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Hydrometallurgy 12

Hydrometallurgy 12

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12

HYDROMETALLURGICAL PROCESSES

Here will be given a description of a few important hydrometallurgical processes to exemplify applications of the unit processes dealt with in this compendium, which are pretreatment, leaching, leaching equipment, solution purification and metal extraction. • • Hydrometallurgical production of copper from oxide and secondary sulphide ores. Hydrometallurgical production of zinc from zinc concentrates.

12.1

Production of copper from oxide and secondary sulphide ores

Heap leaching of oxide copper ores was treated in Chapter 6, LEACHING EQUIPMENT. Since the first SX-EW plant was commissioned in 1968 at the Ranchers Bluebird plant in Arizona production of copper through heap leaching followed by SX-EW has steadily increased. Bioheap leaching of secondary sulphide ores has is steadily increasing since the beginning of the 1990’s. Approximately 35% of worlds copper production in 2005 was produced through SX-EW where 5-10% originates from heap bioleaching of secondary sulphides. The most important oxide copper minerals are malachite (CuCO3 ⋅ Cu(OH)2), azurite, (2CuCO3 ⋅ Cu(OH)2) and crysocolla (CuSiO3 ⋅ H2O). They can all be leached with sulphuric acid. Below is shown, as an example, the leaching of crysocolla with sulphuric acid: CuSiO3 ⋅ H2O + H2SO4 Cu2+ + SO42- + 3H2O + SiO2

Thus, the leaching consumes sulphuric acid and this consumption does not only depend on the copper oxide content but also on other minerals present in the ore such as calcite, dolomite and others. If the ore has a high content of such minerals, the costs of sulphuric acid may become prohibitive for the process economy. In the case of heap bioleaching of secondary sulphides the minerals chalcocite (CuS2) and covellite (CuS) are the most important. In bioleaching of sulphides an oxidant is needed to oxidise the sulphur to sulphate which is accomplished by blowing air into the heap. Bioleaching of covellite proceeds according to the following sum formula: CuS + 2O2 Cu2+ + SO42-

The oxidation is mediated by ferric iron and the ferrous iron and elemental sulphur obtained is oxidised by the bacteria, as is discussed in chapter 8, BIOLEACHING. As described previously, a dilute sulphuric acid solution is sprinkled over the ore heaps and copper is leached according to the reaction formulas above. The pregnant copper bearing leach solution that is collected on the bottom of the heap usually contains between 1 and 6

whose general structures are shown in Figure 12-2. the raffinate after copper extraction is recycled back to the heap. Before copper can be recovered from the solution. this is done almost exclusively through solvent extraction. for leaching while the barren and the pregnant electrolyte circulate between the stripping and electrowinning stage.grams of copper per litre with a pH value of between 1. usually by means of electrowinning.2. As can be seen in the figure the organic phase with the extractant circulates between the extraction and stripping stages. . two rather conflicting properties. namely aldoximes and ketoximes. The principle of such a solvent extraction plant is shown in Figure 12-1. eventually after replenishment with acid. it should extract copper selectively over iron and have a low water-solubility and a number of other properties. Impurities in the leach solution consist mainly of iron (1-10 g/l) and minor amounts of nickel. zinc and others. The aqueous phases are also circulating. Copper is extracted and stripped according to the following formula: 2RH(o) + CuSO4(aq) ⇔ R2Cu(o) + H2SO4(aq) There are a fairly great number of possible reagents for the extraction of copper from leach solutions. The only extraction reagents for copper with all these properties are those that contain hydroxyoximes. In addition. Figure 12-1 Solvent extraction plant for the purification and concentration of copper leach solution. These are therefore used exclusively in commercial plants for the solvent extraction of copper in sulphate solutions. There are two modifications of such extraction reagents with adequate properties. cobalt. Nowadays. One condition for such a reagent is that it should have a high extraction capacity while also being easy to strip.5 and 2. the solution must be purified and concentrated.

acid proof steel or copper metal (so-called starting-plates). has a copper content of 20-30 g/l and a sulphuric acid content of about 200 g/l. . To reach a good compromise. oxygen is generated according to the formulas: Cathode reaction: Anode reaction: Sum reaction: Cu Cu2+ + 2e2SO4 + H2O H2SO4 + CuSO4 + H2O Cu + 1 2 1 2 O2 + 2e- O2 + H2SO4 The solution leaving the electrowinning.Figure 12-2 General structure of the hydroxyoximes used for copper extraction. The aldoximes have strong extraction strength for copper. Copper in solution is deposited at the cathode. but also that it is difficult to strip the copper back into the aqueous phase. and at the anode. ketoximes and mixtures of the two. The properties of ketoximes are more moderate in this respect. In the table below are shown the properties of some commercial reagents based on aldoximes. The sulphuric acid content in the solution is about 170 g/l. the copper content in the aqueous phase is about 40 g/l. Table 12.1 Commercial copper extraction reagents Extraction agent Extraction strength Reagent Acorga P 5100 Aldoxime Strong Acorga PT 5050 Aldoxime Strong Acorga M 5640 Aldoxime Strong LIX 84 Ketoxime Moderately LIX 984 Mixture Strong LIX 622 Aldoxime Strong LIX 860 Aldoxime Very strong After stripping. while the iron content is only 1-3 g/l with additional low concentrations of other impurities. the spent electrolyte. which means that it is easy to extract copper from the aqueous phase to the organic phase. it is therefore common to use mixtures of ketoximes and aldoximes. The solution is sent for electrowinning where the electrolysis is done with anodes of lead and cathodes of titanium. This solution is recycled to the stripping stage in the solvent extraction plant.

with a zinc concentration of about 50 g/l and a sulphuric acid concentration of ~200 g/l (2M). The great problem when producing zinc from zinc sulphide concentrates is the separation of iron and the deposition of the iron-bearing waste. 110% iron and 33-35% sulphur.Fe)S to varying extent. according to: Neutral leaching: ZnO + H2SO4 ZnSO4 + H2O After leaching there is a solid liquid separation step and the leachate is sent to solution purification and zinc recovery while the leach residue goes to the hot acid leaching.2 Production of zinc from zinc concentrates The majority of the worlds zinc ore reserves are in the form of sphalerite (ZnS).2. Since the early 1980’s direct leaching of zinc sulphide concentrates has been commercialised. the neutral leaching stage and the hot acid leaching stage. Eventually the residue is treated . solvent extraction and electrowinning. the zinc concentrates produced from these types of ores contain 50-58% zinc. In Namibia at the Scorpion zinc mine there is one operation where zinc is produced from an ore containing zincite (ZnO). that is.5 and at a temperature of about 90º C also with the spent electrolyte.1 Zinc production through the roast – leach – electrowin (RLE) route In the roasting process the zinc sulphide is converted into zinc oxide according to the following formula: ZnS + 3/2O2 ZnO + SO2 The sulphur dioxide that forms in the process is collected and used for production of sulphuric acid. The calcine is then leached in two stages. 12. Direct leaching is applied both as pressure leaching operations in autoclaves and as atmospheric leaching in stirred tanks. depending on the iron content in the concentrate. In the neutral leaching stage the main part of the more easily leached zinc oxide is dissolved at a pH of 4-5 using spent electrolyte from the electrowinning. This is done by precipitation after a solid liquid separation step. the zinc ores almost always also contain a mineral called marmatite. In general. of zinc that is bound into zinc ferrite.12. Under these conditions also the zinc ferrite dissolves: Hot acid leaching: ZnO ⋅ Fe2O3 + 4H2SO4 ZnSO4 + Fe2(SO4)3 + 4H2O The dissolved iron now has to be removed before the zinc in solution can be recovered. The iron content from marmatite present in the concentrate is also oxidised into hematite which reacts further with zinc oxide and forms zinc ferrite (ZnFe2O4). The calcine produced thus contains free zinc oxide and a certain amount. The zinc is recovered through a process involving leaching with sulphuric acid. (Zn. The hot acid leaching is performed at a pH of 1-1. However. Zinc production from zinc sulphide ores is mainly done through the roast – leach – electrowin (RLE) process and this process route constitutes approximately 80% of the worlds zinc production.

Goethite is then precipitated by blowing air into the solution at a temperature of 80° C and calcine is added to maintain the pH at 3.for silver and lead recovery before disposal. or hematite (Fe2O3). The advantage with these precipitates is that they all are crystalline and easy to filter. Nickel and cobalt is more difficult to remove and cementation is therefore carried out at elevated temperatures with activators added and with over-stoichiometric amounts of zinc dust. Precipitation of amorphous ferric hydroxide (Fe(OH)3) caused massive losses of zinc in the precipitate. nickel and cobalt as impurities. Since zinc is among the least noble metals the requirements on solution purification is very high. The jarosite process was first discovered and is also the most frequently used method. The precipitate obtained has a high iron content with the lowest zinc losses but the process is also the most costly because of the equipment needed. Solid liquid separation follows and the precipitate is disposed while the remaining zinc sulphate solution is recycled to the neutral leaching step. In the goethite process the ferric iron in the leachate is first reduced with zinc concentrate: 2Fe3+ + ZnS 2Fe2+ + Zn2+ + S° Calcine is then added in a pre-neutralisation step to a pH of 3. In the first stages copper and cadmium are removed. The hematite process starts with reduction of ferric iron and pre-neutralisation as in the goethite process. . There are three different procedures through which this is achieved where iron is either precipitated as jarosite (NH4Fe3(SO4)2(OH)6). goethite (FeOOH). Hematite is then precipitated in an autoclave at 200° C in an oxygen atmosphere. Before these precipitation processes were invented only the neutral leaching was done and the zinc in zinc ferrite was deposited at landfills. 2Fe2+ + 1/2O2 + H2O + 2ZnO 2FeOOH + 2Zn2+ The goethite precipitate is less bulky than the jarosite and the zinc losses are also smaller. Ammonia or potassium ions are added to the leachate and jarosite is then obtained through the following reaction: 3Fe2(SO4)3 + 5ZnO + 2NH3 + 7H2O 2NH4Fe3(SO4)2(OH)6 + 5ZnSO4 To keep pH at the desired value of 1. The kinetics for the reaction is slow at lower temperatures and is therefore done at a temperature of 90-95° C. The zinc concentration is normally 150 g/l with mainly copper. In all processes the solution leaving the neutral leaching step is sent for solution purification.5 calcine (ZnO) is added during the precipitation. cadmium. The impurities are removed by cementation with zinc dust in several stages. 2Fe2+ + 1/2O2 + 2H2O Fe2O3 + 4H+ In this case the acid produced during precipitation is not needed to be neutralised with calcine. The different precipitates has also given their names to the process they are applied.

The hydrometallurgical production of zinc from zinc concentrate with the jarosite process is summed up schematically in figure 12-3. The electrical energy requirement is about 3000 kWh/ton of zinc produced.After solution purification the solution goes on to electrowinning step for the precipitation of zinc metal according to the formulas: Cathode reaction: Anode reaction: Sum reaction: Zn2+ + 2eZn H2O + SO42H2SO4 + 1/2O2 + 2eZnSO4 + H2O Zn + 1/2O2 + H2SO4 The sulphuric acid that is generated is recycled to the leaching stage to dissolve the zinc calcine. Figure 12-3 The jarosite process for zinc production . the zinc is generally smelted in an induction kiln and is cast into ingots of standard format. The electrowinning is done with anodes of lead and cathodes of aluminium at current densities between 350 and 550 A/m2 with a cell voltage of about 3 volts. The precipitated zinc metal is stripped from the aluminium cathode in special machines. After washing.

i. Enough iron is normally present in the concentrates in the form iron substitution in sphalerite or in marmatite. pyrrhotite (FeS) or pyrite (FeS2). The process in Kokkola and later also in Odda.1 Zinc production through the direct leaching routes In many places in the world where base metals are produced there is an oversupply of sulphuric acid. In the case of a low acid process the iron precipitates either as hematite or jarosite during leaching or stays in solution in the case of a high acid leach process. Pressure leaching was developed in the early 1980’s in Comincos zinc refinery in Trail. The process utilises dilute sulphuric acid at oxygen pressures of 16 atmospheres and at temperatures above 120° C. through pressure leaching or atmospheric leaching.e.2. that is. Direct leaching of zinc concentrates are done through two different routes. It is also a relatively cheap method to increase the zinc production capacity since there is no need to build a new roaster and sulphuric acid plant but only to increase the electrowinning facilities and of course a new leaching plant. During leaching iron is precipitated as jarosite and the sulphuric acid concentration is maintained at a level of 10-40 g/l. A new stand alone plant producing 100 000 tons of zinc per year is planned to be started in Iran.12. Finland. above the melting point of sulphur. Atmospheric leaching was later developed by Outokumpu in Kokkola. The process is therefore catalysed by iron according to the following reactions: ZnS + Fe2(SO4)3 ZnSO4 + 2FeSO4 + S° Fe2(SO4)3 +H2O 2FeSO4 + H2SO4 + 1/2O2 Depending on the acidity in the process which usually is either low or high the iron can then be either precipitated or remaining in the solution. It can therefore in certain cases be beneficial to produce elemental sulphur instead. The process has later been developed for stand alone production with different flowsheets where iron can be deported in different forms depending on actual requirements at the plant or local environmental legislations. Norway which utilises Outokumpu technology were expansions to existing RLE plants. The process operates at ~90° C in tall reactors supplied with oxygen. . Direct oxidation of zinc sulphide by oxygen is a relatively slow process but the process is speeded up by the presence of iron in solution. Canada and was integrated with an existing RLE process.

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