Ind. Eng. Chem. Res.

2003, 42, 777-783 777

MATERIALS AND INTERFACES

De Wet Process for the Beneficiation of Zircon: Optimization of the

Alkali Fusion Step
Arao Manhique, Zola Kwela, and Walter W. Focke*
Institute of Applied Materials, Department of Chemical Engineering, University of Pretoria,
Pretoria 0002, South Africa

Milled zircon, d50 9 m, was fused with caustic soda pearls in open reaction vessels at
temperatures between 650 and 850 C. Fusion times of 1, 2, 4, 24, and 336 h (with intermittent
milling) were investigated. The fusion products were characterized by X-ray diffraction and by
wet-chemical analysis. For prolonged fusion times, the fusion products approached equilibrium
compositions. However, the phases Na2ZrSiO5 and Na4Zr2Si3O12 observed at 850 C did not form
at 650 C. Because these compounds do not hydrolyze completely in water, they limit the recovery
of alkali in the sodium silicate product stream. With short fusion times (2 h), a nonequilibrium
product spectrum is obtained. It is dominated by sodium zirconates and sodium silicates, allowing
reasonable zirconia yields and high alkali recovery in a sodium silicate product stream. This
allows efficient fusion of two moles of NaOH per mole of zircon at 850 C with a zirconia yield
of ca. 57% and an alkali recovery of ca. 78%.

Introduction

Zircon is the naturally occurring form of zirconium

silicate, ZrSiO4. It is the most abundant and widely
distributed commercial zirconium mineral.1-5 It is found
as an accessory mineral in silica-rich igneous rocks such
as granite, pegmatite, and nepheline syenite.1-3 Sedi-
mentary and metamorphic rocks also contain zircon but
only in small amounts.4 Because of its high specific
gravity of 4.6-4.8, zircon is found concentrated with
other heavy minerals, e.g., rutile, in river and beach
sands with iron as the main contaminant.1-5 Zircon is
commonly produced as a byproduct in the mining and Figure 1. Simplified block diagram for the De Wet zirconium
processing of heavy-mineral sands such as the titanium chemical recovery process.
minerals rutile and ilmenite.4
some applications, concerns about and legislation with
Zircon is chemically and thermally very stable. This
respect to radioactive impurities will eventually force a
is due to the high coordination of bisdisphenoid ZrO8
refinement of the raw material. Removal of such impu-
in a tetragonal structure with SiO4 tetrahedra.6,7 Thus,
rities from zircon is only possible via chemical decom-
zircon requires aggressive reaction conditions for de-
position of the zircon lattice.1,8
composition.1,4,8 Decomposition of zircon with alkali at
Owing to dwindling world supplies of baddeleyite
high reaction temperatures is a well-known proce-
(natural zirconia), a greater proportion of zirconium-
dure.1,8-13 Alternative plasma furnace processes gener-
based products will in the future have to be obtained
ally require high temperatures exceeding 1750 C.1,8,9
from the more abundant zircon sands. Figure 1 shows
Plasma-dissociated zircon still requires milling (d50 <
a simplified block diagram of the alkali fusion process
0.1 m) to release zirconia and allow rapid leaching.
for zirconia from zircon. Scheme 1 outlines the De Wet
Further wet-chemical processing to achieve a com-
modification of this zirconium chemical recovery process.
mercially viable product is also required.8,9,14
The main reactants are caustic soda and milled zircon
Zircon on its own has a number of industrial applica- sand. Sodium silicate solution and zirconia are the two
tions.1-4,8 The largest uses are as foundry raw material product streams. Unreacted zircon is separated from
and as opacifier for ceramic tile glazes and porcelain silica waste using gravity-based separation techniques
enamels.2,3 Other uses include refractories and plasma and is recycled to the process. The waste stream
spraying.1-4 The presence of radioactive impurities is contains sodium salts and other impurities. Not shown
a potential problem associated with zircon use.8 For are water and acid feed streams used in the process.
The main inventive step in this process is the in situ
* To whom correspondence should be addressed. Fax: +27 formation of zirconium basic sulfate (ZBS) as a solid
12 811 1174. E-mail: xyris@mweb.co.za. phase. This compound is very stable and insoluble in
10.1021/ie020140c CCC: $25.00 2003 American Chemical Society
Published on Web 01/22/2003
778 Ind. Eng. Chem. Res., Vol. 42, No. 4, 2003
Scheme 1. Outline of the De Wet Alkali Fusion Process for AZST
dilute mineral acids other than sulfuric. This facilitates
the removal of impurities such as iron and radioactive
elements by leaching with hydrochloric acid.
Compared to conventional processes, advantageous
features of the De Wet process are as follows:
(a) Fewer process steps are necessary to manufacture
acid zirconium sulfate tetrahydrate (AZST).
(b) A comparatively low-cost pigment-suitable zirconia
with reduced radioactivity content can be made.
(c) The alkali reactant can be recovered in the form
of a saleable, radioactivity-free, sodium silicate product
stream.
(d) Sulfuric acid economy in the manufacture of AZST.
The overall process requires less than 5% stoichiometric
excess of sulfuric acid.
(e) Radioactivity is leached out of a solid phase instead
of using precipitation steps that require chemical ad-
ditions and generate much waste.
(f) There are fewer effluent streams and less waste
to discard.
In this study we report on the optimization of the
alkali-fusion step of this process. The experiments
described below were designed to provide an indication
of the effect that fusion conditions have on the overall
product yields in terms of the simplified block diagram
shown in Figure 1. The zirconia yield and alkali (NaOH)
recovery in the sodium silicate are important process
parameters that impact the commercial viability of the
overall process. The effect of the operating parameters
such as fusion time and temperature and also reagent
stoichiometry (NaOH/ZrSiO4 mole ratio) on these vari-
ables was determined.
Experimental Section
Commercial-grade zircon, mined at Richards Bay,
South Africa, was obtained from Ferro Industrial Prod-
 Ind. Eng. Chem. Res., Vol. 42, No. 4, 2003 779

Table 1. Observed Phases in the XRD Spectra of the centrifugation. The hydrated silica was dried overnight
Products Obtained for 336-h Fusions in a drying oven at 90 C and calcined at 950 C to silica.
temp mol ratio of time The silica yield was calculated with respect to the silica
[C] NaOH/ZrSiO4 [h] phases observed in XRD in the zircon feed and reported as a percentage.
850 6:1 336 major phase: Na2ZrO3 The zirconium-containing residue remaining, follow-
minor phase: Na2SiO3 ing removal of the sodium silicate, was titrated with a
850 4:1 336 major phase: Na2ZrO3, Na2ZrSiO5, standardized 32% (m/m) analytical-grade HCl solution
Na2SiO3 to a pH 3.8. Repeated washing and centrifugation
850 2:1 336 major phase: Na2ZrSiO5 with a total of 250 mL of distilled water in 4-5 portions
minor phase: ZrSiO4, Na2ZrO3
trace phase: Na4Zr2Si3O12 removed water solubles, including NaCl. The residue
850 1:1 336 major phase: Na4Zr2Si3O12, ZrSiO4 consisted essentially of hydrous zirconia, silica, and
minor phase: Na2ZrSiO5 unreacted zircon. This was reacted with an excess
750 4:1 336 major phase: Na2ZrO3 amount of sulfuric acid (ca. 5% excess) to form AZST.
minor phase: Na2SiO3 Water and excess sulfuric acid were removed by evapo-
trace phase: Na2ZrSiO5 ration by first heating at 150 C and then at 350 C.
750 2:1 336 major phase: Na2ZrO3, ZrSiO4,
Na2ZrSiO5 The solids were allowed to cool to room temperature.
minor phase: Na2SiO3 AZST was dissolved in water and separated from the
750 1:1 336 major phase: Na2ZrSiO5, ZrSiO4 residue by centrifugation. AZST was then crystallized
minor phase: Na2ZrO3 overnight at 90 C by water evaporation and calcined
700 2:1 336 major phase: ZrSiO4, Na2ZrO3, to zirconia at 950 C. The yield was expressed as a
Na2ZrSiO5
percentage of the zirconia in the zircon feed.
minor phase: Na2SiO3
650 6:1 336 major phase: Na2SiO3, Na2ZrO3 The solids remaining after the AZST dissolution were
minor phase: Na4SiO4, ZrSiO4 dried at 90 C and then calcined at 950 C. All of the
650 4:1 336 major phase: ZrSiO4, Na2SiO3, calcined products (zirconia, silica, and residue) were
Na2ZrO3 collected, weighed, and submitted for elemental analy-
minor phase: Na4SiO4 sis. All of these fusion experiments were duplicated, and
650 2:1 336 major phase: ZrSiO4, Na2ZrO3
minor phase: Na2SiO3
in some instances there were with up to eight replica-
strong amorphous halo at ca. 2 ) 13 tions. The validity of the results was checked using
650 1:1 336 major phase: ZrSiO4 internal mass balances.
trace phase: Na2SiO3 XRD measurements between 0.8 and 10 2 were
600 2:1 336 major phase: ZrSiO4 obtained with a Siemens D-501 automated diffractome-
minor phase: Na2ZrO3, Na2SiO3 ter Cu KR (0.15418 nm) with the Soller slits at 2
(diffracted beam side), divergence slits at 1, and receiv-
ucts. A grade with a median particle size of d50 9 m ing slits at 0.05. A scintillation counter detector was
and with the following composition, as determined by used, over the range of 3-65 2 and at a step width of
X-ray fluorescence, was used: ZrO2 + HfO2, 65.7%; SiO2, 0.02, at a scan rate of 30 s/step.
33.6%; Ti, 738 ppm; Fe, 683 ppm; Ca, 666 ppm; P, 455
ppm; U, 331 ppm; Th, 144 ppm. Analytical-grade caustic Results and Discussion
soda, 98% sulfuric acid, and 32% hydrochloric acid were
used in all experiments. Extended Fusion Times. Long fusion times (336 h)
The fusion reactions were carried out in a model TPF were used in order to get an overview of the equilibrium
12/2 high-temperature oven. In each fusion experiment, fusion products that are likely to form. Table 1 lists the
36.6 g of zircon was fused with caustic. The NaOH/ main products identified in the XRD spectra. These data
ZrSiO4 mole ratio was varied from 1 to 6, and fusion were used to construct the simplified phase diagrams
temperatures of 600, 650, 700, 750, and 850 C were shown in Figure 2. The vertical dotted line in these
investigated. After the required fusion time, the oven ternary diagrams shows the locus of the NaOH/ZrSiO4
product was allowed to cool to room temperature. The reactant ratio used in this study. The phase diagram
fusion product was milled using a mortar and pestle to for 850 C is similar to the one accepted in the
homogenize the mixture and was fused again. All fusion literature16,17 that was constructed from results ob-
samples were characterized by X-ray diffraction (XRD) tained by fusing zircon with soda ash at temperatures
to identify the main compounds formed. above 1000 C.
The final fusion product was cooled and then weighed (a) Fusions at 850 C and 336 h. For fusions at 850
before leaching with water to remove the soluble C, the reaction products observed for a reagent ratio
silicates and unreacted sodium hydroxide. The liquids of 2:1 are consistent with the conversion of zircon
were separated from the solids using centrifugation. The according to the following reaction:
solid was dried in an evaporating oven.
The water leach was titrated with a standardized 32% ZrSiO4 + Na2O f Na2ZrSiO5 (I)
(m/m) analytical-grade HCl solution. Bromomethyl or-
ange was used as an indicator and a calibrated pH From a purely stoichiometric viewpoint, one could
meter (Mettler Delta 340) to determine the equivalence expect that the following reaction would be favored at
point at pH 3.8. This value provides an indication of a mole ratio of 4:1:
the alkali recoverable in the sodium silicate product
stream and was expressed as a percentage of the alkali ZrSiO4 + 2Na2O f Na2ZrO3 + Na2SiO3 (II)
used in the fusion.
The resulting hydrated silica was precipitated with However, the yields obtained and the XRD spectra
an ammonia and ammonium chloride solution by ad- recorded show that the products are better explained
justing the pH to 7. The sodium salts were then in terms of both reactions (I) and (II) occurring to
separated from the hydrated silica by washing and approximately the same extent. This implies that higher
780 Ind. Eng. Chem. Res., Vol. 42, No. 4, 2003

Figure 2. Phases observed in the XRD spectra of fusion products

fused for 336 h.

silicates must have formed as well: Figure 3. Effect of stoichiometry and fusion temperature on
yields. Fusions conducted for 336 h with intermediate milling.
ZrSiO4 + 3Na2O f Na2ZrO3 + Na4SiO4 (III)

Thus, the reaction at 850 C, 336-h fusion time, and a

mole ratio of 4:1 may be considered to be a blend of
reactions (I)-(III):

ZrSiO4 + 2Na2O f xNa2ZrO3 + (2x - 1)Na2SiO3 +

(1 - x)Na2ZrSiO5 + (1 - x)Na4SiO4 (IV)

From the silica yields reported below, we estimate x

0.56.
Our results indicate that reaction (IV) is applicable
for all fusion temperatures above 700 C with mole
ratios above 2:1. The value that x assumes in the
resultant product spectrum has important implications
for the zirconia yield and the alkali recovery. Na2ZrSiO5
is insoluble in and does not hydrolyze in water.16 Its
formation, therefore, prevents full recovery of alkali in
the sodium silicate product stream. It must be hydro-
lyzed using a mineral acid, and this gives rise to a
corresponding sodium salt waste stream. On the other
hand, it facilitates high recovery of zirconia per mole of
sodium hydroxide added. Compared to reaction scheme
(II), scheme (I) requires only 2 mol, instead of 4 mol, of
sodium to liberate a mole of zirconium as zirconia.
Figure 3 shows zirconia yields and alkali recoveries
Figure 4. Effect of fusion temperature on the yield for NaOH:
as a function of the stoichiometry used. For a fusion
zircon ) 2:1. Fusions conducted for 336 h with intermediate
temperature of 850 C, the zirconia recovery approaches milling.
100% for a 4:1 stoichiometry. The 90% zirconia yield at
a 2:1 stoichiometry is attributed to the side reaction (II) silicates formed are highly soluble and can be removed
that leads to the formation of Na2ZrO3 and Na2SiO3. by simple water washing. The compounds Na2ZrSiO5
The observed sodium recoveries for prolonged fusions and Na4Zr2Si3O12 are insoluble and remain with the
at 850 C can be explained as follows. All of the sodium solid phase. The zirconium and silica are only released

Figure 5. Effect of fusion time on yields. Fusions conducted at
850 C.
upon hydrolysis with a strong acid. Exhaustive leaching
with water hydrolyzes sodium zirconate to hydrated
zirconia.1,4,16,17
(b) Fusions at 650 C and 336 h. No evidence was
found for the formation of either Na2ZrSiO5 or Na4Zr2-
Si3O12 at any stoichiometry for fusions conducted at 650
C. Thus, reaction scheme (II) describes the main
decomposition reaction at this temperature.
Figure 3 also shows the zirconia yields and alkali
recovery for the 650 C fusion temperature. Because
reaction (I) does not occur at this temperature, high
zirconia yields require a higher NaOH/ZrSiO4 mole ratio
(Figure 3A). At the same time, however, alkali recovery
is always high (Figure 3B). Alkali recovery exceeding
50% is expected for a 4:1 stoichiometry and assuming
complete conversion according to reaction (II) as well
as partial hydrolysis of the compound Na2ZrO3. The
experimentally observed value is ca. 60% and indepen-
dent of stoichiometry over the range investigated here.
In contrast, at a fusion temperature of 850 C, the
sodium recovery is very low (<10%) and increases to
about 65% in the corresponding range of reactant ratios
(Figure 3B).
(c) Fusions at Other Temperatures. Table 1 shows
that the phases formed at 600 C are similar to those
observed for 650 C. The phase Na2ZrSiO5 appears as
a major product in the XRD spectrum at a temperature
Ind. Eng. Chem. Res., Vol. 42, No. 4, 2003 781
Table 2. Observed Phases in XRD Spectra Obtained for
the 2:1 Stoichiometry Fusions
temp mol ratio of time
[C] NaOH/ZrSiO4 [h] phases observed in XRD
850 2:1 336 major phase: Na2ZrSiO5
minor phase: ZrSiO4, Na2ZrO3
trace phase: Na4Zr2Si3O12
850 2:1 24 major phase: ZrSiO4, Na2ZrSiO5
minor phase: Na2SiO3, Na2ZrO3
850 2:1 4 major phase: ZrSiO4, Na2ZrSiO5
minor phase: Na2ZrO3, Na2SiO3
850 2:1 2 major phase: ZrSiO4, Na2ZrSiO5
minor phase: Na2ZrO3, Na2SiO3
850 2:1 1 major phase: ZrSiO4
minor phase: Na2ZrSiO5, Na2SiO3
750 2:1 336 major phase: Na2ZrO3, ZrSiO4,
Na2ZrSiO5
minor phase: Na2SiO3
700 2:1 336 major phase: ZrSiO4, Na2ZrO3,
Na2ZrSiO5
minor phase: Na2SiO3
650 2:1 336 major phase: ZrSiO4, Na2ZrO3
minor phase: Na2SiO3
strong amorphous halo at ca. 2 ) 13
650 2:1 2 major phase: ZrSiO4
minor phase: Na2ZrO3
trace phase: Na2SiO3
600 2:1 336 major phase: ZrSiO4
minor phase: Na2ZrO3, Na2SiO3
of 700 C. The effect of this phase on yields should be
most pronounced at a stoichiometry of 2:1 NaOH/zircon
mole ratio. Consequently, we determined the product
yields at this ratio as a function of temperature. The
results are reported in Figure 4, which suggests two
plateau regions for the zirconia yield values. Below 700
C, the zirconia yield is about 40-50%, and above 750
C, it exceeds 80%. The rapid increase in zirconia yield
between 700 and 750 C is attributed to the formation
of the phase Na2ZrSiO5. The drop in alkali recovery at
high temperatures is also attributed to the appearance
of this compound in the product spectrum.
Effect of Fusion Time. The effect of fusion time was
studied for NaOH/ZrSiO4 ratios of 2:1 and 4:1 and a
fusion temperature of 850 C. The results for the
zirconia yield as well as NaOH and silica recovery in
the sodium silicate stream are presented in Figure 5.
Yields for fusion times of 1, 2, 4, 24, and 336 h are
reported. Unexpectedly, the zirconia yield curve shows
a local maximum at a fusion time of 2 h. This corre-
sponds with local minima in the NaOH and silica
recovery at this fusion time. For 336-h fusions the
zirconia yield exceed 90% and 96% for the 2:1 and 4:1
NaOH/ZrSiO4 reagent ratios, respectively. For the same
fusion time, the NaOH and silica recovery approaches
zero for the NaOH:ZrSiO4 ) 2:1 reagent ratio. In
contrast, the corresponding recoveries were about 56%
at NaOH:ZrSiO4 ) 4:1.
Table 2 lists the main phases identified in the XRD
spectra of these fusion products. We first consider a 2:1
reagent ratio. Table 2 shows that a 1-h fusion time is
clearly insufficient because the zircon peak still domi-
nates the XRD spectrum. Thus, incomplete reaction
explains the high NaOH yet low silica recovery for this
fusion time. Even at a 4-h fusion time, there is still a
significant presence of unreacted zircon. The main
reaction products are Na2ZrSiO5 and Na2ZrO3, whereas
for 2 and 336 h, the main peak in the XRD corresponds
to Na2ZrSiO5. As noted above, the latter product is
insoluble and does not hydrolyze in water. Its formation
thus prevents the recovery of the associated alkali and
782 Ind. Eng. Chem. Res., Vol. 42, No. 4, 2003
Figure 6. Effect of stoichiometry and fusion temperature on
yields. Fusions conducted for 2 h with intermediate milling.
silica in the water leach step. This explains the poor
alkali and silica recovery for the 2- and 336-h fusion
times. The following reaction is consistent with the
observed decrease in zirconia yield and the change in
nature of the main phases present in the XRD when
the fusion time is extended from 2 h to 4 or 24 h:
2Na2ZrSiO5 f Na2ZrO3 + Na2SiO3 + ZrSiO4
Note that equation (V) only provides a rationalization
of the experimentally observed behavior, proven by
several replications of the experiments. A proper physi-
cal explanation as to why a thermodynamically stable
product will initially form, then break down, and
eventually reform, is still extant.
Effect of Temperature and Stoichiometry on
Yields for 2-h Fusion Times. Based on the observed
optimum in the zirconia yield at 850 C, all further
fusions were conducted for 2 h only. Figure 6 shows the
effect of temperature and stoichiometry on the yield of
zirconia and the recovery of silica and sodium hydroxide.
Figure 6A shows that for 2-h fusions the zircon yield
increases with increasing temperature, fusion time, and
NaOH/ZrSiO4 reactant ratio. Almost complete recovery
of zirconia is obtained for the NaOH:ZrSiO4 ) 6:1 mole
ratio and a fusion temperature of 850 C. Figure 6C also
shows that the silica recovery follows similar trends.
Figure 7. Effect of stoichiometry and fusion temperature on the
relative zirconia yields. Fusions conducted for 2 h with intermedi-
ate milling.
Table 3. Observed Phases in XRD Spectra of 2-h Fusions
temp mol ratio of time
[C] NaOH/ZrSiO4 [h] phases observed in XRD
850 6:1 2 major phase: Na2ZrO3
trace phase: Na2ZrSiO5, ZrSiO4
850 4:1 2 major phase: Na2ZrO3
minor phase: ZrSiO4, Na2SiO3
trace phase: Na2ZrSiO5
amorphous halo at ca. 2 ) 16
850 2:1 2 major phase: ZrSiO4, Na2ZrSiO5
minor phase: Na2ZrO3, Na2SiO3
650 6:1 2 major phase: Na2ZrO3
minor phase: Na4SiO4
trace phase: ZrSiO4, Na2Si2O5,
Na6Si2O7
amorphous halo at ca. 2 ) 16
650 4:1 2 major phase: ZrSiO4, Na2ZrO3
trace phase: Na6Si2O7
amorphous halo at ca. 2 ) 16
650 2:1 2 major phase: ZrSiO4
minor phase: Na2ZrO3
trace phase: Na2SiO3
Interestingly, according to Figure 6B, the NaOH recov-
ery in the sodium silicate product stream is almost
independent of the temperature and reagent ratio. Note
that the results for 336-h fusion times differ signifi-
cantly (see Figures 3B and 4B) with the alkali recovery
even approaching zero for NaOH:ZrSiO4 ) 2:1 at 850
C. The implication is that the fusion products obtained
at short fusion times must differ substantially from the
equilibrium product distribution.
XRD analyses of the reaction products formed for 2-h
fusions confirm that kinetic phases form that differ
substantially from the equilibrium phases discussed
(V) above (see Table 3). We believe that the sodium pre-
ferentially attacks silica to form orthosilicate monomers
Na4SiO4, pyrosilicate dimers Na6Si2O7, and metasilicate
chains Na2SiO3. All of these compounds are water
soluble and facile to remove using a water wash.
Obviously, any free alkali present owing to incomplete
conversion is also removed in the water wash.
Concluding Remarks
Farnworth et al.1 state that the main problem with
an alkali fusion route is the disposal of an alkaline
silicate solution. However, in the same paper they also
state that an alkali-based process is environmentally
acceptable because sodium metasilicate is a useful
byproduct. We prefer to agree with the latter because
our investigations have shown that the sodium silicate
solution produced in the De Wet process is essentially
free of radioactivity. Our objective is, therefore, to
maximize the alkali recovery in this product stream.

From a practical point of view, short fusion times and
low reaction temperatures are preferred. The 2-h fusion
results are, therefore, more relevant from a commercial
perspective. Figure 7 shows the zirconia yield per unit
of sodium hydroxide consumed. At a NaOH/ZrSiO4 ratio
of 2, the alkali-utilization efficiency of the 850 C, 2-h
reaction is nearly the same as the 650 C, 336-h fusion.
This is attributed to the nonequilibrium phases that are
formed during the short fusion times. The 2-h reaction
at 850 C with a 2:1 stoichiometry also produces the
least alkali salt waste. However, a plant operating at
these conditions would feature a significantly larger
recycle stream and would have to be about 170% larger
in size than an equivalent plant (with the same output)
operating at the same conditions but with a stoichiom-
etry of 6:1.
Acknowledgment
This paper is dedicated to the memory of our friend
and mentor Dr. Willem De Wet, who passed away so
unexpectedly. Financial support for this research from
the THRIP program of the Department of Trade and
Industry and the National Research Foundation of
South Africa as well as Kumba and Xyris Technology
CC is gratefully acknowledged.
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Revised manuscript received October 12, 2002
Accepted October 12, 2002
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