Merits of using andalusite-based refractories compared to ... · free silica. Since andalusite does not require calcining it offers significant economies in that it saves energy,
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Introduction
The refractory industry in recent years haswitnessed a dramatic increase in the cost ofvirgin raw materials. This has been largely dueto increasing development in the Asianmarket, particularly India and China, whereowing to domestic demand materials such asbauxite and magnesia are no longer readilyavailable for export (Buhr and Spreij, 2009;Industrial Minerals; Hutton, Yates, and Green,2009; Buhr et al., 2006; Schmidt-Whitely,2008; Feytis, 2010; Tran, 2007; Wanecq,2010; O’Driscoll, 2003; Saxby, 2012). In the1990s low-priced Chinese bauxite replacedother alumina-bearing materials such asandalusite, mullite, and in some instanceseven chamotte. At that time it was easy forrefractory suppliers to provide their customerswith new refractories having higher aluminacontents (Buhr and Spreij, 2009). The generalperception was that a higher alumina contentmeant superior performance. For this reason,bauxite-based refractories became a preferredoption where a higher alumina content was
required. With raw materials being the majorcost driver in the refractories business, manyrefractory producers outside China are facingan uncertain future. Escalating costs andfalling quality of imported Chinese rawmaterials put local manufacturers at significantdisadvantage compared to Chinese refractoryproducers, who can export to South Africa atzero rate import duties (Buhr and Spreij, 2009;Feytis, 2010; Saxby, 2012). The situation hassince changed in the past years, especiallysince 2007 (Buhr and Spreij, 2009). This isillustrated in Figure 1.
The objective of this paper is to show thatthe usage of andalusite refractories could berevived in applications where they have beenreplaced by bauxite. This is driven by bothtechnical and economic factors.
Availability of raw materials
Andalusite
Andalusite supply is fairly tight, withcommercial sources limited to South Africa,which is the major producer, and France(Feytis, 2009; Xiong, 2010). Damrec, throughits subsidiary Samrec, has four andalusitemines in South Africa producing more than200 000 t/a. Andalusite Resources, analternative supplier, operates close to theThabazimbi andalusite facility of Imerys,owned by Damrec (Feytis, 2010). Chinaproduces andalusite on a smaller scale, mainlyfor domestic uses. The typical composition ofSouth African andalusite deposits is given inTable I.
Merits of using andalusite-based refractoriescompared to bauxite-based refractoriesby M. Nyoka*, D. Brazier*, T. Courtney*, and R.A. Parry*
SynopsisHistorically bauxite-based refractories have been used in applicationswhere andalusite-based refractories could work. Bauxite-basedrefractories were chosen over andalusite-based refractories mainlybecause of the availability of low-cost Chinese bauxite and alsobecause many furnaces were designed by international companiesthat cannot easily access high-quality products. Currently, theavailability of low-cost bauxite is under threat as a result of highexport duties and tariffs as well as restrictions on the amount ofmaterial that China allows to be exported. South Africa is a majorproducer of andalusite, and this guarantees stability with respect toboth availability and price. Refractories based on andalusite have anadded economic advantage over bauxite-based refractories in thatunlike bauxite, which requires high-temperature calcination beforeuse, andalusite is used in its raw state. This paper constitutes aliterature study of the merits, both technical and economic, of usingrefractories based on andalusite compared to bauxite-based refrac-tories.
Metallurgy, 2013. ISSN 2225-6253. This paperwas first presented at the, Refractories 2013Conference, 23–24 April 2013, Misty Hills Country Hotel and Conference Centre, Cradle ofHumankind, Muldersdrift, South Africa.
647The Journal of The Southern African Institute of Mining and Metallurgy VOLUME 113 AUGUST 2013 ▲
Merits of using andalusite-based refractories compared to bauxite-based refractories
Bauxite
The typical chemical analysis for refractory grade bauxite isgiven in Table II.
The refractories industry is in general dependent on Chinafor raw materials, for example 95% of refractory bauxiteproduction is controlled by China (Buhr and Spreij, 2009;Hutton, Yates, and Green, 2009; Schmidt-Whitely, 2008;Wanecq, 2010; O’Driscoll, 2003). China is also a majorsupplier of refractories (Buhr and Spreij, 2009). In China theintroduction of environmental regulations and energyefficiency policies resulted in the closure of highly pollutingshaft and round kilns (Hutton, Yates, and Green, 2009).Although welcomed environmentally, this move led toshortages in raw materials and increased costs. On the otherhand, China changed its policy, and now discourages theexport of raw materials (Buhr and Spreij, 2009; Hutton,Yates, and Green, 2009; O’Driscoll, 2003). This has beenbrought about by limiting the volume of material by imposinga system of export licenses, fees, and taxes. Exports of rawmaterials such as dead-burned magnesite, graphite, andbauxite, for example, are restricted and heavily taxed (Buhret al., 2005; Tran, 2007; Wanecq, 2010):
➤ The export tax on bauxite is 15%➤ Export licenses are auctioned to selected domestic
bidders only
➤ The export license cost far exceeds the issue price➤ An output VAT of 17% is raised (from 2006).
None of these costs are borne by Chinese domesticproducers, and exports of finished products made from theseraw materials are not taxed (Buhr and Spreij, 2009). Theresult of these measures has been a steep rise in price in theglobal market. It is important to note that refractory productexports are not subject to such limitations. Due to thelicensing and taxation of exported raw materials, Chinesedomestic producers of refractories enjoy a cost advantage inexport markets (Buhr and Spreij, 2009; Tran, 2007; Wanecq,2010).
The net result of these measures by China is that interna-tional demand for raw materials exceeds supply, and theresulting increase in costs is often passed on to the user.With China being a player in the refractories business as well,this strategy is not always an advantage. To remainprofitable/viable, refractory users have to turn to alternativematerials that can serve the same purpose. One such exampleis the use of andalusite refractories in applications wherebauxite is currently being used (Buhr and Spreij, 2009).Being a locally produced raw material, South Africanandalusite is not subject to export restrictions. South Africa isthe major producer of andalusite, and this guaranteesstability with respect to both availability and price. A stablesupply of andalusite as an alternative to bauxite ensures thatthe local refractory manufacturing industry is protected. Thelocal user industry is also guaranteed a consistent supply of ahigh-quality product that is not subject to foreign exchangefluctuations. Compared to bauxite as a refractory rawmaterial, andalusite offers the following advantages:
➤ An andalusite crystal remains stable with a smallincrease in volume after firing, and hence the internalporosity does not change. Andalusite does not,therefore, require any preparatory firing before use(Dubreuil and Sobolev, 1999; Hubert, 2001). Bauxitesuitable for use as a refractory aggregate is producedby calcining the ore at 1600-1650°C (Bradely andHutton, 2011. Calcination is done to drive offchemically combined water, to sinter the material atsufficiently high temperature for it to shrink to a higherdensity and low porosity, and to convert all the aluminaand silica into corundum and mullite so that there is no
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648 AUGUST 2013 VOLUME 113 The Journal of The Southern African Institute of Mining and Metallurgy
Table I
Typical chemical composition of South African andalusite deposits (Hubert, 2001)
Concentrate Al2O3 SiO2 Fe2O3 TiO2 CaO MgO Na2O K2O LOI
Figure 1—Price development of high-alumina refractory raw materials2003–2009 (Industrial Minerals)
free silica. Since andalusite does not require calcining itoffers significant economies in that it saves energy, anadvantage that is certain to be of importance in thelight of increased energy costs (Overbeek, 1989, Ihlen)
➤ Andalusite offers better scope for control ofdimensional tolerances and warpage, especially in themanufacture of complex shapes
➤ Andalusite is one of the minerals that can be used at itsnatural grain size as an aggregate in the manufactureof refractory bricks
➤ Andalusite has a higher chemical purity than otherrefractory raw materials, particularly bauxite andchamotte (Hubert, 2001). Furthermore, the grain sizeis consistent up to a few millimetres, each grain being asingle monolithic crystal with a very low open porosity.The low content of impurities (Figure 2) such as Na2O,K2O, MgO, CaO, Fe2O3, TiO2 results in a small amountof glass phase at high temperatures, and as a resultprovides a high resistance to thermal shocks, a highdeformation temperature, and a good creep resistance(Xiong, 2010; Hubert, 2001; Dubreuil, Filari, andSobolev, 1999). These parameters are much higherthan those of corresponding alumina-containing refrac-tories based on bauxite, mixtures of fireclay andbauxite, or mixtures of bauxite and alumina.
The refractory characteristics of andalusite are related toits ability to form the refractory mullite phase, whichcombines high strength with resistance to physical andchemical corrosion at elevated temperatures (Dubreuil andSobolev, 1999; Overbeek, 1989; Ihlen, 2000; Hubert, 2001;Dubreuil, Filari, and Sobolev, 1999). These properties aredesirable at high temperatures and in chemically corrosiveenvironments. In the fired state a refractory based onandalusite is composed of predominantly mullite as the majorphase, together with glass, whereas a bauxite-based materialis composed of corundum as the major phase with minorquantities of mullite and glass (Overbeek, 1989).
Advantages of andalusite-based refractories overbauxite-based refractories
High refractoriness under load
Refractoriness under load refers to the ability of a material towithstand specific conditions of load, temperature, and time(Baxendale, 2004). It is dependent on the softening point and
the amount of glassy phase within the refractory system.Andalusite-based refractories are associated with a highrefractoriness under load (Xiong, 2010; Hubert, 2001). Thisis due to the low volume and high viscosity of the liquidphase formed and the very rigid structure of the mullitizedmicrostructure.
High creep resistance
Creep in compression is described as plastic deformation of arefractory under a specific stress over time. As with refrac-toriness under load, the ability of a refractory to withstandcreep under compression depends on the softening point andthe amount of glass phase in the refractory system(Baxendale, 2004). Andalusite-based bricks show extremeresistance to creep during thermal cycling between 1000°Cand 1500°C (Xiong, 2010; Hubert, 2001). Because ofimpurities (Figure 2) in bauxite, especially alkalis, a moltenphase forms at temperatures as low as 1100˚C (Buhr andSpreij, 2009). The presence of a molten phase decreases thecreep resistance despite the overall higher alumina content ofbauxite.
Good resistance to chemical attack and penetrationby slag and metal
Andalusite-based refractories offer excellent resistance topenetration and attack by slag and metal. This is due to thedense, homogenous single-crystal structure, in which thereare virtually no channels of weakness along which slag canpermeate and travel (Buhr and Spreij, 2009; Dubreuil andSobolev, 1999). As a result, andalusite-based refractories aresuperior to refractories based on chamotte, bauxite, and
Merits of using andalusite-based refractories compared to bauxite-based refractories
649The Journal of The Southern African Institute of Mining and Metallurgy VOLUME 113 AUGUST 2013 ▲
Figure 2—Chemical impurities in alumina aggregates (Hubert, 2001)
Figure 3—Refractoriness under load of various alumina bricks (Hubert, 2001)
Figure 4—Creep resistance of andalusite and bauxite bricks (Hubert, 2001)
Merits of using andalusite-based refractories compared to bauxite-based refractories
bauxitic clays, in which even the smallest piece of material isstill a composite of minerals between which the slag canpenetrate.
Thermal shock resistance
Refractories based on andalusite exhibit high resistance tothermal shock. This is attributable to their typical networkmicrostructure (Buhr and Spreij, 2009; Xiong, 2010; Dubreuiland Sobolev, 1999; Overbeek, 1989; Ihlen, 2000; Hubert,2001; Dubreuil, Filari, and Sobolev, 1999). The liquid glassyphase that is entrapped in the mullite crystal acts as a shockabsorber that prevents crack initiation during thermal cycling.
Material requirements
The density difference between andalusite and bauxite refrac-tories is typically 8–10% (Buhr and Spreij, 2009). Bauxite-based linings therefore have a higher material demandcompared to andalusite-based linings, a factor that needs tobe considered in economic comparisons of lining concepts.
Conclusion
Andalusite-based refractories possess superior criticalrefractory properties over bauxite based-refractories and canthus be used in applications where bauxite-based refractoriesare currently used. Andalusite-based refractories often conferbetter thermomechanical properties such as hot strength,refractoriness under load, creep resistance, and thermal shockresistance. South Africa, being the single biggest producer ofhigh-quality refractory-grade andalusite, guarantees stabilitywith respect to price and availability, whereas bauxite, whichis an imported product, is subject to export restrictions andforeign exchange fluctuations.
References
BAXENDALE, S. 2004. Testing of refractory materials. Refractories Handbook.
Schacht, C.A. (ed.). CRC Press. pp. 451–473.
BRADELY, M. and HUTTON, A. 2011. An overview of refractory raw materials –
part 1, alumina. The Refractories Engineer, May. pp. 21–22.