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Abstract
Zircon is one of the most stable chemical compound due to the strong bond between zirconia and silica in its molecule. Therefore, any extraction
for zirconium metal or other useful zirconium compounds must start with the breakdown of such bond. The breakdown of zircon using the alkali
fusion method is a well-known techniques and can be more favorable than using traditional chlorination breakdown if less drastic reaction conditions
have been obtained. For such reason, the presence work study the fusion of zircon with equimolar ratio of KOH and NaOH as an alternative for
using NaOH and Na2 Co3 . The influence of varying experimental conditions on the zircon fusion has been studied. These variables included the
amount of alkali used, the temperature of the reaction, and the reaction duration. Using 20% excess of alkali mixture at 550 ◦ C with only 60 min
reaction time was favorable to get 96% zircon decomposition.
© 2007 Elsevier B.V. All rights reserved.
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doi:10.1016/j.jallcom.2007.06.032
578 A.M. Abdelkader et al. / Journal of Alloys and Compounds 460 (2008) 577–580
fact that the melting point of Na2 CO3 is 2.5 times higher than Table 1
that of NaOH (858.1 and 323 ◦ C, respectivly) favor the used of Analysis of Rosetta zircon sand concentrate
NaOH [12]. Another reason for useing caustic soda comes from Compound Weight (%)
its enviromental effect compered with soda ash which evolve ZrO2 + HFO2 66.42
CO2 during the reaction with zircon. SiO2 32.23
NaOH is cheap and available as a byproduct from chemi- Fe2 O3 0.14
cal industry. However, this step still represents a cost problem TiO2 0.22
due to the energy consumption in the high temperature reac- ThO2 0.02
U3 O8 0.04
tion. Improving the economic consideration of this step can be MgO 0.02
achieved by optimizing the reaction condition to increase zir- CaO 0.01
conium recovery or by reducing the energy required to melt RE oxides 0.07
the alkali. The later can be achieved if the reaction temperature Al2 O3 0.06
decreased by using eutectic mixture of alkalis. Also reducing K2 O <0.01
Na2 O <0.01
the reaction temperature will reduced the contraction engineer- P2 O5 0.13
ing materials problems and therefore increases the life of the
equipment. The contamination of the product by the crucible
materials will also minimize. 2.2. Experimental procedure
Gircinov et al. [13] reported that a nearly equimolar ratio of
NaOH and KOH melt at 185 ◦ C. This mixture is available as In each test run, a sample of 183 g zircon (one mole) was mixed with equimo-
lar mixture of KOH–NaOH in proportion ranged from the stoichiometric to 1.5
chemical industrial waste. However, using this alkalis mixture
times stoichiometric as theoretically determined from reaction (4) (zircon: alka-
to breakdown zircon was not reported. The present work has lis mole ratio ranged from 1:4 to 1:6). The mixture then charged in type 316-L
a claim to study the decomposition of Egyptian zircon by the stainless steal crucible having the dimension of 10 cm diameter and 20 cm height.
action of the eutectic mixture at low temperature and determine Electric furnace was used to heat the mixture to the required fusion temperatures
the optimum reaction condition. which changed from 350 to 600 ◦ C. The fusion time also changed from 60 to
150 min to study the effect of the duration time.
The reaction between KOH and zircon can be represented by
After the required fusion time, the reaction product is allowed to cool over
the following reaction: night and then milled using a mortar and pestle (if necessary). The obtained frit
was weighted before it leached with fivefold its weight of hot water to remove
soluble sodium silicate and/or potassium silicate beside any excess amount of
ZrSiO4 + 4KOH → K2 ZrO3 + K2 SiO3 + 2H2 O (3)
NaOH and/or KOH. The solid hydrous zirconium was separated from the silicate
solution by filtration and then dried in oven at 200 ◦ C. To ensure complete drying
The melting point of KOH is 406 ◦ C [11], G for this reaction the sample was removed from the oven and weighed each hour until the weight
at 298 ◦ K is expected to be more negative than that of reaction of sample is constant. The dried powder was then leached with excess amount
of any concentric acid (sulfuric, nitric and hydrochloric acids were used) to
(2) and hence one can expect that the former has slightly more separate the acid soluble zirconium part from the unreacted zircon. The later
decomposition effect on zircon than NaOH. Therefore, when the was filtered off from the solution, dried carefully, and weighted, the extent of
mixed alkalis used, the competition of KOH is longer than that of the decomposition reaction was then determined from the following equation:
NaOH, which mean that the molar percent of KOH may decrease original weight of zircon − unreacted zircon
than that of the eutectic ratio. The melting point of the alkalis zircon decomposition (%) =
original weight of zircon
mixture will raise but the heat generate from the exothermic × 100
reaction can obstruct this problem. The Co-decomposition of
zircon by the two alkalis may also be the mechanism of the
reaction. This can be illustrated by the following equation:
3. Results and discussions
ZrSiO4 + 2KOH + 2NaOH → NaKSiO3 + H2 O (4) 3.1. Effect of temperatures and zircon to alkalis ratio
Fig. 1. Effect of temperature and KOH–NaOH excess amount on the zircon Fig. 3. Effect of time on the digestion of zircon with KOH–NaOH at 550 ◦ C and
decomposition. 40% excess alkalis.
4. Conclusions
ature and the time required for heating the reactant. Using of [7] J.L. Rodrı́guez, M.A. Rodrı́guez, S. De Aza, P. Pena, J. Eur. Ceram. Soc.
20% excess of alkali mixture at 550 ◦ C with only 60 min reac- 21 (3) (2001) 343–354.
tion time have been selected as the optimum reaction condition. [8] C.K. Gupta, S. Venkatachalam, A.C. Bidaye, Metall. Mater. Trans. 30B
(1999) 205–213.
Such conditions succeed to obtained 96% decomposition of zir- [9] W.W. Stephens, in: G.D. Franklin, R.B. Adamson (Eds.), Extractive Met-
con. Another approved advantage for the present method comes allurgy of Zirconium—1945 to the Present Paper Published in “Zirconium
from the friable product from the fusion reaction which elimi- in the Nuclear Industry: Sixth International Symposium “ASTM STP 824,
nate further grinding step. However, further work must be done American Society for Testing and Materials, 1984, pp. 5–36.
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(1995) 73–81.
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of Zircon: Optimization of the Alkali Fusion Step, vol. 42, Industrial and
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