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Journal of Alloys and Compounds 460 (2008) 577–580

Novel decomposition method for zircon


A.M. Abdelkader a,∗ , A. Daher a , Emad El-Kashef b
a
Nuclear Materials Authority (NMA), P.O. Box 530, Maadi, Cairo, Egypt
b Department of Petroleum, Mining, and Metallurgical Engineering, Cairo University, Egypt
Received 29 March 2007; accepted 5 June 2007
Available online 13 June 2007

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.

Keywords: Zircon decomposition; Alkali fusion; Zirconia

1. Introduction silicon parts in the compound. Several industrial methods are


used to decompose zircon include the fusion of zircon with cous-
Zircon sand (ZrSiO4 ) is the source of many industrial useful tic soda (at 600–650 ◦ C) or with soda ash (at 900 ◦ C) [4], thermal
zirconium compounds such as zirconium phosphate, basic sul- dissociation by plasma [5], sintering with a source of alkaline
fate, oxychloride and oxynitride, tetrahalides and pure or doped earth oxides [6,7], chlorination of sand by mixing it with coal
zirconium oxide. From such compounds, it is possible to produce at 900–1000 ◦ C in blast furnace or chlorination at 350–450 ◦ C
zirconium metal by different pyro- and electro-metallurgical of zirconium carbide after carburization of zircon in a mixture
techniques. Furthermore, zirconium alloys can be produced by of coal in an electric arc furnace at 2000–2200 ◦ C [8,9], and
co-reduction or the co-electrodeposition of a precursor contain- mechanochemical treatment of zircon followed by acid attack
ing zirconium and the alloy element or elements. Zircon is a [10].
coproduct or byproduct of the mining and processing of heavy The fusion of zircon with alkalis is one of the earliest decom-
mineral sands for the titanium minerals ilmenite and rutile or the position method. Conventialy, zircon is sintered with soda ash
tin minerals cassiterite and stannite. In Egypt, zircon is associ- or sodium hydroxide to convert to sodium zirconate and sodium
ated with other economic heavy mineral in the black sand which silicate beside carbon dioxide or water vapor according to the
occur infront of the Nile Delta as submerged bars and shoals [1]. following reactions:
Zircon is one of the most chemical stable compounds
(G◦1400 K = 1489.1 kJ/mol) [2]. This is due to the high coor- ZrSiO4 + 2Na2 CO3 → Na2 ZrO3 + Na2 SiO3 + 2CO2 (1)
dination of bisdisphenoid ZrO8 in a tetragonal structure with ZrSiO4 + 4NaOH → Na2 ZrO3 + Na2 SiO3 + 2H2 O (2)
SiO4 tetrahedra [3]. Therefore, mineral acid other than HF can-
not attack zircon and very aggressive reaction conditions are El-Barawy et al. [4] and Focks et al. [11] reported the pres-
require to breakdown the strong binding between zirconium and ence of water insoliuble compounsd such as Na2 ZrSiO5 , and
Na4 Zr2 Si2 O12 specially when the less coustic (Na2 Co3 ) have
been used. These compound will dissociate ducring the acid
∗ Corresponding author. Tel.: +20 122258282. leaching of the product and increase the silica content in the
E-mail address: amr eg@hotmail.com (A.M. Abdelkader). produced zirconium componds. This result combined with the

0925-8388/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
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 shows the results of zircon breakdown with different


2. Experimental work amounts of eutectic alkalis mixture up to 50% excess than sto-
ichiometry at different temperature (350–600 ◦ C) for 2 h. From
2.1. Materials such figure, general scheme can easily observed in which the
decomposition of zircon increased by increasing temperature
Zircon sand concentrate having about 97% assay and produced from black
sands deposits mined at Rosetta beach was supplied by the physical ore dress- and/or alkalis amount. Also, the relationship between zircon
ing department of the production sector, nuclear material authority. The mean decomposition and the excess amount of alkalis seams to be
particle size of concentrate is 63 ␮m and the chemical composition illustrated linear in the chosen zircon: alkali range and for all the tested
in Table 1 as determined by the standard chemical analysis methods. The caus- temperatures. A precision view for the same figure will execute
tic soda and caustic potash used in the presence work were in the analytical
to realize that, the increase in the alkalis amount has slightly
grad (95.9 and 85% purity, respectively). Three type of solution have been used
i.e. sulfuric acid (Adwic 98%), nitric acid (Merck 65%), and hydrochloric acid effect on the breakdown process, the breakdown increased by
(Adwic 32%). All the necessary solutions were freshly prepared using distilled only about 7% when the alkalis increased from 100 to 150% its
water. stoichiometry through all the studied range of temperature.
A.M. Abdelkader et al. / Journal of Alloys and Compounds 460 (2008) 577–580 579

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.

When Daher [18] used 150 g of zircon and NaOH individually


The change in the reaction extent versus the change in temper-
as decomposing agent he observed that; by increasing the initial
ature at 40% salt mixture higher than stoichiometry and for 2 h is
alkali amount in the reactant mixture the obtained frit would
separately reported in Fig. 2, which suggests two plateau regions.
become coarser and harder and additional milling step must be
Below 450 ◦ C the reaction extent ranges from 75 to 84%, and
applied before water leaching. Also, the product in such a high
above 500 ◦ C it increases to 94% and slightly increases to 96.5%
alkali content reaction would tend to adhere to the internal side
at 600 ◦ C. The rapid increase in the reaction extent from 450 to
wall of the reaction vessel and would form layer of a refractory
500 ◦ C indicates phase transformation step, which may be the
materials that is not only difficult to remove after cooling but also
transformation of the phase KNaZrSiO5 to the phases KNaZrO3
hinders the heat transformation from the heating chamber to the
and KNaSiO3 or their similar. Consequently, the temperature of
reactants. He attribute the formation of such hard and adherent
550 ◦ C at 20 mol% excess than stoichiometry has been selected
products to agglomeration and segregation of the alkalis.
as the optimum condition.
In the present work the produced frit from the mixed alka-
Digesting of zircon using NaOH only as the decomposition
lis zircon fusion is almost friable. The hard or coarse clusters
agent has been reported by a number of workers. Daher et al. [14]
were not observed even at the high zircon to alkalis ratio in the
select 650 ◦ C and 40% of excess NaOH as the optimum condi-
reactant and at the low temperature. The low melting point of
tion for 2 h with a zirconium recovery of 97.11%. El-Barawy et
the eutectic alkalis mixture (118 ◦ C) make the reaction start at
al. [4] observed the complete reaction between zircon and NaOH
lower temperature and hence consumption of the present alkalis
at 600 ◦ C and 50% of excess soda for the same time. El-Yamani
mixture would faster than that in the case of high melting point
et al. [15] choose 650 ◦ C and 60% of excess NaOH at 2 h as
salt and therefore would decreased the segregation or channel-
the optimum conditions and obtained 97.6% zircon decompo-
ing of the alkalis. This may also provide another explanation for
sition but they used commercial grade sodium hydroxide. The
the highly salts recovery observed here.
complete dissociation observed by El-Barawy et al. was also
confirmed by the treatment of other zircon concentrate around
3.2. Effect of fusion time
the world as reported by Focke et al. [11] for Richards Bay (South
Africa) zircon, Saha and Chandran [16] for Indian zircon, and
Fig. 3 summarized the result obtained from heating zircon
recently by Naher and Haseeb [17] for Bengaline zircon. All
with KOH (using 130% salt stoichiometry) to a fixed tempera-
these workers used extensive reaction conditions and relatively
ture of 700 ◦ C for different periods. From these results we can
small amount of zircon as a started reaction materials.
concluded that the decomposition of zircon increased sharply
below 60 min where its value reaches about 96%. Unlike NaOH,
the curve represents the relation between zircon decomposition
and time fastened directly above 60 min and no transition region
observed. The reaction extend increased with only 2% when the
reaction time increased from 60 to 150 min which lead to con-
sider the time between 60 and 90 min as the suitable candidate
and more favorable 90 min to give 97.4% zircon decomposition.

4. Conclusions

The fusion of zircon with the equimolar ratio of KOH–NaOH


has been investigated in the present work. It has been proved
Fig. 2. Effect of temperature on the zircon decomposition at 40% excess that using alkalis mixture reducing the energy requirements than
KOH–NaOH mixture. the using of individual alkali by reducing the reaction temper-
580 A.M. Abdelkader et al. / Journal of Alloys and Compounds 460 (2008) 577–580

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