Key Engineering Materials Vols. 206-213 (2002) pp.

1891-1894 2002 Trans Tech Publications, Switzerland

Use of Selected Minerals as Secondary Raw Materials in Cement Industry. Part I: Effect on the Burnability of Raw Mix Tsivilis S.1, Kakali G.1, Perraki T.2, Stamatakis M.3, Kolovos K.1, Aivaliotis J.1, Perraki M.2
1

National Technical University of Athens, Chemical Engineering Department, 9 Heroon Polytechniou St., 15773 Athens, Greece
2

National Technical University of Athens, Mining Engineering Department, 9 Heroon Polytechniou St., 15773 Athens, Greece
3

National University of Athens, Department of Geology, Panepistimiopolis, Ano Ilissia, 15784 Athens, Greece

Keywords: cement, raw mix, mineral additions, burnability. Abstract. It is well known that the most energy demanding stage in the cement industry, is the sintering process. The decrease of the energy consumption during the sintering can be brought about either by the improvement of the kiln design and performance or by the addition of mineralising or fluxing agents that accelerate the solid reactions and/or lower the melting point of the clinker liquid phase. It has been found that certain foreign elements, despite their low concentration in cement raw mix, may accelerate the sintering reactions and improve the reactivity of the cement raw mix. The subject of this paper is to investigate the possibility to introduce small amounts of minerals, containing these elements, in the cement raw mix. The minerals, iron rich wolframite, stibnite and a wolframite-stibnite assemblage, were selected in order to introduce W, Sb and S in the cement raw mix. One reference and twelve modified mixtures, prepared by mixing the reference sample with 0.5, 1.0, 1.5 and 2.0 % w/w of the above minerals, were studied. The effect on the reactivity of the raw mix is evaluated on the basis of the unreacted lime content in samples sintered at 1000, 1100, 1200, 1300, 1350, 1400 and 1450oC. It is concluded that minerals containing Sb promote the consumption of the free lime, in the most effective way. In addition, the sintering reactions in all samples were recorded by means of differential thermal analysis (DTA). As it is shown, the added minerals affect mainly the final stages of the sintering and specifically the reactions that proceed in the presence of the liquid phase. This fact indicates that the constituents of the added minerals affect mainly the formation and the properties of the melt and therefore change the reactivity of the mixture at high temperatures. Introduction The manufacture of cement requires a high degree of energy utilization. Among all the processes involved for cement manufacture, the most energy demanding stage is the sintering process. The decrease of the energy consumption during sintering can be brought about either by the improvement of the kiln design and performance or by the addition of selected materials that they can act as mineralizing or/and fluxing agents, accelerating the solid reactions and/or lowering the melting point of the clinker liquid phase [1]. Secondary materials that can be used as mineralizers or fluxes are industrial by-products (blast furnace slag, spent catalysts etc.), industrial wastes and minerals [2]. As a precondition, secondary materials must satisfy a number of requirements, regarding the properties and the performance of the clinker and the cement made, as well as the

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uniformity and stability of the production process. Furthermore economical incentives should stimulate their use [3]. Previous work carried out in our laboratory has led to the conclusion that certain foreign elements exert a positive effect during burning by accelerating sintering reactions and by improving the reactivity of the raw mix, despite of their low concentration [4]. This work belongs to a project concerning the use of selected Greek minerals as burning aids in cement raw mix. In this paper, their effect on the burnability of the raw mix is discussed. Their effect on the structure of the produced clinker is presented in Part II. Experimental The minerals wolframite, stibnite and a wolframitestibnite assemblage (coming from Kilkis region, Greece) were selected in order to introduce the elements W, Sb and S in the cement raw mix. Table 1 presents the mineral name, the principal constituent and the chemical composition of the samples. Table 1. Codification, principal constituent and chemical composition of the selected minerals. Code 1 2 3 Mineral name Wolframite Wolframite-stibnite assemblage Stibnite Principal constituent FeWO4 (FeMn)WO4- Sb2S3 Sb2S3 Chemical composition (w/w) WO3: 60%, Fe2O3: 40% WO3: 47%, Sb2O3: 20%, Fe2O3: 13% Sb: 72%, S: 28%

The chemical composition of the raw mix as well as the mineral composition (according to Bogue) and the moduli of the obtained clinker are presented in Table 2. Table 2. Characteristics of the raw mix and the produced clinker. Raw mix Chemical composition (% w/w) SiO2 13.76 Al2O3 3.23 Fe2O3 2.45 CaO 43.11 MgO 0.55 K2O 0.28 LOI 35.62 Clinker Mineral composition (Bogue) (% w/w) C3 S 71.1 C2 S 7.7 C3 A 6.9 C4AF 11.6 Moduli LSF SM AR HM 0.981 2.42 1.32 2.22

One reference and twelve modified mixtures, prepared by mixing the reference sample with 0.5, 1.0, 1.5 and 2.0 % w/w of the above minerals, were examined. The samples were pressed to form pellets and were thermally treated up to 1000, 1100, 1200, 1300, 1350, 1400 and 1450oC for 20 minutes in an electrical furnace. The effect on the burnability is evaluated on the basis of the unreacted lime content in samples sintered at the above mentioned temperatures. The sintered pellets were ground and analyzed by the ethylene glycol method in order to estimate the free CaO (fCaO) content. In addition, the sintering reactions in all samples were recorded by means of Differential Thermal Analysis using a Mettler Toledo TGA/SDTA 851 instrument. The

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temperature was raised at a constant rate (10oC/min) from ambient to 1450oC. The experiments were conducted in a static atmosphere. Results and Discussion Using the fCaO values of sintered samples, the burnability of the raw mix can be estimated from Eqs. (1) and (2), as following: C=fCaO1000+2fCaO1100+2fCaO1200+3fCaO1300+4fCaO1350+4fCaO1400+2fCaO1450 BC = 600/C where BC is the burnability capacity of the raw mix. Fig. 1 presents the fCaO ratio at 1450oC (ratio of fCaO content in modified samples to the fCaO content in the reference sample) as a function of the added mineral and doping concentration. The ratio of BC in modified samples to the BC in the reference sample is presented in Fig. 2, as a function of the added mineral and doping concentration. Values of fCaO ratio less than 1 and BC ratio greater than 1 indicate that the added mineral favors the sintering process. (1) (2)

1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0 0.0 0.5 1.0

fCaO ratio at 1450 C

Fig. 1. fCaO ratio of modified samples burned at 1450oC in relation to the added mineral and the doping concentration.
1.5 2.0

Mineral content (%)

1.4 1.3 1 3 2 1.2 1.1 1.0 0.9 0.8 0.7 0.0 0.5 1.0 1.5 2.0

BC ratio

Fig. 2 BC ratio of modified samples in relation to the added mineral and the doping concentration.

Mineral content (%)

As it is concluded from Figs. 1 and 2, the addition of the stibnite (sample No. 3) or the wolframitestibnite assemblage (sample No. 2) improves the burnability of the raw mix. The

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positive effect of these minerals is proportional to the doping concentration. Wolframitestibnite assemblage exerted the best results, with an optimum addition of 1.5% w/w. Wolframite mineral (sample No. 1) had a negative effect, especially at low concentration. The evaluation of the DSC curves of the modified samples led to the following remarks: In all modified samples the reactions associated with the decomposition of CaCO3 (in the temperature range of 800-900oC) and clinkerization (1200-1450oC) are recorded, suggesting satisfactory burning of all samples and clinkerization. The added minerals do not affect the decomposition of CaCO3. On the opposite, considerable alterations are observed concerning the reactions that proceed in the presence of the liquid phase. This fact indicates that the constituents of the added minerals are dissolved in the liquid phase, affecting mainly the formation and the properties of the melt and therefore change the reactivity of the mixture at high temperatures. Conclusions From the present study the following conclusions can be drawn, concerning the effect of the selected minerals on the burnability of the cement raw mix: Minerals containing Sb promote the consumption of free lime, in the most effective way and the positive effect increases by the increase of the doping concentration. The wolframite-stibnite assemblage exerted the best results, improving the burnability of the raw mix, with an optimum addition of 1.5% w/w. The added minerals affect mainly the final stages of sintering and specifically the reactions that proceed in the presence of the liquid phase. Aknowledgements The authors wish to express their thanks to the Greek General Secretariat of Research and Technology for the financial support of the research, under program Grant No.: PENED 99ED 568. References [1] G.K. oir, F.P. Glasser: Proc. 9th Int. Congress on the Chemistry of Cement, Delhi (1992), pp. 125. [2] J.I. Bhatty: Role of minor elements in cement manufacture and use (Portland Cement Association, Skokie, Illinois, U.S.A. 1995). [3] S. Sprung, M. Delort: Proc. 9th Int. Congress on the Chemistry of Cement, Delhi (1992), pp. 155. [4] K. Kolovos, P. Loutsi, S. Tsivilis, G. Kakali: Cem Concr Res Vol 31 (2001), pp. 425.