COPPER, LEAD AND ZINC SMELTING AND REFINING*  

 

* Adapted from EPA 1995.

 

Copper

Copper is mined in both open pits and underground mines, depending upon the ore grade and the nature of the ore deposit. Copper ore typically contains less that 1% copper in the form of sulphide minerals. Once the ore is delivered above the ground, it is crushed and ground to a powdery fineness and then concentrated for further processing. In the concentration process, ground ore is slurried with water, chemical reagents are added and air is blown through the slurry. The air bubbles attach themselves to the copper minerals and are then skimmed off the top of the flotation cells. The concentrate contains between 20 and 30% copper. The tailings, or gangue minerals, from the ore fall to the bottom of the cells and are removed, dewatered by thickeners and transported as a slurry to a tailings pond for disposal. All water used in this operation, from dewatering thickeners and the tailings pond, is recovered and recycled back into the process.

 

Copper can be produced either pyrometallurgically or hydrometallurgically depending upon the ore-type used as a charge. The ore concentrates, which contain copper sulphide and iron sulphide minerals, are treated by pyrometallurgical processes to yield high purity copper products. Oxide ores, which contain copper oxide minerals that may occur in other parts of the mine, together with other oxidized waste materials, are treated by hydrometallurgical processes to yield high purity copper products.

 

Copper conversion from the ore to metal is accomplished by smelting. During smelting the concentrates are dried and fed into one of several different types of furnaces. There the sulphide minerals are partially oxidized and melted to yield a layer of matte, a mixed copper-iron sulphide and slag, an upper layer of waste.

 

The matte is further processed by converting. The slag is tapped from the furnace and stored or discarded in slag piles onsite. A small amount of slag is sold for railroad ballast and for sand blasting grit. A third product of the smelting process is sulphur dioxide, a gas which is collected, purified and made into sulphuric acid for sale or for use in hydrometallurgical leaching operations.

 

Following smelting, the copper matte is fed into a converter. During this process the copper matte is poured into a horizontal cylindrical vessel (approximately 10ґ4 m) fitted with a row of pipes. The pipes, known as tuyиres, project into the cylinder and are used to introduce air into the converter. Lime and silica are added to the copper matte to react with the iron oxide produced in the process to form slag. Scrap copper may also be added to the converter. The furnace is rotated so that the tuyиres are submerged, and air is blown into the molten matte causing the remainder of the iron sulphide to react with oxygen to form iron oxide and sulphur dioxide. Then the converter is rotated to pour off the iron silicate slag.

 

Once all of the iron is removed, the converter is rotated back and given a second blow of air during which the remainder of the sulphur is oxidized and removed from the copper sulphide. The converter is then rotated to pour off the molten copper, which at this point is called blister copper (so named because if allowed to solidify at this point, it will have a bumpy surface due to the presence of gaseous oxygen and sulphur). Sulphur dioxide from the converters is collected and fed into the gas purification system together with that from the smelting furnace and made into sulphuric acid. Due to its residual copper content, slag is recycled back to the smelting furnace.

 

Blister copper, containing a minimum of 98.5% copper, is refined to high purity copper in two steps. The first step is fire refining, in which the molten blister copper is poured into a cylindrical furnace, similar in appearance to a converter, where first air and then natural gas or propane are blown through the melt to remove the last of the sulphur and any residual oxygen from the copper. The molten copper is then poured into a casting wheel to form anodes pure enough for electrorefining.

 

In electrorefining, the copper anodes are loaded into electrolytic cells and interspaced with copper starting sheets, or cathodes, in a bath of copper sulphate solution. When a direct current is passed through the cell the copper is dissolved from the anode, transported through the electrolyte and re-deposited on the cathode starting sheets. When the cathodes have built-up to sufficient thickness they are removed from the electrolytic cell and a new set of starting sheets is put in their place. Solid impurities in the anodes fall to the bottom of the cell as a sludge where they are ultimately collected and processed for the recovery of precious metals such as gold and silver. This material is known as anode slime.

 

The cathodes removed from the electrolytic cell are the primary product of the copper producer and contain 99.99+% copper. These may be sold to wire-rod mills as cathodes or processed further to a product called rod. In manufacturing rod, cathodes are melted in a shaft furnace and the molten copper is poured onto a casting wheel to form a bar suitable for rolling into a 3/8 inch diameter continuous rod. This rod product is shipped to wire mills where it is extruded into various sizes of copper wire.

 

In the hydrometallurgical process, the oxidized ores and waste materials are leached with sulphuric acid from the smelting process. Leaching is performed in situ, or in specially prepared piles by distributing acid across the top and allowing it to percolate down through the material where it is collected. The ground under the leach pads is lined with an acid-proof, impermeable plastic material to prevent leach liquor from contaminating groundwater. Once the copper-rich solutions are collected they can be processed by either of two processes-the cementation process or the solvent extraction/electrowinning process (SXEW). In the cementation process (which is rarely used today), the copper in the acidic solution is deposited on the surface of scrap iron in exchange for the iron. When sufficient copper has been cemented out, the copper-rich iron is put into the smelter together with the ore concentrates for copper recovery via the pyrometallurgical route.

 

In the SXEW process, the pregnant leach solution (PLS) is concentrated by solvent extraction, which extracts copper but not impurity metals (iron and other impurities). The copper-laden organic solution is then separated from the leachate in a settling tank. Sulphuric acid is added to the pregnant organic mixture, which strips the copper into an electrolytic solution. The leachate, containing the iron and other impurities, is returned to the leaching operation where its acid is used for further leaching. The copper-rich strip solution is passed into an electrolytic cell known as an electrowinning cell. An electrowinning cell differs from an electrorefining cell in that it uses a permanent, insoluble anode. The copper in solution is then plated onto a starting sheet cathode in much the same manner as it is on the cathode in an electrorefining cell. The copper-depleted electrolyte is returned to the solvent extraction process where it is used to strip more copper from the organic solution. The cathodes produced from the electrowinning process are then sold or made into rods in the same manner as those produced from the electrorefining process.

 

Electrowinning cells are used also for the preparation of starting sheets for both the electrorefining and electrowinning processes by plating the copper onto either stainless steel or titanium cathodes and then stripping off the plated copper.

 

Hazards and their prevention

The major hazards are exposure to ore dusts during ore processing and smelting, metal fumes (including copper, lead and arsenic) during smelting, sulphur dioxide and carbon monoxide during most smelting operations, noise from crushing and grinding operations and from furnaces, heat stress from the furnaces and sulphuric acid and electrical hazards during electrolytic processes.

 

Precautions include: LEV for dusts during transfer operations; local exhaust and dilution ventilation for sulphur dioxide and carbon monoxide; a noise control and hearing protection programme; protective clothing and shields, rest breaks and fluids for heat stress; and LEV, PPE and electrical precautions for electrolytic processes. Respiratory protection is commonly worn to protect against dusts, fumes and sulphur dioxide.

 

Table 82.1 lists environmental pollutants for various steps in copper smelting and refining.

 

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Table 82.1     Process materials inputs and pollution outputs for copper smelting and refining

 

Process

Material input

Air emissions

Process wastes

Other wastes

Copper concentration

Copper ore, water, chemical reagents, thickeners

 

Flotation wastewaters

Tailings containing waste minerals such as limestone and quartz

Copper leaching

Copper concentrate, sulphuric acid

 

Uncontrolled leachate

Heap leach waste

Copper smelting

Copper concentrate, siliceous flux

Sulphur dioxide, particulate matter containing arsenic, antimony, cadmium, lead, mercury and zinc

 

Acid plant blowdown slurry/sludge, slag containing iron sulphides, silica

Copper conversion

Copper matte, scrap copper, siliceous flux

Sulphur dioxide, particulate matter containing arsenic, antimony, cadmium, lead, mercury and zinc

 

Acid plant blowdown slurry/sludge, slag containing iron sulphides, silica

Electrolytic copper refining

Blister copper, sulphuric acid

 

 

Slimes containing impurities such as gold, silver, antimony, arsenic, bismuth, iron, lead, nickel, selenium, sulphur and zinc

 

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Lead

The primary lead production process consists of four steps: sintering, smelting, drossing and pyrometallurgical refining. To begin, a feedstock comprising mainly of lead concentrate in the form of lead sulphide is fed into a sintering machine. Other raw materials may be added including iron, silica, limestone flux, coke, soda, ash, pyrite, zinc, caustic and particulates gathered from pollution control devices. In the sintering machine the lead feedstock is subjected to blasts of hot air which burn off the sulphur, creating sulphur dioxide. The lead oxide material existing after this process contains about 9% of its weight in carbon. The sinter is then fed along with coke, various recycled and cleanup materials, limestone and other fluxing agents into a blast furnace for reducing, where the carbon acts as a fuel and smelts or melts the lead material. The molten lead flows to the bottom of the furnace where four layers form: “speiss” (the lightest material, basically arsenic and antimony); “matte” (copper sulphide and other metal sulphides); blast furnace slag (primarily silicates); and lead bullion (98% lead, by weight). All layers are then drained off. The speiss and matte are sold to copper smelters for recovery of copper and precious metals. The blast furnace slag which contains zinc, iron, silica and lime is stored in piles and partially recycled. Sulphur oxide emissions are generated in blast furnaces from small quantities of residual lead sulphide and lead sulphates in the sinter feed.

 

Rough lead bullion from the blast furnace usually requires preliminary treatment in kettles before undergoing refining operations. During drossing, the bullion is agitated in a drossing kettle and cooled to just above its freezing point (370 to ). A dross, which is composed of lead oxide, along with copper, antimony and other elements, floats to the top and solidifies above the molten lead.

 

The dross is removed and fed into a dross furnace for recovery of the non-lead useful metals. To enhance copper recovery, drossed lead bullion is treated by adding sulphur-bearing materials, zinc, and/or aluminium, lowering the copper content to approximately 0.01%.

 

During the fourth step, the lead bullion is refined using pyrometallurgical methods to remove any remaining non-lead saleable materials (e.g., gold, silver, bismuth, zinc, and metal oxides such as antimony, arsenic, tin and copper oxide). The lead is refined in a cast iron kettle by five stages. Antimony, tin and arsenic are removed first. Then zinc is added and gold and silver are removed in the zinc slag. Next, the lead is refined by vacuum removal (distillation) of zinc. Refining continues with the addition of calcium and magnesium. These two materials combine with bismuth to form an insoluble compound that is skimmed from the kettle. In the final step caustic soda and/or nitrates may be added to the lead to remove any remaining traces of metal impurities. The refined lead will have a purity of 99.90 to 99.99% and may be mixed with other metals to form alloys or it may be directly cast into shapes.

 

Hazards and their prevention

The major hazards are exposure to ore dusts during ore processing and smelting, metal fumes (including lead, arsenic and antimony) during smelting, sulphur dioxide and carbon monoxide during most smelting operations, noise from grinding and crushing operations and from furnaces, and heat stress from the furnaces.

 

Precautions include: LEV for dusts during transfer operations; local exhaust and dilution ventilation for sulphur dioxide and carbon monoxide; a noise control and hearing protection programme; and protective clothing and shields, rest breaks and fluids for heat stress. Respiratory protection is commonly worn to protect against dusts, fumes and sulphur dioxide. Biological monitoring for lead is essential.

 

Table 82.2 lists environmental pollutants for various steps in lead smelting and refining.

 

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Table 82.2     Process materials inputs and pollution outputs for lead smelting and refining

 

Process

Material input

Air emissions

Process wastes

Other wastes

Lead sintering

Lead ore, iron, silica, limestone flux, coke, soda, ash, pyrite, zinc, caustic, baghouse dust

Sulphur dioxide, particulate matter contain-ing cadmium and lead

 

 

Lead smelting

Lead sinter, coke

Sulphur dioxide, particulate matter contain-ing cadmium and lead

Plant washdown wastewater, slag granulation water

Slag containing impurities such as zinc, iron, silica and lime, surface impoundment solids

Lead drossing

Lead bullion, soda ash, sulphur, baghouse dust, coke

 

 

Slag containing such impurities as copper, surface impoundment solids

Lead refining

Lead drossing bullion

 

 

 

 

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Zinc

Zinc concentrate is produced by separating the ore, which may contain as little as 2% zinc, from waste rock by crushing and flotation, a process normally performed at the mining site. The zinc concentrate is then reduced to zinc metal in one of two ways: either pyrometallurgically by distillation (retorting in a furnace) or hydrometallurgically by electrowinning. The latter accounts for approximately 80% of total zinc refining.

 

Four processing stages are generally used in hydrometallurgic zinc refining: calcining, leaching, purification and electrowinning. Calcining, or roasting, is a high-temperature process (700 to ) that converts zinc sulphide concentrate to an impure zinc oxide called calcine. Roaster types include multiple-hearth, suspension or fluidized-bed. In general, calcining begins with the mixing of zinc-containing materials with coal. This mixture is then heated, or roasted, to vaporize the zinc oxide which is then moved out of the reaction chamber with the resulting gas stream. The gas stream is directed to the baghouse (filter) area where the zinc oxide is captured in baghouse dust.

 

All of the calcining processes generate sulphur dioxide, which is controlled and converted to sulphuric acid as a marketable process by-product.

 

Electrolytic processing of desulphurized calcine consists of three basic steps: leaching, purification and electrolysis. Leaching refers to the dissolving of the captured calcine in a solution of sulphuric acid to form a zinc sulphate solution. The calcine may be leached once or twice. In the double-leach method, the calcine is dissolved in a slightly acidic solution to remove the sulphates. The calcine is then leached a second time in a stronger solution which dissolves the zinc. This second leaching step is actually the beginning of the third step of purification because many of the iron impurities drop out of the solution as well as the zinc.

 

After leaching, the solution is purified in two or more stages by adding zinc dust. The solution is purified as the dust forces deleterious elements to precipitate so that they can be filtered out. Purification is usually conducted in large agitation tanks. The process takes place at temperatures ranging from 40 to  and pressures ranging from atmospheric to 2.4 atmospheres. The elements recovered during purification include copper as a cake and cadmium as a metal. After purification the solution is ready for the final step, electrowinning.

 

Zinc electrowinning takes place in an electrolytic cell and involves running an electric current from a lead-silver alloy anode through the aqueous zinc solution. This process charges the suspended zinc and forces it to deposit onto an aluminium cathode which is immersed in the solution. Every 24 to 48 hours, each cell is shut down, the zinc-coated cathodes removed and rinsed, and the zinc mechanically stripped from the aluminium plates. The zinc concentrate is then melted and cast into ingots and is often as high as 99.995% pure.

 

Electrolytic zinc smelters contain as many as several hundred cells. A portion of the electrical energy is converted into heat, which increases the temperature of the electrolyte. Electrolytic cells operate at temperature ranges from 30 to  at atmospheric pressure. During electrowinning a portion of the electrolyte passes through cooling towers to decrease its temperature and to evaporate the water it collects during the process.

 

Hazards and their prevention

The major hazards are exposure to ore dusts during ore processing and smelting, metal fumes (including zinc and lead) during refining and roasting, sulphur dioxide and carbon monoxide during most smelting operations, noise from crushing and grinding operations and from furnaces, heat stress from the furnaces and sulphuric acid and electrical hazards during electrolytic processes.

 

Precautions include: LEV for dusts during transfer operations; local exhaust and dilution ventilation for sulphur dioxide and carbon monoxide; a noise control and hearing protection programme; protective clothing and shields, rest breaks and fluids for heat stress; and LEV, PPE, and electrical precautions for electrolytic processes. Respiratory protection is commonly worn to protect against dusts, fumes and sulphur dioxide.

 

Table 82.3 lists environmental pollutants for various steps in zinc smelting and refining.

 

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Table 82.3      Process materials inputs and pollution outputs for zinc smelting and refining

 

Process

Material input

Air emissions

Process wastes

Other wastes

Zinc calcining

Zinc ore, coke

Sulphur dioxide, particulate matter containing zinc and lead

 

Acid plant blowdown slurry

Zinc leaching

Zinc calcine, sulphuric acid, limestone, spent electrolyte

 

Wastewaters containing sulphuric acid

 

Zinc purification

Zinc-acid solution, zinc dust

 

Wastewaters containing sulphuric acid, iron

Copper cake, cadmium

Zinc electrowinning

Zinc in a sulphuric acid/aqueous solution, lead-silver alloy anodes, aluminium cathodes, barium carbonate or strontium, colloidal additives

 

Dilute sulphuric acid

Electrolytic cell slimes/sludges

 

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