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Abstract
Zircon is the most important commercial source of zirconium, its compounds and alloys. Several methods are used for
industrial processing of zircon for production of zirconium dioxide and tetrachloride. These methods include sintering of zircon
with sodium carbonate or sodium hydroxide or calcium oxide or calcium carbonate and with potassium fluorosilicate,
chlorination of zircon mixture with coal in blast furnace and carbidization of zircon in a mixture of coal in electric arc furnace.
All these methods are carried out at high temperatures and have many disadvantages.
The present work illustrates a study of a new technique for extracting zirconium from Egyptian zircon concentrate by its
simultaneous ball-milling and pressure alkaline leaching, to improve the recovery of zirconium from zircon. Experiments were
carried out in stainless steel ball-mills of cylindrical shape under different conditions of temperature, pressure and time. The
ball-mills were heated and mechanically rotated in an electric furnace by means of roll mechanism.
The filtrate after leaching of zircon, containing excess of sodium hydroxide was regenerated by its treatment with calcium
hydroxide for purification from silicon impurity. Then, the solution was evaporated to the desired concentration (500 g/l Na2O)
and recycled to the reactor of leaching.
The results obtained show that complete recovery of zirconium from zircon (99.7%) by simultaneous ball-milling and
alkaline leaching was attained at 250 8C within 3 h, using amount of sodium hydroxide 150% of theoretical requirement
(satisfying favourable conditions of zirconate cake for subsequent acid leaching).
The standard free energy (DF o) and equilibrium constant (K) of the reaction of zircon with sodium hydroxide were
calculated as19.58 k cal mol 1 and 2.29 d 1014, respectively. The kinetics of the technological alkaline processing of zircon
in ball-mall autoclaves was studied over the temperature range 150275 8C.
D 2005 Elsevier B.V. All rights reserved.
1. Introduction
occurs widespread as a common accessory mineral tetrachlorides and carbidization of zircon in a mixture
in pegmatites, particularly in syenitic and granitic of coal in an electric arc furnace at 20002200 8C with
pegmatites and granites, diorites and gneisses. Zir- the formation of zirconium carbide, which may be
con, being a heavy mineral and being resistant to subjected to chlorination at 350450 8C for produc-
chemical decomposition and erosion, is concentrated tion of zirconium tetrachloride.
with other heavy resistant minerals in placer depos- Sintering of zircon with sodium carbonate or
its, principally in river and beach sands. Large sodium hydroxide are commonly used for production
commercial detrital deposits are found in Australia, of zirconium dioxide in industry. Chlorination of
Brazil, Ceylon, India, Madagascar, USA and Egypt. zircon mixture with coal and its carbidization, fol-
Zircon is commonly associated with other heavy lowed by chlorination are used for production of
minerals such as illmenite, magnetite, monazite zirconium tetrachloride. All these methods of proces-
and rutile (Abdel-Rehim, 2002a,b; Rittman and sing of zircon are carried out at high temperatures
Nakhla, 1958; Stanley et al., 1975; Tauber and and have many disadvantages; the most important of
James, 1971). them are preliminary high degree of grinding of
In Egypt, zircon occurs as large reserves in rich zircon concentrate, difficulty of equipment design,
deposits of black sands that are found along the rapid corrosion of furnaces and their coatings, high
northern beaches of the Nile Delta from Rosetta to temperature and consequently large expense of elec-
Damietta. The black sand concentrate is composed tric energy.
of ilmenite, magnetite, zircon, rutile, monazite and The present work deals with a study of a new
garnet and makes up about 80% of the concentrate. technique for extracting zirconium from Egyptian zir-
Mineralogical analysis of typical concentrates fol- con by its processing with sodium hydroxide solutions
low: ilmenite 55%, magnetite 1520%, zircon 7 in ball-mill autoclaves; where grinding and leaching
8%, garnet 46%, rutile 1.5% and monazite 0.5 of zircon are combined together in one process at
1%. Zircon is concentrated by gravity, magnetic and lower temperature and shorter time.
electrostatic methods (Abdel-Rehim, 1974a,b; Ritt-
man and Nakhla, 1958; Said, 1990; Stanley et al.,
1975). 2. Experimental techniques
Several methods are used for industrial proces-
sing of zircon to extract zirconium and production This research was carried out using zircon concen-
of zirconium dioxide and tetrachloride (Abdel- trate separated from Egyptian black sands.
Rehim, 1973, 1974a,b, 1990, 1997, 2002a,b; Abdel-
Rehim and Khalil, 1975; Anwar and Abdel-Rehim, 2.1. Characterization of zircon concentrate sample
1972; Bidaye and Venkatachalan, 1999; Doyle and
Duyvesteyn, 1982; Farah and El-Yamani, 1963; Haba- Zircon grains are colorless to pale brown in thin
shi, 1980; Habashi, 1999; Jamrack, 1965; Kaplan et sections, showing short and long prismatic form with
al., 1958; Lustman, 1959; Meerson and Zelikman, rounded ends grains, weak pleochroism, high relief,
1965; Safronov and Evtshovsky, 1956; Stefanyuk straight extinction and high birefringence. Cracking
and Morosov, 1965; Welham and Enhancing, 2000; and inclusions are observed in metamict zircon. Some
Zelikman et al., 1964). These methods include sinter- zircon grains are zoned and twinned. Zircon crystal-
ing of zircon with sodium carbonate at 900 8C; sinter- lizes in tetragonal system and is optically positive.
ing with sodium hydroxide at 600650 8C; sintering Zircon is associated with traces of mineral grain impu-
with calcium oxide or calcium carbonate at 1400 rities such as monazite, rutile, garnet, hornblende, epi-
1500 8C and with calcium oxide and flux (calcium dote, quartz and others.
chloride) at 10001100 8C; sintering with potassium The mineralogical and chemical composition of the
fluorosilicate at 650700 8C; sintering of zircon with zircon concentrate are given in Table 1. It was
aluminium fluoride at 870 8C; chlorination of a mix- observed that the zircon content of the concentrate
ture with coal at 9001000 8C in blast furnace, result- was 97.8% and the remainder 2.2% included the
ing in the distillation of zirconium and silicon associated mineral impurities.
236 A.M. Abdel-Rehim / Int. J. Miner. Process. 76 (2005) 234243
sion of the fine particles of zircon and the reaction rate controlling. The alkali solution reaches the
products. This phenomenon was observed in spite mineral with difficulty. In order that leaching of
of performing the leaching of zircon in ball-mill zircon proceeds, the alkali must diffuse through
autoclaves. The fine zircon particles are surrounded the product layer to reach the surface of the
by compact saturated layer of sodium zirconate and mineral. Therefore, the process is controlled by
silicate. For this suspension of very fine mineral the rate of diffusion of alkali through this layer.
particles and products, the velocity of rotation of In this case, the rate of the reaction may be deter-
autoclave and balls are beyond the critical value mined by application of Janders equation and
such that diffusion through the product layer is CrankGinstlingBrounshteins equation (Eqs. (11)
Zircon concentrate
Regenerated NaOH
Dilution
up to 3% NaOH
Filtration
Filtration
Residue Filrate
H2SiO3 ZrO(SO4) and
Filtrate Residue H2[ZrO(SO4)2]
CaSiO3, CaO.Al2O3 H2SO4
Evaporation Hydrolysis
Filtration
Hydrated zirconium
basic sulphate Filtrate
x ZrO2 . y SO3 . z H2O H2SO4
Drying
lgnition
ZrO2
and (12) respectively). (Habashi, 1980; Blazek, 1973) (2) At 150 and 175 8C, the leaching efficiency of
as the following: zircon is low even at 6 h, reaching 33.4% and
h i2 55.6%, respectively. This is due to the low
kt 1 1 a1=3 11 vapor pressure over the pulp of leaching (3.2
and 5.6 kg/cm2, respectively) and the diffusion
controlled process of leaching of zircon through
kt 1 2=3a 1 a2=3 12 the product layer.
(3) At 250 and 275 8C, complete recovery of
where a=fraction of zircon reacted by time t and zirconium from zircon (99.7%) is attained
k=rate constant of the reaction. within 3 h and remains unchanged with time.
If leaching of zircon is controlled by diffusion At 275 8C and longer time than 8 h, there is a
through the product layer, the experimental data in small decrease of recovery, which may be due
Fig. 4 must give a linear relation, when the right-hand to the partial dehydration of sodium zirconate
side of Eqs. (11) and (12) are plotted vs. time t. As or the formation of complex sodium zirconium
shown in Figs. 7 and 8, they give straight lines at 150 silicate.
and 175 8C, indicating a diffusion controlled model, (4) The calculated values of the standard free
where the slopes of the straight lines give the rate energy (DF o) and the equilibrium constant (K)
constant of the reaction (k). The calculated values of of the reaction of alkaline processing of zircon
the reaction rates at 150 and 175 8C for Fig. 7 with sodium hydroxide solution at 298.15 K (25
(8.4 d 107 and 2.4 d 106 s1) using Janders equation 8C) are19.58 kcal mol1 and 2.29 d 1014,
are in good agreement with those for Fig. 8, 8.3 d 107 respectively. These values reflect the irreversi-
and 2.2 d 106 s1, respectively using CrankGins- bility of the reaction.
tlingBrounshteins equation. (5) The kinetic study of the technological proces-
It is concluded that at 150 and 175 8C, the alkaline sing of zircon by its alkaline leaching in ball-
processing of zircon is a diffusion controlled process, mill autoclaves is governed by the structure of
depending on the rate of flow of alkali solution and its zircon and the condition of the product surface
velocity of diffusion through the product layer to the coating. The experimental data reveal that the
surface of zircon particles. The diffusion resistance rate of the reaction of zircon leaching is con-
through the coherent product layer controls the overall trolled by diffusion through the product layer at
kinetic process. 150 and 175 8C. At 200 8C and higher tempera-
The suggested flow sheet of the technological pro- tures, it is chemically rate-controlled, as con-
cessing of Egyptian zircon is shown in Fig. 9. firmed by the high value of the calculated
apparent activation energy (27.01 kcal mol 1)
and other observations. The rate of leaching of
6. Conclusions zircon is therefore a function of temperature,
time and solidliquid contact.
The study of the technological processing of Egyp- (6) It was found that the most favourable conditions
tian zircon by its alkaline leaching in ball-mill auto- of the technological processing of zircon with
claves revealed the following conclusions: sodium hydroxide, at which complete recovery
of zirconium (99.7%) could be attained, are 250
(1) In general, the recovery of zirconium from zir- 8C within 3 h using 150% of theoretical require-
con increases at different rates, depending on ment of alkali at concentration 500 g/l Na2O.
the temperature and time. The higher the tem- (7) Zircon leaching with alkali solution was
perature and the longer the retention time, the mechanically activated and accelerated in ball-
larger the increase of zirconium recovery will mill autoclaves as a result of the grinding action
be. The increase of zirconium recovery with of steel balls, that caused continuous removal of
temperature is due to the increase of vapor sodium zirconate and silicate from the reacting
pressure over the pulp of zircon leaching. particle surfaces. This leads to the exposing of
A.M. Abdel-Rehim / Int. J. Miner. Process. 76 (2005) 234243 243
fresh zircon particle surfaces to the alkali leach Anwar, Y.M., Abdel-Rehim, A.M., 1972. High pressure hydrome-
solution. tallurgy of leaching of zircon. Bull. Fac. Sci. Alex. Univ. 10,
173 193.
(8) The main advantages of the present technologi- Bidaye, A.C., Venkatachalan, S., 1999. Studies on chlorination of
cal processing of Egyptian zircon can be sum- zircon. Metall. Mater. Trans., B 30 (2), 205 213.
marized as the following: Blazek, A., 1973. Thermal Analysis. Van Nostrand, pp. 61 63.
(a) No preliminary grinding of zircon is required. Doyle, F.M., Duyvesteyn, S., 1982. Aqueous processing of miner-
als, metals and materials. JOM 45 (4), 46 54.
(b) Simultaneous grinding and leaching of zir-
Farah, M.Y., El-Yamani, S.I., 1963. On the alkali sintering of Rosetta
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(c) Relatively low temperature requirement (250 Gerasimov, Ya.I., et al., 1963. Thermodynamics of W, Mo, Ti, Zr,
8C) for alkaline leaching and moderate time, Nb, Ta and their compounds, Chemical Thermodynamics in
compared with sintering processes of zircon. Nonferrous Metallurgy, vol. 3. Metallurgizdat, Moscow,
(d) Cheap and common reagents (sodium hydro- pp. 170 203.
Habashi, F., 1980. Principles of Extractive Metallurgy, vol. 1.
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