CN101575673A - Method for separating and extracting copper and cobalt-nickel in low-grade complex mixed copper-cobalt ore - Google Patents
Method for separating and extracting copper and cobalt-nickel in low-grade complex mixed copper-cobalt ore Download PDFInfo
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Abstract
The invention provides a method for separating and extracting copper and cobalt-nickel in low-grade complex mixed copper-cobalt ore, which uses low-grade complex mixed copper-cobalt ore (sulfide and oxide) as a raw material to extract an intermediate product of the copper and cobalt-nickel by adopting process flows of crushing and grinding ore into slurry, leaching the slurry with acidic villaumite by a wet method, extracting copper powder by reduction and replacement, vulcanizing and depositing nickel (cobalt), concentrating, drying, baking and hydrolyzing deposited mother solution at low temperature and the like. The method comprises main technical points that metallic elements in the mixed copper-cobalt ore are dissolved and leached by the acidic villaumite under normal pressure; copper in leaching liquor is reduced and deposited by a reducing agent; the cobalt and nickel are deposited by a vulcanizing agent to obtain the intermediate product; the mother solution is concentrated, dried, baked and hydrolyzed at low temperature after cobalt-nickel deposition to obtain metal oxide, metal oxychloride and hydrogen chloride containing iron, magnesium and the like; hydrogen chloride is reclaimed to obtain hydrochloric acid, and baked solid is leached into water to obtain chloride solution; and the hydrochloric acid and the chloride solution are used for leaching of ore slurry. The method comprehensively reclaims the copper, the cobalt-nickel and the like, and has the characteristics of high leaching rate of the copper and the cobalt-nickel, less energy consumption, low cost, closed circulation of chlorine (hydrochloric acid), less investment of project engineering and the like. The whole process is concise, clean and environment-friendly. The method is particularly applicable to large-scale industrial production.
Description
Technical field
The present invention relates to a kind of method of handling extraction separation copper in the low-grade complex mixed copper cobalt ore, cobalt nickel and comprehensive utilization valuable metal.
Background technology
Copper, cobalt, nickel etc. are important non-ferrous metals, occupy extremely important status in global economy.Copper, cobalt and nickel in earth mineral, often symbiosis; How to exist with its sulfide, oxide compound.Since the difference of geographical environment of living in, the content difference of total content, sulphide ores and the oxidized ore of copper cobalt nickel, and the copper cobalt ore of weathering is hidden mainly based on the oxidized ore mineral fully under wet heat condition, and mostly with sulfide and oxide mineral coexistence.
For the processing of the higher COMPLEX MIXED copper of low-grade mixed copper cobalt ore, especially silicon, iron, Mg content, still there is not a ripe smelting technology with inside and outside.Comprehensive domestic and international research, the method for handling the cupric oxide cobalt ore at present has three kinds: (1) flotation process; Use flotation medicines such as lipid acid, amine organism or neutral oil emulsion that mineral are carried out direct flotation, and mineral are carried out carrying out sulfide flotation with the flotation medicine again after the sulfidizing.(2) high temperature pyrogenic attack; By the high temperature reduction melting, valuable metal in the mineral is smelted into alloy (copper-cobalt alloy) (3) chemistry soak the ore deposit; With chemical reagent valuable metal dissolving in the ore is separated with gangue mineral, carry out enrichment and refining again, wherein sulfuric acid leaching-extraction-electrodeposition flow process is to be widely used.
All in all, chemical deposit impregnating technology has become the main flow of handling low grade ore.For copper cobalt ore based on sulfide mineral, the hydrometallurgy route that adopts sulfurization roasting-sulfuric acid to leach, based on the copper cobalt ore of oxide ore, the hydrometallurgy route that adopts direct acidleach to go out; Include chemical neutralisation deironing, organic solvent extractionprocess extraction and other valuable metals such as separating copper, cobalt, nickel and zinc in the subsequent technique.Typical research technology has the technology of the high silicon low-grade complex of the processing low-sulfur copper cobalt ore that the investigators of China Beijing Mine and Metallurgy General Inst propose: sulfurization roasting-sulfuric acid leaches in copper, cobalt, nickel, the zinc-extracting and separating copper-lime carbonate and deironing-P204 extracts dezincification-neutralization precipitation enriched in cobalt, nickel-cobalt, the acidleach of nickel slag and goes out-Neutral ammonium fluoride deliming, magnesium-P204 abstraction impurity removal-Cyanex272 extracting and separating cobalt, nickel; This technology has realized the comprehensive recovery of valuable metals such as copper, cobalt, nickel and zinc.Processing technological flow is long, the wet process system is big, running cost is high.
The present invention proposes a kind of Wet-process metallurgy method of separation and Extraction copper, cobalt nickel from low-grade complex mixed copper cobalt ore of lacking flow process, low cost, few comprehensive utilization of resources that drops into.
Summary of the invention
The prior art versatility is strong in order to overcome, comprehensive utilization of resources deficiency etc., the invention provides a kind of less investment, comprehensive utilization of resources, the mineral scope of application is wide, technology is succinct, energy consumption is low, production cost is low, acid and closed circuit the following of water do not produce pollution, environmentally friendly, as the to adapt to scale operation method of separation and Extraction copper, cobalt nickel from low-grade complex mixed copper cobalt ore.
The present invention realizes by following technical proposal, comprises following processing step;
(1) acid villaumite soaks the ore deposit: ore reduction, comminution are made ore pulp, ore pulp soaks the ore deposit agent with metal chloride and mixing of hydrochloric acid and carries out the normal pressure agitation leach, copper in the ore, cobalt nickel, magnesium and small part iron are entered in the leach liquor with muriate, and most of iron is suppressed in the leached mud;
(2) precipitate reduction extracts copper powder: with leach liquor and the leached mud solid-liquid separation that obtains in (1) step; Adjust pH of leaching solution to 1.0～2.5, reductive agent is added leach liquor, make that copper precipitates with copper powder in the solution, and and solution separating, the copper powder product obtained;
(3) direct sulfide precipitation enriched in cobalt nickel: precipitate and separate iron not, directly in carrying the copper mother liquor, add vulcanizing agent, make cobalt nickel with sulfide precipitation and obtain enrichment, solid-liquid separation obtains the sulfide enriched substance;
(4) mother liquor concentrates-dry, roasting: the sulfide precipitation mother liquid evaporation is concentrated, and atomization drying, roasting hydrolysis, generate the solid mixture of hydrogen chloride gas, metal oxide and oxychloride;
(5) reclaim hydrogenchloride and make hydrochloric acid; Hydrogen chloride gas absorbs through water makes hydrochloric acid; Water logging baked solid product gets acidic mixed chloride soln and mixed oxide solid; Regeneration hydrochloric acid and muriate mixing solutions return and soak the ore deposit.
In described (1) step, ore reduction, comminution made the ore pulp process be: to the ore of extraction carry out fragmentation (preferably be crushed to-30mm), when the ore water content be suitable for less than 15% the time do broken, when the ore water content is suitable for greater than 15% the time wet broken; The liquid-solid ratio that adds the water mill slurry is 1～2: 1, and slurry is crossed 100 mesh sieves.
In described (1) step, soak the mixing solutions that the ore deposit agent is metal chloride and hydrochloric acid, wherein muriate is one or more the mixture in iron(ic) chloride and magnesium chloride, sodium-chlor, the calcium chloride etc.; Control chloride content 120～200g/L when soaking the ore deposit.The dosage of iron(ic) chloride and hydrochloric acid can be allocated more iron(ic) chloride into according to the proportioning of sulfide in the ore and oxide compound when sulfide content is higher, oxide compound is allocated more hydrochloric acid more for a long time into.
In described (1) step, leach and in the normal pressure stirred leaching tank, carry out; Normal pressure is pressure 0.1MPa; Normal temperature is 10～90 ℃ of temperature; Total liquid and solid weight ratio are 3: 1～4: 1 in the process control material; Extraction time 1～4 hour.
Solid-liquid separation in described (2) step is by the solid-liquid separation operation leached mud that step (1) leaches after finishing to be separated with leach liquor; Leach liquor is the solution that contains cupric chloride, cobalt chloride, iron(ic) chloride, magnesium chloride etc., and leached mud is mainly quartzy and irony thing.
In described (2) step, adjusting the pH value of solution value is to add acid neutralizing agent in leach liquor, and making pH value of solution is 1.0～2.5; Acid neutralizing agent can be NaOH, Na
2CO
3, CaO, CaCO
3, MgO, MgCO
3And other alkaline matters, this makes acid neutralizing agent with bright preferred use by the water logging slag (mixed oxide solid) that produces in the step (5), wherein comprises MgO, Fe
2O
3Deng; Neutralization operation is carried out in stirred reactor, 10～90 ℃ of neutral temperatures; After neutralization operation is finished, remove excessive solid neutralizing agent and other solidss by solid-liquid separation.
In described (2) step, when adjustment pH value of solution value was carried out under comparatively high temps, available scorching hot hydrogen chloride gas heated solution indirectly.
In described (2) step, used reductive agent is based on metal or alloy class powder, comprise reduced iron powder, aluminium powder, magnesium powder, zinc powder, and the alloy powder of two kinds of elements, three kinds of elements or four kinds of elements in the iron, aluminium, magnesium, zinc, or other can be reduced into cupric ion in the solution reductive agent of elemental copper; To use iron powder, magnesium powder or iron magnesium alloy powder is good, and can not give in the solution increases impurity, and inexpensive relatively.The present invention preferentially uses iron powder.
In described (2) step, restoring operation is carried out in stirred reactor, 10～90 ℃ of reduction temperatures; After restoring operation is finished, remove to collect copper powder by solid-liquid separation.
In described (3) step, carry the copper mother liquor and be the mother liquor behind completing steps (2) the separation and Extraction copper powder; Carry in the copper process, mother liquor pH value will raise to some extent, reach 1.5～3.5.
In described (3) step, used vulcanizing agent be sodium, ammonium, calcium, magnesium etc. simple sulfide, polysulfide, contain sulfhydrate, or in the above-mentioned sulfide one or more, the present invention preferentially uses sodium sulphite solid vulcanizing agent.
In described (3) step, sulfide precipitation carries out in stirred reactor, 10～90 ℃ of service temperatures; Vulcanizing agent is slowly to add under solution constantly stirs.
In described (3) step, the sulfide enriched substance is the mixture based on the sulfide of cobalt, nickel and iron, is after the sulfide precipitation operation, and the solid product that obtains after the solid-liquid separation is used for further making with extra care the raw material of cobalt, nickel product.
(2) pH value of solution adjustment, (2) precipitate reduction or sulfide precipitation enriched in cobalt nickel in (3) step in the step in the step, all in stirred reactor, carry out 10～90 ℃ of service temperatures; When adopting non-normal-temperature operation, preferred to adopt the scorching hot hydrogen chloride gas that is produced by roasting be that thermal source carries out indirect heating to material.Adopting the mixed oxide solid is in the operation of neutralizing agent, and scorching hot solids also can be used as thermal source.
In described (4) step, the sulfide precipitation mother liquor is that solid-liquid separation goes out mother liquor behind the sulfide solid in (3) step, mainly contains the metal chloride of magnesium chloride, iron protochloride etc.
In described (4) step, evaporation concentration is by to mother liquor heating, and transpiring moisture makes that chloride concentration increases in the solution, reaches Cl total amount 260～320g/L; Heating medium can be deep fat, water vapor and other hot-fluids; The present invention preferentially adopts the high-temp chlorination hydrogen that pyrohydrolysis produces in (4) step, can adopt the mode of direct heating or indirect heating.
In described (4) step, atomization drying, roasting are the concentrated mother liquors that total chlorine is reached 260～320g/L, finish drying, roasting by spray atomization step in 350～500 ℃ of air atmospheres, also can be by spraying drying, the two-part of roasting operation in 350～500 ℃ of air atmospheres again in 200～350 ℃ of air atmospheres earlier; Product of roasting is a hydrogen chloride gas, and contains the oxide compound of magnesium, iron etc. and the solid mixture of oxychloride.
In described (4) step, roasting can be a fuel with various coals, coke, Sweet natural gas, water-gas, liquefied petroleum gas (LPG), petroleum-type product (as: diesel oil, heavy oil, kerosene etc.) etc.; Fuel can use separately, also can mix use.
In described (5) step, reclaiming hydrogenchloride salt manufacturing acid, is to absorb by the hydrogen chloride gas water after the heat exchange cooling in evaporation concentration, the atomizing roasting process, to make hydrochloric acid; Reclaiming hydrochloric acid returns as the ore leaching with sour.
In described (5) step, water is directly handled scorching hot baked solid mixture, and the metal oxychloride is decomposed obtain metal oxide solid and mixed chloride solution, solid-liquid separation, the mixed chloride solution that contains iron(ic) chloride is used to soak the ore deposit;
In described (5) step, the mixed oxide that obtains with water treatment roasting mixed oxidization solid is rich ferriferous oxide, is used for ironmaking or iron product raw materials for production as iron ore concentrate after treatment;
Described (2), (3), (5) are in the step, and solid-liquid separation can be used with in the filters such as thickener, Hhigh-efficient thickener, flame filter press, vacuum filter, band filter one or more.
The present invention is directed to that low-grade complex mixed copper cobalt ore copper, cobalt grade are low, the characteristics of silicon magnesium iron level height, oxidized ore and sulphide ores coexistence, provide a kind of scheme complete, help the circulation of material, the method for copper, cobalt nickel, iron and magnesium comprehensive development and utilization in the low-grade complex mixed copper cobalt ore of saving cost.It is fast that this method compared with prior art has leaching velocity, copper, cobalt nickel leaching yield height, but the chlorine circulation realizes advantages such as hydrochloric acid recycle, and Technology, equipment, economy and environmental protection aspect can both meet big industrial production requirement.Thereby treatment process of the present invention also is effectively to extract the processing method of copper, cobalt nickel from low-grade complex mixed copper cobalt ore.
Advantage of the present invention and positively effect are as follows:
1, adopt the mixing of villaumite and hydrochloric acid to soak the ore deposit agent, the high-recovery of copper, cobalt nickel.
The present invention adopts the mixing solutions of villaumite and hydrochloric acid as soaking the ore deposit agent, because hydrochloric acid is the highest acid of sour activity in the mineral acid, therefore and in chloride solution, have higher activity, mix and soak the ore deposit agent and have the highest acid activity, adopt hydrochloric acid leaching valuable metal from oxide mineral most effectively; Reasonable disposition is soaked the content of iron(ic) chloride in the agent of ore deposit, and acidic ferric chloride is sulfurized and effectively soaks the ore deposit agent, adopts iron(ic) chloride leaching valuable metal from sulphide ores effectively.Adopt the mixed configuration of iron(ic) chloride and hydrochloric acid, can effectively handle oxide compound and sulfide mixing ore deposit, high efficiency extraction copper, cobalt nickel.
Adopt the method for cementation of high yield to extract copper, sulfide precipitation extraction cobalt nickel among the present invention, thereby make the rate of recovery of valuable metal copper, cobalt nickel reach higher level.
2, adopt reduction method to extract copper, can extract cobalt nickel by direct sulfide precipitation without separation of iron, technology is succinct, reduced investment.
When adopting reduction method to extract copper, high price iron in the solution is reduced into iron at a low price, the hydrolysis of high price iron when avoiding cobalt nickel sulfide precipitation; Because in the sulfide precipitation process, cobalt nickel has higher resolution with iron at a low price, after the process of therefore extracting copper is finished, does not need the technological process of later separation iron, can directly carry out sulfide precipitation and extract cobalt nickel, and low, the cobalt nickel enrichment height of iron level in the sulfide precipitation.
Preferential iron, magnesium or the iron magnesium alloy powder of using carries out transformation approach and extracts copper among the present invention, do not increase new impurity to system, and the reductive agent of adding can obtain recycling in subsequent process.
Adopt reduction method to extract copper, can shorten the processing technological flow of cupric oxide cobalt ore, reduce construction investment, reduce technology running cost.
3, rationally be provided with in the technology process conditions, make full use of in the process from product comprehensive utilization of resources.
Among the present invention in the mineral leaching of valuable metal use recovery hydrochloric acid in a large number; Reclaiming hydrochloric acid is that the hydrogenchloride that produces in the water absorption roasting hydrolytic process makes.Realize the closed cycle of chlorine element in the whole technology, regeneration hydrochloric acid is used to soak the ore deposit.
The incomplete hydrolysis of low temperature is adopted in the muriate hydrolysis among the present invention, and the metal oxychloride of generation is handled to decompose through the aqueous solution and obtained chloride soln, is directly used in and soaks the ore deposit, has realized that iron(ic) chloride soaks the regeneration of ore deposit agent.
The acid of solution neutralization in the technology, the preferential water logging slag (mixed oxide) of roasting hydrolysis solid product that adopts is made neutralizing agent among the present invention, neutralization is ferric oxide and magnesium oxide and other metal oxide that utilizes wherein under the high acidity, under the low acidity neutralization be utilization mainly be magnesium oxide in the mixed oxide.
Use hydrolysate to make acid neutralizing agent, do not increase other impurity, form muriate by neutralization reaction and acid simultaneously, enter the pyrohydrolysis process with chlorine, obtain recycling as the carrier of chlorine to system; Use metal oxide as acid neutralizing agent in the technology, simple to operate, control convenience.
4, adopt the incomplete hydrolysis of low temperature, and rationally utilize heat energy, the energy efficiency height, energy consumption is low.
Process heat energy mainly consumes at muriatic drying and roasting hydrolysing step, and the present invention adopts diversified fuel, but the based on fuel tone of market rationally use, minimum to reach cost.
The present invention adopts the incomplete hydrolysis of low temperature, reduces by 300～500 ℃ of temperature with traditional complete hydrolysis, has greatly reduced energy consumption.
The hydrogenchloride that produces is high-temperature gas, and must absorb by cooling ability water becomes hydrochloric acid; The heat that the present invention discharges the hydrogenchloride cooling is used for solution intensification, the evaporation concentration of chloride soln (sulfide precipitation mother liquor) and the spraying drying of concentrated solution etc.Flexible way has been adopted in thermal utilization, and utilizing high-temp chlorination hydrogen is these characteristics of hot-fluid, can be directly, also can treat heatable substance indirectly and heat.
By rationally utilizing heat energy, realized the efficient utilization of energy in the technology, unit consumption of energy is low.
5, flow process is succinct, cost is low;
The extraction and separation method of copper, nickel cobalt and iron etc. in the mixed copper cobalt ore of the present invention, comprise that hydrochlorate mixture process ore pulp leaching valuable metal, reduction replacement extraction copper, sulfide precipitation extract cobalt nickel, chloride soln is handled and reclaimed 4 formant operations such as hydrochloric acid and muriate leaching agent, technology is succinct, and flow process is short.Owing in invention, rationally use unit operation, utilize resources synthetically, the chlorine closed cycle utilizes self-produced hydrochloric acid, iron(ic) chloride and mixed metal oxide etc., do not increase other new impurity, do not use numerous and diverse removal of impurities or separating step, make that the preparation of ore cost is low to system.
Description of drawings
Accompanying drawing is a process flow sheet of the present invention.
Embodiment
Below in conjunction with concrete enforcement the present invention is described further.The present invention can implement by arbitrary mode of summary of the invention.Providing of these embodiment limits the present invention anything but.
Embodiment is respectively with the valency that the mainly contains metal content in the mixed copper cobalt ore: Cu 3.88; Co 0.87; Ni0.31; Fe 4.96; Ca 0.35; Mg 3.40; Mn 0.26; S 2.51.By mainly containing the valency metalliferous mineral, apparent sulfuration rate 20.8%; By the 1.0kg ore deposit, whole sulphide oress high price iron oxidation dissolution, theoretical consumption iron(ic) chloride 0.255kg; All the theoretical amount of the acid of oxidized ore dissolving consumption HCl is 0.219kg.
The copper cobalt ore is through coarse breaking; 1: 1 (wt) adds the water mill pulping by material-water ratio, and crosses 100 mesh sieves.
Embodiment 1 adds the hot dipping ore deposit
A. getting copper cobalt ore slurry pumps in the stirred reactor, by liquid-solid ratio 4.0: 1, acid material (weight) than being 1.2～1.4: 1, salt (solid Iron trichloride hexahydrate) material is added water than being 0.28～0.30: 1 adding hydrochloric acid (HCl content is more than 28%), solid Iron trichloride hexahydrate; Heat, carry out agitation leach.
B. leaching condition control: agitation leach is 1.0 hours under 60～70 ℃, 0.1MPa.
C. filter, residue is washed.
The comprehensive leaching yield of valuable metal is respectively: Cu 94.7%; Co+Ni 92.7%; Mg 96.2%; Fe42.7%.
Embodiment 2 normal temperature soak the ore deposit
A. getting-100 order slurries pumps in the stirred reactor, by liquid-solid ratio 3.0: 1, acid material (weight) than being 0.8～1.0: 1, salt (solid Iron trichloride hexahydrate+magnesium chloride hexahydrate) material is added water than being 0.35～0.38: 1 adding hydrochloric acid (HCl content is more than 28%), solid Iron trichloride hexahydrate; Carry out agitation leach.
B. leaching condition control: agitation leach is 3.0 hours under normal temperature, the 0.1MPa.
C. filter, residue is washed.
The comprehensive leaching yield of valuable metal is respectively: Cu 93.7%; Co+Ni 93.1%; Mg 95.4%; Fe31.6%.
Leach the mixed copper cobalt ore through hydrochlorate mixing leaching agent, leach liquor major metal constituent content (g/L) is respectively: Cu8.70; Ni+Co 2.62; Mg+Ca 8.47 Fe 21.01; Leach liquor acidity is: H
+0.72mol/L.Following embodiment is based on this leach liquor.
Embodiment 3 normal temperature cemented coppers
A. pH of leaching solution adjustment: leach liquor is pumped in the stirred reactor, and normal temperature stirs down, slowly at the uniform velocity adds the water logging slag of baked solid product, makes leach liquor pH rise to 1.0～1.5, stops to feed in raw material, and continues to stir 0.5 hour; The pH value of solution value continues to rise to some extent; Filter.
B. precipitate reduction extracts copper powder: will adjust liquid pump and go in the stirred reactor, normal temperature stirs down, slowly at the uniform velocity adds reduced iron powder; Press the reduction chemical reaction quantifier of copper amount in the solution and high price iron level, the iron powder add-on is 1.1 times of theoretical amount, reinforced 2.0 hours time, 2.5 hours stirring reaction time.
C. separation and Extraction copper powder: filter; Collect filtered liquid, enter down step sulfide precipitation enriched in cobalt nickel; Filter residue is through salt acid elution, water washing, to the no Cl of washings check
-Collect, dry.
The cementation rate of copper is 99.4%, copper powder Cu99.1%.
Embodiment 4 heating cemented coppers
A. pH of leaching solution adjustment: leach liquor is pumped in the stirred reactor, and heated and stirred, temperature rise to 50～60 ℃, slowly at the uniform velocity add the water logging slag of baked solid product, make leach liquor pH rise to 1.0～1.5, stop to feed in raw material, and continue to stir 0.5 hour; The pH value of solution value continues to rise to some extent; Filter.
B. precipitate reduction extracts copper powder: will adjust liquid pump and go in the stirred reactor, and keep 55～60 ℃ of temperature, and stir, and slowly at the uniform velocity add reduced iron powder; Press the reduction chemical reaction quantifier of copper amount in the solution and high price iron level, the iron powder add-on is 1.2 times of theoretical amount, reinforced 0.5 hour time, 1.0 hours stirring reaction time.
C. separation and Extraction copper powder: filter; Collect filtered liquid, enter down step sulfide precipitation enriched in cobalt nickel; Filter residue is through salt acid elution, water washing, to the no Cl of washings check
-Collect, dry.
The cementation rate of copper is 99.2%, copper powder Cu98.4%.
Leach liquor extracts copper through iron powder conversion, carries that major metal constituent content (g/L) is respectively in the copper mother liquor: Ni+Co2.67; Mg+Ca 14.60 Fe 35.31; PH2.0～2.5.Following embodiment is based on this mother liquor.
Embodiment 5 bakings precipitation
A. solution heating: will carry copper stepmother liquid pump and go in the stirred reactor, heating, stirring make the mother liquor temperature rise to 70～80 ℃.
B. sulfide precipitation: holding temperature 70～g0 ℃, stir, by per 1.0 liters of mother liquor amount 20～22g (press the sulfide precipitation chemical reaction quantifier of cobalt nickel amount in the solution, the sodium sulphite add-on is 2.0 times of theoretical amount), slowly add solid sodium sulfide (Na
2S.9H
2O), the reinforced 1.0 hours time, 0.5 hour stirring reaction time is continued in the back of having fed in raw material.
C. filtering separation is extracted cobalt nickel enriched substance: filter; Collect filtered liquid, enter down and go on foot concentrated-drying-roasting; Filter residue is collected, is dried through water washing.
Cobalt nickel sulfide precipitation rate is 97.3%, iron sulfide precipitation rate 6.2%.
Embodiment 6 room temperature vulcanizations precipitation
A. solution is prepared: will carry copper stepmother liquid pump and go in the stirred reactor, and stir.
B. sulfide precipitation: normal temperature, stir, by per 1.0 liters of mother liquor amount 25～28g (press the sulfide precipitation chemical reaction quantifier of cobalt nickel amount in the solution, the sodium sulphite add-on is 2.5 times of theoretical amount), slowly add solid sodium sulfide (Na
2S.9H
2O), the reinforced 2.0 hours time, 1.0 hours stirring reaction time is continued in the back of having fed in raw material.
C. filtering separation is extracted cobalt nickel enriched substance: filter; Collect filtered liquid, enter down and go on foot concentrated-drying-roasting; Filter residue is collected, is dried through water washing.
Cobalt nickel sulfide precipitation rate is 98.2%, iron sulfide precipitation rate 8.6%.
Behind sulfide precipitation enriched in cobalt nickel, major metal constituent content (g/L) is respectively in the mother liquor: Mg+Ca 12.70Fe 28.73 Na+4.1; Mother liquor pH3.6～4.0, total Cl 98.3g/L.Following embodiment is based on this mother liquor.
Embodiment 7
A gets the mother liquor behind the precipitate cobalt nickel, is adjusted to Cl total amount 300～320g/l through concentrating.
B keeps 350～380 ℃ of tubular type vertical furnace bore temperatures; Adjusted mother liquor is introduced furnace roof portion's nozzle and be sprayed in the stove metal chloride drying and roasting in the realization mother liquor.
The C furnace gas through heat exchange, gather dust, water absorbs; Furnace gas is emptying behind multistage absorption; Absorb the hydrochloric acid that obtains greater than 28%HCl by the first step.
The D slag is directly used water extraction, and the control solid-to-liquid ratio is 2.0～2.5: 1; Filter, get rich ferriferous oxide solid and iron(ic) chloride and magnesium chloride mixture solution.
Embodiment 8
A gets the mother liquor behind the precipitate cobalt nickel, is adjusted to Cl total amount 260～280g/l through concentrating.
B keeps 250～300 ℃ of vertical furnace bore temperatures; Adjusted mother liquor is introduced furnace roof portion's nozzle and be sprayed in the stove metal chloride drying in the realization mother liquor.
C introduces the muriate crystallization in the rotary kiln, 350～400 ℃ of control kiln temperature; Draw furnace gas (hydrogenchloride) from kiln hood, obtain the mixed oxide solid from the kiln tail.
The D furnace gas is through cooling, and water absorbs that water absorbs to the water; Furnace gas is emptying behind multistage absorption; Absorb the hydrochloric acid that obtains greater than 28%HCl by the first step.
The E slag is directly used water extraction, and the control solid-to-liquid ratio is 2.0～2.5: 1; Filter, get rich ferriferous oxide solid and iron(ic) chloride and magnesium chloride mixture solution.
Claims (12)
1, the method for extraction separation copper, cobalt nickel from low-grade complex mixed copper cobalt ore is characterized in that, comprises following processing step:
(1) acid villaumite soaks the ore deposit: ore reduction, comminution are made ore pulp; Ore pulp soaks the ore deposit agent with metal chloride and mixing of hydrochloric acid and carries out the normal pressure agitation leach, and the copper in the ore, cobalt nickel, magnesium and part iron are entered in the leach liquor with muriate, and most of iron is suppressed in the leached mud;
(2) precipitate reduction extracts copper powder: with leach liquor and the leached mud solid-liquid separation that obtains in (1) step; Adjust pH of leaching solution to 1.0～2.5, reductive agent is added leach liquor, make that copper precipitates with copper powder in the solution, and and solution separating, the copper powder product obtained;
(3) direct sulfide precipitation enriched in cobalt nickel: directly add vulcanizing agent in carrying the copper mother liquor, make cobalt nickel with sulfide precipitation and obtain enrichment, solid-liquid separation obtains the sulfide enriched substance;
(4) mother liquor concentrates-dry, roasting: the sulfide precipitation mother liquid evaporation is concentrated, and atomization drying, roasting hydrolysis, generate the solid mixture of hydrogen chloride gas and metal oxide and oxychloride;
(5) reclaim hydrogenchloride and make hydrochloric acid; Hydrogen chloride gas absorbs through water makes hydrochloric acid; Water logging baked solid mixture gets acidic mixed chloride soln and mixed oxide solid; Regeneration hydrochloric acid and mixed chloride solution return and soak the ore deposit.
2, according to claim 1 from low-grade complex mixed copper cobalt ore the method for extraction separation copper, cobalt nickel, it is characterized in that: in described (1) step, soak the mixing solutions that the ore deposit agent is metal chloride and hydrochloric acid, wherein muriate is one or more in iron(ic) chloride and magnesium chloride, sodium-chlor, the calcium chloride; Soak ore deposit agent chloride content 120～200g/L.
3, according to claim 1 from low-grade complex mixed copper cobalt ore the method for extraction separation copper, cobalt nickel, it is characterized in that: in described (2) step, adopt the mixed oxide solid that produces in (5) to make acid neutralizing agent, adjust the pH value of solution value.
4, according to claim 1 or 2 or 3 described from low-grade complex mixed copper cobalt ore the method for extraction separation copper, cobalt nickel, it is characterized in that: the hydrochloric acid allotment of mixed chloride solution and generation is used as and soaks the ore deposit agent in (5).
5, according to claim 1 or 2 or 3 described from low-grade complex mixed copper cobalt ore the method for extraction separation copper, cobalt nickel, it is characterized in that in described (4) step: mother liquid evaporation concentrates Cl total amount in the mother liquor is increased to 260～320g/L; Concentrated mother liquor is atomization drying, roasting in 350～500 ℃ of air atmospheres, obtains the oxide compound of hydrogen chloride gas and iron, magnesium metal and the solid mixture of oxychloride; Hydrogen chloride gas absorbs into hydrochloric acid through water, is used for the leaching of ore pulp metallic element.
6, according to claim 1 from low-grade complex mixed copper cobalt ore the method for extraction separation copper, cobalt nickel, it is characterized in that: the water logging slag of roasting mixed oxide solid after water logging is rich ferriferous oxide, is used to smelt iron as iron ore concentrate after treatment or raw material that iron product is produced.
7, according to claim 1 from low-grade complex mixed copper cobalt ore the method for extraction separation copper, cobalt nickel, it is characterized in that: in described (2) step, used reductive agent is based on metal or alloy class powder, comprise reduced iron powder, aluminium powder, magnesium powder or zinc powder, or the alloy powder of two kinds of elements, three kinds of elements or four kinds of elements in the iron, aluminium, magnesium, zinc.
8, according to claim 7 from low-grade complex mixed copper cobalt ore the method for extraction separation copper, cobalt nickel, it is characterized in that: in described (2) step, used reductive agent is iron powder, magnesium powder or iron magnesium alloy powder.
9, according to claim 1 from low-grade complex mixed copper cobalt ore the method for extraction separation copper, cobalt nickel, it is characterized in that adopting the scorching hot hydrogen chloride gas that produces in (4) step be the thermal source of concentrated, the concentrated solution atomization drying of sulfide precipitation mother liquid evaporation in (4) step.
10, according to claim 1 or 9 described methods from extraction separation copper, cobalt nickel from low-grade complex mixed copper cobalt ore, it is characterized in that: pH value of solution adjustment, (2) precipitate reduction or sulfide precipitation enriched in cobalt nickel in (3) step in the step in (2) step, all in stirred reactor, carry out 10～90 ℃ of service temperatures; When adopting non-normal-temperature operation, employing be that the scorching hot hydrogen chloride gas that roasting produces is that thermal source carries out indirect heating to material.
11, according to claim 1 from low-grade complex mixed copper cobalt ore the method for extraction separation copper, cobalt nickel, it is characterized in that: in described (1) step, leach and in non-pressurized stirred leaching tank, carry out; Normal pressure is pressure 0.1MPa; 10～90 ℃ of temperature; Total liquid and solid weight ratio are 3: 1～4: 1 in the process control material; Extraction time 1～4 hour.
12, according to claim 1 from low-grade complex mixed copper cobalt ore the method for extraction separation copper, cobalt nickel, it is characterized in that: in described (3) step used vulcanizing agent be sodium, ammonium, calcium, magnesium etc. simple sulfide, polysulfide, contain sulfhydrate, or in the above-mentioned sulfide one or more; Described sulfide enriched substance is used for the raw material of further refining cobalt, nickel product based on the sulfide of cobalt, nickel and iron.
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