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F. Habashi*

Ceramics in Hydrometallurgical Processes

THE AUTHOR
Fathi Habashi is Professor Emeritus of Extractive Metallurgy at Laval University in Quebec City. He holds a B.Sc. degree in Chemical Engineering from the University of Cairo, a Dr. techn. degree in Inorganic Chemical Technology from the University of Technology in Vienna, and Dr.Sc. h.c. from the Saint Petersburg Mining Institute in Russia (1993). He was a postdoctoral fellow at the Department of Chemistry, University of Vienna . Then he enjoyed the benefits of the Canadian Government Scholarship in Ottawa and lectured at Montana College of Mineral Science & Technology. After this, he worked at the Extractive Metallurgical Research Department of Anaconda Company in Tucson, Arizona before joining to Laval in 1970. In 1998 he was appointed to a Fellow of the Canadian Institute of Mining, Metallurgy, and Petroleum. In 1999 he received its silver medal. He is an Honorary Professor at the Technical University of Oruro in Bolivia, Honorary Citizen of the city of Oruro, Governor at the Foundation de lUniversit Laval, and Member of Le Cercle des Ambassadeurs in Qubec City. He is the author of a number of textbooks on extractive metallurgy and editor of Handbook of Extractive Metallurgy in 4 volumes.

ABSTRACT
Acid-resisting bricks are necessary in the protection of reactors in hydrometallurgical processes. Leaching reactions utilizing such reactors are used for treating laterites, sulfide concentrates, complex oxides, and other mineral raw material. Glasslined vessels and fiber glass reactors also are used.

KEYWORDS
acid digesters, sorel slag, autoclaves, oxyhydrolysis, glass-lined vessels, fiber glass tanks, leaching of sulphide concentrates, platinum metals concentrates, baking process Interceram 58 (2009) [5]

1 Introduction Ceramics are not only used by pyrometallurgists to line furnaces handling molten material but by hydrometallurgists to line reactors handling aqueous slurries. In hydrometallurgy they are known as acid-resisting bricks. A variety of reactors use acid-resistant bricks with varying sizes and shapes and operate in manifold conditions that may be ambient pressure or high pressure. Usually, the temperature does not exceed 200 C. 2 Construction options Metallurgical reactors may be operated at ambient pressure or at high pressure. Temperatures may vary from 80 to 250 C [1]. 2.1 Ambient pressure reactors

Ambient pressure reactors are varied depending on the material to be leached. Those reactors with acid-resistant brick lining vary in shape and size.
2.1.1 Digesters for titanium slag Titanium slag, which also is known as Sorel slag, is produced by a partial reduction of ilmenite with anthracite in an electric furnace. It is used for manufacturing pigment or titanium metal. Digesters used for leaching titanium slag with concentrated sulphu* Laval University, Quebec Coty, Canada G1V 0A6

ric acid are large tanks with a height of 10 m, a diameter of 4 m, a discharge opening of 15 cm at the bottom and a similar opening at the top of the tank. They consist of mild steel with an acid-resistant brick lining, or concrete with lead lining and acid-resistant brick (Figure 1). The finely divided solid with a mass of nearly 18 tons is mixed with the acid (nearly 23 tons). This mixture is heated with high pressure steam to a temperature of about 180 C in order to start the reaction. Once this temperature is reached, the material reacts vigorously since the reaction is exothermic. After a few moments the reaction mass solidifies, and agitation becomes impossible. As a result, it is left in the reactor for about 13 hours until the reaction is completed by its own heat. After cooling, dilute sulphuric acid or water is added in order to dissolve and to discharge the cake. The process is known as baking process and is applied 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 200 C. Hence the term baking is used. 2.1.2 Digesters for zinc sulphide A plant under construction at San Luis Potosi in Mexico shall leach concentrates of zinc

sulfide in an acid medium at a temperature of 80 C with continuous feeding of oxygen. This plant consists of large vertical tanks lined with acid-resistant bricks (Figure 2). 2.2 High-pressure reactors Two currently accepted options of construction of high-pressure vessels are used for leaching sulfide concentrates in an acid medium and at a high temperature: Titanium clad steel A carbon steel shell protected by an impermeable membrane and acid-resistant bricks. Historically, the most common design of reactors for oxidation applications at highpressures consists of horizontal vessels with a carbon steel shell, lead and/or vinyl ester membranes, and two layers of acid-resistant brick linings (Figure 3). The fundamentals of the design of such linings have been the subject of a number of papers. Among other things, the irreversible chemical swelling of the bricks should be noted. Prior to a newly lined vessel going into operation it is cured in an acid solution at a temperature around the boiling point of the solution. During this curing, a chemical reaction occurs in the brick causing an irreversible swelling of the brick with a simultaneous rise of the stresses and tightness of the lining system.

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Fig. 1 Brick lined digester used for leaching titanium slag with concentrated sulphuric acid at 200 C

Fig. 2 Reactors lined with acid-resisting bricks proposed for atmospheric leaching of zinc sulphide concentrates Fig. 3 Brick lining of a metallurgical reactor

When refractory-lined autoclaves are compared with metal-clad vessels, it has to be noted that operational conditions will play a key role in selecting the type of lining to be utilized. For refractory lining, the advantages are: Good corrosion resistance in sulfuric acid environment Excellent abrasion resistance

Fig. 4 Steam-agitated autoclave lined with acidresisting bricks for treating laterites by concentrated sulphuric acid at 250 C and 4,000 kPa.

53rd INTERNATIONAL COLLOQUIUM ON REFRACTORIES 2010

September 8th and 9th, 2010 . EUROGRESS, Aachen, Germany

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Refractories for Metallurgy

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ECREF European Centre for Refractories gemeinntzige GmbH Feuerfest-Kolloquium c/o An der Elisabethkirche 27 53113 Bonn GERMANY Tel.: +49(0)228-91508-45 Fax: +49(0)228-91508-55 E-Mail: info@feuerfest-kolloquium.de www.feuerfest-kolloquium.de

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Fig. 5 Horizontal autoclave

Fig. 6 Installing acid-resisting brick in a horizontal autoclave

Fig. 7 Rotating horizontal cylindrical autoclave

Fig. 8 Cross section of rotating spherical autoclaves

Excellent resistance to oxidation and ignition. The disadvantages, however, are: Increased on-going maintenance costs Requirement of larger vessels to accommodate refractory lining Lower temperature limitations On the other hand, the advantages for titanium-clad lining system are: Excellent corrosion resistance to oxidizing environment Titanium can be in direct contact with process media resulting in smaller and lighter vessels High-temperature limitation up to 300 C The disadvantages are: Potential for ignition in enriched oxygen environment Reduced abrasion resistance with low alloy grades Susceptible to pitting and/or crevice corrosion in reducing environment. According to their shape, autoclaves may be in the form of cylinders vertically mounted or horizontally installed, spherical, or in form of a long horizontal tube. The method of agitation in an autoclave may be affected by injecting high-pressure steam. The high-

pressure steam may be injected either mechanically or by rotating the whole autoclave. Vertical autoclaves usually are agitated by means of steam or sometimes mechanically. Horizontal autoclaves are agitated mechanically by impellers and sometimes by rotation, while spherical autoclaves are agitated by rotating the whole autoclave slowly around its horizontal axis. Some horizontal autoclaves also are agitated by rotation. In general, industrial autoclaves have volumes of 10 to 70 m3 and operate at a pressure of 2,5005,000 kPa. However, autoclaves with a volume of 700 m3 have been introduced recently. When the operating media are corrosive, the components of the equipment consist of special steel alloys, titanium, and other high-grade materials. In some cases, the interior surface of the autoclaves is lined with rubber or ceramic material. Autoclaves are usually connected in series to achieve continuous operation. When laid horizontally they usually are mounted on a slope of about 8 degree of angle in order to provide a gravity induced flow from one to the next.

2.2.1 Steam-agitated autoclaves This is the simplest type, and is used for leaching a material that requires no aeration. An autoclave for this purpose is a vessel capable of withstanding the pressure of operation and with the necessary openings for feeding and discharging the pulp. The diameters vary from 1.5 to 2 m, while the heights vary from 6 to 12 m. The upper part of the vessel contains apertures for feeding the pulp, a manometer, safety valve, and a discharging pipe. The steam is fed through the bottom of the vessel for the purpose of heating and mixing. Autoclaves with acid-resistant brick linings are used for leaching oxidized ores, e.g., laterites, by means of concentrated sulphuric acid at a temperature of 250 C and a pressure of 4,000 kPa. In the Moa plant, Cuba, the steel shell is first lined in the inside with a 6 mm thick layer of lead (Figure 4). The protective brick lining consists of an acid-proofed brick and of a carbon brick. Under usual operating conditions, acid-resistant bricks are exposed to crack processes, while carbon bricks are not exposed to crack processes. Thus, the carbon brick protects the acid-resistant brick from corrosion and erosion. All interior

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Fig. 10 View of metallurgical plant using glass lined reactors for leaching platinum metals concentrates

11

Fig. 9 Oxyhydrolysis reactor

parts of the autoclave and also the connecting pipes are made of titanium. Stainless steel only is used in areas where the temperature is lower than 100 C. 2.2.2 Horizontal autoclaves These are usually designed with four compartments (Figure 5), large reactors with six compartments. Oxygen or air for leaching is always injected at a point under the bottom impeller to utilize the impeller for dispersion. Reagents are injected into the liquid phase. Slurry is discharged from the autoclave through a dip-pipe or by overflow through a nozzle located at the desired operating level. Figure 6 shows workers installing acid-resistant bricks inside an autoclave. 2.2.3 Rotating autoclaves The rotating autoclaves may be cylindrical or spherical in shape and constructed of steel with a proper lining. They turn on heavy pivots at a rate of 815 rpm. The loading and unloading of the pulp and the admission of steam are carried out through one of these pivots. The driving and turning of the autoclave are accomplished through the other pivot. Figure 7 shows a rotating cylindrical autoclave used for leaching concentrates of tungsten and molybdenum at a temperature of 225 C and a pressure of 2,500 kPa, while Figure 8 presents a rotating spherical autoclave used for treating titanium ores. 3 Selection of ceramic materials The selection of suitable masonry materials for an autoclave lining system is a challenging task considering the mechanical, thermal, and mechanical stresses encountered in pressure hydrometallurgical processes [2]. The design of brick linings has to take into account the almost non-elastic behavior of the brick inside a relatively high elastic steel vessel. Bricks which have been successfully applied in autoclaves have a low content of Al2O3 (nearly 23 %) and an increased content of SiO2 (nearly 70 %). Bricks with a higher content of Al2O3 are distinguished by an elevated solubility in acids. Depending on the abrasive characteristics of the slurry, ceramic bricks with an increased content of silicon carbide bricks (90 % SiC) can be used. Clay bonded SiC materials have been successfully installed. Two types of fireclay masonry are used in autoclaves: Pressure vessel grade, is a less dense material that offers excellent acid resistance and good thermal shock resistance Standard duty acid brick, is a dense material that offers excellent acid resistance but poor thermal shock resistance The mortar used for joining the brick is a key component of a chemically resistant lining system. Resin mortars are formulated as two-component systems: liquid resins which act as a binder, a powder containing inert filler and a catalyst. The catalyst causes the resin to cure when the two components are mixed prior to usage. Furan resin mortars have been used commercially for more than fifty years. They are synthesized by polymerization of furfuryl alcohol, co-polymerization of furfuryl alcohol and furfural, or by condensation of furfuryl alcohol and formaldehyde under acidic conditions. The inner filler is selected for its chemical resistance; carbon, silica, and barite powders are commonly used. Furan resins are resistant to most acids and alkali compounds, but not to strong

Fig. 11 Medium temperature autoclaves made of fiber glas

oxidizing agents. Hence they only are suitable for processes not using oxidants, e.g., in the up-grading of Sorel slag at a temperature of 150 C and in hydrochloric acid medium. Maximum service temperature ranges from 175 to 220 C. A disadvantage of these resins is their relatively high shrinkage during the curing process which may cause the brick to crack. The cracks, however, can be repaired easily by filling them with mortar resin before commissioning the vessel. 4 Reactors for oxyhydrolysis Oxyhydrolysis is an oxidation reaction accompanied by hydrolysis and is used to recover hydrochloric acid from aqueous solutions of ferrous chloride which is generated in leaching processes: 2FeCl2 + 1/2O2 + 2H2O Fe2O3 + 4HCl The reaction is performed in a reactor as shown in Figure 9. 5 Other reactor options Besides brick-lined reactors there also exist glass-lined vessels (Figure 10) as well as fibre glass tanks and autoclaves (Figure 11).
References
[1] Habashi, F.: Textbook of Hydrometallurgy, 2nd edition. Mtallurgie Extractive Qubec, Sainte-Foy, Qubec City 1999 (distributed by Laval University bookstore) [2] Collins, M.J. and Papangelakis, V.G. (eds.): Pressure Hdrometallurgy. Canadian Institute of Mining, Metallurgy, and Petroleum, Montreal 2004

Received: 24.07.2009