-09-13 | 2013-03-27 | 郴州市金贵银业股份有限公司 | Technology for recovering metallic copper from high-lead copper matte |
-
2013
- 2013-03-29 CN CN201310106140.2A patent/CN103301929B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101690910A (en) * | 2009-10-16 | 2010-04-07 | 株洲市湘麒科技开发有限公司 | Method for separating lead and silver from manganese in anode sludge |
| CN102994747A (en) * | 2011-09-13 | 2013-03-27 | 郴州市金贵银业股份有限公司 | Technology for recovering metallic copper from high-lead copper matte |
| CN102527497A (en) * | 2011-12-29 | 2012-07-04 | 中南大学 | Beneficiation method for separating zinc sulfide ores from sulphur in wet-method zinc smelting slag |
| CN102583598A (en) * | 2012-03-19 | 2012-07-18 | 赤峰中色锌业有限公司 | Cycle production method for recovering zinc from beneficiation wastewater of high leaching slag |
| CN102899491A (en) * | 2012-10-12 | 2013-01-30 | 中南大学 | Method for floating and separating high-concentration iron ions from zinc sulfate leachate |
Non-Patent Citations (1)
| Title |
|---|
| 王肖飞等: "《含铜硫精矿铜、硫分离浮选试验研究》", 《黄金》, vol. 31, no. 5, 31 May 2010 (2010-05-31), pages 43 - 46 * |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103480495B (en) * | 2013-09-27 | 2015-08-26 | 浙江华友钴业股份有限公司 | A kind of method selecting smelting to combine recovery copper cobalt from copper cobalt ore acidleach metallurgical slag |
| CN103480495A (en) * | 2013-09-27 | 2014-01-01 | 浙江华友钴业股份有限公司 | Method for recycling copper and cobalt from copper-cobalt pickling and smelting slags in beneficiating-smelting combined manner |
| CN103613116A (en) * | 2013-12-09 | 2014-03-05 | 衡阳师范学院 | Method for simultaneously and comprehensively recycling zinc ash and high-arsenic zinc oxide in iron and steel plant |
| CN103613116B (en) * | 2013-12-09 | 2014-11-05 | 衡阳师范学院 | Method for simultaneously and comprehensively recycling zinc ash and high-arsenic zinc oxide in iron and steel plant |
| CN103752416A (en) * | 2014-01-14 | 2014-04-30 | 兰坪金利达矿业有限责任公司 | Zinc oxide mineral collector and use method thereof |
| CN104475265A (en) * | 2014-11-21 | 2015-04-01 | 广西大学 | Method for flotation removal of coronadite out of manganic concerntrate |
| CN104475265B (en) * | 2014-11-21 | 2017-01-18 | 广西大学 | Method for flotation removal of coronadite out of manganic concerntrate |
| CN105170339A (en) * | 2015-09-30 | 2015-12-23 | 广西大学 | Floating method for recycling sulfur oxygen mixed minerals in tailings |
| CN110052327B (en) * | 2018-04-28 | 2021-03-16 | 巴彦淖尔紫金有色金属有限公司 | Method for sorting zinc oxide-containing high-sulfur high-copper zinc concentrate |
| CN110052327A (en) * | 2018-04-28 | 2019-07-26 | 巴彦淖尔紫金有色金属有限公司 | A kind of Zinc Ore with High Copper Content method for separating of high-sulfur containing zinc oxide |
| CN109663663A (en) * | 2019-01-22 | 2019-04-23 | 昆明理工大学 | A kind of extracting method of the minal vulcanization after cure product of heavy metal oxidation mineral |
| CN109663663B (en) * | 2019-01-22 | 2020-11-27 | 昆明理工大学 | Method for extracting sulfide product of heavy metal oxidized mineral after pure mineral vulcanization |
| CN110142144A (en) * | 2019-06-03 | 2019-08-20 | 云南金鼎锌业有限公司 | The method that low-grade difficulty selects Flotation of Zinc Oxide in oxysulphied lead-zinc ore tailings |
| CN111349794A (en) * | 2019-12-06 | 2020-06-30 | 中国船舶重工集团公司七五0试验场 | Automatic control method for lead-zinc ore smelting and selecting combined process |
| CN111349794B (en) * | 2019-12-06 | 2022-04-12 | 中国船舶重工集团公司七五0试验场 | Automatic control method for lead-zinc ore smelting and selecting combined process |
| CN111118286A (en) * | 2020-01-16 | 2020-05-08 | 尤灵革 | Comprehensive recovery process for copper-lead-zinc bulk concentrates difficult to separate |
| CN114950712A (en) * | 2022-05-27 | 2022-08-30 | 华刚矿业股份有限公司 | Combined treatment process for comprehensively recovering copper and cobalt |
| CN114950712B (en) * | 2022-05-27 | 2023-10-13 | 华刚矿业股份有限公司 | Combined treatment process for comprehensively recovering copper and cobalt |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103301929B (en) | 2015-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103301929B (en) | Smelting and selection combined process of selective zinc oxide leaching and weak acidic zinc sulfide flotation | |
| CN101698904B (en) | Method for extracting sulfide minerals of nonferrous metals and method for recycling sulfur in extracted filtered residues thereof | |
| US11293076B2 (en) | Method for preparing iron ore concentrates by recycling copper slag tailings | |
| CN110117720B (en) | Method for comprehensively extracting valuable metals from sulfate slag through phosphorylation roasting, leaching and extraction | |
| CN102808087B (en) | Method for extracting zinc, potassium and sodium by using secondary dust of rotary hearth furnace | |
| Zhou et al. | Extraction and separation of copper and iron from copper smelting slag: A review | |
| CN102643983B (en) | Stage-by-stage dump leaching technology for low-grade mixed copper ore | |
| CN101961673A (en) | Combined concentration and smelting method for mixed copper ore | |
| CN102108447B (en) | Technology for removing iron and arsenic from leaching solution of purification slag generated in zinc hydrometallurgy | |
| CN102094127A (en) | Method for recovering nickel and magnesium elements from high-magnesium low-grade nickel sulfide ore | |
| CN104815746A (en) | Recovery method of high-iron highly-argillaceous alkaline gangue refractory oxide copper ore | |
| CN102703694A (en) | Method for treating low-grade zinc oxide ores by wet method | |
| CN102703690A (en) | Method for separating high-ferrosilicon complex zinc oxide lean ores through combined treatment | |
| CN101182600A (en) | Combined technology for separating and extracting vanadium from high calcium and high ferro steel scoria | |
| CN102327809B (en) | Method for removing magnesium oxide from collophanite | |
| CN104745811A (en) | Acid ore washing biological leaching process used for high mud alkaline uranium ore | |
| CN103934096A (en) | Mixed copper ore recycling method | |
| CN102134653B (en) | Separation-smelting combined process for treating difficultly separated copper-containing gold sulfide ores | |
| CN113846214A (en) | Method for treating zinc-containing material in zinc hydrometallurgy production | |
| CN108239701B (en) | Method for comprehensively recovering lead and zinc in high-mud carbonate type lead-zinc oxide ore | |
| CN105110300A (en) | Method for extracting manganese and sulfur from composite manganese mine containing manganese sulfide | |
| CN103157560B (en) | Flotation method of vulcanizing lead and zinc by weak acid full pulp | |
| CN107739841A (en) | A kind of method for separating arsenic from containing the high copper dross slag of arsenic, reclaiming copper | |
| CN102002602B (en) | Method for increasing recovery rates of lead and zinc during lead-zinc sulfide ore dressing-smelting joint application | |
| CN101530826B (en) | Method for combined treatment of high calcium and magnesium low-grade oxidized lead zinc ore by means of concentration |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |