CN103301929B - Smelting and selection combined process of selective zinc oxide leaching and weak acidic zinc sulfide flotation - Google Patents
Smelting and selection combined process of selective zinc oxide leaching and weak acidic zinc sulfide flotation Download PDFInfo
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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 Pb-Zn deposits hydrometallurgy and flotation technology field.
Background technology
China is zinc metal first big producing country and consumption big country, and zinc resource problem in short supply shows especially day by day, about has the zinc raw material of 1/3rd to need import every year, and resource provisioning deficiency has become the key factor of restriction social sustainable development.But the zinc ore of the especially low-grade high impurity of China's zinc resource does not obtain Appropriate application again owing to lacking effective processing treatment technology.
At present, China has at least the low-grade refractory of more than 5,000 ten thousand tons to select complicated oxysulphied Pb-Zn deposits, particularly the Lan Ping mining area of China the western regions of the Yunnan Province has more than 4,000 ten thousand tons of such ores, potential economic worth is more than 30,000,000,000 RMB, because its ore properties is extremely complicated, there is oxygenation efficiency high, the features such as clay content is large and poor, thin, assorted, never effective technology extracts zinc wherein, these ores can only be passed into disuse, not only cause the significant wastage of resource, define huge pressure also to mine safety environmental protection simultaneously.Therefore, select for low-grade refractory the technology that complicated oxysulphied Development of lead-zinc mine is new, become very urgent and the problem of reality.
The method of traditional process oxysulphied lead-zinc ore first adopts flotation practice enrichment and improves plumbous zinc metal content, then adopts pyrogenic process or wet process smelting technique to produce zinc ingot metal and lead pig.After this first choosing, the technique of smelting is extensive single, only can develop the lead-zinc that part is greater than more than 15% containing zinc, a large amount of grade lower than 10% plumbous Zinc oxide and oxysulphied Pb-Zn deposits, be difficult to effectively develop by conventional method.In addition, prior art is in zinc sulphide flotation, oxysulphied lead-zinc ore segmentation associating flotation, in lead-zinc pyrogenic process pretreatment floatation process, first flotation vulcanized lead, rear flotation zinc sulphide, last Flotation of Zinc Oxide again, the accommodation that above three kinds of floatation process all exist raw material and granularity is little, technological process is long, the multiplex amount of medicament kind is large, the tail gas hazard-free intractability produced is large, PbS concentrate is higher containing zinc, ZnO concentrate and ZnS concentrate grade low, mine tailing is high containing zinc, plumbous and zinc recovery is low, ZnO concentrate is difficult to produce the problems such as electrolytic zinc with conventional hydrometallurgy containing amine organic matter.
The character feature of complicated oxysulphied Pb-Zn deposits is selected for above-mentioned low-grade refractory, from 2000 to 2012, successively there are 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 Deng Duosuo scientific research institutions of Central South University and colleges and universities to combine with applicant and relevant unit thereof, carried out large quantifier elimination, research of technique and engineer testing.The various processes such as development test " ore pretreatment-flotation " technique, " diffeential floatation " technique, " ore deposit dense media-flotation acidleach associating " technique, " first Flotation of Sulfide Ores desliming-zinc oxide flotation " technique, Pb-Zn deposits hot pressing conversion technology, " pretreatment-flotation of Pb-Zn deposits pyrogenic process " technique.These processes more or less achieve the scientific achievement of some stages all respectively.But all also have that technological process is long, installations and facilities are many, tail gas and mine tailings harmless environmental protection intractability are comparatively large, are 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, complicated oxysulphied Pb-Zn deposits is selected with the PROCESS FOR TREATMENT low-grade refractory of routine existing " first flotation-smelt afterwards ", through repeatedly small-scale test and half industrial production test, zinc oxide ore floatation process production target is relatively poor, the zinc oxide concentrate grade of flotation is lower, Zn content only can reach 17.85 ~ 26.47%, zinc recovery is only 53.02 ~ 68.86%, also containing a large amount of lauryl amines and octadecylamine organic matter foaming agent in concentrate, these organic matters can cause serious bubbling in zinc leaching process, have a strong impact on zinc electrolysis to separate out, zinc hydrometallurgy is caused to be difficult to normally produce.Flotation of Zinc Oxide concentrate is the smelting operation and the production that are difficult to carry out direct acidleach-electrolysis, and after generally having to pass through " pyrogenic process roasting reagent removal " process, the hydrometallurgy that just can enter leaching and electrolysis is produced.This just makes zinc abstraction technological process longer, and installations and facilities are more, the heat material of production and energy consumption excessive, tail gas hazard-free difficult treatment, production technology difficulty is not large, easy to operate and control, and cost is higher, and this is not only uneconomical but also not environmentally.Lot of domestic and international expert unanimously thinks for many years, and this kind of low-grade refractory selects the mineral processing technology of oxidase complex zinc ore and oxysulphied Pb-Zn deposits to be not only a domestic difficult problem, the difficult problem in the Ye Shi world.Prior art also has a kind of process integration adopting organic solvent extracting zinc and zinc hydrometallurgy, and as Chinese patent 200610010938.7, the strip liquor in its technique after zinc back extraction also will be transmitted back to the leaching operation of flowsheet of wet zinc smelting, adopts this technique, containing H in back washing agent
2sO
4usually up to 150 ~ 200 grams per liters, not only acid consumption is high, also must further purified treatment in actual production, increases cleaning procedure, extends production procedure, adds fire coal, cleanser etc. and produces and consume, raised production cost.In addition, the flotation of prior art is normally carry out lead-zinc sulfide ore flotation under the weak basic condition of 8 ~ 11 in ore pulp pH value, 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, the zinc sulfide concentrates obtained and the grade of concentrate of lead sulfide ore and the rate of recovery also lower.
For a long time, fail to develop that a kind of technological process is short both at home and abroad all always, technically reliable, be easy to operate and control, production material consumption and energy consumption is lower, metal recovery rate is high, better economic benefit, the process low-grade refractory with better industrialization prospect select complicated oxysulphied Pb-Zn deposits technology.
Summary of the invention
Object of the present invention is just in order to solve the deficiency that above-mentioned prior art exists, for the difficulty in treatment of oxysulphied Pb-Zn deposits, provide that a kind of technological process is short, technically reliable, be easy to operate and control, production material consumption and energy consumption is lower, metal recovery rate is high, after better economic benefit, practical first hydrometallurgy the Selectively leaching zinc oxide of flotation and the smelting of Weak-acid flotation zinc sulphide select process integration.
The object of the invention is to be achieved through the following technical solutions.
Process integration is selected in the smelting of Selectively leaching zinc oxide and Weak-acid flotation zinc sulphide, this technique is for oxysulphied lead-zinc ore, zinc wet method smelting process is combined with zinc floatation process, first adopt wet method smelting process by the zinc oxide portion Selectively leaching in ore, then with floatation process, the zinc sulphide part in ore is flotated.
Zinc wet method smelting process of the present invention uses sulfuric acid as solvent, added by sulfuric acid in the ore pulp of oxysulphied lead-zinc ore, the zinc oxide in ore pulp and other oxide dissolution are entered ZnSO
4in solution, the leached mud of output Containing Sulfur zinc and other sulfide, realizes Selectively leaching zinc oxide simultaneously.In the oxysulphied lead-zinc ore ore pulp ground, 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 ZnSO that Selectively leaching zinc oxide obtains by the present invention
4solution, by zinc extraction, zinc back extraction, Zinc electrolysis, obtains zinc product.The waste liquid produced after Zinc electrolysis is also transmitted back to zinc back extraction operation and again carries out Zinc electrolysis after back extraction by the present invention.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 back washing agent
4content is 120 ~ 150 grams per liters, and Zn content is 50 ~ 70 grams per liters.The ZnSO that Selectively leaching zinc oxide can obtain by the present invention
4solution first carries out Ca, Mg and separates out process, and then by zinc extraction, zinc back extraction, Zinc electrolysis, obtains zinc product.Described to ZnSO
4solution carries out Ca, Mg and separates out process, is by ZnSO
4solution cools to 20 DEG C ~ 40 DEG C, adds CaSO in cooling procedure
42H
2o crystal seed and active additive, crystallization CaSO
4and MgSO
4, form calcium magnesium slag.
Zinc sulphide part in ore is carried out flotation by the leached mud floatation process containing zinc sulphide formed during Selectively leaching zinc oxide by the present invention, floatation process leached mud is carried out ore grinding size mixing, make the faintly acid ore pulp that pH value is 1 ~ 7, then carry out full flotation of ore pulp, obtain ZnS concentrate.During flotation of the present invention, the moisture content of leached mud is not more than 28%, and in leached mud, zinc oxygenation efficiency is not more than 30%.The present invention is the poor zinc mine tailing flotation PbS produced after full flotation of ore pulp is obtained ZnS concentrate, and the poor plumbous mine tailing produced after obtaining PbS concentrate carries out flotation FeS again
2, obtain FeS
2concentrate.The present invention adopts isoamyl xanthate as the collecting agent of flotation zinc sulphide.
The present invention at least has the following advantages:
(1) the present invention's technique of having smelted after having broken traditional first flotation, proposes the technique of flotation after first hydrometallurgy innovatively, achieves smelting choosing and combine, closely help each other, create technical conditions mutually.Adopt acid leaching process Selectively leaching zinc oxide, while fully reclaiming Zinc oxide minerals, for basic gangue has been taken in follow-up flotation in advance away, can reduce flotation difficulty, what also reduce flotation backwater contains calcium concentration, is beneficial to recycling of flotation backwater.Floatation process is after fully reclaiming zinc sulfide mineral, and its flotation leached mud inherently finally decreases the volume of cargo in storage of leached mud, reduces the harm to environment.
(2) the present invention is for the leached mud of Containing Sulfur zinc, is to carry out full flotation of ore pulp under the solutions of weak acidity of 1 ~ 7 in pH value, creating process conditions, being convenient to improve leaching rate for improving acidleach leaching intensity.It is lead-zinc sulfide ore flotation mode under 8 ~ 11 weak basic conditions that the present invention has broken conventional pH value completely.Weak-acid flotation process is without the need to broken and corase grind, without the need to regulating slurry pH with lime, compare alkalescent flotation and decrease equipment investment and floating agent dosage, decrease 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 to carrying out full flotation of ore pulp under mildly acidic conditions, to solve under weak basic condition isoamyl xanthate should not as the collecting agent of flotation zinc sulphide, only should as the technical barrier of the collecting agent of flotation lead oxide, make full use of the outstanding advantage that the collecting rate of isoamyl xanthate to zinc sulphide is the strongest in xanthate collectors, consumption is minimum again, successfully adopt isoamyl xanthate as the collecting agent of flotation zinc sulphide first.
(3) higher for the solution of zinc sulfate sulfur acid calcium of Selectively leaching zinc oxide output, magnesium sulfate, obtain the continuous crystallization of meeting in the technological process of zinc product in subsequent production and bring the problem of harm, also in order to reduce production cost, this technique is taked to cool, add CaSO
42H
2o 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 obtained also can be used as product and sells.
(4) this invention simplifies zinc extraction procedure, optimize technique.Strip liquor after zinc back extraction is directly carried out electrodeposition by the present invention, and electrolysis waste solution is all for 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 decreases cleaning procedure.By increasing back extraction progression, adopting the multistage continuous back extraction of more than three grades, will the H of the back washing agent of electrolysis waste solution be mainly
2sO
4content is reduced to 120 ~ 150 grams per liters, and Zn content is increased to 50 ~ 70 grams per liters, both ensure that back extraction ratio and strip liquor are containing Zn>=75 grams per liter, reach again the object reducing acid consumption and cost.
(5) selective comparatively strong due to extraction process itself, the ZnSO that the present invention obtains
4the impurity such as Co, Ni, As, Sb, F, Cl contained in solution can not be extracted and cut off with strip liquor in follow-up extraction process, then also removed by adding a small amount of zinc powder under normal temperature before extraction process by Cd, Cu impurity of microextraction or extractant mechanical entrapment, all dirt is without the need to passing through except cobalt, high/low temperature are except purification and impurity removal matter operations such as NI-Gs, greatly can shorten production procedure, reduce consumption that is coal-fired, cleanser, effectively reduce production cost.And tradition ZnSO
4the technique that solution produces electrolytic zinc also must adopt complicated operation first to remove ZnSO by adding the auxiliary materials such as a large amount of zinc powders
4electrolysis zinc could be obtained after the impurity such as Co, Ni, As, Sb, F, Cl contained in solution.
(6) during the sulfuration phase metal of the present invention in flotation of ores, first floatingly select zinc sulphide, and then flotation vulcanized lead and iron 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 advantage such as newborn waste gas and harmful dangerous waste residue in process, achieve the utilization of resources and environmental friendliness doulbe-sides' victory.
The present invention significantly can improve the rate of recovery that low-grade complex difficulty selects plumbous zinc metal in oxysulphied Pb-Zn deposits, and plumbous zinc overall recovery can up to more than 90%, and the plumbous zinc metal overall recovery comparing conventional " first flotation-smelt afterwards " process integration improves 20 ~ 30%.This technique forms three class solution closed circuit circulatory systems, and one is leachate, and two is strip liquors, and three is flotation fluids, and whole flow process produces without waste water.Present invention process flow process continuity is good, production procedure is short, operation controls easily, to be conducive to selecting promotion and application in the large-scale industrial production of oxysulphied Pb-Zn deposits at complicated difficult.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
Detailed description of the invention
As shown in the figure, the smelting of Selectively leaching zinc oxide of the present invention and Weak-acid flotation zinc sulphide selects process integration to be for oxysulphied lead-zinc ore, zinc wet method smelting process is combined with zinc floatation process, adopt first wet method smelting process by the zinc oxide portion Selectively leaching in ore, then with floatation process, the zinc sulphide part in ore is flotated.
Zinc wet method smelting process of the present invention is with sulfuric acid as solvent, with the oxide in the technology process raw ore of Selectively leaching.Be specially in ore pulp sulfuric acid being added oxysulphied lead-zinc ore, the zinc oxide in ore pulp and the oxide such as cupric oxide, cadmium oxide, under the condition of acidity, high temperature, stirring, dissolve and enter ZnSO by ore pulp completely
4in solution, the leached mud of output Containing Sulfur zinc and sulfide simultaneously.ZnSO
4solution obtains zinc metal sheet by zinc extraction, zinc back extraction, Zinc electrolysis, and zinc metal sheet is produced through founding and obtained zinc ingot metal product.
In Selectively leaching process, when ore grinding slurrying, the weight of the breeze of control Mo ore particle Du≤0.0018mm accounts for more than 80% of total breeze amount, and the weight percent concentration of ore pulp controls 35 ~ 50%, uses ZnSO as far as possible during modulation ore pulp solution
4raffinate is sized mixing.Selectively leaching technique comprises meutral innersion, acidic leaching and pulp and washes three process sections, and leaching agent is sulfuric acid and raffinate.First the ore pulp being 35 ~ 50% by the concentration ground carries out meutral innersion, meutral innersion starting point acid pH is 1.5 ~ 2.5, terminal acid pH is 4.5 ~ 5.2, Leaching way can adopt interruption Leaching way, also continuous Leaching way can be adopted, the ore pulp that meutral innersion is ended be pumped into concentrator natural subsidence and concentrate to realize solid-liquor separation, the supernatant overflowed is namely containing Zn SO
4solution.In Selectively leaching process, Zn SO
4solution is low containing zinc ion concentration, and zinc extraction and zinc back extraction need be adopted ZnSO
4the enrichment of solution zinc ion concentration is increased to more than 75g/L, then obtains electrolytic zinc plate through Zinc electrolysis, and zinc metal sheet is produced through founding and obtained zinc ingot metal product.ZnSO
4solution preferably first carries out Ca, Mg and separates out process, first crystallization calcium sulfate wherein, magnesium sulfate, prevent obtaining the continuous crystallization of Ca, Mg in the technological process of zinc product in subsequent production and bring adverse effect to obtaining zinc product, the calcium magnesium slag obtained can be used as product and sells, for enterprise creates benefit.To ZnSO
4solution carries out Ca, Mg and separates out process, is cool ZnSO4 solution to 20 DEG C ~ 40 DEG C, adds CaSO in 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, other also can be adopted to have the active additive of same purpose.ZnSO
4solution is separated out after process through Ca, Mg, then obtains zinc metal sheet by zinc extraction, zinc back extraction, Zinc electrolysis, and further founding obtains qualified zinc ingot metal product up to standard.Thickener underflow carries out acidic leaching, dissolves other oxide in leached mud further completely, other oxide is entered in solution with sulphate form, to reclaim and to extract other valuable metal in ore.The acid pH of acidic leaching process section starting point is 0.5 ~ 1.5, terminal acid pH is 2.0 ~ 3.5, and the pressing filtering liquid after acidic leaching turns back to meutral innersion section.The raffinate pulp washing again of filter-press residues after acidic leaching, to reduce the oxide in acid leaching residue, the pressing filtering liquid after pulp washing returns acidic leaching process section, and filter-press residues and leached mud enter flotation.Leached mud after press filtration is containing H
2o≤28%, zinc oxygenation efficiency≤30% in leached mud, thinks that the full flotation of ore pulp of follow-up faintly acid is produced, creates necessary operating condition.The main P204 that adopts of zinc extraction, as extractant, with 260# kerosene as diluent, is mixed with organic extraction agent of P204 content 30%, carrys out extracting and enriching and improve ZnSO
4zinc ion concentration in solution.Zinc back extraction uses containing Zn50 ~ 70 grams per liter, H
2sO
4the zinc electrolytic waste liquid of 120 ~ 150 grams per liters is as back washing agent, and back extraction zinc load organic phases, strip liquor directly delivers to zinc electrolysis operation.ZnSO of the present invention
4neutral supernatant, without the need to prior art through high temperature zinc powder cleaning process technology and means except impurity such as Cu, Cd, Co, Ni, coal-fired consumption and zinc powder consumption can be reduced, effectively can improve zinc metal recovery rate and reduce consumption and production cost.The waste liquid produced after Zinc electrolysis can be transmitted back to zinc back extraction operation and again carry out Zinc electrolysis after back extraction by the present invention.Zinc back extraction of the present invention adopts 3 ~ 6 grades of continuous back extractions, by the H of back washing agent
2sO
4content is reduced to 120 ~ 150 grams per liters, and Zn content is increased to 50 ~ 70 grams per liters, both ensure that back extraction ratio and strip liquor are containing Zn>=75 grams per liter, reach again the object reducing acid consumption and cost.Back washing agent used is mainly electrolysis waste solution.Selective comparatively strong due to extraction process itself, ZnSO
4the impurity such as Co, Ni, As, Sb, F, Cl contained in solution can not be extracted and cut off with strip liquor in follow-up extraction process, then also removed by adding a small amount of zinc powder under normal temperature before extraction process by Cd, Cu impurity of microextraction or extractant mechanical entrapment, all dirt is without the need to passing through except cobalt, high/low temperature are except purification and impurity removal matter operations such as NI-Gs, greatly can shorten production procedure, reduce consumption that is coal-fired, cleanser, effectively reduce production cost.Zinc extraction of the present invention, zinc back extraction, zinc electrolysis, founding zinc ingot metal, precipitation Ca, Mg all can adopt prior art.
ZnS is contained, also containing PbS, FeS by what formed during Selectively leaching zinc oxide
2leached mud floatation process the zinc sulphide part in ore is carried out flotation, floatation process leached mud is carried out ore grinding size mixing, and makes the faintly acid ore pulp that pH value is 1 ~ 7, carry out full flotation of ore pulp, obtain ZnS concentrate.The poor cadmia produced after full flotation of ore pulp is obtained ZnS concentrate carries out flotation again, obtains PbS concentrate and iron concentrate.The pulp density of the full flotation of ore pulp of faintly acid is 25 ~ 35%.The major pharmaceutical agent of flotation has waterglass, calgon, pine tar, copper sulphate, vulcanized sodium, isoamyl xanthate, butyl xanthate, all directly can 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 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 waterglass consumption is 50 ~ 100g/t ore deposit, and pine tar consumption is 10 ~ 20g/t ore deposit, and copper sulphate consumption is 50 ~ 80g/t ore deposit, and amount of sodium sulfide is 500 ~ 1500g/t ore deposit.Owing to carrying out full flotation of ore pulp under mildly acidic conditions, solving under weak basic condition isoamyl xanthate should not 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 isoamyl xanthate as the collecting agent of flotation vulcanized lead zinc first.Solving under meta-alkalescence condition calgon should not, as the inhibitor of impurity and gangue, only should, as the technical barrier of the inhibitor of flotation lead oxide zinc, successfully adopt calgon as the inhibitor of flotation vulcanized lead zinc simultaneously first.Flotation adopts diffeential floatation ZnS, selects PbS again, finally selects FeS
2three sections of flotation flowsheets, three sections of flotation all adopt one roughing, scan for twice, triple cleaning flow process, and the sulfide ore pulp floatingly selected becomes ZnS, PbS, FeS after press filtration
2concentrate product, flotation tailing sends into tailings reservoir for piling.In process of production, because leached mud granularity≤80 object accounts for 92.31%, without the need to using broken and corase grind equipment, only needing a rod mill to stir and sizing mixing.Corresponding equipment investment and the energy consumption decreasing fragmentation and corase grind two sections, in operation process, also regulate slurry pH to 8 ~ 11 without the need to adding pulverized limestone, can effectively reduce floating agent kind and consumption, flow process power consumption and the new water yield less, reach energy-saving and cost-reducing object, effectively can improve grade and the rate of recovery of zinc sulphide and concentrate of lead sulfide ore simultaneously.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%.In the present invention, ore grinding is sized mixing, roughly select, scan, the method such as selected all can adopt prior art.
Applicant adopts present invention process to select oxysulphied Pb-Zn deposits to carry out industrialness trial production by 100 tons of/day blue level ground low-grade refractories.
Trial production uses the existing low-grade refractory of Lanping Lead-Zinc Mine to select the raw ore main component of oxysulphied Pb-Zn deposits as follows:
Raw ore in Selectively leaching process, the ZnSO of meutral innersion output
4solution zinc ion concentration is lower, only reaches Zn ion 13 ~ 27 grams per liter, does not reach the electrolyte Zn ion>=75 grams per liter requirement of zinc hydrometallurgy zinc, zinc extraction and multistage zinc back extraction means need be adopted to carry out enrichment and improve ZnSO
4the zinc ion concentration of solution, to reach the zinc ion concentration requirement needed for zinc electrolyte.After 3 ~ 5 grades of back extractions, zinc ion concentration obtains enrichment, and realize strip liquor containing Zn >=75 grams per liter, strip liquor is directly sent into Zinc electrolysis operation and obtained negative electrode zinc metal sheet and electrolysis waste solution, electrolysis waste solution is all for back extraction operation, and zinc metal sheet produces the standard zinc ingot metal product containing zinc >=99.99% through founding.ZnSO
4solution is after extraction, and raffinate turns back to leaching operation, recycles.Raffinate is containing Zn5.5 ~ 13.7 grams per liter, H
2sO
412.7 ~ 23.68 grams per liters.
The leached mud main component of sulfur compound is as follows:
Leached mud is in the full flotation of ore pulp process of faintly acid, the zinc sulfide concentrates of output reaches 93 ~ 98% containing Zn >=27.3%, Pb≤4.29%, S >=26.75%, zinc flotation recovery rate, the concentrate of lead sulfide ore of output is containing Pb >=31.76%, Zn≤5.37%, S >=29.79%, and the iron concentrate of output is containing S >=48.54%, Fe >=35.62%.
In industrialness trial production, the overall recovery that hydrometallurgy of the present invention leaches zinc oxide and flotation zinc sulphide reaches 91 ~ 93%.
By experimental production preliminary proof, present invention process achieves smelting choosing and organically combines, maximize favourable factors and minimize unfavourable ones, both the advantage that acidleach fully can reclaim Zinc oxide minerals had been played, play again flotation and can fully reclaim zinc sulfide mineral advantage, can realize making full use of low-grade refractory on the whole to select complicated oxysulphied Pb-Zn deposits, expand and can utilize zinc resource, not increase process gas, waste water simultaneously, reach effective utilization of resource and eco-friendly double goal.
Claims (10)
1. process integration is selected in the smelting of Selectively leaching zinc oxide and Weak-acid flotation zinc sulphide, it is characterized in that, this technique is for oxysulphied lead-zinc ore, zinc wet method smelting process is combined with zinc floatation process, adopt first wet method smelting process by the zinc oxide portion Selectively leaching in ore, then the zinc sulphide part in ore is flotated by the leached mud floatation process containing zinc sulphide formed during Selectively leaching zinc oxide; Zinc wet method smelting process, by zinc oxide Selectively leaching, zinc extraction, zinc back extraction, Zinc electrolysis, obtains zinc product; Floatation process the leached mud containing zinc sulphide is carried out ore grinding size mixing, and makes the faintly acid ore pulp that pH value is 1 ~ 7, then carry out full flotation of ore pulp, obtain ZnS concentrate.
2. process integration is selected in the smelting of Selectively 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 ore pulp and other oxide dissolution are entered ZnSO
4in solution, the leached mud of output Containing Sulfur zinc and other sulfide, realizes Selectively leaching zinc oxide simultaneously.
3. process integration is selected in the smelting of Selectively 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 ground, 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%.
4. process integration is selected in the smelting of Selectively leaching zinc oxide according to claim 1 and Weak-acid flotation zinc sulphide, it is characterized in that, the waste liquid produced is transmitted back to zinc back extraction operation and again carries out Zinc electrolysis after back extraction after Zinc electrolysis.
5. process integration is selected in the smelting of Selectively leaching zinc oxide according to claim 1 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 back washing agent
2sO
4content is 120 ~ 150 grams per liters, and Zn content is 50 ~ 70 grams per liters.
6. process integration is selected in the smelting of Selectively leaching zinc oxide according to claim 1 and Weak-acid flotation zinc sulphide, it is characterized in that, by the ZnSO that Selectively leaching zinc oxide obtains
4solution first carries out Ca, Mg and separates out process, and then by zinc extraction, zinc back extraction, Zinc electrolysis, obtains zinc product.
7. process integration is selected in the smelting of Selectively leaching zinc oxide according to claim 6 and Weak-acid flotation zinc sulphide, it is characterized in that, described to ZnSO
4solution carries out Ca, Mg and separates out process, is by ZnSO
4solution cools to 20 DEG C ~ 40 DEG C, adds CaSO in cooling procedure
42H
2o crystal seed and active additive, crystallization CaSO
4and MgSO
4, form calcium magnesium slag.
8. process integration is selected in the smelting of Selectively leaching zinc oxide according to claim 1 and Weak-acid flotation zinc sulphide, and it is characterized in that, the moisture content of leached mud is not more than 28%, and in leached mud, zinc oxygenation efficiency is not more than 30%.
9. process integration is selected in the smelting of Selectively leaching zinc oxide according to claim 1 and Weak-acid flotation zinc sulphide, it is characterized in that, the poor zinc mine tailing produced after full flotation of ore pulp is obtained ZnS concentrate carries out flotation PbS again, and the poor plumbous mine tailing produced after obtaining PbS concentrate carries out flotation FeS again
2, obtain FeS
2concentrate.
10. process integration is selected in the smelting of Selectively leaching zinc oxide according to claim 1 and Weak-acid flotation zinc sulphide, it is characterized in that, adopts isoamyl xanthate as the collecting agent of flotation zinc sulphide.
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| 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 |
| 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 |
| CN104475265B (en) * | 2014-11-21 | 2017-01-18 | 广西大学 | Method for flotation removal of coronadite out of manganic concerntrate |
| CN105170339B (en) * | 2015-09-30 | 2017-07-18 | 广西大学 | The method for floating of sulphur oxygen mixed mineral in a kind of recovery mine tailing |
| 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 |
| 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 |
| 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 |
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