Study of the recovery of silica from

the zircon chemical treatment

Zirconium silicate (ZrSiO4), commonly known as zircon, is the most abundant Laura Rocha and Carlos Morais.
Centro de Desenvolvimento da
mineral of zirconium and the main source for the production of metallic zir-
Tecnologia Nuclear, Comissão
conium, as well as its compounds and alloys. The present work aims at studying Nacional de Energia Nuclear (CDTN/
CNEN), Brazil
the recovery of silica present in the product of the fusion of zircon with sodium
hydroxide. During the alkaline fusion, the zirconium silicate (ZrSiO4) is con-
verted into sodium zirconate and sodium silicate. The study of silicon recovery
was performed by leaching the silicate from the product of the fusion with
water (alkaline leaching) followed by the precipitation of silica and by leaching
the fusion product with nitric acid (acid leaching) for the dissolution of zirco-
nium. After the leaching process, the solid-liquid separation was carried out
through vacuum filtration, the residue was dried and the chemical analysis of
the residue and the liquor was performed. From an alkaline molten product
of zircon containing 31.8% ZrO2, 14.1% SiO2 and 47.8% Na2O and 5.7% humidity,
in the alkaline leaching, a dissolution of approximately 73% of silica, a liquor
with about 15 g/L of silica and a residue with 89% of ZrO2 and 6.7% of SiO2 was
obtained. In the acid leaching carried out with HNO3, the dissolution of ZrO2
was approximately 92%, obtaining a nitric liquor containing 20 g/L of Zr (27 g/L
ZrO2). The content of SiO2 in the acid leaching residue was 92% with a mass
reduction of approximately 80%.

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INTRODUCTION
Zircon is a tetragonal zirconium orthosilicate (ZrSiO4). The chemical composition of the mineral
mass contains approximately 65% of ZrO2, 32% of SiO2, and other elements at low concentrations,
such as Hf, Fe and Ti (Habashı, 1997; Manhıque et al, 2003; Bertolıno et al, 2008). By presenting high
thermal and chemical stability, the decomposition of zircon, requires drastic conditions. Different
techniques are used in the decomposition of the mineral and may occur by thermal or chemical
decomposition at high temperatures. The alkaline fusion with sodium hydroxide is a method for
chemical decomposition of zircon and is the most used process in obtaining metallic zirconium.
This fusion occurs at temperatures between 550-700 ° C. The variables that affect the characteristics
of the product of the fusion are: mass ratio, temperature and reaction time (Abdel-Rehim, 2005;
Zolfonoun et al 2010).
The decomposition of zircon generates large ammounts of sodium silicate, along with zirconium
oxide, according to Equation 1 (Abdel-Rehim, 2005).

ZrSiO 4 + 4 NaOH → Na 2 ZrO 3 + Na 2SiO 3 + H 2 O (1)

According to Bıswas et al, 2010, considering the reaction presented in Equation 1, it is possible to
form other products, besides zirconate and sodium silicate, such as Na4SiO4, Na2Si2O6, Na6Si2O7,
Na4ZrSi3O12.
The recovery of the silica present in zircon is fundamental as the environmental and economic
issues are concerned, since silica is an inorganic material widely used in a variety of applications
such as resins, molecular sieves, catalyst carriers, as raw material in the glass, and electronic
industry, amongst other applications. This removal is generally accomplished by alkaline leaching
using water as a leaching agent. In this step there is a very high consumption of water and a highly
pollutant effluent having a high content of silica is produced. An alternative method evaluated in
this work was the leaching of sodium zirconate, keeping the silica insoluble. This new route can
reduce the cost of the process with satisfactory results. The process variables investigated were:
reaction time, temperature, percentage of solids and nitric acid concentration (HNO3).

METHODOLOGY

Reagents and solutions

The sample of zircon concentrate used in this work was provided by the Nuclear Industries of
Brazil - INB. Prior to this study, the decomposition of the zircon concentrate by alkaline fusion with
sodium hydroxide was performed. In the study of the separation of Zr/Si; 100 kg of zircon
concentrate was melted, generating approximately 200 kg of molten mass (alkaline melt product).
The sample was homogenized and reduced to fractions of different masses in order to enable the
laboratory experiments and the chemical characterization.

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The sodium hydroxide used was of commercial grade (99% w/w) and the nitric acid (HNO3) was of
analytical grade. Distilled water was used for alkaline leaching and also in the preparation of the
solutions.

Methodology
The leaching studies were performed in a 250 mL beaker using mechanical agitation at controlled
temperature. After the reaction time stated, the pulp was vacuum filtered using buchner funnil and
kitasato. After filtration, the solid was transferred for drying in an oven at 110°C. Then the residue
was weighted and the volume of the filtrate was measured and sent to chemical analysis. The
metals present in the residue and in the leaching liquor were analyzed by Energy Dispersive X-ray
Fluorescence Spectrometry - EDXRF - using an X-ray spectrometer of dispersive energy brand
SHIMADZU, model EDX-720. The nitrate content in the liquor was determined by molecular
absorption spectrophotometry in the ultraviolet region (302 nm) using an UV – visible
spectrometer, brand VARIAN model Cary 50 conc.

RESULTS AND DISCUSSION

Chemical characterization
The chemical composition of the main components of the zircon concentrate and of the molten mass
(fusion product) of zircon used in the experiments of recovery of silica is shown in Table 1, below.

Table 1 Chemical composition of zircon before and after the alkaline fusion.

Species / Content (%)

Sample
ZrO2 SiO2 HfO2 Na2O H2 O Er2O2 Y2O3 Al2O3 TiO2 Fe2O3 BaO
Zircon 65.0 29.0 1.33 _ _ 0.58 0.18 2.22 0.94 0.53 0.58
Fusion 31.8 14.1 0.57 47.8 5.70 _ _ _ _ _ _

product

Alkaline leaching
The chemical opening of zircon performed through fusion with sodium hydroxide produces a
strongly alkaline molten mass. This allows to use water as the leaching agent for the the dissolution
of the sodium silicate formed during melting. In the study of silica dissolution with water (alkaline
leaching) the following process parameters were investigated: percentage of solids, temperature
and reaction time.

Reaction time
The reaction time was investigated ranging from 1 to 6 hours, within a percentage of solids of 10%
and at room temperature. The results showed that there was only a slight variation in the
percentage of the silicate dissolution – 73 to 76%. Considering the small diference in the silicate

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dissolution obtained in this step of the study, the reaction may be conducted with 1 hour of stirring
at room temperature.

Variation of the solids percentage and the temperature

The influence of the solids percentage and temperature on the sodium silicate dissolution was
investigated for percentages of 10%, 15%, 20% and 30% at temperatures of 25°C and 70°C with a
reaction time of two hours. The results are presented below in Table 2.

Table 2 Effect of the percentage of solids in the dissolution of sodium silicate generated in the
alkaline fusion of zircon
Percentage of solids Temperature (oC) Dissolution (%)
10 25 73
10 70 76
15 25 75
15 70 73
20 25 72
20 70 72
30 25 71
30 70 72
As can be seen in Table 2, the influence of the percentage of solids and the temperature on the
dissolution of sodium silicate was not significant. However, one can observe a slight tendency
towards higher dissolution in solids percentages between 10 and 15%. In the intervals investigated,
the dissolution of the silicate ranged from 71 to 76%, considering an experimental error of about 4%,
it can be said that the dissolution of the silicate present in the fusion product is not influenced by
temperature.

Final products of the alkaline leaching

At the end of the experiments presented in this paper, an alkaline liquor containing approximately
15 g/L of Si and a residue containing 89% of ZrO2 and 6.7% of SiO2 was obtained. The silicon
present in the liquor was precipitated through acidification with hydrochloric acid 5.0 mol/L up to
pH 1.0. The chemical composition of the alkaline solution, the residue of leaching and silica
obtained in the neutralization liquor is given in Table 3.
The mass reduction in the alkaline leaching was approximately 45%. The dissolution of the residue
of the alkaline leaching with HNO3 generated a liquor containing around 50g/L Zr, 2.5 g/L Si, 3.5
g/L Na, 1.0 g/L Hf and 0.2 g/L Fe. The yield of the dissolution of Zr and Hf from the residue of the
alkaline leaching was 97%.

Table 3 Chemical characterization of the products of the alkaline leaching

Species / Content (%)
Sample SiO2 ZrO2 HfO2 Na2O Fe2O3 TiO2 CaO
Alkaline Liquor (g/L) 31.1 0.09 0.002 67.1* _ _ 0.08
Residue of leaching (%) 6.73 89.,4 0.96 0.98 1.14 0.54 0.26
Silica (%) 95.3 2.30 0.09 0.57 0.04 _ 0.20
*NaOH = 86.6 g/L

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Acid leaching
As shown in Table 3, the residue of the alkaline leaching had a SiO2 content of 6.7%, which is not
desirable in the process. Therefore, another process route was investigated; the dissolution of Zr
without previously removing the silicon. The dissolution of Zr was made by leaching with HNO3 in
a beaker using mechanical stirring at controlled temperature. The process variables investigated
were: acid concentration, temperature, reaction time and percentage of solids.

Variation of the concentration of HNO3 and temperature

The influence of the concentration of HNO3 in the dissolution of zirconium from the fusion product
was investigated at the range of 4 mol/L to 12 mol/L at three different temperatures: 25°C, 50°C and
70°C. The experiments were performed in triplicates and the results are shown in Figure 1. As seen
in Figure 1, there is an increased dissolution of Zr as the temperature increases. The influence of
temperature is more significant for lower concentrations of HNO3 (4.0 mol/L). The dissolution of
silica was below 2% for all the concentrations of HNO3 investigated. The subsequent experiments
were carried out in acidity of 12 mol/L. The high acidity of HNO3 is justified by the fact that in the
next stage of the study, which comprises the separation of Zr/Hf by solvent extraction, is performed
at high acidity. The behavior of Hf was similar to that of Zr and therefore was not reported in
Figure 1.

100 25 degree Celcius

Zr recovery (%)

95 50 degree Celcius

70 degree Celcius
90

85

80

75

70
4 6 8 10 12
Nitric acid conc. (mol/L)

Figure 1 Influence of temperature and HNO3 concentration in the dissolution of zirconium.

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Reaction time
The reaction time was varied from 0.5 to 4 h, using a HNO3 concentration of 12.0 mol/L (ratio
acid/water of 3:1) at a temperature of 70°C and using a percentage of solids of 10%. The
experiments indicated a progressive increase in the dissolution of the zirconium with an increase of
time, however negligible. For the reaction time of 30 min. (0.5 h), the dissolution of Zr was
approximately 89% and 95% for the time of 4 hours. The results are shown in Table 4 below. The
subsequent tests were performed at a reaction time of 3 h. The dissolution of Si was lower than 2%
in all experiments.

Table 4 Effect of reaction time on the dissolution of SiO2 and Zr

Time (h) Dissolution of Zr (%) Dissolution of Hf (%) Purity of Si (%)

0.5 88.7 85.6 84.2
1.0 91.5 89.4 85.5
1.5 92.0 91.2 86.5
2.0 92.7 92.7 86.7
2.5 94.0 92.0 88.7
3.0 92.9 91.6 87.0
4.0 94.9 93.5 89.3

Percentage of solids
The influence of the percentage of solids, in the dissolution of Zr, was investigated at intervals
between 5% and 30%. The experiments were conducted with 3 hours stirring at 70°C and 2.0 mol/L
HNO3. The results are shown in Table 5. As can be seen there is a reduction in the dissolution of Zr
as well as the purity of the silica when the solids content is higher than 15%. Under the
experimental conditions, the dissolution of Si was below 2%.

Table 5 Influence of the percentage of solids in the dissolution of Zr and the in the purity of the
silica.

Percentage of solids (%) Dissolution of Zr (%) Dissolution of Hf (%) Purity of Si (%)

5 94.7 93.3 91.3
10 93.4 91.0 90.0
15 91.7 89.8 87.0
20 90.4 87.0 85.8
25 90.3 85.8 85.0
30 86.2 82.9 81.2

Final products of the acid leach

The best results obtained in the zirconium leaching without the prior removal of silica were: (i) a Zr
liquor containing about 20g/L of Zr, 1.2 g/L Si, 0.4 g/L Hf and 20 g/L Na; the Fe content in the liquor
was below 0.05 g/L, (ii) a residue containing about 43% Si (92% SiO2), 6% Zr and 0.2% Hf, (iii) the Zr
recovery was of approximately 95% and the mass reduction in the leaching was around 80%.

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CONCLUSION
The previous dissolution of the sodium silicate by alkaline leaching before the dissolution of the
zirconium, is already being used industrially, however the drawback of this route is the high water
consumption, as water plays an important role in the sustainability of the environment. The route
of zirconium leaching without the prior leaching of sodium silicate has the advantage of
demanding lower water consumption besides saving one step in the purification of zirconium.
However, the quality of the product obtained by acid leaching was lower when compared with the
product obtained from the alkaline leaching. The liquor obtained fron the alkaline leaching residue
was richer in Zr when compared to that obtained from direct acid leaching. For a more noble
application, the silica obtained from acid leaching needs to go through a purification step.

ACKNOWLEDGEMENTS
The Authors are grateful to FAPEMIG, FINEP, CNPq and CAPES for the financial support and also
thankful to the CDTN’s technicians involved in this study, mainly Luiz C. da Silva, Walmir M.
Garcia and Liliane P. Tavares.

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