ZINC EXTRACTION PROCESSES

he most important raw material for production of Zinc is Zinc Sulphide (ZnS) ore

commonly known as Sphalerite. Next in the importance are Zinc Carbonates (Calamine/Smithsonite) and Zinc Silicate. Most of the zinc production worldwide originates from sulphide ores. The principal processes by which zinc is extracted from its ores can be categorised under pyro-metallurgical processes and hydro-metallurgical processes. A. Pyrometallurgical Processes: i) Horizontal Retort Process ii) Vertical Retort Process iii) Electro Thermal Process iv) Imperial Smelting Process B. Hydrometallurgical Processes: i) Roast Leach Electrowin Process ii) Pressure Leaching Process

HYDRO-METALLURGICAL PROCESSESS

bout 80% of worlds total zinc output is produced through conventional

hydrometallurgical route i.e. Roast-leach-electrowin (RLE) route. The three out of the four plants installed in India are operating on hydrometallurgical process route, whereas the fourth one at Chittaurgarh, Rajasthan, which was commissioned in the year 1991 is based on imperial smelting process route for simultaneous extraction of lead and zinc. The pre-requisite condition for zinc metal extraction from sulphide concentrate through a hydro-metallurgical route is the elimination of its sulphur content in order to make it amenable to further treatment by leaching, i.e., the zinc mineral into dissolved state in solution. Since zinc sulphide mineral is not easily leached, it is first converted into zinc oxide, which is easily leached. This is predominantly accomplished by roasting of zinc concentrate in fluid bed roasters and fixation of SO2 bearing off gases thus generated as sulphuric acid by contact process. In the recent past, an alternative technology to

conventional roasting followed by leaching, has been developed by Sherritt-Gordon of Canada, commonly known as Pressure Leach Process which eliminates the need of roasting step prior to leaching. The process fixes the sulphide content of concentrate as elemental sulphur, thus eliminates the need for a separate sulphuric acid production facility, whereas the zinc metal content of the concentrate is converted into a zinc sulphate solution, thus combining both roast-leach steps of conventional process into a single unit operation.Thus there are two-process route for extraction of zinc hydrometallurgically:

PRESSURE LEACH ELECTROWIN PROCESS ROASTLEACHELECTROWIN (RLE) PROCESS

ROAST LEACH ELECTROWIN (RLE) PROCESS: The main purpose of roasting of zinc sulphide concentrate is to convert it into a product, which is amenable to further treatment through hydrometallurgical process for extraction of zinc. Secondly, to fix the sulphide contents into sulphur dioxide gases for subsequent economical recovery as sulphuric acid.The principal reaction during fluid bed roasting is: 2 ZNS + 3O2 = 2ZnO + 2SO2

These rich gases are cleaned and cooled to recover dust content as zinc calcine and to remove the various harmful impurities such as Hg, Se, F, Cl, As, etc., before being led to double contact and double conversion process (DCDA) plant for manufacture of sulphuric acid. The dead roasted product, zinc calcine, is subjected to leaching with recycled electrolyte to extract zinc content. The enriched zinc sulphate solution is further subjected to purification with zinc dust to eliminate impurities like copper, cadmium, cobalt, nickel etc. before being subjected to elecrolysis. The zinc sulphate solution is fortified with return electrolyte solution, undergoes electrolysis in lined concrete cells for deposition of zinc on aluminium cathodes. The lead- silver plates are used as anodes. The deposited zinc on the cathodes are periodically stripped by automatic stripping machines, melted in induction furnace and cast into saleable zinc ingots man automatic casting and stacking machine. In order to maximise zinc extractions the leach residues mainly zinc- ferrites, a bye product of leaching process, are subjected to treatment to hydrolyse its iron content into disposable Jarosite / goethite / hematite. The zinc plants are also integrated with bye-product cadmium recovery unit in order to maximise sales realization. The standard zinc product is Special High Grade zinc (normally obtained from RLE process route), with an assay of 99.995% zinc, i.e. it can contain a maximum of 50

parts per million of impurities. There is also a grade of 98.5% zinc, the main impurity being lead, and this used to be the standard grade, called GOB (Good Ordinary Brand) or PW (Prime Western), normally a product from the Imperial smelting process (ISP). A SHG product from the ISP can also be produced by distillation process of refining. PRESSURE LEACH PROCESS: The pressure leach technique was first successfully commercially applied for zinc extraction with the commissioning of first plant in 1981 at Cominco, Trail, Canada. There are presently three electrolytic zinc plants in the world where this technique has been integrated into the existing facilities. A fourth green field plant with two-stage counter-current pressure leach-electrowin is under consideration. In this process zinc sulphide or bulk zinc concentrates are oxidized under oxygen overpressures of 1200 kpa abs. at a temperature of 1500C in sulphuric acid medium to produce zinc sulphate solution directly and the sulphide content is precipitated as elemental sulphur according to the following overall reaction:
ZnS + H2S04 + 0.5 02 = ZnSO4 + H20 + S

The various factors influencing the kinetics of above reaction are the particle size, mineralogy, surface active additives, acidities, reaction time, temperature and oxygen over-pressures where by maximising metal extraction and fixation of lead and iron constituents into disposable Jarosite and other types of residues. The zinc sulphate solution thus produced is amenable to further processing for final zinc extraction through conventional leach-electrowin units.

ATOMIC NUMBER30ATOMIC WEIGHT 65.37 DENSITY(AT 25C) 7140 kg/m3 MELTING POINT419.5C (692.7 K) BOILING POINT(760 mm Hg907C(1180 K) MODULUS OF ELASTICITY7x104 MN/m2 SPECIFIC HEAT (20C)0.382 kJ/kg.K LATENT HEAT OF FUSION(419.5C)100.9 kJ/kg LATENT HEAT OF VAPORIZATION(906C)1.782MJ/kg HEAT CAPACITY SolidCp = 22.40 + 10.5 x 10-3 TJmol-1 (298 - 692.7 K) Liquid Cp = 31.40 Jmol-1 GasC p = 20.80 Jmol-1 LINEAR COEFFICIENT OF THERMAL EXPANSION (polycrystalline 20-250C) 39.7m/m.K VOLUME COEFFICIENT OF THERMAL EXPANSION(20-400C)0.89 x 10 -6/K THERMAL CONDUCTIVITY : solid (18C)113W/m.K ELECTRICAL RESISTIVITY(polycrystalline at 20 C)5.9m STANDARD ELECTRODE POTENTIAL(against H2 electrode)- 0.762 V

Smelters use a mix of zinc-containing concentrates or secondary zinc material such as zinc oxides as feed to their roasting plant. Nyrstars Auby and Balen smelters, in particular, are characterised by a relatively high input of secondary materials. Smelters located inland receive their feed by road, rail or canal depending on site-specific logistical factors and the type of feedstock (eg, secondary zinc oxides come in smaller volumes and are typically transported by road). Concentrate deliveries typically happen in large batches (eg, 5,000 to 10,000 tonnes). Nyrstars European smelters are strategically located close to the Antwerp seaport that serves as a global concentrate hub and provides for an extensive multi-modal logistical infrastructure connecting Belgium, the Netherlands and France. Nyrstars Australian smelters are located on or near the coast, allowing for direct maritime access, while Clarksville is connected to the major seaport of New Orleans via the Mississippi and Cumberland Rivers. Most zinc smelters use several sources of concentrates. These different materials are blended to obtain an optimal mix of feedstock for the roasting process. Through the roasting process, the zinc sulphides in the concentrates are converted into zinc oxide, known as calcine. A roasting furnace operates at a temperature of approximately 950 C, generating enough energy to make the process autogenous. The roasting process is fully automated, controlled and operated from a central control room. Nyrstar operates some of the worlds largest roasters, which are modelled after those used throughout the industry (e.g., the Lurgi-VM fluidised-bed roaster, which was developed in Balen). The roasting step results in the production of calcine material (which is transported to the subsequent leaching plant) and sulphur dioxide-rich waste gases. Waste heat boilers remove the calcine contained in these gases as well as recovering the heat in the form of steam that is used in the leaching plant and/or converted into electricity. Finally, the sulphur dioxide is converted into sulphuric acid in a contact process, generating an important smelter by-product. The main purpose of the leaching process is to dissolve the zinc oxide contained in the roasted calcine material and to transform it into zinc sulphate prior to the electrolysis stage. For this process, diluted sulphuric acid is used. Approximately 90% of the zinc in roaster calcine is in the form of zinc oxide, with the balance being present as zinc ferrite, an iron-zinc oxide. Zinc oxide can be leached with weak sulphuric acid solutions, but leaching the zinc from ferrites requires more aggressive acid conditions. The contained zinc dissolves while the other metals come out as a solid generically called Leach Product. This leach-residue containing precious metals is sold as a by-product to third parties for further refining. The dissolved iron is removed from the zinc sulphate solution as goethite, jarosite or haematite which is usually stored in ponds. The leach solution is subsequently sent to a purification installation that removes other non-iron dissolved impurities such as cadmium, copper, cobalt or nickel, which could also affect the electrolysis operation. These impurities are removed through cementation by adding zinc dust to the solution. The resulting by-products are generally sold to third parties for further refining. The purified zinc sulphate solution is sent to the cell house for the electro-winning phase of the smelting process.

Zinc metal is extracted from the purified solution by means of electrolysis. An electric current is passed through the solution and the zinc is deposited on aluminium cathodes. At regular intervals, these cathodes are removed from the cells and the zinc deposit is stripped from the cathodes. Most of the Nyrstar smelters use a mechanised and automated process of stripping machines, which was initially developed at the Balen plant. The zinc produced with the electrolysis process is typically of SHG grade containing 99.995% zinc. The electrolysis phase uses large amounts of electrical energy and is responsible for the high proportion of the energy-cost in the overall smelting process (typically about one third of total plant cash costs) [to be validated based on actual financials]. Hence, cell house productivity (and electrical current and energy efficiency in particular) is a crucial driver in overall plant efficiency. Nyrstar runs some of the industrys largest and most efficient cell houses. Depending on the type of end-products produced, the zinc cathodes coming out of the electro-winning plant can undergo an additional transformation step in a foundry. Zinc cathodes are melted in induction furnaces and cast into marketable products such as ingots. Other metals and alloy components may be added to produce zinc containing alloys used in die-casting or general galvanization applications. Finally, molten zinc may be transported to nearby conversion plants or third parties using specially-designed insulated containers. This is the case with Balen and Budel.