CN103695662A - Comprehensive utilization method of slag iron concentrates of wet-type zinc smelting furnace - Google Patents
Comprehensive utilization method of slag iron concentrates of wet-type zinc smelting furnace Download PDFInfo
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Abstract
The invention relates to a comprehensive utilization method of slag iron ore concentrates of a wet-type zinc smelting furnace and belongs to the technical field of metallurgy. The method comprises the following steps: performing two-section counterflow leaching on raw material (slag iron ore concentrates in the wet-type zinc smelting furnace) in the presence of a hydrochloric acid aqueous solution serving as a leaching agent so that valuable metals such as iron, silver, copper, lead, zinc and arsenic in the slag iron ore concentrates enter a leachate; purifying the leachate by utilizing processes of metal iron powder replacement, control over pH (Power Of Hydrogen) value, arsenic sedimentation, sulfuration precipitation and the like, separating the valuable metals such as copper, silver, lead, zinc and arsenic, wherein the purified leachate is a pure FeCl2 aqueous solution; performing thermal decomposition on the pure FeCl2 aqueous solution in a spraying manner so as to obtain Fe2O3 powder; and absorbing the generated HCL gas with water so as to regenerate hydrochloric acid which returns to the leaching process. By the method, the valuable elements in the slag iron ore concentrates of the wet-type zinc smelting furnace are comprehensively separated and recycled; and the hydrochloric acid taken as a leaching agent can be recycled, so that the method realizes resource conservation and is friendly to the environment. During the whole process, the discharge of three wastes is basically avoided; all the resources are utilized to the greatest extent; and obtained products are convenient for subsequent treatment and processing. The method has the advantages of environmental friendliness, economical performance, energy conservation and high resource utilization rate, thereby being convenient for industrial production.
Description
Technical field
The present invention relates to a kind of method of comprehensive utilization of zinc hydrometallurgy kiln slag iron ore concentrate; Belong to metallurgical technology field.
Background technology
China's metallic zinc output in 2011 reaches 4,460,000 tons, wherein approximately 85% adopts wet production.Zinc hydrometallurgy has the kinds of processes such as conventional leaching, the high Ore Leaching of high temperature, normal pressure and hyperbaric oxygen soak, and in China, is all applied, and wherein conventional extract technology output accounts for 50% of China's wet method zinc output.In conventional extract technology, roasted ore is through neutral and low sour two sections of counterflow leachings, and wherein Pb, Au, Ag, In, Ge, Ga and 60%Cu, 30%Cd and 15% Zn enter in leached mud.Leached mud adopts waelz process to process, and after being dried, allocates 45～55% coke powder into, sends into rotary kiln after mixing, under 1100～1300 ℃ of high temperature, and the reduction volatilization output secondary zinc oxides such as Zn, Pb, Cd, the slag of semi-melting state is discharged shrend from kiln tail and is become kiln slag.
In above-mentioned kiln slag, mainly containing valency elemental composition (massfraction) is: Cu0.7%～1.2%, Fe35%～40%, C15%～18%, Au0.1～0.3g/t, Ag250～300g/t, In100～250g/t, Ge100～300g/t.Adopt conventional extract technology, the about output leached mud of every production 1t electricity zinc 1.05t, kiln slag 0.8t.Annual about output kiln slag 1,500,000 t of China.Kiln slag hardness is high, fine size, and its composition, thing phase and embedding cloth state complex thereof are gone through many decades research, and its comprehensive recycling process does not make a breakthrough yet, generally stores up processing in the past, causes resource waste and pollution environment.
In recent years, the physical separation method that Some Domestic enterprise adopts weight, magnetic separation etc. to combine is processed above-mentioned kiln slag, the materials such as difference output coke powder, iron ore concentrate and mine tailing.Coke powder is as fuel utilization, and mine tailing is for manufacture of cement.In iron ore concentrate enrichment the valuable metals such as Cu, Ag, In, iron content can reach quality percentage composition 65% left and right.At present, this class iron ore concentrate has two kinds of purposes: the first is as flux, to use in sintering-Lead Smelting in Blast Furnace technique, this makes the valuable metals such as Cu, Ag wherein and In obtain partially recycled, but along with sintering-Lead Smelting in Blast Furnace technique because energy consumption is high, pollute large etc. formerly thereby progressively eliminate, this application is on the one hand tending towards disappearing; The second is as iron-smelting raw material, but because the harmful element content such as its S, As are higher, so can only mix on a small quantity, this class iron ore concentrate price is generally lower, simultaneously wherein the valuable metal such as contained copper, silver, indium can not be recycled in iron manufacturing process, causes the wasting of resources.
For the comprehensive recovery of zinc hydrometallurgy kiln slag iron ore concentrate, also once experimental study two kinds of new techniques: the first is to adopt sulfuric acid leaching, after leach liquor recovering copper and dissipated metal element, manufactures polyaluminum sulfate iron product.Owing to only having part iron, copper, zinc to enter leach liquor in sulfuric acid leaching, most silver, lead and part copper, zinc are still stayed in leached mud, can not reclaim rare precious metal and other valuable elements.And bodied ferric sulfate produce market is less, this technique fails to realize suitability for industrialized production; The second is that the founding of kiln slag iron ore concentrate is become to iron anode, adopts electrolysis process to process it, and negative electrode output pure iron product is as powder metallurgy prepared using, and other valuable elements reclaim respectively from electrolytic solution or the anode sludge.This Technology difficulty is large, pure iron product marketing restriction in addition, and economic benefit is difficult to guarantee, also industrial, is not applied.
In sum, zinc hydrometallurgy kiln slag iron ore concentrate output is large, valuable element content is high, is the metals resources that a kind of value is higher, but still there is no so far a kind of good technique, and it is processed to realize the Comprehensive recovery of resource.Under this background, invented a kind of method of comprehensive utilization of zinc hydrometallurgy kiln slag iron ore concentrate just.
Summary of the invention
The present invention is directed to the problem that existing zinc hydrometallurgy kiln slag iron ore concentrate comprehensive utilization technique exists, a kind of method of comprehensive utilization of zinc hydrometallurgy kiln slag iron ore concentrate is proposed, the present invention has advantages of environmental protection, economy, energy-conservation, resource utilization is high, and the present invention can realize comprehensive recovery and the comprehensive utilization of the valuable element such as silver, copper, zinc, lead, arsenic, iron in zinc hydrometallurgy kiln slag iron ore concentrate.
The method of comprehensive utilization of a kind of zinc hydrometallurgy kiln slag of the present invention iron ore concentrate, comprises the steps:
Step 1 zinc hydrometallurgy kiln slag iron ore concentrate Leaching in Hydrochloric Acid
With the hydrochloric acid of 0.5～3mol/L, zinc hydrometallurgy kiln slag iron ore concentrate is carried out to low Ore Leaching processing, the low acid leaching liquor of gained is standby, the low acid leaching slag of gained carries out high Ore Leaching with the hydrochloric acid of 3～6mol/L, high Ore Leaching gained leach liquor returns for low Ore Leaching, and high Ore Leaching gained leached mud is processed in sulfuric acid operation;
Step 2 iron replacement copper, silver
The pH value of above-mentioned low acid leaching liquor is transferred to 0.5～1.5, toward wherein adding iron powder, carries out liquid-solid separation after replacement(metathesis)reaction, obtain silver-bearing copper slag and displaced liquid; The add-on of iron powder is 1.1～2.5 times of theoretical consumption that displace all silver ionss and the required fe of cupric ion in described low acid leaching liquor;
Step 3 is sunk arsenic
The pH value of displaced liquid is transferred to 2.0～3.5, and the arsenic that sinks at 60～95 ℃ is processed, and obtains liquid after heavy arsenic slag and heavy arsenic;
Step 4 is plumbous, zinc sulfide precipitation
Vulcanizing agent is added after heavy arsenic in liquid, makes lead, zine ion in solution generate sulfide precipitation, obtain plumbous cadmia and purify after liquid; The add-on of vulcanizing agent is that all lead ions in liquid after described heavy arsenic are become to 2～6 times of the required theoretical consumption of plumbous cadmia with zine ion sulfide precipitation; Described vulcanizing agent is metallic sulfide or the H of divalent sulfur
2s;
Step 5 FeCl
2aqueous solution spraying thermolysis
Pack liquid after purification into automiser spray, using oxygen-containing gas as carrier gas, at 400～1000 ℃, carry out spray pyrolysis, obtain Fe
2o
3powder and HCl gas, HCl gas is made concentrated hydrochloric acid after water absorbs, and returns to high Ore Leaching operation and uses.
The method of comprehensive utilization of a kind of zinc hydrometallurgy kiln slag of the present invention iron ore concentrate, main component is as follows by percentage to the quality for described zinc hydrometallurgy kiln slag iron ore concentrate:
In described iron ore concentrate, also comprise silver, the content of silver is 10～1000g/t.
The method of comprehensive utilization of a kind of zinc hydrometallurgy kiln slag of the present invention iron ore concentrate, leaches described in step 1 as counterflow leaching, and during low Ore Leaching, controlling extraction temperature and be room temperature to 90 ℃, time is that 30～240min, liquid-solid ratio are 5:1～20:1ml/g; During high Ore Leaching, control extraction temperature and be room temperature to 80 ℃, extraction time is that 30～180min, liquid-solid ratio are 5:1～20:1ml/g; After two sections of counterflow leachings, more than 99.0% silver, more than 95.0% copper, more than 55.0% zinc, more than 99.0% lead, more than 90.0% arsenic, more than 90.0% iron enter in leach liquor.
The method of comprehensive utilization of a kind of zinc hydrometallurgy kiln slag of the present invention iron ore concentrate, in step 2, the specific surface area of iron powder used is 0.17～0.36m
2/ g; During replacement(metathesis)reaction, controlling temperature and be room temperature to 50 ℃, time is 20～120min.
The method of comprehensive utilization of a kind of zinc hydrometallurgy kiln slag of the present invention iron ore concentrate, in step 3, makes arsenic precipitate with ferric arsenate or scorodite form by controlling pH and temperature, and the time that heavy arsenic is processed is 30～240min.
The method of comprehensive utilization of a kind of zinc hydrometallurgy kiln slag of the present invention iron ore concentrate, in step 4, when lead, zinc sulfide precipitation, the temperature of controlling solution is room temperature to 80 ℃.
The method of comprehensive utilization of a kind of zinc hydrometallurgy kiln slag of the present invention iron ore concentrate, in step 4, the metallic sulfide that vulcanizing agent is divalent sulfur or hydrogen sulfide, the metallic sulfide of described divalent sulfur is Iron sulfuret or pyrite, FeS in described pyrite
2quality percentage composition>=90%.
The method of comprehensive utilization of a kind of zinc hydrometallurgy kiln slag of the present invention iron ore concentrate, in step 4, the time of the plumbous cadmia of sulfide precipitation is 60～240min; The quality percentage composition >45% of Zn in described plumbous cadmia, the quality percentage composition >30% of Pb, the quality percentage composition >20% of S.
The method of comprehensive utilization of a kind of zinc hydrometallurgy kiln slag of the present invention iron ore concentrate, in step 5, is 400～1000 ℃ in temperature, under oxidizing atmosphere condition, by FeCl
2solution spray thermolysis is Fe
2o
3and HCl, HCl gas generation hydrochloric acid returns to leaching.
The advantage of the inventive method and positively effect:
1, the present invention adopts the mode of two sections of counterflow leachings, low Ore Leaching and high Ore Leaching are organically combined, by controlling the concentration of different leaching stages hydrochloric acid used, the temperature leaching, ore pulp liquid-solid ratio and extraction time, take full advantage of iron in superiority that chlorination salt dissolves in hydrochloric acid and zinc hydrometallurgy kiln slag iron ore concentrate, silver, copper, zinc, plumbous, the valuable elements such as arsenic there is characteristic, make iron in zinc hydrometallurgy kiln slag iron ore concentrate, silver, copper, zinc, plumbous, the valuable elements such as arsenic are after two sections of hydrochloric acid counterflow leachings, more than 99.0% silver, more than 95.0% copper, more than 55.0% zinc, more than 99.0% lead, more than 90.0% arsenic, more than 90.0% iron enters in leach liquor, substep enrichment and recovery valuable metal in leach liquor.Through test, also find, by control the hydrochloric acid used of different leaching stages concentration, soak ore pulp liquid-solid ratio and extraction time can or approach in the temperature range of room temperature in room temperature, make the valuable elements such as iron in zinc hydrometallurgy kiln slag iron ore concentrate, silver, copper, zinc, lead, arsenic obtain maximum dissolving and leaching; At lower temperature, realize effective dissolving and the leaching of the valuable elements such as iron, silver, copper, zinc, lead, arsenic, this is conducive to the energy-conservation efficient utilization with realizing resource; In the leached mud of high Ore Leaching, be mainly zinc sulphide and iron sulphide, by returning to zinc, smelt roasting system recovery zinc;
2, iron in zinc hydrometallurgy kiln slag iron ore concentrate, silver, copper, zinc, plumbous, after the valuable elements such as arsenic are effectively dissolved and are leached, the present invention selects preferentially from leach liquor, to isolate silver, copper, this is based on iron in leach liquor, silver, copper, zinc, plumbous, the characteristic of the valuable elements such as arsenic, especially silver-colored, copper standard potential is than on the how positive basis of the standard potential of other elements, select iron powder as their displacer, by controlling the pH value of strict leach liquor and the consumption of iron powder, well by silver, copper cements out, and in solution, other metallic elements and metalloid element can not be doped in the form of solid the silver cementing out in a large number, among copper, this not only can reach the effect effectively separated with other metallic element, and can also realize to greatest extent silver and the recovery of copper, owing to adopting iron powder reducing, in whole system, do not introduce other impurity element, when making subsequent disposal, this does not need to consider other impurity metallic elements adverse effect of introducing, this is the precondition that simplifies the operation, raises the efficiency, because the Component comparison of gained silver, copper ashes is simple, be easy to just can obtain high-purity copper and silver, this is very favorable for reducing production costs, owing to having controlled the granularity of iron powder and speed that specific surface area makes whole replacement(metathesis)reaction, become very fast, this is convenient to increase work efficiency,
3, the present invention is in heavy arsenic process, now the pH value of displaced liquid is adjusted to 2.0～3.5, and temperature is controlled to 60-95 ℃, at this, under condition, lead, zinc and iron ion all can not separated out with sedimentary form, and ferric ion can generate ferric arsenate or scorodite precipitation with arsenic in solution, this makes arsenic substantially be removed by sedimentary form, clearance >=95% of arsenic; Due to the reagent without adding especially, when this makes subsequent disposal, do not need to consider reagent adverse effect especially, thereby prerequisite is provided for simplifying the operation, raising the efficiency;
4, will sink after arsenic liquid adds Iron sulfuret or pyrite or hydrogen sulfide at room temperature to 80 ℃, utilize hydrogen sulfide or Iron sulfuret or pyrite to come enriched lead, zinc, successful not only, and can not bring other metallic elements into, this just provides prerequisite for simplifying follow-up technique;
5, utilize spray pyrolysis can prepare the ferric oxide that purity is higher, simple to operate, be convenient to control, utilize air as oxidizing atmosphere, the economic and practical and convenience of drawing materials, recovery HCl prepares hydrochloric acid and can return to leaching operation, economic environmental protection;
In a word, the rational operation collocation of the present invention, by the conditional parameter in each operation of strict control, make silver in solution, copper, arsenic, zinc, plumbous, iron is recycled by the order of silver-bearing copper-arsenic-zinc lead-iron and effectively utilizes, reached environmental protection, economical, energy-conservation, the object of high resource utilization, realize silver, copper, zinc, plumbous, arsenic, comprehensive recovery and the comprehensive utilization of the valuable elements such as iron, due to what adopt, be massive pollution and the not high problem of the utilization of resources that wet processing has avoided pyrogenic process to bring, owing to having gone out silver-bearing copper by iron replacement, this is very favorable for reducing production costs, because the control of pH value is proper, the throw out that makes arsenic neither can extensive enrichment in silver-bearing copper slag, do not have lead yet, zinc, iron obtains in the throw out of accumulation of sediment and arsenic, this is not only convenient to the recovery of silver-bearing copper, also be conducive to the recovery of arsenic, this high-level efficiency that is conducive to resource reclaims and utilizes, because the plumbous cadmia obtaining by sulfide precipitation is by also can be from recycling after suitably processing, because the purity of spray pyrolysis gained ferric oxide is higher, its market demand and value are all much larger than ferric sulfate, gained HCl prepares hydrochloric acid can return to leaching operation, the essentially no three wastes of whole technique are got rid of, all resources obtain maximum efficiency utilization, products therefrom is all convenient to follow-up treatment and processing, so the present invention has the advantage of environmental protection, economy, energy-conservation, high resource utilization.
Accompanying drawing explanation
Fig. 1 is principle flow chart of the present invention.
Embodiment
Below technical scheme of the present invention is described in detail, wherein said percentage composition is total mass number.
Main containing weight of iron percentage composition 40%～68% in the raw material the present invention relates to, silver content 10～1000g/t, copper mass percentage composition 0.5%～5%, zinc quality percentage composition 0.5%～5%, plumbous quality percentage composition 0.5%～5%, arsenic quality percentage composition 0.1%～5%, sulphur quality percentage composition 2.3%～10%, Al
2o
3quality percentage composition 1%～3%, SiO
2quality percentage composition 2.3%～6.8%.
As shown in Figure 1:
1, Leaching in Hydrochloric Acid operation is to weight of iron percentage composition 40～68%, silver content 10～1000g/t, copper mass percentage composition 0.5%～5%, zinc quality percentage composition 0.5%～5%, plumbous quality percentage composition 0.5%～5%, arsenic quality percentage composition 0.1%～5%, sulphur quality percentage composition 3%～10%, Al
2o
3quality percentage composition 1%～3%, SiO
2the zinc hydrometallurgy kiln slag iron ore concentrate of quality percentage composition 2.3%～6.8% adopts two sections of counterflow leachings, first with the hydrochloric acid of lower concentration, leach, concentration of hydrochloric acid is 0.5～3mol/L, is preferably 2～3mol/L, 3mol/L more preferably, solution temperature is room temperature to 90 ℃, is preferably 30～60 ℃, more preferably 60 ℃, ore pulp liquid-solid ratio is 5:1～20:1, low Ore Leaching is advisable at 10:1, and extraction time is 30～240min, is preferably 120min; And then the low acid leaching slag of Leaching in Hydrochloric Acid of using high density, concentration of hydrochloric acid is 3～6mol/L, with the Leaching in Hydrochloric Acid effect of 5mol/L, is advisable, extraction temperature is room temperature to 80 ℃, be preferably 30～60 ℃, more preferably 60 ℃, ore pulp liquid-solid ratio is 5:1～20:1, high Ore Leaching is advisable at 5:1, extraction time is 30～180min, is preferably 120min, and after high Ore Leaching, leach liquor concentration of hydrochloric acid is 0.5～3.0mol/L, return to low Ore Leaching operation, complete two sections of adverse currents;
2, iron replacement operation is that silver, copper in the leach liquor of Leaching in Hydrochloric Acid gained are adopted to iron replacement, hydrochloric acid leachate pH value is transferred to 0.5～1.5, with 0.5, be advisable, time swap is 20～120min, general control is at 30～60min, solution temperature is room temperature to 50 ℃, generally adopts room temperature, and the add-on of iron powder is 1～2.5 times of theoretical consumption that displaces all silver ionss and the required fe of cupric ion in described low acid leaching liquor; Be preferably 2 times;
3, heavy arsenic operation is that the displaced liquid of iron replacement gained is carried out to reaction precipitation, and displaced liquid pH value is transferred to 2.0～3.5, reaction 30～240min, and general control is at 180～240min, and solution temperature is 60～95 ℃;
4, sulfide precipitation operation is to utilize the metallic sulfide of divalent sulfur or hydrogen sulfide to carry out sulfide precipitation to liquid after the heavy arsenic of heavy arsenic gained, makes lead, zine ion in solution generate sulfide precipitation, obtains plumbous cadmia and purifies rear liquid; The add-on of vulcanizing agent is that all lead ions in liquid after described heavy arsenic are become to 2～6 times of the required theoretical consumption of plumbous cadmia with zine ion sulfide precipitation, is preferably 3～5 times, the metallic sulfide that described vulcanizing agent is divalent sulfur or H
2s, the metal-salt of described divalent sulfur is selected from Iron sulfuret or pyrite, FeS in described pyrite
2quality percentage composition>=90%; During the heavy plumbous zinc of sulfuration, control solution temperature is room temperature to 80 ℃, and ℃ better with room temperature to 60, the control reaction times is 60～240min, is preferably 120～240min;
5, spray pyrolysis operation is that liquid after the purification of sulfide precipitation is carried out to spray pyrolysis, and described oxygen-containing gas is air or oxygen, is preferably air; Described heat decomposition temperature is 400～1000 ℃, is preferably 600～900 ℃; Described HCl gas is made concentrated hydrochloric acid after water absorbs, and returns to high Ore Leaching operation and uses.
Below embodiments of the invention.
Embodiment 1:
The zinc hydrometallurgy kiln slag iron ore concentrate of take is raw material, and the main component of raw material is: Fe40%, Ag10g/t, Cu5.0%, Zn5.0%, Pb5.0%, As5.0%, Al
2o
31.0%, S10.0%, SiO
26.8%;
At room temperature leach kiln slag iron ore concentrate, during low Ore Leaching, the concentration of hydrochloric acid is 0.5mol/L, and liquid-solid ratio is 10:1ml/g, and extraction time is 240min; The low acid leaching liquor of gained is standby, the low acid leaching slag of gained is that 20:1ml/g carries out high Ore Leaching 180min with the hydrochloric acid of 3mol/L by liquid-solid ratio, after high Ore Leaching, leach liquor concentration of hydrochloric acid is 0.65mol/L, can return to low Ore Leaching operation, according to low Ore Leaching condition, continue to leach, high Ore Leaching gained leached mud is for sinter process; After low Ore Leaching and high Ore Leaching, the leaching yield that in raw material, the leaching yield of Fe is 92.21%, Ag is 98.95%, and the leaching yield that the leaching yield that the leaching yield that the leaching yield of copper is 95.07%, Pb is 99.34%, As is 88.57%, Zn is 57.92%;
Now the pH value of low acid leaching liquor is 1.5, requirement to pH while meeting reduction silver, copper, so at room temperature, in above-mentioned low acid leaching liquor, add metal iron powder to carry out replacement(metathesis)reaction 120min, then solid-liquid separation, obtains silver-bearing copper slag and displaced liquid, the add-on of iron powder is 1.5 times of theoretical consumption that displace all silver ionss and the required fe of cupric ion in described low acid leaching liquor, after iron powder reducing, in solution, the reduction ratio of silver is 99.1%, and the reduction ratio of copper is 99.0%;
Now the pH value of displaced liquid is 2.0, the requirement to pH while meeting heavy arsenic, so displaced liquid is warming up to 60 ℃, the arsenic that sink is processed 240min, and filtration obtains liquid after arsenic slag and heavy arsenic; After heavy arsenic is processed, the clearance of arsenic is 95.42%, and described arsenic slag is ferric arsenate or scorodite;
To sink after arsenic after liquid is warming up to 80 ℃ toward wherein adding FeS
2the pyrite of quality percentage composition>=90% vulcanize heavy plumbous zinc and process 240min, obtain plumbous cadmia and purify after liquid; Pyritous add-on is that all lead ions in liquid after described heavy arsenic are become to 5 times of the required theoretical consumption of plumbous cadmia with zine ion sulfide precipitation; At sulfide precipitation, become the plumbous cadmia while also can remove residual arsenic, after the heavy plumbous zinc processing of sulfuration, after heavy arsenic, in liquid, the clearance that the clearance of lead is 99.95%, Zn is 97.55%, through heavy arsenic, processes and vulcanizes after heavy plumbous zinc processing, and total clearance of arsenic reaches 99.8%;
Packing liquid after purification in automiser spray atomization is fine mist, and in air atmosphere, temperature of reaction is 800 ℃, and thermolysis obtains Fe
2o
3powder and HCl gas, recovery HCl gas makes hydrochloric acid soln and returns to leaching operation.
Embodiment 2:
The zinc hydrometallurgy kiln slag iron ore concentrate of take is raw material, and the main component of raw material is: Fe55.0%, Ag1000g/t, Cu0.5%, Zn5.0%, Pb5.0%, As3.5%, Al
2o
32.0%, S5.0%, SiO
24.6%, all the other are the oxygen in each element oxide; At 60 ℃, leach kiln slag iron ore concentrate, during low Ore Leaching, the concentration of hydrochloric acid is 2.5mol/L, and liquid-solid ratio is 10:1ml/g, and extraction time is 180min; The low acid leaching liquor of gained is standby, the low acid leaching slag of gained is that 5:1ml/g carries out high Ore Leaching 30min with the hydrochloric acid of 5mol/L by liquid-solid ratio, after high Ore Leaching, leach liquor concentration of hydrochloric acid is 2.6mol/L, can return to low Ore Leaching operation, according to low Ore Leaching condition, continue to leach, high Ore Leaching gained leached mud is for sinter process; After low Ore Leaching and high Ore Leaching, the leaching yield that in raw material, the leaching yield of Fe is 91.36%, Ag is 99.95%, and the leaching yield that the leaching yield that the leaching yield that the leaching yield of copper is 96.34%, Pb is 99.55%, As is 90.54%, Zn is 60.79%;
Now the pH value of low acid leaching liquor is 1.5, requirement to pH while meeting reduction silver, copper, so at 40 ℃, in above-mentioned low acid leaching liquor, add metal iron powder to carry out replacement(metathesis)reaction 60min, then solid-liquid separation, obtains silver-bearing copper slag and displaced liquid, the add-on of iron powder is 1.1 times of theoretical consumption that displace all silver ionss and the required fe of cupric ion in described low acid leaching liquor, after iron powder reducing, in solution, the reduction ratio of silver is 99.95%, and the reduction ratio of copper is 99.95%;
Now the pH value of displaced liquid is 2.4, adjusts after the pH value to 3.0 of displaced liquid, is warming up to 95 ℃, the arsenic that sink processing 30min, and filtration obtains liquid after arsenic slag and heavy arsenic; After heavy arsenic is processed, the clearance of arsenic is 99.0%, and described arsenic slag is ferric arsenate or scorodite;
The liquid after arsenic that will sink passes into H
2s gas vulcanizes heavy plumbous zinc and processes 240min, obtains plumbous cadmia and purifies rear liquid; H
2the add-on of S is that all lead ions in liquid after described heavy arsenic are become to 6 times of the required theoretical consumption of plumbous cadmia with zine ion sulfide precipitation; At sulfide precipitation, become the plumbous cadmia while also can remove residual arsenic, after the heavy plumbous zinc processing of sulfuration, after heavy arsenic, in liquid, the clearance that the clearance of lead is 99.95%, Zn is 97.55%, through heavy arsenic, processes and vulcanizes after heavy plumbous zinc processing, and total clearance of arsenic reaches 99.99%;
Packing liquid after purification in automiser spray atomization is fine mist, and in purity oxygen atmosphere, temperature of reaction is 400 ℃, and thermolysis obtains Fe
2o
3powder and HCl gas, recovery HCl gas makes hydrochloric acid soln and returns to leaching operation.
Embodiment 3:
The zinc hydrometallurgy kiln slag iron ore concentrate of take is raw material, and the composition of raw material is: Fe56.5%, Ag256g/t, Cu2.5%, Zn2.5%, Pb0.99%, As0.49%, Al
2o
31.8%, S4.75%, SiO
23.4%, all the other are the oxygen in each element oxide; At 90 ℃, leach kiln slag iron ore concentrate, during low Ore Leaching, the concentration of hydrochloric acid is 3.0mol/L, and liquid-solid ratio is 5:1ml/g, and extraction time is 30min; The low acid leaching liquor of gained is standby, the low acid leaching slag of gained is that 5:1ml/g carries out high Ore Leaching 30min with the hydrochloric acid of 6.0mol/L by liquid-solid ratio, after high Ore Leaching, leach liquor concentration of hydrochloric acid is 3.2mol/L, can return to low Ore Leaching operation, according to low Ore Leaching condition, continue to leach, high Ore Leaching gained leached mud is for sinter process; After low Ore Leaching and high Ore Leaching, the leaching yield that in raw material, the leaching yield of Fe is 90.92%, Ag is 99.91%, and the leaching yield that the leaching yield that the leaching yield that the leaching yield of copper is 98.32%, Pb is 99.74%, As is 92.69%, Zn is 62.49%;
Now the pH value of low acid leaching liquor is 0.5, requirement to pH while meeting reduction silver, copper, so at room temperature, in above-mentioned low acid leaching liquor, add metal iron powder to carry out replacement(metathesis)reaction 30min, then solid-liquid separation, obtains silver-bearing copper slag and displaced liquid, the add-on of iron powder is 2.5 times of theoretical consumption that displace all silver ionss and the required fe of cupric ion in described low acid leaching liquor, after iron powder reducing, in solution, the reduction ratio of silver is 98.9%, and the reduction ratio of copper is 98.5%;
Now the pH value of displaced liquid is 2.1, adjusts after the pH value to 3.0 of displaced liquid, is warming up to 80 ℃, the arsenic that sink processing 180min, and filtration obtains liquid after arsenic slag and heavy arsenic; After heavy arsenic is processed, the clearance that the clearance of arsenic is arsenic is 99.5%, and described arsenic slag is ferric arsenate or scorodite;
To sink after arsenic after liquid is warming up to 80 ℃ and process 180min toward wherein adding Iron sulfuret to vulcanize heavy plumbous zinc, obtain plumbous cadmia and purify after liquid; The add-on of Iron sulfuret is that all lead ions in liquid after described heavy arsenic are become to 3 times of the required theoretical consumption of plumbous cadmia with zine ion sulfide precipitation; At sulfide precipitation, become the plumbous cadmia while also can remove residual arsenic, after the heavy plumbous zinc processing of sulfuration, after heavy arsenic, in liquid, the clearance that the clearance of lead is 99.93%, Zn is 99.42%, through heavy arsenic, processes and vulcanizes after heavy plumbous zinc processing, and total clearance of arsenic reaches 99.9%;
Packing liquid after purification in automiser spray atomization is fine mist, and in air atmosphere, temperature of reaction is 1000 ℃, and thermolysis obtains Fe
2o
3powder and HCl gas, recovery HCl gas makes hydrochloric acid soln and returns to leaching operation.
Embodiment 4:
The zinc hydrometallurgy kiln slag iron ore concentrate of take is raw material, and the main component of raw material is: Fe60.0%, Ag350g/t, Cu2.8%, Zn2.2%, Pb2.1%, As2.0%, Al
2o
31.6%, S5.8%, SiO
22.8%;
At 60 ℃, leach kiln slag iron ore concentrate, during low Ore Leaching, the concentration of hydrochloric acid is 3.0mol/L, and liquid-solid ratio is 10:1ml/g, and extraction time is 120min; The low acid leaching liquor of gained is standby, the low acid leaching slag of gained is that 5:1ml/g carries out high Ore Leaching 120min with the hydrochloric acid of 5mol/L by liquid-solid ratio, after high Ore Leaching, leach liquor concentration of hydrochloric acid is 3.1mol/L, can return to low Ore Leaching operation, according to low Ore Leaching condition, continue to leach, high Ore Leaching gained leached mud is for sinter process; After low Ore Leaching and high Ore Leaching, the leaching yield that in raw material, the leaching yield of Fe is 92.58%, Ag is 99.93%, and the leaching yield that the leaching yield that the leaching yield that the leaching yield of copper is 99.15%, Pb is 99.47%, As is 92.38%, Zn is 57.94%;
Now the pH value of low acid leaching liquor is 1.3, requirement to pH while meeting reduction silver, copper, so at 50 ℃, in above-mentioned low acid leaching liquor, add metal iron powder to carry out replacement(metathesis)reaction 30min, then solid-liquid separation, obtains silver-bearing copper slag and displaced liquid, the add-on of iron powder is 2 times of theoretical consumption that displace all silver ionss and the required fe of cupric ion in described low acid leaching liquor, after iron powder reducing, in solution, the reduction ratio of silver is 99.7%, and the reduction ratio of copper is 99.6%;
Now the pH value of displaced liquid is 2.5, and the pH value of solution is adjusted to 3.5, sinks arsenic process 240min at 75 ℃, filters and obtains liquid after arsenic slag and heavy arsenic; After heavy arsenic is processed, the clearance that the clearance of arsenic is arsenic is 95.2%, and described arsenic slag is ferric arsenate or scorodite;
To sink after arsenic after liquid is warming up to 80 ℃ and process 240min toward wherein adding Iron sulfuret to vulcanize heavy plumbous zinc, obtain plumbous cadmia and purify after liquid; The add-on of Iron sulfuret is that all lead ions in liquid after described heavy arsenic are become to 4 times of the required theoretical consumption of plumbous cadmia with zine ion sulfide precipitation; At sulfide precipitation, become the plumbous cadmia while also can remove residual arsenic, after the heavy plumbous zinc processing of sulfuration, after heavy arsenic, in liquid, the clearance that the clearance of lead is 99.84%, Zn is 99.77%, through heavy arsenic, processes and vulcanizes after heavy plumbous zinc processing, and total clearance of arsenic reaches 99.1%;
Packing liquid after purification in automiser spray atomization is fine mist, and in purity oxygen atmosphere, temperature of reaction is 800 ℃, and thermolysis obtains Fe
2o
3powder and HCl gas, recovery HCl gas makes hydrochloric acid soln and returns to leaching operation.
Embodiment 5:
The zinc hydrometallurgy kiln slag iron ore concentrate of take is raw material, and the composition of raw material is: Fe68%, Ag500g/t, Cu5.0%, Zn0.5%, Pb0.5%, As0.1%, Al
2o
33.0%, S3.0%, SiO
22.3%, all the other are the oxygen in each element oxide; At room temperature leach kiln slag iron ore concentrate, during low Ore Leaching, the concentration of hydrochloric acid is 3.0mol/L, and liquid-solid ratio is 10:1ml/g, and extraction time is 30min; The low acid leaching liquor of gained is standby, the low acid leaching slag of gained is that 10:1ml/g carries out high Ore Leaching 30min with the hydrochloric acid of 6mol/L by liquid-solid ratio, after high Ore Leaching, leach liquor concentration of hydrochloric acid is 2.9mol/L, can return to low Ore Leaching operation, according to low Ore Leaching condition, continue to leach, high Ore Leaching gained leached mud is for sinter process; After low Ore Leaching and high Ore Leaching, the leaching yield that in raw material, the leaching yield of Fe is 91.27%, Ag is 99.0%, and the leaching yield that the leaching yield that the leaching yield that the leaching yield of copper is 99.0%, Pb is 98.1%, As is 93.2%, Zn is 55.1%;
Now the pH value of low acid leaching liquor is 0.5, requirement to pH while meeting reduction silver, copper, so at 30 ℃, in above-mentioned low acid leaching liquor, add metal iron powder to carry out replacement(metathesis)reaction 20min, then solid-liquid separation, obtains silver-bearing copper slag and displaced liquid, the add-on of iron powder is 2 times of theoretical consumption that displace all silver ionss and the required fe of cupric ion in described low acid leaching liquor, after iron powder reducing, in solution, the reduction ratio of silver is 99.5%, and the reduction ratio of copper is 99.3%;
Now the pH value of displaced liquid is 2.7, is warming up to 80 ℃, and the arsenic that sinks is processed 240min, filters and obtains liquid after arsenic slag and heavy arsenic; After heavy arsenic is processed, the clearance that the clearance of arsenic is arsenic is 98.2%, and described arsenic slag is ferric arsenate or scorodite;
To sink after arsenic after liquid is warming up to 80 ℃ and process 240min toward wherein adding Iron sulfuret to vulcanize heavy plumbous zinc, obtain plumbous cadmia and purify after liquid; The add-on of Iron sulfuret is that all lead ions in liquid after described heavy arsenic are become to 2 times of the required theoretical consumption of plumbous cadmia with zine ion sulfide precipitation; At sulfide precipitation, become the plumbous cadmia while also can remove residual arsenic, after the heavy plumbous zinc processing of sulfuration, after heavy arsenic, in liquid, the clearance that the clearance of lead is 96.8%, Zn is 95.6%, through heavy arsenic, processes and vulcanizes after heavy plumbous zinc processing, and total clearance of arsenic reaches 99.0%;
Packing liquid after purification in automiser spray atomization is fine mist, and in purity oxygen atmosphere, temperature of reaction is 800 ℃, and thermolysis obtains Fe
2o
3powder and HCl gas, recovery HCl gas makes hydrochloric acid soln and returns to leaching operation.
Claims (8)
1. a method of comprehensive utilization for zinc hydrometallurgy kiln slag iron ore concentrate, is characterized in that comprising the steps:
Step 1 zinc hydrometallurgy kiln slag iron ore concentrate Leaching in Hydrochloric Acid
With the hydrochloric acid of 0.5～3mol/L, zinc hydrometallurgy kiln slag iron ore concentrate is carried out to low Ore Leaching processing, the low acid leaching liquor of gained is standby, the low acid leaching slag of gained carries out high Ore Leaching with the hydrochloric acid of 3～6mol/L, high Ore Leaching gained leach liquor returns for low Ore Leaching, and high Ore Leaching gained leached mud is processed in sulfuric acid operation;
Step 2 iron replacement copper, silver
The pH value of above-mentioned low acid leaching liquor is transferred to 0.5～1.5, toward wherein adding iron powder, carries out liquid-solid separation after replacement(metathesis)reaction, obtain silver-bearing copper slag and displaced liquid; The add-on of iron powder is 1.1～2.5 times of theoretical consumption that displace all silver ionss and the required fe of cupric ion in described low acid leaching liquor;
Step 3 is sunk arsenic
The pH value of displaced liquid is transferred to 2.0～3.5, and the arsenic that sinks at 60～95 ℃ is processed, and obtains liquid after heavy arsenic slag and heavy arsenic;
Step 4 is plumbous, zinc sulfide precipitation
Vulcanizing agent is added after heavy arsenic in liquid, makes lead, zine ion in solution generate sulfide precipitation, obtain plumbous cadmia and purify after liquid; The add-on of vulcanizing agent is that all lead ions in liquid after described heavy arsenic are become to 2～6 times of the required theoretical consumption of plumbous cadmia with zine ion sulfide precipitation; Described vulcanizing agent is metallic sulfide or the H of divalent sulfur
2s;
Step 5 FeCl
2aqueous solution spraying thermolysis
Pack liquid after purification into automiser spray, using oxygen-containing gas as carrier gas, at 400～1000 ℃, carry out spray pyrolysis, obtain Fe
2o
3powder and HCl gas, HCl gas is made concentrated hydrochloric acid after water absorbs, and returns to high Ore Leaching operation and uses.
2. the method for comprehensive utilization of a kind of zinc hydrometallurgy kiln slag iron ore concentrate according to claim 1, is characterized in that:
Described zinc hydrometallurgy kiln slag iron ore concentrate comprises following main component by percentage to the quality:
In described iron ore concentrate, also comprise silver, the content of silver is 10～1000g/t.
3. the method for comprehensive utilization of a kind of zinc hydrometallurgy kiln slag iron ore concentrate according to claim 1, it is characterized in that: described in step 1, leach as counterflow leaching, during low Ore Leaching, controlling extraction temperature and be room temperature to 90 ℃, time is that 30～240min, liquid-solid ratio are 5:1～20:1ml/g; During high Ore Leaching, control extraction temperature and be room temperature to 80 ℃, extraction time is that 30～180min, liquid-solid ratio are 5:1～20:1ml/g.
4. the method for comprehensive utilization of a kind of zinc hydrometallurgy kiln slag iron ore concentrate according to claim 1, is characterized in that: in step 2, the specific surface area of iron powder used is 0.17～0.36m
2/ g; During replacement(metathesis)reaction, controlling temperature and be room temperature to 50 ℃, time is 20～120min.
5. the method for comprehensive utilization of a kind of zinc hydrometallurgy kiln slag iron ore concentrate according to claim 1, is characterized in that: in step 3, described heavy arsenic slag is ferric arsenate or scorodite.
6. the method for comprehensive utilization of a kind of zinc hydrometallurgy kiln slag iron ore concentrate according to claim 1, is characterized in that: in step 4, when lead, zinc sulfide precipitation, the temperature of controlling solution is room temperature to 80 ℃.
7. the method for comprehensive utilization of a kind of zinc hydrometallurgy kiln slag iron ore concentrate according to claim 1, is characterized in that: in step 4, the metallic sulfide of described divalent sulfur is Iron sulfuret or pyrite, FeS in described pyrite
2quality percentage composition>=90%.
8. the method for comprehensive utilization of a kind of zinc hydrometallurgy kiln slag iron ore concentrate according to claim 1, is characterized in that: in step 5, by the FeCl after purifying
2solution adopts spraying pyrolysis technique to prepare Fe under oxygen or air atmosphere
2o
3powder also reclaims HCl and prepares hydrochloric acid, and spraying heat decomposition temperature is controlled at 400～1000 ℃.
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