Int. J. Miner. Process.

76 (2005) 234 243

www.elsevier.com/locate/ijminpro

A new technique for extracting zirconium form

Egyptian zircon concentrate
Aly M. Abdel-Rehim
Alexandria University, 69 Sultan Hussein St., Shallalat, Alexandria, Egypt
Received 31 October 2004; received in revised form 7 February 2005; accepted 21 February 2005

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.

Keywords: Egyptian zircon; alkaline processing; kinetics

1. Introduction

Zircon is the most important commercial source

E-mail address: a _rehim@hotmail.com. of zirconium, its compounds and alloys. Zircon
0301-7516/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.minpro.2005.02.004
 A.M. Abdel-Rehim / Int. J. Miner. Process. 76 (2005) 234243
occurs widespread as a common accessory mineral
in pegmatites, particularly in syenitic and granitic
pegmatites and granites, diorites and gneisses. Zir-
con, being a heavy mineral and being resistant to
chemical decomposition and erosion, is concentrated
with other heavy resistant minerals in placer depos-
its, principally in river and beach sands. Large
commercial detrital deposits are found in Australia,
Brazil, Ceylon, India, Madagascar, USA and Egypt.
Zircon is commonly associated with other heavy
minerals such as illmenite, magnetite, monazite
and rutile (Abdel-Rehim, 2002a,b; Rittman and
Nakhla, 1958; Stanley et al., 1975; Tauber and
James, 1971).
In Egypt, zircon occurs as large reserves in rich
deposits of black sands that are found along the
northern beaches of the Nile Delta from Rosetta to
Damietta. The black sand concentrate is composed
of ilmenite, magnetite, zircon, rutile, monazite and
garnet and makes up about 80% of the concentrate.
Mineralogical analysis of typical concentrates fol-
low: ilmenite 55%, magnetite 1520%, zircon 7
8%, garnet 46%, rutile 1.5% and monazite 0.5
1%. Zircon is concentrated by gravity, magnetic and
electrostatic methods (Abdel-Rehim, 1974a,b; Ritt-
man and Nakhla, 1958; Said, 1990; Stanley et al.,
1975).
Several methods are used for industrial proces-
sing of zircon to extract zirconium and production
of zirconium dioxide and tetrachloride (Abdel-
Rehim, 1973, 1974a,b, 1990, 1997, 2002a,b; Abdel-
Rehim and Khalil, 1975; Anwar and Abdel-Rehim,
1972; Bidaye and Venkatachalan, 1999; Doyle and
Duyvesteyn, 1982; Farah and El-Yamani, 1963; Haba-
shi, 1980; Habashi, 1999; Jamrack, 1965; Kaplan et
al., 1958; Lustman, 1959; Meerson and Zelikman,
1965; Safronov and Evtshovsky, 1956; Stefanyuk
and Morosov, 1965; Welham and Enhancing, 2000;
Zelikman et al., 1964). These methods include sinter-
ing of zircon with sodium carbonate at 900 8C; sinter-
ing with sodium hydroxide at 600650 8C; sintering
with calcium oxide or calcium carbonate at 1400
1500 8C and with calcium oxide and flux (calcium
chloride) at 10001100 8C; sintering with potassium
fluorosilicate at 650700 8C; sintering of zircon with
aluminium fluoride at 870 8C; chlorination of a mix-
ture with coal at 9001000 8C in blast furnace, result-
ing in the distillation of zirconium and silicon
235
tetrachlorides and carbidization of zircon in a mixture
of coal in an electric arc furnace at 20002200 8C with
the formation of zirconium carbide, which may be
subjected to chlorination at 350450 8C for produc-
tion of zirconium tetrachloride.
Sintering of zircon with sodium carbonate or
sodium hydroxide are commonly used for production
of zirconium dioxide in industry. Chlorination of
zircon mixture with coal and its carbidization, fol-
lowed by chlorination are used for production of
zirconium tetrachloride. All these methods of proces-
sing of zircon are carried out at high temperatures
and have many disadvantages; the most important of
them are preliminary high degree of grinding of
zircon concentrate, difficulty of equipment design,
rapid corrosion of furnaces and their coatings, high
temperature and consequently large expense of elec-
tric energy.
The present work deals with a study of a new
technique for extracting zirconium from Egyptian zir-
con by its processing with sodium hydroxide solutions
in ball-mill autoclaves; where grinding and leaching
of zircon are combined together in one process at
lower temperature and shorter time.
2. Experimental techniques
This research was carried out using zircon concen-
trate separated from Egyptian black sands.
2.1. Characterization of zircon concentrate sample
Zircon grains are colorless to pale brown in thin
sections, showing short and long prismatic form with
rounded ends grains, weak pleochroism, high relief,
straight extinction and high birefringence. Cracking
and inclusions are observed in metamict zircon. Some
zircon grains are zoned and twinned. Zircon crystal-
lizes in tetragonal system and is optically positive.
Zircon is associated with traces of mineral grain impu-
rities such as monazite, rutile, garnet, hornblende, epi-
dote, quartz and others.
The mineralogical and chemical composition of the
zircon concentrate are given in Table 1. It was
observed that the zircon content of the concentrate
was 97.8% and the remainder 2.2% included the
associated mineral impurities.
236 A.M. Abdel-Rehim / Int. J. Miner. Process. 76 (2005) 234243

Table 1 acid (amount 150% of theoretical requirement) at 70

Mineralogical and chemical composition of zircon concentrate 8C within 30 min in a beaker with electric stirrer.
Mineralogical composition Chemical composition The zirconyl sulphate solution was filtered under
Mineral Content (%) Chemical component Content (%) vacuum and the insoluble residue was washed with
Zircon 97.8 ZrO2 65.75 dilute acid and then water. Filtrate and washed water
Monazite 0.41 SiO2 32.87 were added together and analyzed for the zirconium
Rutile 0.40 Fe2O3 0.43 content.
Ilmenite 0.10 Al2O3 0.40
Garnet 0.32 TiO2 0.41
Epidote 0.11 RE2O3 0.25 2.4. Measurement of vapor pressure
Hornblende 0.12
Feldspar 0.10 Before starting the experiments of zircon proces-
Quartz 0.46 sing, the vapor pressure over sodium hydroxide solu-
tions of different concentrations was measured at
different temperatures, in a specially designed auto-
2.2. Apparatus and procedure clave connected to a manometer.

Experiments of ball-milling and alkaline leaching

of zircon were carried out in stainless steel ball-mill 3. Determination of thermodynamic constants
autoclaves of cylindrical shape with a volume of 250
ml. A number of ball-mills were heated and mechani- Before the study of the technological processing
cally rotated in an electric furnace by means of a roll of zircon, an attempt was made to calculate the
mechanism Abdel-Rehim, 1998, 2002a,b). The tem- thermodynamic constants of the reaction. The ther-
perature was regulated automatically within F 2 8C. A modynamic data given in Table 2 were used in
400-g charge of balls was used, which was equivalent calculations.
to 45% of the total autoclave volume. The weight ratio The free energy of sodium zirconate may be calcu-
of steel balls of diameters 5, 10 and 15 mm was lated from the following equation.
0.5:1.5:2. The number of revolutions of the ball mill
autoclaves was taken as 70% of the critical velocity Na2 ZrO3 YNa2 O ZrO2 1
(186 rpm) and equals 130 rpm.
At equilibrium conditions,
2.3. Alkaline processing of zircon
o o o o
DFreaction DFNa DFZrO
DFNa 0
A 25-g zircon concentrate at 92%
0.25 + 0.1 mm 2O 2

90:06
244:4
DFNao
2 ZrO3
0
2 ZrO3
was charged into the autoclave without preliminary o
DFNa 2 ZrO3

334:46 kcal=mol:
grinding with sodium hydroxide solution of definite 2
concentration. After a predefined stirring period at a
given temperature, the autoclave was cooled to room The reaction of leaching of zircon with sodium
temperature. The pulp obtained after leaching was hydroxide may be represented as:
discharged from the autoclave into a beaker and
diluted with hot water to a ratio S:L= 1:4 to improve
ZrSiO4 4NaOHYNa2 ZrO3 Na2 SiO3 2H2 O
the solubility of sodium silicate. To avoid hydrolysis
of sodium silicate, certain alkalinity of solution was 3
fixed at sodium hydroxide content 3%. The pulp was
The standard free energy of the reaction:
filtered under vacuum and the cake of sodium zirco-
o o o
nate was washed with dilute sodium hydroxide solu- DFreaction DFNa2 ZrO3
DFNa2 SiO3
2DFHo 2 O
tion (3% NaOH). o

DFZrSiO o

4DFNaOH
4
The leaching efficiency of zircon was determined
by the dissolution of the hydrated cake in sulphuric
19:580kcal=mol: 4
 A.M. Abdel-Rehim / Int. J. Miner. Process. 76 (2005) 234243 237

Table 2 pounds are insoluble and remain in the residue. Dur-

Thermodynamic data used ing dilution process, some hydrolysis of sodium
Thermodynamic Value, Reference zirconate and silicate takes place according to the
function kcal mol
1
following reactions:
DF o ZrSiO4 (c)
436.80 Abdel-Rehim, 1974a,b
DF o ZrO2 (c)
244.40 Robie and Waldbaum, 1968; Na2 ZrO3 2H2 OYZrOOH2 2NaOH 6
Gerasimov et al., 1963.
DF o Na2O (c)
90.06 Robert Weast et al., 1979
DF o Na2SiO3 (aq)
343.00 Robert Weast et al., 1979 Na2 SiO3 2H2 OYH2 SiO3 2NaOH 7
DF o NaOH (aq)
100.184 Robert Weast et al., 1979
DF o Na2O (aq)
56.69 Robert Weast et al., 1979 To avoid this hydrolysis, certain alkalinity of solution
was maintained at 3% NaOH.
The equilibrium constant of the reaction of alkaline The acidic dissolution of the hydrated zirconium
leaching of zircon may be calculated from the equa- cake in sulphuric acid takes place according to the
tion relating to 25 8C. following reactions:

DF o
RT lnK Na2 ZrO3 2H2 SO4 YZrOSO4 Na2 SO4 2H2 O

8
o

DF
logK 14:3597
4:5756  298 ZrOSO4 H2 SO4 YH2 ZrOSO4 2  9

K 2:29d 1014 5 4.1. Vapor pressure data

The vapor pressure data measured over sodium

The equilibrium constant is large and the reaction
hydroxide solutions of different concentrations at dif-
of leaching of zircon with sodium hydroxide may be
ferent temperatures are shown in Fig. 1. The vapor
considered in practice to be irreversible.
pressure over sodium hydroxide solutions generally
increases as the temperature rises. A sharp increase of
vapor pressure for all concentrations was observed at
4. Results and discussion

The technological processing of Egyptian zircon

by its alkaline leaching in ball-mill autoclaves is
based on the formation of sodium zirconate and
silicate according to the chemical reaction (Eq.
(3)). Besides sodium metazirconate and metasilicate,
other compounds are also formed as orthozirconate
and complex zirconium silicate and different sodium
silicates as Na2Si2O5 and Na2Si2O7 (Meerson and
Zelikman, 1965). The titanium impurity (in the form
of rutile and ilmenite) react with sodium hydroxide
with the formation of sodium titanate and iron and
aluminium impuities form sodium ferrite and alumi-
nate, respectively.
The separation of zirconium from silicon is based
Fig. 1. Relation between the vapor pressure over sodium hydroxide
on the dilution of the pulp of leaching with water, solutions of different concentrations (200, 300, 400 and 500 g/l
where sodium silicate being soluble is separated in Na2O) and temperature and also over the product of zircon leaching
solution, while sodium zirconate and other com- using alkali concentration 500 g/l Na2O.
238 A.M. Abdel-Rehim / Int. J. Miner. Process. 76 (2005) 234243
Fig. 2. Relation between the recovery of zirconium from zircon and
concentration of sodium hydroxide solution at 250 8C using 150%
theoretical requirement of sodium hydroxide.
temperatures higher than 190 8C. On the other hand,
as the concentration of sodium hydroxide solutions
increases, the vapor pressure decreases.
Also, the vapor pressure was measured over the
product of zircon leaching with sodium hydroxide
solution of concentration 500 g/l Na2O using 150%
theoretical requirement of sodium hydroxide. It is
observed that this vapor pressure is higher than that
of the corresponding pure sodium hydroxide solution
of concentration 500 g/l Na2O by a value 0.21 kg/
cm2 at temperatures up to 200 8C and by 1.23.5 kg/
cm2 at higher temperatures.
4.2. Alkaline processing of zircon
4.2.1. Effect of alkali concentration
Fig. 2 shows the results of alkaline processing of
zircon at different concentrations of sodium hydro-
xide solution at (200, 300, 400 and 500 g/l Na2O)
at 250 8C for 3 and 4 h (using 150% theoretical
requirement of sodium hydroxide). The recovery of
zirconium from zircon sharply increases with increas-
ing the concentration of sodium hydroxide solutions
from 200 to 400 g/l Na2O. Then, this increase is
gradual up to concentration 500 g/l Na2O, at which
complete leaching of zircon is attained. On the other
hand, as the concentration of sodium hydroxide solu-
tions increases, the vapor pressure decreases. The
increase of recovery of zirconium from zircon with
concentration of alkali solution follows the law of
mass action.
4.2.2. Effect of amount of sodium hydroxide
To determine the optimum amount of sodium
hydroxide at which complete leaching of zircon is
attained, a series of experiments were carried out at
250 8C for 3 and 4 h, each using 500 g/l Na2O
solution strength of different amounts of sodium
hydroxide. Fig. 3 indicates that the recovery of zirco-
nium from zircon sharply increases with increasing
stoichiometric amount of sodium hydroxide up to
125%, beyond which the effect is negligible. The
suitable amount of sodium hydroxide for complete
leaching of zircon may be considered as 150% theo-
retical requirement.
4.2.3. Effect of temperature and time
The effect of temperature and time on the alkaline
processing of zircon was investigated at different
temperatures from 150 up to 275 8C at different
times, using 150% of theoretical requirement of
sodium hydroxide at concentration, 500 g/l Na2O.
From the results obtained (Fig. 4), the following con-
clusions may be drawn:
(1) The recovery of zirconium from zircon gener-
ally increases as the temperature and time
Fig. 3. Relation between the recovery of zirconium from zircon and
amount of sodium hydroxide at 250 8C using 500 g/l Na2O solution
strength.
 A.M. Abdel-Rehim / Int. J. Miner. Process. 76 (2005) 234243
Fig. 4. Relation between the recovery of zirconium from zircon and
time at different temperatures using 150% theoretical requirement of
NaOH at concentration of 500 g/l Na2O.
increase, except at 275 8C and longer time than
8 h, it decreases slowly. The increase of zirco-
nium recovery is at different rates, depending on
the temperature and retention time. The higher
the temperature, the larger the increase of zirco-
nium recovery.
The increase of recovery of zirconium from
zircon with temperature is due to the increase
of vapor pressure over the pulp (at 150, 175,
200, 225, 250 and 275 8C, the vapor pressure
is 3.2, 5.6, 10, 17.8, 30.7 and 42.4 kg/cm2
respectively) as shown in Fig. 1.
(2) At 150175 8C, the recovery of zirconium
sharply increases during the first 6 h, then
gradually increases. At these temperatures,
complete recovery of zirconium is not attained
even at 6 h (33.4% at 150 8C and 55.6% at
175 8C).
(3) At 200 and 225 8C, the recovery of zirconium
from zircon sharply increases during the first 4 h
(reaching 97.6% at 225 8C), then gradually
increases with time. Complete recovery of zir-
conium (99.6%) is attained within 5 h at 225 8C
and 8 h at 200 8C.
(4) At 250 and 275 8C, the recovery of zirconium
sharply increases during the first 2 h, reaching
86.6% and 96.8%, respectively. At both tem-
peratures, complete leaching of zircon (99.7%)
is attained within 3 h and remains unchanged
239
with time at 250 8C and up to 8 h at 275 8C,
after which there is a gradual and small decrease
of leaching of zircon. This decrease may be due
to the partial dehydration of the sodium zirco-
nate produced or the formation of complex
sodium zirconium silicate as the temperature
and time increase (Meerson and Zelikman,
1965).
From these data, it is concluded that complete
leaching of zircon (99.7%) is attained at 250 8C within
3 h.
5. Kinetics of alkaline processing of zircon
The kinetics of the technological processing of
zircon with sodium hydroxide solutions in ball-mill
autocleaves was studied over the temperature range
150275 8C during different times, according to the
experimental data obtained (Fig. 4). The kinetics of
alkaline leaching of zircon is governed by the struc-
ture of zircon and the condition of the surface coating
of the products of leaching, namely sodium zirconate
and silicate. The rate of the reaction of leaching of
zircon was studied for two models controlled by
chemical reaction or diffusion through the product
layer, depending on the temperature of leaching.
5.1. Rate controlled by chemical reaction
The alkaline leaching of zircon is mechanically
activated by its processing in ball-mill autoclaves.
At 200275 8C, the surface coatings of sodium zirco-
nate and silicate produced, are easily and continuously
removed as formed, by the grinding action of steel
balls. This leads to the exposing of fresh zircon par-
ticle surfaces to the alkaline leach solutions. In this
condition, there will be no resistance to the flow of
alkali solution reaching the interface and the rate of
the reaction is not affected by the surface coatings.
The process of leaching is therefore controlled by the
chemical reaction at the interface and the kinetics of
the reaction may be described by the following equa-
tion (Habashi, 1980):
h i
kt 1
1
a1=3 10
240 A.M. Abdel-Rehim / Int. J. Miner. Process. 76 (2005) 234243
Fig. 5. Plot of [1
(1
a)1/3] vs. time t.
where k=rate constant of the reaction and a=fraction
of zircon reacted by time of leaching t.
The experimental data in Fig. 4 were plotted as a
function of [1
(1
a)1/3] vs. time t (Eq. (10)] for the
temperature range 200275 8C, as shown in Fig. 5. It
is observed that the data display a linear relation with
respect to the chemical model. The slopes of such
straight lines determine the rate of the reaction (k).
The rate of zircon leaching increases as the tempera-
ture increases and reaches its maximum 8.1 d 105 s
1,
at 275 8C, and low value, 2.5 d 105 s
1 at 200 8C. At
the optimum temperature of leaching 250 8C, repre-
senting complete extraction of zirconium, the rate of
the reaction reaches a quite high value 5.7 d 105 s
1.
Fig. 6. Arrhenius plot of zircon leaching as a function of log K vs.
103/T (K
1).
Fig. 7. Plot of [1
(1
a)1/3]2 vs. time t.
From the Arrhenius plot (Fig. 6), the calculated
apparent activation energy (E) of the reaction of zir-
con leaching is 27.01 kcal mol
1. This value is
consistent with values of activation energy reported
for chemically controlled reactions. This confirms that
the alkaline processing of zircon at 200 8C and higher
temperatures is controlled by the chemical reaction
occurring at the surface of zircon particles.
5.2. Rate controlled by diffusion through the product
layer
At 150 and 175 8C, the alkaline processing of
zircon leads to the formation of dense thick suspen-
Fig. 8. Plot of [1
(1
2/3 a
(1
a)2/3] vs. time t.
 A.M. Abdel-Rehim / Int. J. Miner. Process. 76 (2005) 234243 241

sion of the fine particles of zircon and the reaction
products. This phenomenon was observed in spite
of performing the leaching of zircon in ball-mill
autoclaves. The fine zircon particles are surrounded
by compact saturated layer of sodium zirconate and
silicate. For this suspension of very fine mineral
particles and products, the velocity of rotation of
autoclave and balls are beyond the critical value
such that diffusion through the product layer is
rate controlling. The alkali solution reaches the
mineral with difficulty. In order that leaching of
zircon proceeds, the alkali must diffuse through
the product layer to reach the surface of the
mineral. Therefore, the process is controlled by
the rate of diffusion of alkali through this layer.
In this case, the rate of the reaction may be deter-
mined by application of Janders equation and
CrankGinstlingBrounshteins equation (Eqs. (11)

Zircon concentrate
Regenerated NaOH

Ball-Milling Sodium hydroxide

Leaching (250oC, 3h) Solution (500g/l Na2O)

Dilution
up to 3% NaOH

Filtration

Filtrate Zirconate cake

Na2SiO3, NaOH, NaA1O2 Na2ZrO3, ZrO(OH)2, H2SiO3
Ca(OH)2 Acid Sulphuric
acid
Regeneration of Dissolution
NaOH
Filtration
Regeneration of H2SO4

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

Fig. 9. Flow sheet of technological processing of Egyptian zircon.

242 A.M. Abdel-Rehim / Int. J. Miner. Process. 76 (2005) 234243
and (12) respectively). (Habashi, 1980; Blazek, 1973)
as the following:
h i2
kt 1
1
a1=3 11
kt 1
2=3a
1
a2=3 12
where a=fraction of zircon reacted by time t and
k=rate constant of the reaction.
If leaching of zircon is controlled by diffusion
through the product layer, the experimental data in
Fig. 4 must give a linear relation, when the right-hand
side of Eqs. (11) and (12) are plotted vs. time t. As
shown in Figs. 7 and 8, they give straight lines at 150
and 175 8C, indicating a diffusion controlled model,
where the slopes of the straight lines give the rate
constant of the reaction (k). The calculated values of
the reaction rates at 150 and 175 8C for Fig. 7
(8.4 d 107 and 2.4 d 106 s
1) using Janders equation
are in good agreement with those for Fig. 8, 8.3 d 107
and 2.2 d 106 s
1, respectively using CrankGins-
tlingBrounshteins equation.
It is concluded that at 150 and 175 8C, the alkaline
processing of zircon is a diffusion controlled process,
depending on the rate of flow of alkali solution and its
velocity of diffusion through the product layer to the
surface of zircon particles. The diffusion resistance
through the coherent product layer controls the overall
kinetic process.
The suggested flow sheet of the technological pro-
cessing of Egyptian zircon is shown in Fig. 9.
6. Conclusions
The study of the technological processing of Egyp-
tian zircon by its alkaline leaching in ball-mill auto-
claves revealed the following conclusions:
(1) In general, the recovery of zirconium from zir-
con increases at different rates, depending on
the temperature and time. The higher the tem-
perature and the longer the retention time, the
larger the increase of zirconium recovery will
be. The increase of zirconium recovery with
temperature is due to the increase of vapor
pressure over the pulp of zircon leaching.
(2) At 150 and 175 8C, the leaching efficiency of
zircon is low even at 6 h, reaching 33.4% and
55.6%, respectively. This is due to the low
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
the product layer.
(3) At 250 and 275 8C, complete recovery of
zirconium from zircon (99.7%) is attained
within 3 h and remains unchanged with time.
At 275 8C and longer time than 8 h, there is a
small decrease of recovery, which may be due
to the partial dehydration of sodium zirconate
or the formation of complex sodium zirconium
silicate.
(4) The calculated values of the standard free
energy (DF o) and the equilibrium constant (K)
of the reaction of alkaline processing of zircon
with sodium hydroxide solution at 298.15 K (25
8C) are19.58 kcal mol
1 and 2.29 d 1014,
respectively. These values reflect the irreversi-
bility of the reaction.
(5) The kinetic study of the technological proces-
sing of zircon by its alkaline leaching in ball-
mill autoclaves is governed by the structure of
zircon and the condition of the product surface
coating. The experimental data reveal that the
rate of the reaction of zircon leaching is con-
trolled by diffusion through the product layer at
150 and 175 8C. At 200 8C and higher tempera-
tures, it is chemically rate-controlled, as con-
firmed by the high value of the calculated
apparent activation energy (27.01 kcal mol
1)
and other observations. The rate of leaching of
zircon is therefore a function of temperature,
time and solidliquid contact.
(6) It was found that the most favourable conditions
of the technological processing of zircon with
sodium hydroxide, at which complete recovery
of zirconium (99.7%) could be attained, are 250
8C within 3 h using 150% of theoretical require-
ment of alkali at concentration 500 g/l Na2O.
(7) Zircon leaching with alkali solution was
mechanically activated and accelerated in ball-
mill autoclaves as a result of the grinding action
of steel balls, that caused continuous removal of
sodium zirconate and silicate from the reacting
particle surfaces. This leads to the exposing of
 A.M. Abdel-Rehim / Int. J. Miner. Process. 76 (2005) 234243
fresh zircon particle surfaces to the alkali leach
solution.
(8) The main advantages of the present technologi-
cal processing of Egyptian zircon can be sum-
marized as the following:
(a) No preliminary grinding of zircon is required.
(b) Simultaneous grinding and leaching of zir-
con, which can be achieved in one process.
(c) Relatively low temperature requirement (250
8C) for alkaline leaching and moderate time,
compared with sintering processes of zircon.
(d) Cheap and common reagents (sodium hydro-
xide and sulphuric acid) can be used in the
leaching of zircon and acid dissolution of
zirconate cake and they can be regenerated.
(e) Simplicity of design and construction of the
reactor of leaching.
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