Coordenao de Processos Minerais COPM

SOME ASPECTS OF TRICALCIUM ALUMINATE HEXAHYDRATE FORMATION ON THE BAYER PROCESS

Silvia Cristina Alves Frana Paulo Fernando Almeida Braga Jorge Aldi Juarez Moraes Amrico Borges

CT2010-029-00 Comunicao Tcnica ao TMS The Minerals, Metals e Materials Society, em Seattle, Estados Unidos e publicado na Light Metals, pag. 63-66, 2010

Light Metals 2010 Edited by: John A. Johnson TMS (The Minerals, Metals & Materials Society), 2010

SOME ASPECTS OF TRICALCIUM ALUMINATE HEXAHYDRATE FORMATION ON THE BAYER PROCESS

Silvia C. A. Frana1, Paulo F. A. Braga1, Jorge Aldi 2, Juarez Moraes2 & Amrico Borges2
1

CETEM (Center for Mineral Technology), Av. Pedro Calmon, 900 Cidade Universitria Rio de Janeiro-RJ 21941-908 Brazil 2 ALUNORTE (Alumina do Norte do Brasil S.A.), Rod. PA 481, Murucupi, Barcarena-PA 21941-908 Brazil Keywords: Tricalcium aluminate; Filtration; Particle size; Morphology; Bayer process

Abstract Tricalcium aluminate hexahydrate (TCA) - Ca3Al3(OH)12 - is used in the Bayer process as a filter aid during the pregnant liquor polishing. The filtration efficiency depends on some TCA characteristics, such as particle size distribution and morphology and how these particles are formed by physical-chemical reactions that take place during the alumina production. To reach a high performance in the filtration step, it is important to understand the influence of variables like source of calcium - CaO or Ca(OH)2 residence time, stirring speed and temperature in the TCA formation. This study is being developed as partnership CETEM/ Alunorte Alumina do Norte do Brasil S.A., using liquor from the plant streams, to evaluate the efficiency of their process. Preliminary results shown that the formation of TCA particles begins partially, in the first minutes of reaction, and that its morphology and particle size distribution can change, during the experiment, depending on the particle size distribution of lime and impurities, which play an important role in the lime reactivity and in the kinetic of the TCA formation.

with a very well particle size distribution Wittinghton and Cardile (1996). The efficiency of filtration has strong correlation with the particle size distribution of the filter aid; so is important to develop a deep study that can provides knowledge enough helping to control all the variables involved in the TCA formation. Objective The objective of this paper is to study the variables involved in the TCA formation, comprising lime quality, impurities, lime slaking, and reaction time to evaluate the evolution of TCA particle size distribution and morphology, and stoichiometric ratio between Al2O3/NaOH and Al2O3/CaO.

Methodology TCA is produced in two operational lines at ALUNORTE plant. The difference between them is the stoichiometric ratio of slaked lime in the liquor stream, reaction time and stirring conditions. The industrial experience relates differences in the quality of the formed products, which should be sampled and studied to understanding of the influence of such differences in the liquor filtration efficiency. The study of TCA preparation was run in different steps, as follows: 3.1 - Studies of production of TCA in laboratory and determination of the variables that affect its formation The chemical reactions involved in the production of TCA in the Bayer process lime slaking to form calcium hydroxide (Eq.1); Hydroxide components react with can react competitively with carbonates (Eq. 2) and also with aluminate (Eq. 3), as reported by Young (1982): CaO + H2O Ca(OH)2 + heat Ca(OH)2 + Na2CO3 2NaOH + CaCO3 3Ca(OH)2 + 2NaAlO2 3CaOAl2O3.(x)H2O + 2NaOH (1) (2) (3)

Introduction The tricalcium aluminate hexahydrate (TCA), whose chemical composition is Ca3Al3(OH)12, is used in the alumina industry (Bayer Process) as a filter aid, in the step of pregnant liquor polishing, before the crystallization process. Considering a material for filter aid, the particles morphology and size distribution have great importance in the efficiency of that filtration process. As reported in the literature and considering the knowledge from industrial processes, since particles of TCA are formed due to Bayers process chemical reactions, in order to avoid operational or process problems it is indispensable a deep knowledge and the correlation among main process variables, in order to control it and achieves high efficiency. Among the variables that have an important role in the process, it is important to mention temperature, addition of reagents (source of calcium, concentrations, etc), presence of impurities, stirring speed and reaction time are decisive in the quality of TCA formed in the Bayer process (Young, 1982; Whittington and Cardile, 1996; Whittington et al, 1997). The particle size distribution from the TCA formed by the chemical reactions between alumina and Ca(OH)2, for instance, can be changed by the presence of organic matter in the reaction environment. Due to the disturbance provoked in such process by this organic matter, we can add this compound aiming to control the reaction kinetics, enhancing the process to preparing a TCA

It is important to emphasize that reaction rates and its efficiency have strong correlations with the main liquor parameters, like alumina concentration and temperature. The experiments were run with liquor sampled at Alunorte plant stream and any necessary variation in the concentration was obtained by dilution or addition of analytical grade reagents. In

63

this research work, the chemical characteristics of the liquor were 125 g/L Al2O3 and Al2O3/NaOH ratio is 0.41, spent liquor. The lime sample was also supplied by Alunorte, to reproduce, as closer as possible, the industrial process. The slaking process was run in an adiabatic reactor and obtained by the dissolution of CaO in tap water (200 g/L CaO). To study the variables and the answers from productive process of TCA, the following variables were investigated in laboratory and batch scale: i) ii) Independent variables: temperature, alumina and calcium concentration in the liquor and reaction time; Dependent variables: particle size morphology and products formation. distribution and

spectrum was done by comparison with standard contained in the PDF02 (ICDD, 1996) data bank, using a Bruker Diffracplus software. Results and Discussions The first results presented in this section are related to the industrial TCA. It was important to proceed with its characterization in order to know some characteristics and use them as a pattern to obtain a similar product in the laboratory. After presenting such results following will be presented the characterization for TCA products obtained in the laboratory, in batch experiments. After lime slaking the Ca(OH)2 suspension is pumped through basket filters before to be sent to TCA tanks. A TCA sample taken at the bottom of the TCA tank (Alunorte) was characterized by scanning electronic microscopy (SEM/EDS) and the results are shown in the Figures 1(a) to (b).

The reaction took place in a 5L adiabatic reactor, filled with 3.0L of spent liquor and 1.5L of slaked lime (ratio 2:1), at controlled temperature 90oC. The suspension was sampled at each 30 minutes after the beginning of reaction, for chemical and mineralogical determinations.

3.2 - Characterization of TCA produced in the Laboratory Samples of TCA produced in the laboratory were characterized to determine particle size distribution and mineralogical characterization. The liquor used in the reactions was analyzed before and after the reaction to determination of Al2O3 and the ratio Al2O3/NaOH. The characterization will be run to the intermediate and final products, step by step, to evaluate the influence of retention time. The techniques used in these determinations are detailed below. Chemical analyses To determine the chemical assays for the liquor, the analyses were run in a METHRON automatic titrator, using standard reagents.
100 cps

(a)

Particle size distribution The particle size distribution from TCA products obtained by the reaction was measured by laser diffraction technique, using a Mastersizer 2000 MU Malvern Instruments, under constant stirring (1450 rpm) and sonication for 30 minutes before the size determination. The particle size distribution curves were obtained by using Mie theory, and refraction index 1.627 (solids) and 1.33 (water). Such procedure aims to avoid particle agglomeration and mistakes in the in the particle size determination. Particle Morphology It was determined using a Scanning Electronic Microscopy (SEM) FEI Quanta 400, linked to an Energy Dispersion X-ray Spectrometer (EDS) Bruker SDD 4030, 133 eV (resolution). This equipment can operate in a large range of vacuum (0.98-20 Torr). Mineralogical Analysis by X-ray Diffraction The mineral constituents of TCA products was determinate by means of Bruker AXS D5005 diffractometer CoK radiation (35 KV/40 mA); 2 by path, with 1s by path counting time and data collection from 5 to 80o 2. The qualitative interpretation of the
Ca 50 Al Ag Na Ag O Si Ag Ca Ca 0 5 10 Energy (keV)

(b)

Figure 1 Scanning electron micrograph of TCA formed in the industrial plant (Alunorte): (a) agglomerates and hexagonal particles; (b) ED spectrum for the hexagonal particles with the elements

Some authors also report the thin hexagonal or rhombohedral crystalline shapes like TCA by-products (Whittington et al, 1996), specially when the reaction occurs in the presence of Na2CO3, NaCl, Na2SO4 or aluminum hydroxide precipitated from the alkaline solution in the Bayer process (Habashi, 1999). However, in this study the TCA sample was analyzed with no washing, the Na and Al observed in the ED spectrum (Figure 1b) are probably due to remaining liquor covering the particles.

64

The decreasing of Al2O3 concentration is shown in the Figure 2. It can be observed that the concentration decreases strongly in the first 15 minutes of reaction, reaching almost 50% Al2O3 content, a typical behavior from fast reaction kinetics. After such time, the decrease on the concentration is very discrete and up to the end of the experiment the reduction is around 10%. The decrease in the Al2O3 concentration clearly indicates an alumina migration process from the liquor to the TCA formation products. Some papers in the literature report that this reaction may happen in different steps, forming intermediate products considered other calcium aluminate products (Young, 1982; Whittington and Cardile, 1996).

comparing the diffractograms obtained to these two different products, it can be perceived an increasing in the intensity of peaks of TCA along reaction time, probably due to the evolution in the structural formation of TCA. Considering the morphological analysis, the Figures 4 and 5 show the results obtained by scanning electronic microscopy to TCA products, produced during the reaction, at 30 and 120 minutes, respectively. The grains of TCA are fine and homogeneous, and it can be perceived that their morphology become more structured as the time goes on: at 30 minutes the grains are still under formation and shape definition and we can see typical a behavior of particle agglomeration phase; after 120 minutes, the grains shape is better defined and look like bi-pyramidal or octahedral shape (Figure 5).

Figure 2 Variation of Al2O3 concentration with reaction time during the TCA formation

Analyzing the TCA products X-ray diffratogram (Figure 3) obtained at 30 and 120 min time intervals, it is possible to detect the presence of portlandite and TCA (or some byproducts) which subsequently reacts to form TCA, as reported also by Whittington and Cardile (1996).

Figure 4 Scanning electron micrograph of TCA (reaction time 30 min)

TCA

Port

TCA

TCA

Port

TCA Port

70 60 50

Port

Intensity (cts)

40 30 20 10 0 -10 5 10 15 20 25
0

TCA

TCA

TCA

Port
30 min 120 min
45 50 55 60

30

35

40

2 (CoK)

Figure 5 Scanning electron micrograph of TCA (reaction time 120 min)

Figure 3 X-ray diffractogram to products of TCA formation reaction (TCA Tricalcium aluminate; Port Portlandite). The results obtained by x-ray diffraction, for some products of reaction shown the presence of TCA in the sample (standard 861311). The still low peak intensities (around 100 counts) can be explained by the poor crystalline index of the products, once spent liquor (130 g/L Al2O3) was used to produce TCA. However, The evolution in TCA formation can also be observed when taking a look at the results of particle size distribution analysis, as shown in the Figure 6. It is possible to observe the discrete increasing in the average diameter d50 from 6 to 10 m, as the reaction goes on. The same fact was observed by Whittington et al (1997), with an additional comment about the importance of the

65

CaO kind in TCA reaction kinetics, which will have direct effect on the particle size distribution and morphology.
Particle Size Distribution

4.5 4 3.5 V o lu m e (% ) 3 2.5 2 1.5 1 0.5 0 0.1

linear and what the heat released due to exothermic reaction depends on the quality of limes. Hereby, this effect might be investigated on more details during the study, in the future. References Brown, J.P. Studies on filter aid selection to polish alumina plant liquor - Optimization of filtration rate through an effective filter aid particle size distribution, Individual Inquiry, Department of Chemical Engineering, University of Queensland, Australia, May, 2001. Habashi, F. Textbook of Hydrometallurgy. 2nd Edition, Laval University, Quebec City, Canada, 1999. Hassibi, M. An overview of lime slaking and factors that affect the process. 3rd International Sorbalit symposium November 3-5, 1999 New Orleans, LA, USA. HuiLing, V.C., Optimal concentration of filter aid for Bayer alumina precoat filters - Optimization of filtration rate through an effective filter-aid particle size distribution. Individual Inquiry, Department of Chemical Engineering, University of Queensland, Australia, May, 2002. Libby, S.C. The effects of lime/limestone characteristics on causticisation. Light Metals, p. 275-293, 1983. Stutts, D. S. Experimental Planning and Design. Missouri University of Science and Technology, 2004. Whittington, B.I. The chemistry of CaO and Ca(OH)2 relating to the Bayer process. Hydrometallurgy, vol. 43, p. 13-35, 1996. Whittington, B.I. and Cardile, C.M. The chemistry of tricalcium aluminate hexahydrate relating to the Bayer industry. Int. Journl of Mineral Processing, Int. J. Miner. Processing, vol. 48, p.21-38, 1996. Whittington, B.I., Fallows, T.M. and Willing, M.J. Tricalcium aluminate hexahydrate (TCA) filter id in the Bayer industry: factors affecting TCA formation and morphology. Hydrometallurgy, vol. 49, p. 1-29, 1997. Young, R.C. Chemistry of Bayer liquor causticisation. Light Metals, p. 97-117, 1982.

30 min

120 min

10 Particle Size (m)

100

1000

Figure 6 Particle size analyses for the TCA products at different reaction time At industrial plant, the median particle size of TCA for the expected filtration efficiency is around 12-15m, obtained after 6 hours of residence time (formation and growth) in the stirred tanks at 95-105oC. When comparing with the TCA obtained in the laboratory, which has a d50 around 10 m (2 hours), it is possible to conclude that lasting experiments probably can promote the particles growing and probably led to particle sizes closer to typical industrial number. It is also important to pay special attention in control temperature because, as reported by some authors, it has strong influence in the reaction kinetics and, as a consequence, in the particle size distribution. Whittington et al. (1997) observed that despite the fast reaction between the CaO and the aluminate solution in order to form TCA, the remaining Ca(OH)2 can be coated with small TCA particles, producing TCA with broad particle size distribution and smaller d50. On the other hand some authors establish that the slaking temperature is the utmost factor that can affects the causticisation process as well as the particle size distribution and the specific surface of hydrate particles (Libby, 1983). As reported by Hassib (1999), as closer the slaking temperature to 116C as finer the particle size and greater the specific surface would be. Conclusions Some aspects that can affect the reaction and morphology of TCA in the Bayer process were investigated. A comparison with the industrial data for morphology and median particle size have showed that under certain controlled temperature conditions and kind of Ca added, it is possible to obtain TCA particles that can match the Bayer process requirements, in shorter reaction time. As reported by industrial experiences, the presence of fine particles of portlandite (Ca(OH)2) is not desirable, due to the clogging effect that can hinders the filter aid media porosity, having sharp effect in the filtration efficiency. However, it is important to evaluate the Al2O3/CaO ratio as closer as possible to the stoichiometric, possibly having aluminate solution in excess, aiming to avoid the excess of Ca(OH)2 in the reaction. It will be also necessary to determine the particle size distribution of the slaked lime, because this variable will have direct influence in the TCA formation, due to your reactivity. On the present paper the slaking temperature is not considered in a direct way, despite to be well known that the relationship between temperature, specific surface and particle size is not

66