CN104017989A - High ferroalloy treatment process - Google Patents

Abstract

The invention discloses a high ferroalloy treatment process which comprises the following steps: (1) selecting dissolved iron, namely carrying out a reaction on high ferroalloy powder and a post-electrodeposition liquid returned by a copper electrodeposition system in a liquid-solid ratio of (5:1)-(30:1), wherein Cu<2+> in the post-electrodeposition liquid and Fe in the alloy react, so that almost Fe in the alloy powder enters into the solution in a form of Fe<2+> while Cu<2+> in the solution is converted into single substance Cu powder; (2) oxidizing and selecting leached copper, cobalt and nickel, namely supplementing a proper amount of sulfuric acid into the solution obtained by dissolved iron reaction, the copper powder and the alloy powder till the acid concentration of the solution is 0.5-4mol/L and adding an additive at the same time, and jointly conveying to a leaching reaction kettle to oxidize and leach, wherein the use level of the additive is 5-15g/L and the additive can be salts of ammonium salt, manganese salt and chlorides; (3) carrying out electrolytic deposition of copper and electrolytic decoppering, namely oxidizing and selecting to obtain sulfate of copper and cobalt without Fe and directly entering into the copper electrodeposition system to be electrodepositioned so as to obtain standard cathode copper; (4) extracting cobalt from a post-decoppering liquid.

Description

A kind of high ferro alloy treatment technique

Technical field

The invention belongs to hydrometallurgy field, relate in particular to a kind of high ferro alloy treatment novel process, for the treatment of high ferro copper-cobalt alloy.

Background technology

High iron alloy is that a kind of iron content obtaining through pyrometallurgical smelting is not less than 3%, also contains wherein alloy or the metallic compound of one or more valuable metal such as copper, nickel, cobalt.The object of processing this kind of raw material is, by valuable metal separating-purifying wherein, to obtain corresponding metal or salt series products.

The key issue of high iron alloy wet processing is to remove foreign metal Fe in the process of purifying in metal separation.Existing technical process, is leached in acidic medium solution the thinner alloy powder of the broken acquisition of alloy for first, makes whole soluble metal compositions in alloy enter solution with ionic forms, and particularly impurity iron also all enters leach liquor.Leach liquor enters Cu extraction and electrolytic system afterwards, obtains standard cathode copper products.The remaining liquid of extraction Cu must, through entering cobalt extracting system except after Fe, obtain Co salt, Ni product salt after the separation of purifying.The shortcoming of above-mentioned traditional treatment method is, the one, and in alloy, cupric sulfide composition can not leach completely, and the direct yield of copper is low; The 2nd, because the Fe in alloy enters solution with ionic forms, increase the consumption of copper extractant; The 3rd, enrichment in electrolytic solution, reduces current efficiency of copper electrowinning; The 4th, from raffinate, deironing need to consume a large amount of alkali and oxygenant and the energy, and deironing cost is very high.

Summary of the invention

The problem that object of the present invention exists for prior art, provides a kind of high ferro alloy treatment novel process, for the treatment of high ferro copper-cobalt alloy.

Above-mentioned purpose realizes by following proposal:

A high ferro alloy treatment technique, is characterized in that, described treatment process comprises and comprising the following steps:

(1) select molten iron, nickel and cobalt: after the electrodeposition that high iron alloy powder returns with copper electrodeposition system, liquid reacts according to liquid-solid ratio 5:1-30:1, make the Cu in liquid after electrodeposition ²⁺react with the Fe in alloy, make in alloy powder most Fe with Fe ²⁺form enters solution, and Cu in solution ²⁺be converted into simple substance Cu powder;

(2) oxidation selectively leaching copper, cobalt and nickel: in solution, copper powder and the alloy powder obtaining to step (1), add sulfuric acid to adjust solution acid concentration to 0.5-4mol/L, add the salt of ammonium salt or manganese salt or chloride-based as additive simultaneously, jointly be delivered in Leaching reaction still and carry out Oxidation Leaching, additive amount is 5-15g/L; By oxidation selectively leaching, make Cu, Co, Ni valuable metal in alloy enter solution with ion kenel, Fe precipitates with the scum form of pyrrhosiderite or hydrous iron oxide;

(3) electrolytic deposition of copper and electrolysis decopper(ing): the sulfate liquor that acquisition is soaked in the middle oxidation choosing of step (2) directly enters copper electrodeposition system and carries out electrodeposition, obtains standard cathode copper; After electrodeposition, the heavy copper process of displacement is returned in liquid circulation, to utilize sulfuric acid and concentrating cobalt and nickel; Cobalt in electrolytic solution is enriched to after certain concentration, by equal amount open circuit part, containing liquid after cobalt electrolysis, in the recycle system independently, carries out deep electrolytic decopper(ing);

(4) after decopper(ing), liquid is carried cobalt: the cobalt sulfate solution after electrolysis decopper(ing), enter Co extracting system after removing sulfuric acid, and obtain pure cobalt salt solution, producing cobalt salt product, deep processing makes cobalt oxide product or electrodeposition obtains electrodeposited cobalt.

Beneficial effect of the present invention: 1) select molten iron process, make Fe in alloy material not consumption acids with ionic forms, enter solution, reduced the usage quantity of acid in production process.2) in oxidation selectively leaching process, can make more than 98% Cu in material, whole Co, Ni leach, the while pure pyrrhosiderite of output or aqua oxidation scum, this part scum can directly be taken out.3) by the enforcement of this technique, with less process links, realize valuable metal in alloy material and farthest leach, foreign metal iron is removed with precipitation forms simultaneously, reduce greatly supplementary product onsumption, reduce process links, compared with traditional technology, compare obviously and increase economic efficiency.

Accompanying drawing explanation

Fig. 1 is schema of the present invention.

Embodiment

Referring to Fig. 1, high ferro alloy treatment novel process of the present invention comprises the following steps: (1) selects molten iron.After the electrodeposition that high iron alloy powder returns with copper electrodeposition system, liquid reacts according to liquid-solid ratio 5:1-30:1, makes the Cu in liquid after electrodeposition ²⁺react with the Fe in alloy, make in alloy powder most Fe with Fe ²⁺form enters solution, and Cu in solution ²⁺be converted into simple substance Cu powder.(2) oxidation selectively leaching copper, cobalt and nickel.The solution, copper powder and the alloy powder that through molten iron reaction, obtain, supplement and allocate a certain amount of sulfuric acid adjustment solution acid concentration into 0.5-4mol/L, add additive simultaneously, jointly be delivered to and in Leaching reaction still, carry out Oxidation Leaching, additive amount is 5-15g/L, can be the salt of ammonium salt, manganese salt, chloride-based, and its object is to increase the electronics transfer rate that GOLD FROM PLATING SOLUTION belongs to ion, accelerate the sedimentation speed of Fe, improve reaction efficiency.By oxidation selectively leaching, make the valuable metals such as Cu, Co in alloy, Ni enter solution with ion kenel, Fe is with the scum form precipitation of pyrrhosiderite or hydrous iron oxide.Purer oxidation scum is outer selling directly.Oxidation selectively leaching comprises that air or oxygen atmospheric pressure oxidation leaches and air or oxygen pressure oxidation is leached, and waits the normal pressure of other oxygenant or pressure oxidation to leach.(3) electrolytic deposition of copper and electrolysis decopper(ing).Oxidation choosing is soaked acquisition and containing sulfate liquors such as the copper of Fe, cobalts, is not directly entered copper electrodeposition system and carry out electrodeposition, obtains standard cathode copper.After most of electrodeposition, the heavy copper process of displacement is returned in liquid circulation, to utilize sulfuric acid and concentrating cobalt and nickel.Cobalt in electrolytic solution is enriched to after certain concentration, by equal amount open circuit part, containing liquid after cobalt electrolysis, in the recycle system independently, carries out deep electrolytic decopper(ing).Electrolytic deposition and electrolysis decopper(ing) processing unit are conventional electrolyzer or other the electrolyzer form of not limitting form, as cyclone electrolytic cell groove etc.It is the electrolytic process of copper in essence.(4) after decopper(ing), liquid is carried cobalt.Cobalt sulfate solution after electrolysis decopper(ing), enters Co extracting system after removing sulfuric acid, obtains pure cobalt salt solution, producing cobalt salt product, deep processing makes cobalt oxide product or electrodeposition obtains electrodeposited cobalt.Ni in the raffinate of cobalt extracting system is also purified and is reclaimed.

embodiment 1

Mass percent composition is Cu 67.87%, Co 5.71%, the alloy powder of Fe 23.46%, after being placed in electrodeposition according to liquid-solid ratio 30:1, liquid carries out molten iron reaction, temperature of reaction is room temperature-60 ℃, having reacted the copper powder of acquisition and alloy and solution enters in the lump and in leaching kettle, carries out Oxidation Leaching, it is 0.5mol/l that solution adds sulfuric acid to acid concentration, service temperature is 370K, and reaction pressure is 0.6MPa, 3 hours reaction times, additive add-on is 5g/L, after the scum filtering drying obtaining, composition is (mass percent %) Cu 0.1, and Co 0.08, Fe50.7.Leach liquor composition (grams per liter) Cu 44.83, Co 3.77, and Fe 0.04, and the leaching yield of copper reaches more than 99%, and the leaching yield of cobalt reaches more than 99.3%.

The sulfate liquor that contains copper, cobalt and the nickel of Fe0.04g/L, obtains standard cathode copper through electrolytic deposition.After most of electrolysis, liquid returns to selectively leaching operation, to utilize sulfuric acid and enriched in cobalt and nickel.Cobalt in electrolytic solution is enriched to after 30g/L, by the part of equal amount open circuit containing liquid after cobalt electrolysis, the recycle system independently carry out deep electrolytic decopper(ing) to cupric lower than 0.5g/L.

Cobalt sulfate solution after electrolysis decopper(ing), enters Co extracting system after removing sulfuric acid, obtains pure cobalt salt solution, and to produce cobalt salt product, the Ni in the raffinate of cobalt extracting system is also purified and reclaims.

embodiment 2

Mass percent composition is Cu 18%, Co 12%, the high ferro copper-cobalt alloy powder of Fe 65%, after being placed in electrodeposition according to liquid-solid ratio 5:1, liquid carries out molten iron reaction, temperature of reaction is room temperature-60 ℃, the alloy and the solution that have reacted acquisition enter pressure leaching operation in the lump, it is 4mol/l that solution adds sulfuric acid to acid concentration, service temperature is 410K, and reaction pressure is 0.7MPa, 3 hours reaction times, additive add-on is 15g/L, after the scum filtering drying obtaining, composition is (mass percent %) Cu 0.08, and Co 0.05, Fe55.6.Leach liquor composition (grams per liter) Cu 44.83, Co 3.77, and Fe 0.04, and the leaching yield of copper reaches more than 99%, and the leaching yield of cobalt reaches more than 99.3%.

Containing the sulfate liquor of Fe0.05g/L copper, cobalt and nickel, through electrolytic deposition, obtain standard cathode copper.After most of electrolysis, liquid returns to selectively leaching operation, to utilize sulfuric acid and enriched in cobalt and nickel.Cobalt in electrolytic solution is enriched to after 30g/L, by the part of equal amount open circuit containing liquid after cobalt electrolysis, the recycle system independently carry out deep electrolytic decopper(ing) to cupric lower than 0.5g/L.

Cobalt sulfate solution after electrolysis decopper(ing), enters Co extracting system after removing sulfuric acid, obtains pure cobalt salt solution, and to produce cobalt salt product, the Ni in the raffinate of cobalt extracting system is also purified and reclaims.

Claims (1)

1. a high ferro alloy treatment technique, is characterized in that, described treatment process comprises and comprising the following steps:

(1) select molten iron, nickel and cobalt: after the electrodeposition that high iron alloy powder returns with copper electrodeposition system, liquid reacts according to liquid-solid ratio 5:1-30:1, Cu2+ in liquid and the Fe in alloy after electrodeposition are reacted, make most Fe in alloy powder enter solution with Fe2+ form, the Cu2+ in solution is converted into simple substance Cu powder;

(2) oxidation selectively leaching copper, cobalt and nickel: in solution, copper powder and the alloy powder obtaining to step (1), add sulfuric acid, adjust solution acid concentration to 0.5-4mol/L, add the salt of ammonium salt or manganese salt or chloride-based as additive simultaneously, jointly be delivered to and in Leaching reaction still, carry out Oxidation Leaching, additive amount is 5-15g/L, temperature of reaction 370K-410K, reaction times 3h, reaction pressure 0.6KPa-0.70KPa; By oxidation selectively leaching, make Cu, Co, Ni valuable metal in alloy enter solution with ion kenel, Fe precipitates with the scum form of pyrrhosiderite or hydrous iron oxide;

(3) electrolytic deposition of copper and electrolysis decopper(ing): the sulfate liquor that acquisition is soaked in the middle oxidation choosing of step (2) directly enters copper electrodeposition system and carries out electrodeposition, obtains standard cathode copper; After electrodeposition, the heavy copper process of displacement is returned in liquid circulation, to utilize sulfuric acid and concentrating cobalt and nickel; Cobalt in electrolytic solution is enriched to after certain concentration, by equal amount open circuit part, containing liquid after cobalt electrolysis, in the recycle system independently, carries out deep electrolytic decopper(ing);

(4) after decopper(ing), liquid is carried cobalt: the cobalt sulfate solution after electrolysis decopper(ing), enter Co extracting system after removing sulfuric acid, and obtain pure cobalt salt solution, producing cobalt salt product, deep processing makes cobalt oxide product or electrodeposition obtains electrodeposited cobalt.