Acta Metallurgica Slovaca, 12, 2006, (197 - 202) 197

LITHIUM EXTRACTION FROM ZINNWALDITE WASTES AFTER GRAVITY

DRESSING OF Sn-W ORES

Kondás J., Jandová J.

Department of Metals and Corrosion Engineering, Institute of Chemical Technology Prague,
Technická 5, 166 28 Prague 6, Czech Republic, e-mail: Jan.Kondas@vscht.cz

ZÍSKÁVÁNÍ LITHIA Z CINVALDITOVÝCH ODPADŮ PO GRAVITAČNÍ ÚPRAVĚ

Sn-W RUD

Kondás J., Jandová J.

Ústav kovovývh materiálů a korozního inženýrství, Vysoká škola chemicko-technologická Praha,
Technická 5, 166 28 Praha 6, Česká Republika, e-mail: Jan.Kondas@vscht.cz

Abstrakt
Pro zpracování Li-cinvalditového koncentrátu byla ověřována sádrová metoda. Li –
cinvalditový koncentrát byl připraven z gravitačních odpadů po těžbe Sn-W rud suchou
magnetickou separací. Podstatou této metody je spékání Li-cinvalditového koncentrátu s
určitým množstvím CaSO4 a Ca(OH)2 v rozmezí teplot 850-975oC, při kterém se Li vázané
v cinvalditu převede na Li2SO4. Vzniklé spečence byly louženy destilovanou vodou při teplotě
90°C, poměru kapalné a pevné fáze 5-15:1.

Abstract
In this study, a possibility of processing of Li - zinnwaldite concentrate by gypsum
process was examined. Li - zinnwaldite concentrate were prepared from gravity wastes after
mining of Sn-W ores using dry magnetic separation. The process is based on sintering Li -
zinnwaldite concentrate with certain amount of CaSO4 and Ca(OH)2 at temperature range 850-
975°C. During the sintering, lithium from the zinnwaldite concentrate is converted to soluble
Li2SO4. The sinters were leached with distilled water at temperature of 90°C and liquid-to-solid
ratio 5-15:1.

Key words: lithium recycling, zinnwaldite, Li2CO3, water leaching

1. Introduction
In 2005, the world production of lithium was estimated to about 20,000 tones and it is
possible to forecast its gradual growth. The main area of lithium consumption is in production of
lightweight alloys for automobile, aviation and aerospace industries. A rapid growth of demand
for lithium is expected from production of primary and secondary lithium batteries, which are
used as a source of electrical energy in portable telephones, portable computers, cameras and
video cameras, clocks and watches, signal equipments, etc. With the development of new
generation of electric vehicles, the lithium demand will dramatically grow. Another significant
use of lithium is lithium compounds, namely Li2CO3.
The most important lithium minerals are spodumene LiAlSi2O6 (6.0-7.5% Li2O),
petalite LiAlSi4O10 (3.5-4.5% Li2O), lepidolite (lithium mica) Li,Al]3[Al,Si]4O10[F,OH]2 (3.30-
7.74% Li2O). Zinnwaldite K[Li,Al,Fe]3[Al,Si]4O10[F,OH]2, regarded as a variety of lepidolite
Acta Metallurgica Slovaca, 12, 2006, (197 - 202) 198

has the content of Li2O from 2 to 5% and contains relatively high iron content. Other important
lithium mineral is amblygonite [Li, Na]Al[F,OH]PO4, which contains up to 9.88% Li2O [1, 2].
Significant reserves of zinnwaldite are located in Czech Republic at Krušné
Mountains in Cinovec area. This zinnwaldite is bound to deposits of Sn-W ores, which were
mined heavily in the past. Tin and tungsten concentrates were separated from these ores by
pneumatic classification. The waste sludges containing 0.21-0.30% Li in form of zinnwaldite
were dumped in Cínovec area. The reserves have been estimated to be 1.25 mil. tones and so it
is the most accessible raw material for an alternative production of lithium in the Czech
Republic.
A number of methods for the recovery of lithium compounds from its minerals exist
in the literature and in the industrial practice. Their basis is conversion of lithium minerals into
soluble form. Majority of published works have dealt with processing concentrates, which
contain spodumene, petalite, lepidolite and amblygonite. In choosing suitable technologies for
processing of zinnwaldite it is advantageous to begin with procedures recommended for
processing of lepidolite. Lepidolite belongs to the same mica group as zinnwaldite and basically
differs from zinnwaldite only by a higher content of FeO.
On principle, basic methods for processing of lithium raw materials can be classified
into:
• Acid digestion, its basis is decomposition of materials with H2SO4 at 250-400°C. This
procedure is suitable for processing of lepidolite, amblygonite and zinnwaldite. The
product is lithium carbonate.
• Alkali digestion is suitable for thermal decomposition of spondumene a lepidolite
largely by treatment of potassium carbonate, so called the limestone method. The
product is lithium hydroxide.
• Sulfate process that is used for processing of lepitolite. Its basis is high temperature
decomposition of lithium minerals by using potassium and/or sodium sulfate. The
product is lithium carbonate.
• Gypsum process, which is mentioned in literature for decomposition of lepidolite by
treatment of a mixture consisted of calcium sulfate with calcium oxide and/or
hydroxide. The product is lithium carbonate.
• Ion-exchange, so-called brine processes were based on replacement of lithium cations
by sodium and/or potassium. These processes involve either heating of lithium minerals
with alkali salts or in more advanced hydrothermal processes decomposition in
solutions containing Na2CO3, NaOH, Na2SO4 and/or other alkali salts at elevated
temperature and under high pressure. Ion-exchange processes were applied for
processing of spodunmene, petalite and partly even zinnwaldite [1,2].
The present study deals with processing concentrates for preparation of lithium
carbonate using gypsum method. Zinnwaldite concentrates were prepared from zinnwaldite
wastes after gravity dressing of Sn-W ores using dry magnetic dressing. The aim of this study
was to determine the optimum conditions of sintering the zinnwaldite concentrates with the
mixture of CaSO4 and Ca(OH)2 depending on the temperature, the zinnwaldite concentrate to
CaSO4 to Ca(OH)2 ratio and cooling regime. The introductory sintering conditions were chosen
based on knowledge of previous Czechoslovak research works, which were suspended in the
beginning of 1990s [3, 4, 5].
Acta Metallurgica Slovaca, 12, 2006, (197 - 202) 199

2. Experimental
2.1 Preparation of Li – zinnwaldite concentrate
Representative sample of approximately 200kg Li-zinwaldite waste was mined from
the landfill of wastes from gravity dressing of Sn-W ores in Cínovec area. It contains on average
0.19wt% Li. After drying and grinding the Li - waste under 1mm, 175kg of the waste were
subjected to dry magnetic separation. From the magnetic concentrate, which contains 1.21wt%
Li a fraction >100 µm was separated. This so called Li – concentrate + 100 µm contained
1.37wt% Li. Lithium content in zinnwaldite mica is about 1.7wt% Li [6]. The chemical and
mineralogical composition of Li – zinnwaldite waste, Li – zinnwaldite concentrate, Li –
zinnwaldite concentrate + 100 µm and fine fraction - 100 µm are given in the Table 1 and 2. All
experiments were preformed with Li – zinnwaldite concentrate + 100 µm.
Table 1 Average chemical composition of Li – zinnwaldite waste, Li – zinnwaldite concentrate, Li – zinnwaldite
concentrate + 100 µm and fine fraction - 100 µm
Elemental content (wt.%)
Sample
Li Fe Si Al K Ca Na Mn Rb Cs

Li-zinnwaldite waste 0.21 1.11 37.50 5.76 4.38 0.62 0.29 0.36 0.38 0.03

Li- zinnwaldite concentrate 1.21 5.87 30.53 13.27 10.37 0.63 0.30 1.32 1.70 0.03

Li- zinnwaldite concentrate +100 µm 1.37 6.88 28.22 14.25 11.57 0.28 0.13 1.62 2.01 0.05

Fine fraction -100 µm 0.64 5.60 33.93 10.39 7.37 1.13 0.42 0.63 0.88 0.03

Table 2 Mineralogical composition of of Li – zinnwaldite waste, Li – zinnwaldite concentrate, Li – zinnwaldite

concentrate + 100 µm and fine fraction - 100 µm
Mineralogical phase
Sample
Zinnwaldite Quartz Orthoclase Anorthite

Li - zinnwaldite waste KAl(Fe,Li )(Si3Al)O10F2 SiO2 - -

Li - zinnwaldite concentrate KAl(Fe,Li )(Si3Al)O10F2 SiO2 - -

Li - zinnwaldite concentrate +100 µm KAl(Fe,Li )(Si3Al)O10F2 SiO2 - -

Fine fraction -100 µm KAl(Fe,Li )(Si3Al)O10F2 SiO2 K(Al,Fe)Si2O8 Ca(Al2Si2O8)

2.2 Sintering conditions

Li – zinnwaldite concentrate + 100 µm was sintered in a laboratory muffle furnace
with an exact temperature regulation. The treated samples placed in alumina crucibles were
inserted into the furnace under the laboratory temperature. The sintering temperature of samples
was reached within 2h and the reaction time was 1h. After completion the sintering most of the
sinters were slowly cooled in the furnace up to the laboratory temperature. For comparison a part
of the sinters were withdrawn from the furnace and freely cooled under air atmosphere.
Based on research works [3, 4, 5] and our previous studies [6, 7] the following
conditions for sintering of Li - zinnwaldite concentrate and calcium compounds were
established: ratio of Li concentrate to CaSO4 to Ca(OH)2 = 6.00 to 4.20-5.10 to 1.40-2.65. CaSO4
was used both as CaSO4.2H2O of p.a. purity or as a commercial gypsum (CaSO4.0.5H2O). The
second donor of Ca2+ ions was in every case Ca(OH)2 of p.a. purity. In the case of using
Acta Metallurgica Slovaca, 12, 2006, (197 - 202) 200

CaSO4.2H2O the ratio of Li – concentrate to CaSO4 was 6.00 to 4.20, whilst using
CaSO4.0.5H2O corresponded to the ratio of Li – concentrate to CaSO4 = 6.00 to 5.10. The
sintering temperature varied from 850 to 975°C. Samples of individual sinters were subjected to
the chemical and X-ray diffraction (XRD) analysis.

2.3 Leaching conditions

The pulverized sinters were leached in termostated, stirred glass reaction vessel with
water cooler. During leaching, samples were withdrawn at selected time intervals to determine
the reaction rate of lithium dissolution. Leaching conditions were as follow: distilled water,
liquid-to-solid ratio (l:s) 5-15:1, 90°C, 1h. Most leaching experiments were conducted under l:s
= 10:1.

3. Results and discussion

Mineralogical composition of selected sinters including conditions of their
preparation and Li extraction are described in Table 3. Time dependencies of lithium extraction
efficiency on the sintering temperature obtained at different ratio of Ca(OH)2 addition are shown
in Fig. 1 and 2. Presented data correspond to l:s = 10:1, temperature of 90°C and leaching time
of 60 min.
Table 3 Mineralogical composition of selected sinters
Identified phases Li extraction
Sintering conditions:
Chemical formula Mineralogical name [%]
T = 850oC Ca(SO4) Anhydrite
Li-conc. : CaSO4 : Ca(OH)2 = K(Al Fe Li )(Si3 Al)O10(OH)F Zinnwaldite 41
6.0: 4.2 : 1.4 SiO2 Quartz
Ca(SO4) Anhydrite
T = 950oC
Ca3(Cr0.81 Al0.19)2 (SiO4)3 Uvarovite aluminian
Li-conc. : CaSO4 : Ca(OH)2 = 89
LiKSO4 -
6.0: 4.2 : 2.0
Ca Al2 Si2 O8 Anorthite
Ca(SO4) Anhydrite
T = 975oC LiKSO4 -
Li-conc. : CaSO4 : Ca(OH)2 = Ca3All.84 Fe1.16 Si3O12 Andradite aluminian 93
6.0: 4.2 : 2.0 Ca Al2 SiO6 -
Ca Al2 Si2O8 Anorthite

100

80
Li extraction (%)

60

40

1.40 Ca(OH)2
20
2.00 Ca(OH)2
2.65 Ca(OH)2

0
850 875 900 925 950 975
Temperature (°C)
Fig.1 Dependeceies of lithium extraction efficiency on the sintering temperature for sinters in which the ration of CaSO4
to Ca(OH)2 was 5.10 : 1.40-2.65
Acta Metallurgica Slovaca, 12, 2006, (197 - 202) 201

100

80

Li extraction (%)
60

40

1.40 Ca(OH)2
20
2.00 Ca(OH)2
2.65 Ca(OH)2

0
850 875 900 925 950 975
Temperature (°C)
Fig.2 Dependeceies of lithium extraction efficiency on the sintering temperature for sinters in which the ration of CaSO4
to Ca(OH)2 was 4.20 : 1.40-2.65

rom the results obtained it is obvious that under optimum conditions it is possible to
extract 93% of lithium from the concentrate to the solution. From the phase composition of the
sinters it is evident that in the temperature range of 900 – 975oC well leachable LiKSO4 is
forming. Sintering temperature of 850°C is not satisfactory for the complete lithium transfer
from zinnwaldite to LiKSO4. Following sintering conditions provided almost 93% extraction
efficiency of lithium from Li – concentrate +100 µm into water solutions were established:
900°C, Li – concentrate +100 µm to CaSO4 to Ca(OH)2 = 6.00 to 5.10 to 2.00-2.65 or 950-
975°C, Li – concentrate +100 µm to CaSO4 to Ca(OH)2 = 6.00 to 4.20 to 1.40-2.00.
The influence of l:s ratio and the cooling regime of the sinter on the lithium extraction
efficiency are illustrated in Fig.3 and 4. It could be concluded, that both above mentioned factors
do not influence the lithium yield during the sintering and leaching process. Lithium dissolution
runs very fast and it is completed practically within 10 min. Lithium concentration differences
establishes for various l:s ratios do not exceed the accuracy of used analytical methods.
100

80
Li extraction (%)

60

40

20 air cooling
furnace cooling

0
0 20 40 60
Time (min)
Fig.3 Time dependeceies of lithium extraction at different cooling conditions: T=950°C, Li conc. : CaSO4: Ca(OH)2 : =
6.00 : 5.10 : 2.00
Acta Metallurgica Slovaca, 12, 2006, (197 - 202) 202

100

80

Li extraction (%)
60

40

l:s = 15:1
20 l:s = 10:1
l:s = 5:1

0
0 20 40 60
Time (min)
Fig.4 Time dependeceies of lithium extraction at different liquid to solid ratio: T=975°C, Li conc. : CaSO4 : Ca(OH)2 =
6.00 : 4.20 : 2.00

4. Conclusion
he results obtained in this study confirmed the feasibility of applying gypsum process
on the treatment of Li – zinnwaldite waste from the landfill in Cínovec area. Sintering of Li –
zinnwaldite concentrate +100 µm with CaSO4 and Ca(OH)2 at ratio 6.00 to 5.10 to 1.40-2 at
temperature 900°C or at ratio 6.00 to 4.20 to 2.00-2.65 and temperature moving from 950 to
975°C resulted in approximately 87-93% yield of lithium from Li – concentrate into lithium
liquors. From the economical point of view the most promising method of processing Li –
zinnwaldite concentrate appear sintering the mixture containing Li – zinnwaldite concentrate
+100 µm with CaSO4 and Ca(OH)2 at ratio 6.00 to 5.10 to 2.00-2.65 and temperature 900°C and
the subsequent leaching of sinters at l:s = 5:1 at temperature 90°C. Such liquors, which contain
about 1.4 g/L Li are convenient intermediate solutions for Li2CO3 separation.

Acknowledgement
he work was supported by the research project FF-P2/057 of the Czech Ministry of
Industry and Trade and by the research intention MSM No. 223100002.

Literature
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1990
[3] Ternbachová Z., Hodek V.: Treatment of siliceous lithium concentrates (in Czech),
Research work VÚAnChu, Ústí nad Labem 1987
[4] Ternbachová Z., Šlemeda V.: Treatment of siliceous lithium concentrates (in Czech),
Research work VÚAnChu, Ústí nad Labem 1990
[5] Morštadt J.: Treatement of siliceous lithium concentrates (in Czech), Literature retrieval,
VÚANCH, Geofond Praha, P61609/1, Ústí nad Labem 1987
[6] Jandová J., Kondás J., Vu H. N.: Overview of methods for the treatment of lithium-bearing
waste raw material (in Czech), Partial research work of project FF-P2/057, ICT Prague,
Prague 2003
[7] Jandová J., Kondás J., Vu H. N., Selucká J., Havlák L.: Li2CO3 recovery from waste raw
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