J. Mater. Sci. Technol., Vol.21 No.

5, 2005 767

• Research Notes
Laboratory Study on the Removal of Fluorine from High
Fluorine Bearing Zinc Oxide Ore
Yaozhong LAN1)† , Liaoyuan YE1) and Rose W.Smith2)
1) Materials Department, Yunnan University, Kunming 650091, China
2) Metallurgical and Materials Department, Nevada University of Reno, NV89503, Nevada, USA
[Manuscript received November 25, 2004, in revised form March 17, 2005]

An ever increasing demand for zinc has resulted in worldwide efforts to exploit complex and lean grade reserves of zinc
oxide ore. In this study experiments were done on zinc recovery from high-fluorine bearing zinc oxide ore. First the
effect of different variables on fluorine removal was investigated. Optimum experimental conditions occurred when
the temperature was 1173 K, roasting time was 90 min and air flow was at a velocity of 5 m/min, the fluorine removal
from the samples reached over 93%. The results obtained indicate that fluorine removal is not enhanced by adding
diluted sulfuric acid or water as a binder. Second the roasted materials were leached with a diluted sulfuric acid,
neutralized, flocculated and filtrated. The residual fluorine content in the leached solutions was less than 38 mg/L,
which satisfies the requirement of fluorine content in the leached solutions for the production of electrolytic zinc.
KEY WORDS: High-fluorine bearing zinc oxide ore; Roasting; Leaching; Zinc recovery

1. Introduction 38 mg/L, which satisfies the requirement of fluorine con-

tent in leached solutions for the production of electrolytic
With an ever increasing demand for zinc and the daily zinc.
depletion of high grade zinc oxide ore reserves, research
is necessary on how to use zinc oxide ore reserves with 2. Experimental
their complex chemical composition, their low zinc con-
tent and their difficult treatment[1∼8] . The mineralogical and chemical compositions of the
In Yunnan Province of China there is a large reserve high F bearing zinc oxide used in the present work are
of zinc oxide ore with a lean grade and complex com- presented in Tables 1 and 2, respectively. The sample
position. Its fluorine content reaches up to 0.38%. If a was crushed and then ground to pass −75 µm sieve.
process of direct leaching with sulfuric acid is adopted, To reduce the emission of dust during the roasting ex-
the fluorine in the zinc oxide ore enters the leaching so- periments, high fluorine bearing zinc oxide pellets with
lution, resulting in a high content of fluorine. a diameter of 0.4∼0.5 mm were prepared using water or
diluted sulfuric acid as binders during this process, next
Fluorine in the leached solution is a detrimental el-
dried 24 h and then kept in a desiccator.
ement because it harms the production of electrolytic
An electrically heated horizontal-tube furnace was
zinc, for example, it corrodes cathode and anode, de-
used for the roasting study. The reaction tube was
grades the quality of electrolytic zinc and makes zinc
800 mm long with an internal diameter of 60 mm and
peeling difficult[9,10] . In the production of zinc salt, flu-
a constant temperature zone of 10 mm long. With the
orine lowers the quality of zinc salt, so limits the use
aid of a digital controller and by careful adjustment of the
of zinc salt[11∼14] . Therefore, it is necessary to control
set-point of the furnace the temperature was controlled
the fluorine content in the leached solution. An effective
to plus or minus 1 K.
method to remove fluorine from a high fluorine solution
A 40 mm long and 30 mm wide porcelain boat shaped
is not yet available.
dish was used as the reaction vessel. The test sample
This study was a test to remove fluorine from high
with 10 grams for each test run was introduced after the
fluorine zinc oxide ore by roasting, leaching roasted ma-
furnace reached the desired temperature and the pellets
terials with diluted sulfuric acid and purifying the leached
was roasted for different durations. The roasted materi-
solution. The main parameters that affect the roasting
als were removed from the furnace and cooled in an argon
process of high fluorine zinc oxide were investigated. Op-
flow.
timum experimental conditions occurred when the roast-
The roasted material was leached. The leaching ex-
ing temperature reached 1173 K. The roasting time was
periments were carried out in a 250 ml beaker with mag-
1.5 h and the air flow rate through the reaction tube
netic stirring at a constant speed, solution being added
was at a velocity of 5 m/min per minute, fluorine re-
in the proportion of 3.0 L per kg of the roasted materi-
moval reached 93%. The roasted materials were then
als. The reaction time was 2 h and the temperature was
leached with a sulfuric acid solution, purified and filtered.
323 K. At the end of each leaching test the pulp was vac-
The residual fluorine content in the filtrate was less than
uum filtered and the solid residue that was obtained was
† Prof., to whom correspondence should be addressed,
washed with 500 ml water. After filtration and washing,
E-mail: Lanyz2003@yahoo.com. the filtrate and the leached solid residue were sent for
768 J. Mater. Sci. Technol., Vol.21 No.5, 2005

Table 1 Chemical composition of high F bearing zinc ore (wt pct)

Zn Fe F S Pb Cd Cl As CaO MgO Al2 O3 SiO2 Sb

32.43 0.69 0.35 4.16 8.10 0.19 0.03 0.18 4.11 2.61 0.51 11.0 0.16

Table 2 Mineralogical composition of high F bearing zinc ore (wt pct)

Zinc carbonate Zinc silicate Zinc sulfide Others

75.40 6.10 18.31 0.19

Table 3 Effect of binder type

Binders Roasted material Removal/%

Zn Pb As F Si
130 g/L H2 SO4 15% 38.54 10.03 0.16 0.15 19.20 95.10
Water 15% 38.23 9.87 0.18 0.14 18.20 94.83
No binder 39.15 11.03 0.19 0.17 17.80 93.54

Fig.1 Effect of temperature on fluorine removal Fig.3 Effect of velosity of gas flow on fluorine removal

Figure 2 shows the variation of fluorine removal with

Fig.2 Effect of roasting time on fluorine removal
chemical analysis.
3. Results and Discussion
The effect of temperature on fluorine removal is shown
in Fig.1. The fluorine removal increased with an increase
in temperature. When the temperature reached 1173 K,
the fluorine removal was 93%. Fluorine removal was not
significant with higher temperatures.
the roasting time at 1173 K. It could be seen in Fig.2 that
the fluorine removal increased with the roasting time,
but when the roasting time exceeded 90 min, the fluorine
removal did not change greatly with further increasing
roasting time. As a result, the optimum roasting time
was 90 min.
The mineral analysis revealed that the major mineral
in the sample existed in the form of zinc carbonate, which
decomposed in the roasting process. Figure 3 indicates
that the fluorine removal changed with the velocity of air
flow. Fluorine removal increased with an increase in ve-
locity of air flow. The optimum velocity of air flow was
5 m/min.
Table 3 shows the effect of different binders on the
removal of fluorine. The results obtained prove that the
addition of diluted sulfuric acid or water as a binder did
not greatly affect the removal of fluorine.
There was a large amount of zinc silicate in the
roasted materials. Under the condition of acid leach-
ing, zinc silicate was easily dissolved into the solution,
increasing the SiO2 content in the leached solution. To
prevent the formation of silica gel in the process of acid
leaching, we conducted a test of acid leaching of roasted
 J. Mater. Sci. Technol., Vol.21 No.5, 2005 769

Table 4 Chemical composition of filtrate (g/L)

Test run Zn Cd F Cl
J-01 98.74 0.21 0.027 0.024
J-02 99.52 0.19 0.029 0.025
J-03 99.15 0.22 0.030 0.021
J-04 97.45 0.24 0.026 0.023
J-05 98.56 0.23 0.028 0.021

materials, neutralization and flocculation with the fol- Acknowledgement

lowing conditions:
Lixiviant: dilute sulfuric acid at a concentration of
140 g/L H2 SO4 ; Leaching time: 2 h; Liquid-solid ra-
tio: 3:1; Temperature: 338 K; End point of pH value:
1.8∼2.0. After completion of leaching, the pH in the
leached solution was adjusted to 5.5 with lime emulsion
and then polyacrylamide (PAA) was added for floccu-
lation. The filtration began after holding the leached
solution for 2 h. The chemical composition of the fil-
tered solution is shown in Table 4. It could be seen that
the residual fluorine content in the solution was less than
38 mg/L.
4. Conclusion
This study proved that high fluorine zinc oxide ore
could be effectively treated with the process of roast-
ing, leaching roasted material with diluted sulfuric acid,
neutralizing and flocculation. Under experimental con-
ditions when the temperature was 1173 K, the roasting
time 90 min and an air flow at a velocity of 5 m/min,
the fluorine removal from the sample reached over 93%.
For high fluorine zinc oxide ore, the roasting with the
addition of diluted sulfuric acid and water was not as ef-
fective in removing fluorine. With the process of roasting
materials, acid leaching, neutralization and flocculation,
the residual fluorine content in the solution was less than
38 mg/L, which satisfies the requirement of fluorine con-
tent in leached solutions for the production of electrolytic
zinc.
This work was supported by Yunnan Science and Tech-
nology Department (Contract No. PY2002PY01, 2001 HG
04)
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