Copper 4.

Hydrotallurgy
Fathi Habashi
Department of Mining, Metallurgical, and Materials Engineering

Laval University, Quebec City, Canada Fathi.Habashi@arul.ulaval.ca

 The roots of hydrometallurgy may be traced back to the period of alchemists when the transmutation of base metals into gold was their prime occupation. Some of these operations involved wet, i.e., hydrometallurgical methods. For example, when an alchemist dipped a piece of iron into a solution of blue vitriol, i.e., copper sulfate, the iron was immediately covered by a layer of metallic copper. This apparent transmutation of iron into copper is represented in modern terms by the equation: Cu2+ + Fe Cu + Fe2+, but it was not known at that time that blue vitriol contained copper.

In the sixteenth century, the extraction of copper by wet methods received some attention. Heap leaching was practiced in the Harz Mountains area in Germany and in Ro Tinto mines in Spain. In these operations, pyrite containing some copper sulfide minerals was piled in the open air and left for months to the action of rain and air whereby oxidation and dissolution of copper took place. A solution containing copper sulfate was drained from the heap and collected in a basin. Metallic copper was then precipitated from this solution by scrap iron, a process that became known as cementation process.

Hydro- versus pyrometallurgy of copper

In the past fifty years, hydrometallurgists

have been vigorously searching new methods to replace the traditional smelting route for copper production.

Advantages of hydrometallurgy
Sulfur dioxide generation

In the pyrometallurgical treatment of copper sulfide ores, if SO2 formed is in high enough concentration, it must be used for making acid and nearby market for this acid must be found. If the SO2 concentration is too low for making acid, disposal methods must be found. These are available but expensive. As a result, in many cases SO2 is simply emitted to the atmosphere. On the other hand, copper sulfides can be treated by hydrometallurgical methods without generating SO2, thus the independence of sulfuric acid manufacture. In addition elemental sulfur can be recovered; it can be easily stockpiled or transported at low cost.

Material handling

In a copper smelter, the metallurgist is forced to transfer molten slags and matte from one furnace to the other in large, heavy, refractory-lined ladles. Beside the inconvenience and the cost of handling these materials, there is also the inevitable gas emission from them because they are usually saturated with SO2 and during transfer they cool down a little resulting in decreased gas solubility hence the inconvenient working conditions. In hydrometallurgical plants, solutions and slurries are transferred by pipelines without any problem.

Energy consumption

Because of the high temperatures involved in a copper smelter, which is usually around 1200C, the reaction 1200 rates are high but much fuel will be needed. To make a process economical, heat recovery systems are essential. Heat can be readily recovered from hot gases, but rarely from molten material like slag or metal. Thus, a great deal of energy is lost. Further, the equipment needed for heat economy is bulky and expensive. In the hydrometallurgical process, on the other hand, less fuel is needed because of the low temperatures involved (usually 100 - 200C). Heat economy is usually 200 no problem.

Dust formation

Combustion of fossil fuels in furnaces results in the formation of large volume of gases that carry over large amounts of fine dust. This must be recovered to abate pollution and because the dust itself is also a valuable material. The technology of dust recovery is well established but the equipment is bulky and expensive. In hydrometallurgical processes, this is no problem because wet material is usually handled.

Treatment of complex ores Treatment of Cu-Pb-Zn complex ores by pyrometallurgical method is unsuitable because separation is difficult; this is, however most suitable by hydrometallurgy.

Treatment of low-grade ores Treatment of low-grade copper ores in a smelter is unsuitable because of the large amount of energy required to melt the gangue minerals. On the other hand it is especially suitable by hydrometallurgy if a selective leaching agent is used.

Economics

The economics of a copper smelter is usually suitable for large scale operations and this requires a large capital investment. On the other hand, hydrometallurgical processes are suitable for small scale operations that can be increased when needed and therefore requires low capital investment. Hydrometallurgy may also fit a special need that cannot otherwise be met.

Disposal of residues

It is true that residue of a copper smelter is coarse and harmless. For example, slags, which are a silicate phase, can slags, be stored in piles exposed to air and rain without the danger of dissolution and contaminating the streams. They are just unacceptable from the esthetic point of view. On the other hand most residues of hydrometallurgical processes are finely divided solids. If they are dry, they create create dust problems when the wind blows and when wet they will gradually release metal ions in solution that will contaminate the environment. However, disposal of waste solution in hydrometallurgical operations is less troublesome than disposal of gases in pyrometallurgy. Even in a pyrometallurgy. pyrometallurgical process water-scrubbing of a gas will watereventually have a water disposal problem.

LEACHING
Methods and equipment The method used for leaching an ore depends on the grade of the ore and the ease with which the mineral values are dissolved in a particular reagent.

Leaching in place
This method is also known as leaching in situ or solution mining. The ore is simply shattered and leached in place over long periods of time of because it is usually too low in grade to justify mining and transportation expenses. The process involves spraying the acid on the exposed ore body or or injecting it when the ore body is underground, then collecting the the pregnant solution from below. Because of its success, the method has been used for high-grade highcopper oxide ores as well, e.g., at Miami, Arizona. Dilute sulfuric acid sulfuric is used for leaching copper oxide ores. When copper sulfide minerals minerals are also present, these are solubilized by the combined action of air and water. The presence of pyrite enhances the leaching because of its oxidation oxidation and the formation of sulfuric acid and ferric sulfate. In this case the case oxidation reactions are exothermic and the heat generated facilitates facilitates continued oxidation.

Injection technique
In this method the leaching agent is injected in the ore deposit by means of vertical perforated pipes arranged in a regular pattern. For a group of injection pipes there is a recovery well with an underground pump to collect and pump the pregnant solution to the surface. The basic criteria for leaching an underground deposit is that the ore body must be enclosed between impermeable strata that will prevent the loss of solution or contaminating underground water and it must be permeable to the leaching solution

Production wells Producti o line n

Inj e ion ct line

Monitor well

Subsoil Im permeable cl ay

Ce ment

Up per aquifer

Im permeable cl ay

Pump Casing

Ur anium bearing aquifer Im permeable cl ay

Screen

Heap or dump leaching

In this method an area is first cleared from all vegetation then leveled at a slight inclination, compacted, and covered with an asphalt layer or a layer flexible plastic sheet. The crushed ore is then transported from the mine to the prepared site by dump trucks or mobile conveyors to a level of 10100 m high. 10 The leaching agent is then sprayed at the top of the dump through through which it percolates and the leach solution is collected in streams at the streams bottom. When the material is fully leached, the dump is either abandoned or loaded on trucks for disposal and the site re-used for leaching another rebatch. Main problems in operating a heap are the plugging with fine fine clays, ferric hydroxide or basic sulfate, evaporation losses, leakage of leakage solution at the bottom of the heap, and channelling. channelling. The process was applied for leaching stock piled waste rock containing containing small amounts of copper too small to be recovered by any other means. means. It was so economical that many heaps of low-grade copper ores were lowconstructed and leaching applied.

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Percolation or vat leaching

This process is suited to cases where the material is porous and sandy, and is inapplicable to material that tends to pack into impervious masses. Regularity in the size of the particles rather than their actual size is the chief factor governing good percolation. The idea is that where the particles are of unequal size, the small ones pack in the openings between the larger ones, thereby clogging the channels. Extraction becomes slow, and channelling of solutions through the bed takes place. The method is therefore unsatisfactory if much slime is present.

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 The material to be leached is placed in a tank equipped with a false bottom covered with a filtering medium. The leach solution is added at the top of the tank and is allowed to percolate through the material. These tanks are usually arranged so that a countercurrent system is employed and thus a continuous operation is achieved; the new solids being added to the last tank and the weak liquid to the first and pumped successively from one tank to another till it reaches the last tank. Tanks having a capacity of 12 000 tons of ore are in common use. When leaching is finished, the tanks are emptied by mechanical shovels, and a new batch is introduced. Leaching time varies from 2 to 4 days. Its advantages are minimum reagent consumption, the production of high-grade pregnant solution, and highelimination of the use of expensive thickeners or filters.

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 Vat-leaching of copper oxide ore was improved by adopting the so-called Thin Layer Leaching. In this method, the finely crushed moistened ore is sprayed with a limited amount of concentrated H2SO4 in a rotating drum to permit agglomeration. The agglomerated material is then charged in the vat and left to cure for some time. This is then followed by normal heap-leaching by spraying dilute acid on the top.

Agitation or pulp leaching

In this method, the leaching agent is added to the finely ground raw material such that the mixture forms a pulp that has to be agitated continuously to prevent the solids from settling, and to terminate the leaching process in the shortest possible time. It is generally used under the following conditions: - Raw material is of moderate or high grade. - The metal values are of fine grain size and disseminated in the host rock therefore extensive crushing and grinding are necessary before leaching to expose the maximum surface of the solids to the solution. - The metal values are difficult to dissolve and that is why intensive agitation is needed to increase the rate.

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 The equipment used are numerous and expensive, and high recoveries are mandatory. Leaching conditions may be mild using dilute solutions at ambient conditions or it may be severe using concentrated solutions and at high temperature and pressure. Agitation is usually accomplished mechanically by a motor-driven impellers

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 Pulp leaching at high pressure is used for leaching copper sulphide concentrates and the high pressure necessitates the use of pressure reactors (or autoclaves). Air or oxygen must be added as oxidizing agent. The use of oxygen instead of air is more advantageous because for the same oxygen requirement the total pressure in the autoclave is low, and as a result the autoclave design will be less demanding, or decreased in size.

Horizontal autoclaves
They are divided in the inside by partitions. In each chamber is an electrically driven turbine mixer from the top. The body of the autoclave can be lined with lead, with alloy steel, or with rubber. Feed slurry is pumped into one end of the autoclave and cascades from one compartment to the next. The average degree of filling is 6570% static to allow sufficient disengagement space for the exhaust gases and to reduce the possibility of plugging the relief valve nozzle. Horizontal autoclaves are usually designed with four compartments, since too much volume will be lost in providing the static head required for the flow of slurry from one compartment to the next.

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Baking process

This process is supplied when agitation leaching becomes impossible because the ore slurry solidifies to a thick mass in the early stages of leaching. Consequently the solidified mixture is allowed to react without agitation at a temperature around 200C hence the 200 term baking is used. The reaction may be conducted in pugmills. These are horizontal shallow tanks equipped with pugmills. numerous rotating blades that are capable to move a thick paste or cut their way through a solidified cake. This method was suggested for the treatment of copper sulfide concentrates with concentrated H2SO4 but was abandoned. The pugmills may be heated by a steam jacket.

A pugmill

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Leaching processes

Metallic copper Copper oxide ores Copper sulfides Bioleaching of copper sulfides

Leaching of metallic copper

Metallic copper may be obtained from the following sources: Native copper. In Lake Superior district, native copper was found in abundance. At one time, the ore was smelted and the tailings from this process contained 0.4% metallic copper. They were leached by ammonia. Reduction of oxide or silicate ores. Low-grade copper oxide Lowores that are not economically amenable to acid leaching are first reduced to metallic copper then leached with ammonia. This was the case in South Africa where the Bwana MKubwa Company reduced the oxide ore with CO and leached the resultant metallic copper with ammonia. An oxide ore deposit in Australia is treated in a similar way. way.

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 Metallic copper can be leached by dilute sulfuric acid in presence of oxygen but this is not economically possible if gangue minerals such as limestone, dolomite, or iron oxide are present in the ore since they are acid consuming. Under such circumstances leaching by ammonia in presence of oxygen is used since soluble ammine complexes [Cu(NH3)n]2+ are formed where n is a variable number that depends mainly on the free ammonia concentration in the solution.

The dissociation of ammonium hydroxide is small: NH3 + H2O NH4+ + OH and NH3 can be considered as the active complexing agent. The dissolution reaction can be represented by the equations: Oxidation: Cu Cu2+ + 2e Complex formation: Cu2+ + nNH3 [Cu(NH3)n]2+ Reduction: O2 + H2O + 2e 2OH The overall reaction: Cu + nNH3 + O2 + H2O [Cu(NH3)n]2+ + 2OH

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 The rate of dissolution of copper depends on the oxygen partial pressure when the ammonia concentration is low, and is a function of function the ammonia concentration when the oxygen partial pressure is high. high. Ammonium ion alone does not dissolve these metals, but when added added to ammonium hydroxide solution, it increases the rate of dissolution as dissolution a result of inhibiting the ionization of ammonia. For this reason a mixture of ammonium hydroxide and ammonium carbonate is usually used. Ammonium carbonate is selected because it because decomposes readily when the solution is boiled to recover the ammonia, and also because the carbonate ion is present any way in the in solution as a result of contact with air. The process is also known as the Caron Process after its inventor inventor originally for leaching nickel from laterites. laterites.

Leaching is carried out under atmospheric pressure, but the tanks are closed to prevent the loss of ammonia. After filtering the gangue minerals, the solution is boiled to distill off excess ammonia and to decompose the ammine complex to precipitate a hydroxide or a basic carbonate: [Cu(NH3)n]2+ + 2 H2O Cu(OH)2 + nNH3 2[Cu(NH3)n]2+ + 2OH + CO32 Cu(OH)2CuCO3 + 2nNH3

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 The precipitate is filtered, washed, and calcined to yield a high-grade oxide containing 7578 % metal. The gases evolved are absorbed in water and recycled. Also, ammonia retained in the gangue residue is recovered by steam stripping. Instead of calcination, the precipitated basic carbonate is sometimes dissolved in ammonium sulfate solution and the pure metal is precipitated by hydrogen under pressure.

Leaching of copper oxide ores

The main copper ores are sulfides, oxides, or a mixture of sulfides and oxides. The last type is the worlds most extensive copper ore world bodies; they are disseminated, i.e., they are composed of minute grains of copper minerals in large bodies of rock. They contain on the average 2 % Cu and known as porphyry ores. The sulfideoxide ore is usually separated by flotation sulfide into two fractions: a high-grade sulfide concentrate and a highlow-grade oxide fraction. lowWhile the sulfide concentrate is usually treated by pyrometallurgical methods, the oxide fraction is treated by hydrometallurgical methods; copper sulfides are insoluble in dilute acid.

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Sulfuric acid process

Sulfuric acid is the usual leaching agent for oxidized copper ores; copper is recovered from the leach solution by solvent extraction followed by electrolysis, With the exception of cuprite, all copper oxide minerals dissolve to give CuSO4. Copper in cuprite is in the cuprous state; it dissolves according to:

Cu2O + 2H+ Cu2+ + Cu + H2O i.e., half the copper in the mineral dissolves and the other half precipitates as metallic copper, a typical disproportionation reaction of Cu+ ion. In presence of oxidizing agents (air or ferric ion), cuprite dissolves completely: Cu2O + 4H+ + 1/2O2 2Cu2+ + 2H2O

Ammonium hydroxide process

Ammonia is used when the gangue is acid consuming. Dissolution takes place according to:

CuO + 2NH4+ + 3NH3 [Cu(NH3)4]2+ + H2O 2CuCO3Cu(OH)2 + 12NH3 3[Cu(NH3)4]2+ + 2CO32 + 2OH After filtering off the gangue, the solution is boiled so that the above reactions are reversed. Ammonia is then absorbed from the gas phase and the basic carbonate recovered by filtration, which is then calcined to CuO. The process was in operation at Kennecott, Alaska, in the period 1916 to 1931; operation discontinued because the mine exhausted. Similar operation is presently in Australia.

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Copper from manganese nodules

These nodules may be processes only for the recovery of copper, nickel, and cobalt, i.e., by selective leaching. The nodules may, therefore, be treated in practically the same way as copper oxide ores, i.e., leaching agents are selected to dissolve copper, nickel, and cobalt but not MnO2 and Fe2O3. Any leaching agent that solubilizes MnO2 will also solubilize copper, nickel, and cobalt. Manganese dioxide is insoluble in dilute H2SO4, but when reduced to MnO, it readily dissolves to give a solution of MnSO4: MnO + 2H+ Mn2+ + H2O Since manganese is recovered from this solution by electrolysis, the spent electrolyte can be recycled for leaching. Manganese dioxide can also be solubilized in dilute H2SO4 but only in presence of a reducing agent such as sulfur dioxide, coal, or oxalic acid.

The oxidationreduction steps are as follows: Fe2+ Fe3+ + e SO2 + 2H2O H2SO3 + H2O SO42 + 4H+ + 2e C + 2H2O CO2 + 4H+ + 4e (COO)22 2CO2 + 2e MnO2 reacts according to: MnO2 + 4H+ + 2e Mn2+ + 2H2O Because of the insolubility of MnO2 in dilute H2SO4, this reagent has been suggested for treating manganese nodules to selectively extract copper, nickel, and cobalt. However, the process is slow and few days are needed with intensive agitation.

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Manganese dioxide dissolves in hydrochloric acid liberating chlorine: 2Cl Cl2 + 2e MnO2 + 4H+ + 2e Mn2+ + 2H2O The large proportion of acid used per mole MnO2 necessitates its regeneration from the chlorine as well as from the aqueous solutions. Although this technology may be established for the treatment of manganese nodules yet it becomes costly because of the large number of circuits involved. Copper, nickel, cobalt, and iron oxides dissolve readily in hydrochloric acid, forming metal chlorides.

Leaching of copper sulfides

Sulfide

minerals are insoluble in water even at high temperature. They can be solubilized, however, by leaching under oxidizing conditions. Elemental sulfur usually forms but because of its instability in neutral or basic media it oxidizes to sulfates. In acid medium, however, there is a narrow region where elemental sulfur can form.

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 Valid in the temperature region 25 to

150C. Above 150C, the narrow stability region of elemental sulfur disappears and no sulfur can form.

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When solid elemental sulfur is liberated during leaching it is usually usually porous and does not form an obstacle. However, when it melts it usually forms a viscous layer around the mineral particles and retards retards the rate of leaching. This can be solved by adding a surface active agent such as Lignosol during leaching which helps the sulfur globules to coalesce thus they do not cover the mineral particles. Finely crushed coal, when added in small amounts (about 4 kg/ton concentrate), was found to prevent the agglomeration phenomenon. In the elemental form, sulfur can be readily stock-piled, shipped long stockdistances, or transformed into H2SO4 or SO2 when needed. It is thus evident that leaching methods resulting in elemental sulfur formation formation are more attractive than the others. Since elemental sulfur may be a product of leaching, its physical and physical chemical properties will be briefly reviewed.

Elemental sulfur is stable in acid medium but oxidizes slowly in water at high temperature (above 150C) and oxygen pressure to form sulfuric acid: S + 3/2O2 + H2O H2SO4 In basic medium, oxidation takes place in stages whereby, thiosulfate and other sulfur compounds are formed: 2S + O2 + 2OH S2O32 + H2O These finally oxidize to sulfate as follows: S2O32 + 2O2 + 2OH 2SO42 + H2O

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 Other oxidizing agents such as HNO3 and aqueous chlorine solutions react readily with elemental sulfur even at room temperature transforming it into sulfate: S + 2HNO3 H2SO4 + 2NO S + 3Cl2 + 4H2O H2SO4 + 6HCl Concentrated H2SO4 above 200C also attacks elemental sulfur: S + 2H2SO4 3SO2 + 2H2O

Oxidation products of sulfides in neutral or alkaline medium S2O32 SnO62 S2O62 S2O42 SO22 Thiosulfate Polythionate Dithionate Dithionite (or hyposulfite) Sulfoxylate

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Leaching in Presence of Oxidizing Agents Most commonly used oxidizing agents are: Oxygen, ferric ion, nitric acid, concentrated H2SO4, chlorine water, and sodium hypochlorite. Leaching of sulfides in presence of oxidizing agents may be chemical or electrochemical. Chemical processes may lead to the formation of sulfates or elemental sulfur.

Sulfates. These processes usually take place in neutral medium. They are slow at ambient conditions, but rapid at high temperature:
MS M2+ + S2 S2 + 2O2 SO42

Elemental sulfur. This is usually the case for acidsoluble sulfides, e.g., ferrous sulfide:
FeS Fe2+ + S2 S2 + 2H+ H2S H2S + 1/2O2 S + H2O

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 Electrochemical processes usually take place with acid-insoluble sulfides and lead to the initial formation of elemental sulfur which may be oxidized further depending on the leaching conditions (temperature, pH, and electrode potential of the oxidizing agent). The electrochemical process may be represented by: Oxidation: MS M2+ + S + 2e Reduction: Oxidizing agent + ne Reduced species

In neutral medium: 1/2O2 + H2O + 2e 2OH In acid medium: 1/2O2 + 2H+ + 2e H2O Fe3+ + e Fe2+ Oxygen as an oxidizing agent has the advantage that it does not need to be regenerated, and does not result in a foreign ion that contaminates contaminates the product. For example, when FeCl3 is used as a leaching agent, it is reduced to FeCl2 during the course of reaction and has to be separated and oxidized back for recycle. The aqueous oxidation of sulfides by oxygen at ambient conditions is a conditions slow process; it is greatly accelerated if conducted at high temperature temperature and high oxygen pressure. Oxygen can be used in combination with water, dilute acid (usually (usually H2SO4), and ammonium hydroxide. The latter case is used only for leaching copper, nickel, and cobalt since these metals are capable of capable forming ammine complexes in solution.

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Oxygen and water

MS + 2O2(aq) MSO4 The reaction takes place at a reasonable rate only at 200C and an oxygen pressure of 4000 kPa; the reaction is complete in 23 hours.

Oxygen and ammonia

The process has been used successfully since 1953 for the treatment of NiCuCo sulfide concentrate on large scale Ni Cu at the Sherritt-Gordon Plant in Fort Saskatchewan, SherrittCanada. It has minimum corrosion problems and any pyrite present will not be attacked. The overall reaction is: MS + nNH3 + 2O2 [M(NH3)n]2+ + SO42 Oxidation of sulfides in a basic medium takes place in several stages and any of the intermediate compounds: Polysulfide, thiosulfate, etc., may be present in the leach solution. The leach solution is also free from iron, since hydrated ferric oxide is precipitated. In this process all the sulfur is oxidized and recovered as ammonium sulfate and marketed as fertilizer.

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Oxygen and acid

This method is usually conducted at 115150C and about 2000 kPa oxygen pressure so that elemental sulfur can be recovered in good yield. For chalcopyrite the reaction is:
2CuFeS2 + 4H+ + 5/2O2 2Cu2+ + 2FeOOH + 4S + H2O However, industrial operations are also conducted at high temperature where no elemental sulfur is formed. The method is most suitable when the metal values in the leach solution can be recovered by electrolysis or precipitation by hydrogen so that the acid generated during the recovery step can be recycled to the leaching step. Because of the high temperature and the acid medium involved, acid-resisting materials of construction must be used.

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Ferric salts

Leaching of sulfides in acid medium in presence of ferric ion takes place readily with liberation of elemental sulfur. The disadvantage of this route is the formation of ferrous ion, which requires separation and re-oxidation to ferric for recycle. This method has found the following applications: Leaching of copper sulfides in heaps or in situ. The dissolution of cuprous sulfide takes place in steps as follows: 5Cu2S + 2Fe3+ Cu9S5 + Cu2+ + 2Fe2+ Cu9S5 + 8Fe3+ 5CuS + 4Cu2+ + 8Fe2+ CuS + 2Fe3+ Cu2+ + 2Fe2+ + S However, due to the presence of microorganisms in the heaps elemental sulfur is oxidized further to sulfuric acid.

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Purification of molybdenite concentrates Copper sulfide impurities are removed from MoS2 by boiling with FeCl3 solutions. Leaching of chalcopyrite concentrates.
Leaching of chalcopyrite with ferric ion takes place readily at the boiling point: CuFeS2 + 3Fe3+ Cu+ + 4Fe2+ + 2S Copper is solubilized in the cuprous form, but in presence of excess Fe3+ the cuprous is oxidized to cupric: CuFeS2 + 4Fe3+ Cu2+ + 5Fe2+ + 2S Although CuCl has a low solubility in water, yet, due to the presence of Fe2+ ion in the leach solution it is completely soluble. The fact that CuCl can be obtained instead of CuCl2 under carefully controlled conditions is of importance in the subsequent recovery step, since Cu+ ion is easier to reduce than Cu2+ ion, e.g., by precipitation with iron: 2Cu+ + Fe 2Cu + Fe2+ FeCl2 + 1/2Cl2(aq) FeCl Ferrous chloride can be partly crystallized and treated further for HCl regeneration while the remainder in solution is oxidized to FeCl3 for recycle. Oxidation of FeCl2 is usually conducted by chlorine.

Concentrated H2SO4

Leaching of chalcopyrite by concentrated H2SO4 has been developed to a large scale pilot plant known as the Treadwell Process. Below 150C, no reaction. Between 150C and 250C, there is a formation of elemental sulfur, CuSO4, and FeSO4. Since chalcopyrite (Cu2SFe2S3) contains Cu+ and Fe3+ ions in the crystal structure, the formation of CuSO4 and FeSO4 (and not Cu2SO4 and Fe2(SO4)3) must be due to an oxidation reduction reaction that takes place in the solid state during heating:

Cu+ + Fe3+ Cu2+ + Fe2+

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This can be represented by: Cu2SFe2S3 2(CuSFeS) CuSFeS Cu2+ + Fe2+ + 2S + 4e 4H+ + SO42 + 2e SO2 + 2H2O Overall reaction: CuFeS2 + 8H+ + 2SO42 Cu2+ + Fe2+ + 2S + 2SO2 + 4H2O

Above 250C, both elemental sulfur and ferrous ion are oxidized: - Oxidation of elemental sulfur by concentrated H2SO4:H2SO4 SO2 + 1/2O2 + H2O S + O2 SO2 2H2SO4 + S 3SO2 + 2H2O - Oxidation of ferrous ion by concentrated H2SO4: Fe2+ Fe3+ + e 4H+ + SO42 + 2e SO2 + 2H2O Fe2+ + 4H+ + SO42 2Fe3+ + SO2 + 2H2O Overall reaction:
or

2CuFeS2 + 13H2SO4 + 10H+ 2Cu2+ + 2Fe3+ + 17SO2 + 18H2O

2CuFeS2 + 18H2SO4 2CuSO4 + Fe2(SO4)2 + 17SO2 + 18H2O

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It is obvious that the optimal reaction conditions are between 150 and 250C. The residue containing the anhydrous sulfates, elemental sulfur, and the gangue minerals, is leached with water to solubilize the sulfates, precipitate CuCN by HCN, crystallize FeSO4nH2O which is then decomposed to recover the SO3 for recycle as H2SO4. The process has the advantage of forming elemental sulfur, but the disadvantage of solubilizing iron and the necessity of regenerating H2SO4 by decomposing the ferrous sulfate.

Chlorine and hypochlorite

CuS Cu2+ + S + 2e Cl2 + 2e 2Cl At high concentrations, long contact time, or high temperature, elemental sulfur oxidizes to sulfate. The process is applied industrially for the treatment of Ni3S2Cu2S (white metal) at the Falconbridge refinery in Sudbury. Both nickel and copper are solubilized, then separation is effected by adding fresh white metal to solubilize more nickel and precipitate the copper: Ni3S2 + 3Cu2+ 3Ni2+ + CuS + Cu2S When nickel chloride solutions are electrolyzed to recover metallic nickel, chlorine is generated at the anode which is collected and recycled to the leaching step.
Aqueous chlorine solutions solubilize copper sulfides at ambient conditions with formation of elemental sulfur:

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Bioleaching of copper sulfides

Certain microorganisms known as Thiobacillus thiooxidans and Thiobacillus ferrooxidans isolated from mine water and others isolated from sulfur-bearing hot springs are capable of accelerating the rate of oxidation of sulfide minerals. These bacteria, known as autotrophic bacteria can also accelerate the oxidation of elemental sulfur and ferrous ion. They are minute, unicellular microscopic organisms 0.52 mm in size that reproduce by binary fission. Since they utilize oxygen for growth, they are classified as aerobic bacteria. In industrial leaching operation where the continuous flow of leach solution provides nutrient and a balanced environment, the microorganisms multiply following the logarithmic law: n = n0ekt

A leach solution in a heap leaching operation may contain as many as 10 million microorganisms per mL

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They must have oxygen to carry out their function, i.e., the oxidation of mineral substances with release of energy which is necessary for their growth. They utilize CO2 as the principal source of carbon required for the synthesis of organic compounds composing the cell. They absorb certain nutrient from solution, e.g., PO43 ions that are necessary for their metabolic function. They have resistance to high concentrations of metal ions in solution which are usually toxic to most other forms of life. They adapt to live and grow in strongly acidic environments (pH 1.53). 1.5

They are destroyed by light, particularly ultraviolet light. Their maximum activity for Thiobacillus ferrooxidans occurs at 35C while for those isolated from sulfur-bearing hot springs (the thermophilic bacteria), the temperature may be as high as 85C. Below these temperatures they are dormant while above, they are destroyed. They manufacture enzymes and with their aid they catalyze the oxidation process:
CuS(s) Cu2+(aq) + S2(aq) S2 + 2O2 SO42 7/ O + H O Fe2+ + 2SO 2 + 2H+ FeS2 + 2 2 2 4

The adherence of the microorganisms on the sulfide surface makes possible the rapid oxidation of S2 ions liberated by the mineral and catalyzed by the enzymes.

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 Leaching

tanks. The process is cheap but slow and may generate excessive amounts of sulfuric acid and ferrous sulfate that must be neutralized before disposal.

is usually conducted in agitated

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SOLVENT EXTRACTION OF COPPER Extraction data may be represented in two ways: Percentage extraction as a function of a certain variable like acid concentration, pH, etc. In form of extraction isotherms. The extraction isotherms are the plot of the concentration of the metal ion in aqueous phase versus its concentration in the organic phase when the two phases are in equilibrium. Such a plot is useful, since at each point it directly displays the concentrations in both phases and consequently the distribution coefficients can be evaluated.

Extraction isotherm of copper from a sulfate solution

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Extraction isotherms may be constructed in two ways:

An aqueous phase of a certain volume containing a known amount of metal ion is contacted with an organic phase of a certain volume until equilibrium is reached; the concentration of metal ions in both phases is then determined. The process is repeated at least five times with variable volumes of the organic phase. The process is repeated as in the previous case but keeping the organicaqueous ratio constant and varying the initial metal ion concentration in the aqueous phase.

McCabeThiele diagram
With

the addition of an operating line based on the volume ratio of the two phases, the extraction isotherm provides a McCabe Thiele diagram for a stage-wise of extraction in a countercurrent system.

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A McCabeThiele diagram is useful for estimating the number of theoretical stages required to obtain specified results in a solvent extraction system.

Extractants
Oximes, i.e., compounds containing the group =N OH, have been used for many years in analytical chemistry as precipitants for metals. The a-hydroxyoximes are well known as specific for precipitating copper, e.g.:
H CC HO N OH
-Benzoinoxime

H C=NOH OH
Salicylaldoxime

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 The hydroxyoxime, 5,8diethyl-7-hydroxy-6dodecanone oxime, is used in extracting copper from leach solutions, under the trade name LIX-63 introduced to the market by General Mills Corporation, now Henkel Corporation.

H RCCR O N H OH
LIX 63

R is CHC4H9 C 2 H5

42

 Hydroxybenzophenone

oximes are more efficient than the hydroxyoximes, also introduced by Henkel. Other groups of similar structure were introduced by Imperial Chemical Industries (Acorga extractants), and by Shell (SME group). The commercial products are usually mixtures and not pure compounds.

43

Trade name LIX-64 (Henkel)

Chemical name 2-Hydroxy-5dodecylbenzophenone oxime

C N OH

Formula
C12 H25

OH

+ LIX 63

LIX-64N LIX-65N (Henkel)

LIX 65N + 1% by volume LIX 63 2-Hydroxy-5nonylbenzophenone oxime

C N OH OH

C9 H19

LIX-70 (Henkel)

2-Hydroxy-3-chloro-5nonylbenzophenone oxime
C N OH

C9 H19

OH Cl

+ LIX 63

LIX-71 LIX-73 LIX-860 (Henkel)

LIX 70 + LIX 65N LIX 70 + LIX 65N + LIX 63 5-Dodecylsalicyl aldoxime

HC N OH OH

C12H25

Acorga P50 (ICI)

5-Nonyl salicylaldoxime
HC N OH OH

C9H19

SME 529 (Shell)

2-Hydroxy-5-nonyl acetophenone oxime

H3CC N OH OH

C9H19

44

Quinolines, e.g., 8-Hydroxyquinoline, also known as oxine, is a colorless solid, m.p. 75 C, slightly soluble in water:

N OH
8-Hydroxyquinoli

Keelex-100 is -alkenyl-8-hydroxyquinoline:
CH H CH3 H H 3 H3CC CC CC CH H CH3 H CH OH 3 CH 2 N

It is marketed by Ashland Chemicals for the extraction of copper. It has a copper loading capacity of 0.7 g Cu per 1 volume percent. Keelex-120 is composed of 20 % volume of Keelex-100 in para-nonyl phenol.

Extraction of copper from H2SO4 by Keelex at organic/aqueous ratio 1/1

20%Keelex + 10% nonylphenol, o 20% Keelex + 20% nonylphenol

45

Extraction of copper by Keelex from queous phase containing 33.6 g/L Cu and 13.5 g/L H2SO4

20%Keelex + 10% nonylphenol, o 20% Keelex + 10% iso-decanol

Mechanism of Extraction
The chemical process in which copper ions interact with the extractant to form an organometallic complex soluble in the organic phase at the same time an ion from the extractant is transferred stoichiometrically to the aqueous phase:

N OH
8-Hydroxyquinoline

N Cu N

8-Hydroxyquinoline copper complex

46

Cu2+ + H2X CuX + 2H+ Where H2X represents the extractant. It can be seen that one copper ion is exchanged for two hydrogen ions. In stripping, the reaction is reversed by adding concentrated acid. Extraction is usually fast at room temperature, equilibrium being achieved within a few seconds. Extraction of copper ions from aqueous solutions is a slightly exothermic process. Consequently, the distribution ratio decreases with increasing temperature, but the rate of extraction increases with increasing temperature.

The Organic Phase

A certain weight of an extractant has a limited capacity for extracting copper ion from solution. When this limit is reached, the extractant is then saturated with copper and is said to have reached its maximum loading. Maximum loading varies widely from one extractant to the other. The organic phase increases in viscosity with increasing metal ion loading and sometimes it is necessary to operate at a solvent loading below the maximum loading of the extractant. Saturation concentration can be determined by contacting the organic phase several times with fresh aliquots of the aqueous phase until the amount of metal in the organic phase becomes constant. Sometimes the extracting power of a mixture of extractants exceeds the sum of the extracting powers of the components. This phenomenon is known as synergism.

47

Role of diluents
The

diluents themselves are unable to extract copper ions from the aqueous phase, but they greatly affect the extraction behavior of the solvent. The reason is the interaction that may take place between the diluent and the extractant. Further, some diluents favor the polymerization of the extractants while others do not.

Third-phase formation
Third-phase formation depends on the diluent. The addition of a long-chain alcohol such as ndecanol overcomes the difficulty of third phase formation. The amount of decanol required can be determined by equilibrating the organic phase with the aqueous phase and allowing it to settle, the two organic phases are separated and titrated with the alcohol till a single phase is formed. Usually, about 3% alcohol is sufficient to prevent third-phase formation.

48

The Aqueous Phase

Extraction by cationic solvents is greatly affected by the pH of the aqueous phase since H+ ions are taking part in the process. Decreasing the hydrogen ion concentration shifts the equilibrium from left to right thus favoring the extraction. In many other cases, the variation of distribution coefficient with pH may be due to the effect of the latter on the stability of the complexes in the aqueous phase. During the extraction of metal ions by organic solvents, it is found that most inorganic acids are extracted as well. Water is also co-extracted.

Equipment
Only clear filtered solutions can be extracted by organic solvents. Mixer settlers Columns

49

Mixer settlers

These are composed of a mixing chamber where the aqueous and organic phases are mixed together by a rotating impeller, and a settling chamber where the mixed phases are given enough time to separate. Each such unit composes a stage. The apparatus is very efficient but its principal disadvantage is the large space required per stage. Usually many stages are used (3 to 5) and are operated in counter-current in the extraction as well as in the stripping countersteps. Sometimes, a washing step is inserted between extraction and stripping to remove loosely bound metal ions.

50

Columns

The packed column consists of a vertical tower packed with ceramic or plastic rings for increasing the surface area of contact between the aqueous and organic phases. Pulse column is that with screen partitions instead of packing. Efficiency of contact may be improved by introducing a pulsating action in the column. In this column, the two phases are dispersed in each other by pulsating action through the screens. The pulsating action is supplied by leading a pulse leg from the bottom of the column to a reciprocating pump. The pulsating action forces the two phases through the holes in the plates, forming bubbles. They rise (or fall) to the next plate, where they coalesce to await the next pulse. In both cases the organic phase is introduced at the bottom and the aqueous phase near the top. Separation of the phases takes place at the top.

Solve nt outlet Aqueous inlet

Solvent out let Aqueous inle t

Interface

Perf orated plates

Piston Solvent inlet Solv ent inlet Interface

Aqueous outlet

Aqueous out let

51

Applications
The recovery of copper from dump leaching solutions containing around 1 g/L Cu was usually achieved by displacing the copper ion by scrap iron the cementation process. Solvent extraction with subsequent electrodeposition of a marketable product offered a convenient method of recovery. There is the added advantage that acid is liberated in the recovery step and can therefore be used as a stripping solution in the extraction process. Extractants commonly used are LIX-64 and Keelex-100.

52

RECOVERY FROM LEACH SOLUTION

53

Crystallization
Copper sulfate, a byproduct of electrolytic copper refining is used in agriculture as a herbicide.

Solubility of copper sulfate increases with increased temperature and decreases with increased acid concentration

54

Hydrolytic precipitation
Metal ions in aqueous solution are solvated, i.e., they are bound to a number of H2O molecules so oriented that the negative end of water dipole is directed toward the positively charged metal ion.

55

 The loss of H+ from the bound water molecules takes place readily. That is why copper sulfate solutions are acidic: [Cu(H2O)6]2+ [Cu(H2O)5OH]+ + H+ or simply: Cu2+ + H2O CuOH+ + H+

Hydrolysis continues until an uncharged species is formed:

CuOH+ + H2O Cu(OH)2 + H+ In this case the ionic forces keeping the ions apart are thus removed, and therefore precipitation takes place. It is evident that precipitation of a hydrolytic product can be favored by adding OH ions that react with H+ ions formed thus shifting the equilibrium to the right. Hydrolytic reactions may lead to the precipitation of oxides, hydrated oxides, hydroxides, or hydroxy salts depending on temperature, and concentration of solution. High temperature increases greatly the rate of hydrolysis.

56

 Cuprous

chloride when reacted with calcium hydroxide precipitates cuprous oxide due to hydrolysis: CuCl(s) Cu+ + Cl Cu+ + OH CuOH 2CuOH Cu2O + H2O The process was used on a commercial scale in Germany in connection of the recovery of copper from pyrite cinder.

Under certain conditions of pH, temperature, and concentration of metal ion in solution, hydroxy or basic salts of copper are obtained instead of hydroxides. For example, pale blue hydroxy copper sulfate is precipitated according to: 2Cu2+ + SO42 + 2H2O Cu(OH)2CuSO4 + 2H+ Similarly, the hydroxy chlorides and hydroxy carbonates: 2Cu2+ + 2Cl + 2H2O Cu(OH)2CuCl2 + 2H+ 2Cu2+ + CO32 + 2H2O Cu(OH)2CuCO3 + 2H+

57

 Hydroxy carbonates are also precipitated

when a copper ammine complex in an ammoniacal ammonium carbonate solution is heated to distill off NH3: 2[Cu(NH3)n]2+ + 4OH + (NH4)2CO3 Cu(OH)2CuCO3 + 2(n+1)NH3 + 2H2O

Hydroxy salts of copper

Carbonate Sulfate Chloride
Cu(OH)2CuCO3 Cu(OH)2CuSO4 3Cu(OH)2CuCl2

58

Ionic precipitation
Ionic precipitation is based on the fact that
when a reagent is added to a solution containing metal ions, a compound is formed whose solubility is very low under these conditions that precipitation takes place immediately.

Chlorides

The solubility of cuprous chloride in water is low, about 0.062 g/L, and this property is sometimes utilized to separate copper from leach solutions: Cu+ + Cl CuCl(ppt.) When copper is present as Cu2+ ions in leach solutions, reduction to Cu+ is necessary before precipitation. This is achieved by heating with SO2 or metallic copper in absence of air: 2Cu2+ + SO2 + 2H2O 2Cu+ + 4H+ + SO42 Cu2+ + Cu 2Cu+ Precipitation of cuprous chloride is practiced at Mantos Blancos in Chile since copper ore there contains appreciable amounts of chlorides and at Duisburger Kupferhtte in Germany for copper recovery from pyrite cinder leach solution.

59

Cyanides

In acidic or neutral medium, cuprous cyanide is practically the only cyanide insoluble in water. Consequently, processes have been suggested for copper recovery from a leach solution by precipitation as cyanide, as follows: The low-grade ore is leached with sulfuric acid, SO2 being added to the leach solution to reduce cupric to cuprous sulfate; then HCN is passed through the solution to precipitate cuprous cyanide:
HCN H+ + CN Cu+ + CN CuCN

The low-grade ore is leached by sodium cyanide solution:

Cu2O + 6CN + H2O 2[Cu(CN)3]2 + 2OH
[Cu(CN)3]2 + 2H+ CuCN + 2HCN

On acidifying the leach solution with dilute sulfuric acid, CuCN is precipitated, with simultaneous generation of HCN for recycle: There is interference, however, in this case due to traces of iron which may co-precipitate as copper ferrocyanide, Cu2[Fe(CN)6], and contaminate the product. This can be minimized by careful pH adjustment to isolate the complex cyanide prior to precipitating CuCN. Cuprous cyanide is a white, easily filterable precipitate. Both methods are based on processing CuCN to metallic copper by reduction with hydrogen at about 400C whereby HCN is regenerated for recycle:
2CuCN + H2 2Cu + 2HCN

60

Sulfides
Copper is sometimes precipitated from leach solutions as sulfide when its concentration in the solution is low. Hydrogen sulfide, ammonium sulfide, and sodium sulfide are the most common precipitating agents used for this purpose.

Hydrogen sulfide is a poisonous and corrosive gas. In certain concentrations, it explodes in air. In precipitating metal sulfides by H2S, the following points should be taken into consideration. Acid is generated during precipitation:
M2+ + H2S MS + 2H+

and can be used in the leaching circuit, or must be neutralized before disposal.

61

Sometimes, it is desirable to float the precipitated sulfide to economize the cost of filtration. This is especially the case when leaching low-grade copper ore containing fine particles (slimes). Precipitation can be conducted directly in the slurry and CuS is recovered by flotation thus by-passing a filtration step.

Precipitation of sulfides can be selective. For example, at Outokumpu, in Finland, pyrite cinder is leached with water to get a solution at pH 1.5 analyzing 20 g/L Co, 68 Ni, 78 Cu, 1012 Zn, and trace amounts of iron. The solution is purified by selective precipitation with H2S to remove first copper, then zinc, nickel, and finally cobalt sulfides.

62

Sulfites

Copper sulfites are of interest in hydrometallurgy because they can be readily precipitated from leach solutions in a pure form and can be treated in a variety of ways to yield pure metallic copper Cu2SO37(NH4)2SO310H2O Cu2SO3(NH4)2SO3 Cu2SO3CuSO32H2O (Chevreuls salt)

Ammonium copper sulfites

Ammonium sulfite solution (natural pH about 8) extracts copper from oxidized copper ores. When SO2 is bubbled through the solution at room temperature until pH 7 is reached, the cupric species are reduced to the cuprous. The same behavior takes place when SO2 is bubbled into a copper ammine solution (pH 10.5): the dark blue solution becomes colorless because of the oxidationreduction reactions: SO2 + H2O H2SO3 SO32 + 2H+ SO32 + H2O SO42 + 2H+ + 2e
[Cu(NH3)4]2+
blue

+e

[Cu(NH 3)4]+
colorless

At pH 7in sulfite medium the following equilibrium is established: [Cu(NH3)4]+ + 4H+ Cu+ + 4NH4+

63

Two products can be obtained from these solutions:

On cooling, transparent crystals of cuprous ammoniumsulfite, Cu2SO37(NH4)2SO310H2O, are formed. These needle crystals are water-soluble and when acidified, they precipitate metallic copper by disproportionation:
2Cu+ Cu + Cu2+

while the sulfite ion forms SO2:

SO32 + 2H+ SO2 + H2O

When SO2 is bubbled further until pH 3, then a double salt Cu2SO3(NH4)2SO3 is formed. These cream colored shiny hexagonal platelets are insoluble in water and when acidified, they also precipitate metallic copper by disproportionation:
Cu2SO3(NH4)2SO3(s) + 4H+ Cu + Cu2+ + 2SO2 + 2NH4+ + 2H2O Cu+ + e Cu SO32 + H2O SO42 + 2H+ + 2e SO32 + 2H+ SO2 + H2O

When heated with water at 150C in an autoclave in absence of acid,

complete conversion to metallic copper takes place:

Overall reaction:

Cu2SO3(NH4)2SO3 2Cu + SO2 + 2NH4+ + SO42

Chevreuls salt
Named after its discoverer the French chemist Michel Eugne Chevreul, the salt is a red crystalline solid having the composition Cu2SO3CuSO32H2O in which copper is present in two valency states. It can be obtained in a variety of ways. For example: When copper oxide ore is dissolved in sulfurous acid, then the solution is heated:
CuO + H2SO3 Cu2+ + SO32 + H2O SO32 + H2O SO42 + 2H+ + 2e Cu2+ + e Cu+

Overall reaction:

3CuSO3 + 3H2O Cu2SO3CuSO32H2O + H2SO4

64

RECOVERY FROM LEACH SOLUTION

Precipitation by reduction

Precipitation by reduction is an oxidationreduction process: Oxidation: Reduced species Oxidized species + ne Reduction: Mn+ + ne M Overall reaction: Mn+ + Reduced species M + Oxidized species The process may be homogeneous (the reduced species is ionic or non-ionic) or heterogeneous (reduction takes place on a solid surface). Heterogeneous processes may be electrochemical or electrolytic.

65

Ionic reduction

Sulfite ion may be used as an aqueous solution of sulfur dioxide: SO2 + H2O H2SO3 2H+ + SO32 SO32 + H2O SO42 + 2H+ + 2e On passing SO2 into a solution of copper sulfate at room temperature, copper sulfite will precipitate. However, if precipitation is carried out at 150C and 350 kPa, metallic copper is precipitated according to: Cu2+ + SO32 + H2O Cu + 2H+ + SO42

66

The drawback to this process is the low yield of copper, corrosion problems due to the acidic environment, and the presence of small amounts of sulfur in the copper produced. The low yield may be due to the intermediate formation of cuprous ion which disproportionates precipitating half of the copper and regenerating the other half as cupric ion: Cu2+ + e Cu+ 2Cu+ Cu + Cu2+ The decomposition of sulfurous acid at the reaction temperature to H2SO4 and elemental sulfur according to the equation: 3H2SO3 2H2SO4 + S + H2O accounts for the presence of small amounts of sulfur in the copper produced.

This process can be improved by adding an ammoniacal solution of ammonium sulfite instead of SO2, i.e., neutralizing the acid as soon as formed. The following reaction takes place: Cu2+ + SO32 + 2NH3 + H2O Cu + 2NH4+ + SO42 This results in complete precipitation of copper and has the advantage of operating under basic conditions thus eliminating corrosion problems. However, it has the inconvenience of producing ammonium sulfate that has to be crystallized and marketed as fertilizer. In a similar way, cuprous ion in a copper ammine sulfite solution can be reduced to metallic copper when the pH is adjusted to 3 by sulfurous acid to precipitate the double salt Cu2SO3(NH4)2SO3 which, when slurried with water and heated at 150C in an autoclave: Cu+ + e Cu 2 + H O SO 2 + 2H+ + 2e SO3 2 4 SO32 + 2H+ SO2 + H2O Overall reaction: Cu2SO3(NH4)2SO3 2Cu + SO2 + 2NH4+ + SO42

67

Non-ionic reduction

Non-ionic reducing agents such as hydrogen, carbon monoxide, formaldehyde, and hydrazine may be used to precipitate copper from aqueous solutions.

Reducing agent Hydrogen Carbon monoxide Formaldehyde Hydrazine

Reaction H2 2H+ + 2e CO + H2O CO2 + 2H+ + 2e HCHO + H2O HCOOH + 2H+ + 2e HCHO + 3OH HCOO + 2H2O + 2e H2NNH2 N2 + 4H+ + 4e 2H2NNH2 N2 + 2NH+ + 4e 4

68

Hydrogen
Hydrogen at high temperature and pressure leads to the precipitation of copper. Reduction is usually carried out in horizontal stainless steel autoclaves equipped with agitators, baffles, heating or cooling coils, and the necessary connections for feed and gas inlets and outlets. The product of this technique is a high-purity powder that can be used as such or hot pressed and rolled in form of strips.

Cu2+ + H2 Cu + 2H+ the precipitation of copper from CuSO4 solution takes place through the formation of cuprous ion which has been identified in the course of reaction: 2Cu2+ + H2 2Cu+ + 2H+ 2Cu+ + H2 2Cu + 2H+

For the reaction:

Copper can be precipitated from acidic solutions [140

g/L sulfuric acid ]

69

When reduction is conducted in ammoniacal medium the following reactions will take place: [Cu(NH3)n]2+ nNH3 + Cu2+ Cu2+ + H2 Cu+ 2H+ H+ + NH3 NH4+

It can be seen that increasing the ammonia concentration has two opposing effects: Precipitation is favored due to the neutralization of the liberated acid. Precipitation is hindered because of the decrease in the reducible metal ions Cu2+ due to the complexing action.
Therefore, there must be an optimum [NH3]/[Cu2+] ratio at which these opposing effects are balanced. The amount of ammonia in solution also influences the rate of precipitation. The rate of precipitation achieves a maximum when the ratio = 2.

After each reduction, copper particles are allowed to settle to the bottom of the autoclave, while the spent solution is drawn off and replaced with fresh pregnant solution. In this way, copper particles grow to the desired size, at which point the suspension is discharged and the nickel powder then separated.

70

The presence of certain organic or inorganic substances in the aqueous phase greatly affects the physical nature of metal precipitated. It is possible to precipitate copper powder of certain physical property by simply adding a certain amount of additive. However, when organic additives are used, the carbon content in the powder produced is increased and a special heat treatment is necessary to lower it to 0.01%.

Application

Copper scrap is dissolved either in ammoniacal ammonium carbonate at 60C at atmospheric pressure with continuous aeration, or in dilute sulfuric acid. When ammoniacal medium is used, the molar ratio [NH3]/[Cu2+] should be equal to 2.4. After filtration to remove insoluble material, a small amount of antiagglomerating agent is added, then solution is heated to 200C under 6000 kPa hydrogen. The copper powder precipitated is filtered off, washed, and then dried in a reducing atmosphere at 600C.

71

Carbon monoxide

Carbon monoxide has been used for precipitating copper from [Cu(NH3)4]2+ solutions obtained by leaching brass scrap in ammoniacal ammonium carbonate: [Cu(NH3)4]2+ Cu2+ + 4NH3 Cu2+ + CO + H2O Cu + CO2 + 2H+ Precipitation takes place at 150C with CO partial pressure of 5,000 kPa. The solution is then boiled to precipitate zinc as basic carbonate.

RECOVERY FROM LEACH SOLUTION

72

Electrochemical

Precipitation of copper from copper sulfate solution by iron is known as cementation, because copper is usually cemented on the surface of iron. Iron, having more positive (oxidation) potential will pass into solution and displace copper that has a less positive potential. The process is electrochemical in nature. Reactions take place through transfer of electrons at the surface of the solid.

73

Iron used for cementation of copper is in form of scrap, cans, or sponge. Cans are heated in a rotary kiln to remove the tin plating and paint from the surface, and the solder from the seams. They are then passed through a hammer mill, a toothed roll, or a shredding machine to make them more compact and less bulky. Stockpiling of iron usually presents a problem: it occupies large areas and it oxidizes with time. This oxidation not only means an iron loss, but also a decrease in the quality of cement copper produced from such material. Recovery of copper from sulfuric acid leach solution by this technology has been practically abandoned although it was an important process during the 20th century.

74

Side reactions during cementation

Excessive dissolution of iron A part of the iron usually dissolves by a secondary reaction without affecting precipitation, thus increasing metal consumption: Fe + 2H+ Fe2+ + H2 The presence of ferric ion in solution may also contribute to the dissolution of iron by the reaction:
Fe + 2Fe3+ 3Fe2+ In practice, two to four times the theoretical amount of iron is consumed. In all cases, more metal dissolves when it is in powder form than when it is coarse.

Re-dissolution of the cemented copper Unless precautions are taken, the precipitated copper may re-dissolve on standing:
Cu + Cu2+ 2Cu+ Cu + 2H+ + 1/2O2 Cu2+ + H2O

Therefore, the precipitate should be removed as soon as possible from the solution, and excessive agitation should be avoided since it enhances these reactions

75

Precipitaion of hydrolytic products.

The pH should be about 2 to prevent the hydrolysis of Fe2+ and Fe3+ ions and formation of hydroxides or basic salts that may take place and contaminate the copper precipitated thus decreasing its purity. Formation of toxic gases. Due to the presence of trace amounts of arsenic and phosphorus as impurities in iron, the conditions are favorable for the formation of arsine, AsH3, and phosphine, PH3, by the following reactions: Fe3As2 + 6H+ 3Fe2+ + 2AsH3 Fe3P2 + 6H+ 3Fe2+ + 2PH3 Both gases are highly poisonous and were detected when using iron for precipitating copper.

Formation of alloys. Under certain conditions, an alloy is precipitated instead of the pure metal. For example, during the precipitation of copper by iron, the main impurity is iron. There is an indication that this iron impurity occurs in alloy with copper. Cement copper containing 2% Fe is magnetic, and it is not possible to separate iron selectively by magnetic methods.

76

Factors affecting the physical properties of precipitated copper

For the cementation of copper by iron, a finer powder is obtained at high Cu2+ ion concentration. At a constant Cu2+ ion concentration, a fine powder is obtained at high H2SO4 concentration

Morphology of copper precipitate from sulfate solution on aluminum

77

Morphology of copper precipitate from sulfate solution on iron

RECOVERY FROM LEACH SOLUTION

78

Precipitation by substitution
Copper is extracted by organic solvents by forming a coordination bond. When this loaded organic phase is treated by hydrogen at high temperature and pressure in an autoclave, copper precipitates in powder form and the organic phase is regenerated. The process may be described as precipitation by substitution since no ionic species are taking part in the reaction as compared to precipitation by hydrogen from an aqueous phase. The substitution reaction can be represented as follows: H2(g) H2(org) R2Cu(org) + H2(org) 2RH(org) + Cu(s) ) where RH is the organic solvent.

The precipitation of copper powder from hydroxyl quinoline kerosene phase containing copper

79

Thanks

80