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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 235

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

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 mol1
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

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-
Fig. 2. Relation between the recovery of zirconium from zircon and retical requirement.
concentration of sodium hydroxide solution at 250 8C using 150%
theoretical requirement of sodium hydroxide.
4.2.3. Effect of temperature and time
The effect of temperature and time on the alkaline
temperatures higher than 190 8C. On the other hand, processing of zircon was investigated at different
as the concentration of sodium hydroxide solutions temperatures from 150 up to 275 8C at different
increases, the vapor pressure decreases. times, using 150% of theoretical requirement of
Also, the vapor pressure was measured over the sodium hydroxide at concentration, 500 g/l Na2O.
product of zircon leaching with sodium hydroxide From the results obtained (Fig. 4), the following con-
solution of concentration 500 g/l Na2O using 150% clusions may be drawn:
theoretical requirement of sodium hydroxide. It is
observed that this vapor pressure is higher than that (1) The recovery of zirconium from zircon gener-
of the corresponding pure sodium hydroxide solution ally increases as the temperature and time
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 Fig. 3. Relation between the recovery of zirconium from zircon and
hand, as the concentration of sodium hydroxide solu- amount of sodium hydroxide at 250 8C using 500 g/l Na2O solution
tions increases, the vapor pressure decreases. The strength.
A.M. Abdel-Rehim / Int. J. Miner. Process. 76 (2005) 234243 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


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. The kinetics of the technological processing of
zircon with sodium hydroxide solutions in ball-mill
autocleaves was studied over the temperature range
increase, except at 275 8C and longer time than 150275 8C during different times, according to the
8 h, it decreases slowly. The increase of zirco- experimental data obtained (Fig. 4). The kinetics of
nium recovery is at different rates, depending on alkaline leaching of zircon is governed by the struc-
the temperature and retention time. The higher ture of zircon and the condition of the surface coating
the temperature, the larger the increase of zirco- of the products of leaching, namely sodium zirconate
nium recovery. and silicate. The rate of the reaction of leaching of
The increase of recovery of zirconium from zircon was studied for two models controlled by
zircon with temperature is due to the increase chemical reaction or diffusion through the product
of vapor pressure over the pulp (at 150, 175, layer, depending on the temperature of leaching.
200, 225, 250 and 275 8C, the vapor pressure
is 3.2, 5.6, 10, 17.8, 30.7 and 42.4 kg/cm2 5.1. Rate controlled by chemical reaction
respectively) as shown in Fig. 1.
(2) At 150175 8C, the recovery of zirconium The alkaline leaching of zircon is mechanically
sharply increases during the first 6 h, then activated by its processing in ball-mill autoclaves.
gradually increases. At these temperatures, At 200275 8C, the surface coatings of sodium zirco-
complete recovery of zirconium is not attained nate and silicate produced, are easily and continuously
even at 6 h (33.4% at 150 8C and 55.6% at removed as formed, by the grinding action of steel
175 8C). balls. This leads to the exposing of fresh zircon par-
(3) At 200 and 225 8C, the recovery of zirconium ticle surfaces to the alkaline leach solutions. In this
from zircon sharply increases during the first 4 h condition, there will be no resistance to the flow of
(reaching 97.6% at 225 8C), then gradually alkali solution reaching the interface and the rate of
increases with time. Complete recovery of zir- the reaction is not affected by the surface coatings.
conium (99.6%) is attained within 5 h at 225 8C The process of leaching is therefore controlled by the
and 8 h at 200 8C. chemical reaction at the interface and the kinetics of
(4) At 250 and 275 8C, the recovery of zirconium the reaction may be described by the following equa-
sharply increases during the first 2 h, reaching tion (Habashi, 1980):
86.6% and 96.8%, respectively. At both tem-
h i
peratures, complete leaching of zircon (99.7%)
kt 1  1  a1=3 10
is attained within 3 h and remains unchanged
240 A.M. Abdel-Rehim / Int. J. Miner. Process. 76 (2005) 234243

Fig. 7. Plot of [1(1a)1/3]2 vs. time t.


Fig. 5. Plot of [1  (1  a)1/3] vs. time t.
From the Arrhenius plot (Fig. 6), the calculated
apparent activation energy (E) of the reaction of zir-
where k=rate constant of the reaction and a=fraction con leaching is 27.01 kcal mol 1. This value is
of zircon reacted by time of leaching t. consistent with values of activation energy reported
The experimental data in Fig. 4 were plotted as a for chemically controlled reactions. This confirms that
function of [1  (1  a)1/3] vs. time t (Eq. (10)] for the the alkaline processing of zircon at 200 8C and higher
temperature range 200275 8C, as shown in Fig. 5. It temperatures is controlled by the chemical reaction
is observed that the data display a linear relation with occurring at the surface of zircon particles.
respect to the chemical model. The slopes of such
straight lines determine the rate of the reaction (k). 5.2. Rate controlled by diffusion through the product
The rate of zircon leaching increases as the tempera- layer
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 At 150 and 175 8C, the alkaline processing of
the optimum temperature of leaching 250 8C, repre- zircon leads to the formation of dense thick suspen-
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 (K1). Fig. 8. Plot of [1(12/3 a(1a)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 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

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) (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
con, which can be achieved in one process. zircon. 34th Int. Cong. Indust. Chem., Beograd, pp. 168 179.
(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.
xide and sulphuric acid) can be used in the Gordon and Breach, New York, pp. 223 251.
leaching of zircon and acid dissolution of Habashi, F., 1999. A Textbook of Hydrometallurgy, 2nd ed. Metal-
zirconate cake and they can be regenerated. lurgie Extractive Quebec, Sainte-Foy, Quebec. Distributed by
(e) Simplicity of design and construction of the Laval University Bookstore.
reactor of leaching. Jamrack, W.D., 1965. Processes and apparatus of chemico-metal-
lurgical technology of rare metals. Atomizdat, Moscow, 5558,
329332.
Kaplan, G.E., et al., 1958. Alkaline processing of monazite and
References zircon. Proc. Int. Conf. Peaceful Uses of Atomic Energy, Gen-
eva, vol. 3(1). Atomizdat, Moscow, pp. 274 281.
Abdel-Rehim, A.M., 1973. Autoclave leaching of some economic Lustman, B., Kerze Jr., F., 1959. Metallurgy of zirconium. Izda-
minerals. Acta Geol. Acad. Sci. Hung. Hung. Acad. Sci. Publ. telstva Inastrany Literatura, Moscow, pp. 47 78.
17, 307 318. Meerson, G.A., Zelikman, A.N., 1965. Metallurgy of Rare Metals.
Abdel-Rehim, A.M., 1974a. Desilication of zircon with aluminium Metallurgizdat, Moscow, pp. 282 357.
fluoride in presence of graphite. Proc. 4th Int. Conf. Therm. Rittman, A., Nakhla, F.M., 1958. Contribution to the study of
Analysis, Thermal Analysis, vol. 1, pp. 523 539. Egyptian black sands. Egypt. J. Chem. 1 (1), 127 135.
Abdel-Rehim, A.M., 1974b. Beneficiation of low grade zircon con- Robie, R.A., Waldbaum, D.R., 1968. Thermodynamic properties of
centrate. J. Inst. Eng., India 56 (3), 99 102. minerals and related substances at 298.15 K (25 8C) and 1
Abdel-Rehim, A.M., 1990. Application of thermal analysis to atm. U.S. Geol. Surv. Bull. (1259), 16 19.
mineral technology. In: Smykatz-Klos, A.M., Warne, S. (Eds.), Safronov, E.K., Evtshovsky, G.F., 1956. Production of zirconium.
Thermal Analysis in Geoscienas. Springer-Verlag, Berlin, Chemical Science and Industry N.5, 505513.
pp. 188 222. Said, R., 1990. The Geology of Egypt. Balkema, Rotterdam.
Abdel-Rehim, A.M., 1997. Application of thermal analysis to Stanley, J., Lefond, et al., 1975. Industrial minerals and rocks.
mineral synthesis. Presented in the 11th Int. Cong. Therm. American Inst. Min. Metallurgy and Petroleum Eng. Inc., New
Analysis, Philadelphia PA, USA, Aug. 1216, J. Therm. York, pp. 1275 1283.
Anal., vol. 48. John Wiley and Sons Ltd, pp. 177 202. Stefanyuk, S.L., Morosov, I.S., 1965. Kinetics and mechanism of
Abdel-Rehim, A.M., 1998. Production of alumina from Egyptian chlorination of minerals (Laparite Pyrochlore, Zircon and Euxe-
kaolinite. In: Imam, M.A., et al., (Eds.), 3rd Pacific Rim Int. nite). Zhurnal Prikladnoi Khimi 38 (4), 729 735.
Conf. on Advanced Materials and Processing (PRICM3), July Tauber, E., James, R.J., 1971. Zircon and its uses. J. Aust. Ceram.
1216, Hawaii, USA, vol. 2, pp. 2765 2773. Soc. 7, 27 30.
Abdel-Rehim, A.M., 2002a. Synthesis of ceramic composite of Weast, Robert C., et al., 1979. CRC Handbook of Chemistry and
zirconium and aluminium oxides. In: Hui, David (Ed.), Proc. Physics, 59th ed. CRC Press, Inc., pp. D67 D78.
9th Int. Conf. on Composites Engineering, July 16, 2002, San Welham, N.J., Enhancing, 2000. (ZrSiO4) dissolution by ambient
Diego, USA, pp. 1 2. temperature processing Austral. IMM Proc. 35 (1), 173 193.
Abdel-Rehim, A.M., 2002b. An innovative method for processing Zelikman, A.N., Samsonov, G.V., Krein, O.E., 1964. Metallurgy of
Egyptian monazite. Hydrometallurgy 67, 9 17. Rare Metals. Izdatelstva Metallurgia, Moscow, pp. 271 321.
Abdel-Rehim, A.M., Khalil, S.O., 1975. Thermal investigation of
sintering of zircon with calcite. Acta Mineral.Petrogr., Szeged,
Hungary 22 (3), 147 155.