Trends in Zircon Processing 103

Trends in Zircon Processing

A.C. Bidaye and I.G. Sharma
Materials Processing Division, Bhabha Atomic Research Centre, Mumbai-400085, India

ABSTRACT: Zircon is an important industrial mineral and apart from its own applications, serves as the
primary raw material for the production of a series of technologically significant zirconium and hafnium
chemicals. However, due to its high melting point and chemical inertness, processing of zircon is a major
technological challenge and very aggressive methods have to be adopted to open up zircon. This paper will
review some these methods and attempt to determine the trends in the processing of zircon. Along with some
of the other techniques, the carbo-chlorination of zircon in an electro-thermal fluidized bed reactor, which
constituted a part of the Pyro-chemical process for preparing nuclear grade zirconium, was extensively
investigated in our laboratory. The technological challenges and the environmental and economic benefits of
this technique vis-a-vis the other established practices will be discussed, with emphasis on production of
nuclear grade zirconium.

1. INTRODUCTION established practices and other alternate proposals

Zircon is an important industrial mineral with an
annual production in excess of 900,000 tonnes. It
serves as the primary raw material for the
production of a series of industrially significant
zirconium and hafnium chemicals, as also the
metals themselves. Due to its high melting point
and chemical inertness, the mineral itself also
finds major application as refractory linings in
furnaces and kilns and as foundry sands.
However, this very quality makes processing of
zircon a major technological challenge and very
aggressive techniques have to be adopted to open
up zircon.
A wide variety of methods have been
attempted to open up zircon. This paper will
review some of the major techniques and attempt
to determine the trends in the processing of
zircon. Along with some of the other techniques,
the carbo-chlorination of zircon in an electro-
thermal fluidized bed reactor was extensively
investigated in our laboratory. This was part of the
pyro-chemical process studied at the erstwhile
Metallurgy Division, B.A.R.C. to prepare nuclear
grade zirconium. The pyro-chemical process is a
very promising technique for preparing nuclear
grade (N.G.) Zr in an environmentally friendly
and cost effective manner. The technological
challenges and the environmental and economic
benefits of this technique vis-a-vis the other
will be discussed.
2. PROCESSES FOR OPENING ZIRCON
There are three major objectives for opening up of
zircon: (i) to prepare zirconium dioxide, (ii) to
prepare zirconium chemicals, and (iii) to produce
the metal, either without hafnium removal for
alloy making or after hafnium removal for use in
the nuclear industry; hafnium is almost always
produced as a by-product of preparation of Hf
free Zr and finds application both in the nuclear
industry, as a neutron absorber, and for
preparation of alloys such as C-103 (Nb-10Hf-
1Ti) used for space applications.
As mentioned, zircon is a particularly stable
compound (∆Gof,1400 K = –1498.1 kJ/mol zircon
(Barin & Knacke, 1973)). Mineral acids other
than HF do not attack zircon (Blumenthal, 1958).
The technique adopted for opening up of zircon
depends on the end product desired. Some of the
major methods used for the opening up of zircon
are discussed in the following sections.
2.1 Fusion with Caustic Soda
In this technique, caustic soda and zircon are
reacted in steel containers at 600 to 650ºC as
follows
ZrSiO4 + 4NaOH → Na2ZrO3 + Na2SiO3
         + 2H2O …(1)
104  Mineral Processing Technology (MPT 2007)
The resultant frit, on cooling, is leached with
water to remove the soluble silica, with suitable
procedures being incorporated to eliminate all the
silica which would otherwise foul up the
subsequent processing. The silica free solid
residue is next treated with acid to bring the Zr
values into solution. The Zr is re-precipitated as
hydroxide after or without Hf removal, purified
and calcined to obtain ZrO2. For production of Zr
chemicals or the metal, the ZrO2 is mixed with
coke, briquetted and chlorinated to ZrCl4, which
can be further converted to other Zr chemicals.
For producing the N.G. metals, two alternates are
available; the sodium zirconate cake is first
subjected to either the TBP-nitrate process or the
amine-sulphate process for Zr/Hf separation.
These are discussed in a subsequent section.
2.2 Fusion with Potassium Fluosilicate
In an alternate pyro-hydro route, the zircon is
mixed with K2SiF6 and KCl and reacted at 750ºC.
ZrSiO4 + K2SiF6 →K2ZrF6 + 2SiO2 …(2)
The resultant K2Zr(Hf)F6 is leached out with hot
water. Since the K2HfF6 is 1.5 times more soluble
than K2ZrF6, the resultant leach liquor is put
through a series of counter current
solubilisation/precipitation cycles wherein the
precipitate becomes successively richer in Zr and
the mother liquor in Hf. It is possible to get N.G.
Zr in about 12 stages (Sundaram, et. al., 1986).
The low hafnium K2ZrF6 is directly fed to a
molten salt electrolytic cell for production of
zirconium metal. However, while the process
itself is simple, presence of the highly corrosive
and environmentally hazardous fluoride ions
inflate cost of the processing equipment and
effluent treatment. The fluosilicate route was
reportedly practiced in the former USSR.
2.3 Reductive Smelting with Carbon in
Air
In this technique the zircon and carbon mixtures
are smelted in air in an electric arc furnace
resulting in the formation of ZrCN. This carbo-
nitride is then chlorinated in a separate reactor to
produce the ZrCl4. For preparing N.G. metals, the
MIBK-Thiocynate route is followed. The
formation of ZrCN as an intermediate has several
advantages; the technology itself is quite simple,
the chlorination is exothermic and carried out at
low temperatures and since the Si is driven off,
chlorine requirement is reduced and ZrCl4
condensation is also simplified. However, release
of toxic fumes of CO and SiO into the
environment, requirement of large amount of
electric power and the destabilizing effect of arc
furnaces on electric grids worked against the
popularity of this process.
2.4 Carbo-chlorination of Zircon
Anhydrous zirconium tetrachloride is an essential
intermediate in the production of Zr metal (as also
most Zr chemicals). Hence there always was an
interest in developing the more technologically
challenging process for producing ZrCl4 directly
from zircon. Non aqueous techniques, for Zr/Hf
separation had also been established. However,
the highly endothermic nature of the reaction
(∆Hof,1400 K = -230.7 kJ/mol zircon[1]), the high
reaction temperatures (>1100ºC), the corrosive
nature of the reactants and the extremely sluggish
rates of transformation seriously hampered
commercialization of this technique. However,
this scenario underwent a dramatic transformation
with the adaptation of the Electro-thermal
Fluidised Bed Reactor to zircon carbo-
chlorination by Spink and co-workers in 1973
(Manieh and Spink, 1973). Along with some of
the other techniques, the carbo-chlorination of
zircon was also extensively investigated in our
laboratory. The latter was part of the pyro-
chemical process being developed at B.A.R.C.
The direct chlorination of zircon is
thermodynamically unfavourable.
ZrSiO4 + 4Cl2 → ZrCl4 + SiCl4 + 2O2 …(3)
The standard free energy change of the
chlorination of zircon at 1400 K is 312.7 kJ/mol
zircon (Barin & Knacke, 1973). At this
temperature, even if pure chlorine is admitted to
the reactor and flushing conditions maintained,
thermodynamics calculation yield the maximum
possible partial pressures of the products as
Trends in Zircon Processing 105
1 disturbance of the charge to achieve adequate
p ZrCl 4 = p SiCl 4 = pO 2 = 8.58 × 10 -4 atm. …(4) rates of chlorination. Externally heated fluid bed
2
reactors are also energy inefficient. An Electro-
thermal Fluidized bed reactor combines the
Feeder higher reactivities of a fluidized bed reactor with
the convenience and efficiency of direct resistance
heating. It consists of a particulate bed of solids
some fraction of which should be conducting.
To Two or more electrodes are inserted into this bed,
Condenser
the bed is fluidized and voltage applied across the
electrodes. Electric current passes through the bed
resulting in in-situ heating. A sketch of the 125
mm i.d. reactor used in our studies is shown in
Disengaging Fig. 1. It was operated for prolonged periods at
Section around 1150ºC, both for ZrO2 and zircon
chlorination and produced around 1 kg of the
anhydrous chloride per hr from zircon.

Electrodes 2.5 Miscellaneous Processes

A wide variety of methods have been attempted to

Graphite reactor
Charge
Insulation
Distributor
N2 + Cl2
Fig. 1: The Electro-thermal Fluidised Bed
Reactor
Reducing oxygen partial pressure in the system
will increase chlorination efficiency. This can be
achieved by either removing the oxygen along
with the other reaction products or by using
reducing agents to lower the oxygen partial
pressure. The latter is the more practical approach
and is referred to as reduction chlorination. Of all
the reducing agents surveyed, carbon is ideally
suited for zircon reduction chlorination.
Static bed chlorination requires very finely
ground charge (energy intensive), higher
chlorination temperatures and frequent
open up zircon. Some of the more prominent ones
include sintering of zircon with sodium carbonate
at 900°C; sintering with calcium oxide or calcium
carbonate at 1400–1500°C and with calcium
oxide and flux (calcium chloride) at 1000–
1100°C; sintering of zircon with aluminium
fluoride at 870°C (Abdel-Rehim, 1974);
decomposition of zircon in a plasma to produce
ZrO2, mechano-chemical processing of zircon
with Ca and Mg in the dry condition and calcium
hydroxide and sodium hydroxide in the wet
condition (Abdel-Rehim, 2005), etc. Other
processes tried for opening up of zircon include
carbothermic reduction of zircon under reduced
pressure to produce high purity/stabilised zirconia
and amorphous silica (Funahashi et. al., 1988),
microbial leaching with chemolithotrophic and
heterotrophic micro-organisms resulting in
liberation of valuable substances from zircon
(Becker et.al., 1988).
3. PROCESSES FOR ZR/HF SEPARATION
A number of aqueous and non-aqueous
techniques have been established for Zr/Hf
separation. The three major Solvent Extraction
routes followed for Zr/Hf separation in the
nuclear world and the non-aqueous extractive
106  Mineral Processing Technology (MPT 2007)
distillation process studied in our laboratory are
discussed.
3.1 TBP-nitrate Process
This procedure has been adopted for the Indian
Nuclear Programme for production of Zr at the
Nuclear Fuels Complex at Hyderabad (Gupta,
1989). Earlier, it was also practiced by the French.
In this process, the Na2ZrO3 obtained from the
caustic fusion process is leached out with nitric
acid and after suitable purification steps, the
solution is subjected to solvent extraction, in a
series of mixer-settler cells, with tri-Butyl
Phosphate (TBP) in n-hexane, Zr being extracted
in the organic phase. The advantage of this
technique is that since Zr is extracted in the
organic phase, Zr solutions are highly
concentrated and pure, the plant size is small and
N.G. Zr can be prepared in fewer steps. The
disadvantage is that Hf solutions are leaner and
with higher levels of impurities from which it is
very difficult to produce pure Hf, a valuable by-
product. Additionally, nitric acid is more
expensive, demands highly corrosion resistant
materials, not amenable to recycling and also
leaves behind environmentally hazardous effluents.
3.2 Amine Sulphate Process
In an alternate technique adopted by the Japanese,
the sodium zirconate cake is reacted with
sulphuric acid. The reaction is carried out under
adequate insulation and the temperature rises to
200ºC This zirconate is converted to sulphate, and
associated Si to insoluble and highly filterable
silica. The filtered solution is subjected to counter
current extraction using tri-n-octyl amine in n-
paraffin. This procedure uses the cheaper
sulphuric acid, has less corrosion and
environmental problems, but leaner Zr solutions
require larger plant sizes and lower separation
factor results in larger number of SX stages.
3.3 MIBK-Thiocynate
This route was predominantly used in the USA.
The ZrCl4 produced by the chlorination routes is
dissolved in water to which NH4CNS and
NH4OH has been added. In the subsequent
solvent extraction step, Methyl iso-butyl ketone
(MIBK) is utilized as the organic extractant. The
MIBK-thiocynate system has a high separation
factor for Zr/Hf and drastically reduces the no. of
stages required for Hf removal from Zr. However,
Hf is extracted in the organic phase, leaving Zr,
along with other impurities, in the aqueous
raffinate. Thus additional purification/
concentration stages are required to produce N.G.
Zr. The system also needs special materials of
construction and thiocynate demands careful
handling. Further, MIBK is highly volatile and
not suited to temperate climates.
3.4 Extractive Distillation
A large number of non-aqueous routes for Zr/Hf
separation have been studied. Here, only the one
investigated in our laboratory is briefly discussed.
The crude Zr(Hf)Cl4 produced by the chlorination
of zircon is first dissolved in a molten NaCl-KCl
at 300ºC and distilled off at 350ºC whereby the
impurities stay back in the molten eutectic. The
purified Zr(Hf)Cl4 is next fed to an extractive
distillation column wherein molten eutectic of
AlCl3-KCl is flowing down. The ZrCl4 has a
higher solubility in the eutectic and concentrates
in the liquid phase while the vapour phase is
enriched in Hf. Around 60 stages are required to
reach the nuclear specification of 100 ppm Hf in
Zr, starting from 2.5% Hf in natural zircon.
4. METAL PRODUCTION
After each of the above solvent extraction
techniques, the Zr in solution is precipitated by
ammonia as the hydroxide and calcined to ZrO2.
The ZrO2 is mixed with coke, briquetted and
chlorinated to ZrCl4. From the anhydrous routes
the de-hafniated ZrCl4 is directly available. The
chloride undergoes magnesiothermic reduction by
the Kroll’s process yielding Zr sponge. The
sponge, with suitable additions, can be processed
to yield Zr alloys for making nuclear components.
Alternately, if higher purities are desired, the
Trends in Zircon Processing
sponge can be treated by the iodide-crystal bar
technique.
5. CONCLUSION
The pyro-chemical process incorporating zircon
carbo-chlorination appears to be ideally suited for
producing nuclear grade zirconium. The number
of unit operations are reduced, effluent problems
are minimised and the overall process is highly
energy efficient. This translates into a Zr
production cost that is several times lower than
that for the other alternates.
REFERENCES
[1] Abdel-Rehim, A.M., Desilication of zircon with
aluminium fluoride in presence of graphite, Proc.
4th Int. Conf. Therm. Analysis, Thermal Analysis
vol. 1, 523–539, (1974).
[2] Abdel-Rehim, A.M., A new technique for
extracting Zirconium from Egyptian Zircon
107
Concentrate, Intl. J. Min. Process., 76, 234-243,
(2005).
[3] Barin, I., and Knacke, O., Thermochemical
Properties of Inorganic Substances, Springer-
Verlag, Berlin, 1973.
[4] Becker, S., Bullmann, M., Dietze H.S. and Iske
U., Zfi-Mitt, 115, 101-106, (1986)-cited in CA
105:168645 (1986).
[5] Blumenthal, W.B., The Chemical Behaviour of
Zirconium, D. Van Nostrand Co. Ltd., New
York, 1958, p. 227.
[6] Funahashi, T., Ueda, K., Uchimura, R. and
Oguchi Y.; Adv. Ceram., Sci. & Tech. of Zirconia
III, 24A, 227-232, (1988).
[7] Gupta, C.K., Materials in Nuclear Energy
Applications, C.R.C. Press Inc., Boca Raton,
Florida, 1989.
[8] Manieh, A.A. and Spink, D.R., Can. Met. Quar.,
12, No. 3, 331-340, 1973.
[9] Sundaram, C.V., Subramanyam, R.B. and Babu,
R.S., Development of zirconium Process
Metallurgy in India, Trans. I.I.M., 30, 23-38,
(June 1986).