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Hydrometallurgy 109 (2011) 43–46

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Hydrometallurgy
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / h yd r o m e t

Preparation of lithium carbonate from spodumene by a sodium


carbonate autoclave process
Ya Chen ⁎, Qianqiu Tian, Baizhen Chen, Xichang Shi, Ting Liao
School of Metallurgical Science and Engineering, Central South University, Changsha 410083, China

a r t i c l e i n f o a b s t r a c t

Article history: Preparation of lithium carbonate from spodumene concentrate was carried out by a sodium carbonate
Received 8 April 2011 autoclave process. The effects of different operation conditions including liquid-to-solid ratio, Na/Li ratio,
Received in revised form 11 May 2011 agitation speed, reaction temperature and reaction time on the lithium carbonate conversion efficiencies were
Accepted 14 May 2011
initially investigated. The results show that the conversion efficiency is not less than 94% under the optimal
Available online 20 May 2011
conditions. The purity of the obtained lithium carbonate can reaches up to 99.6%, which is higher than that
Keyword:
obtained by sulfuric acid method.
Spodumene © 2011 Elsevier B.V. All rights reserved.
Autoclave process
Lithium carbonate
Carbonation

1. Introduction form lithium carbonate and analcime slurry in an autoclave according


to the following reaction:
As the lightest metal, lithium is now widely used in battery, alloy,
and nuclear power fields. Although this metal element occurs in a β  Li2 O·Al2 O3 ·4SiO2 þ Na2 CO3 þ nH2 O
wide variety of minerals and ores, there are only a relatively few ores ¼ Li2 CO3 þ Na2 O·Al2 O3 ·4SiO2 ·nH2 O ð1Þ
that are sufficiently available and contain a sufficient amount of The slurry was then leached with carbon dioxide and the resulting
lithium to make them attractive as a commercially practicable source bicarbonate solution was heated to derive lithium carbonate (Jandová
of lithium. Among these commercially practicable sources of lithium, et al., 2010; Yi et al., 2007).
spodumene is the mineral that attracts the most interest and various
processes for recovering the lithium values from spodumene ore have Li2 CO3 þ CO2 þ H2 O ¼ 2LiHCO3 ð2Þ
been proposed. In a number of these processes, only two processes
have been practiced: sintering method and sulfuric acid process
2LiHCO3 ¼ Li2 CO3 þ CO2 þ H2 O ð3Þ
(Kondás et al., 2006; Shin et al., 2005; Tu et al., 2003; Yang, 2004), and
sulfuric acid process has become the main method for production of
Although the sodium carbonate autoclave method was proposed
lithium carbonate from spodumene due to its high efficiency.
as an alternative method for production of lithium carbonate from
However, this process has its intrinsic drawbacks, such as high levels
spodumene many years ago, few detail investigation and evaluation
of sulfate and heavy metal ions in the product, sophisticated process
on this method were reported. In this paper, a sodium carbonate
for recovering sodium sulfate, etc.
autoclave process for production of lithium carbonate from spodu-
In order to overcome these drawbacks, an autoclave method for
mene is proposed and the results of investigation on this process
production of lithium carbonate from spodumene has been suggested
are presented. The main objective is to determinate the optimal
as the alternative (Amouzegar et al., 2000; Olivier et al., 1978). During
conditions to prepare high purity lithium carbonate from spodumene
this process, owing to its low reactivity, the α-spodumene was first
concentrate.
roasted and transformed into β-spodumene at high temperature.
Then the β-spodumene reacted with sodium carbonate solution to
2. Experimental work

2.1. Materials

⁎ Corresponding author. Tel./fax: + 86 731 88877352. The spodumene concentrate used in this experiment was collected
E-mail address: chenya1973a@sina.com (Y. Chen). from a company in Jiangsu Province, China. Elemental analysis results

0304-386X/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2011.05.006
44 Y. Chen et al. / Hydrometallurgy 109 (2011) 43–46

of the spodumene concentrate is presented in Table 1. The purity of α-spodumene


spodumene in the concentrate is about 75%. Analytical grade reagents
were purchased in the local market, including sulfuric acid (AR, Crystal transformation
Hengyang Kaixin Chemical Co., Ltd), sodium carbonate (AR, Guangdong
Xilong Chemical Co., Ltd). All aqueous solutions were prepared using Sodium carbonate β-spodumene Water
distilled water.

2.2. Experimental method Carbon dioxide Autoclave process Water

α-spodumene is a monoclinic aluminium silicate, which has compact


structure and hardly reacts with acid or base except hydrofluoric acid. Carbonation
So it is difficult to extract lithium from α-spodumene. As a result, the
α-spodumene must be roasted and converted to its beta form before Filtration
autoclaving carbonation. The effects of roasting conditions on the
conversion ratio have been investigated in our previous work [Tian, et al.
2011]. In this study, the α-spodumene concentrate was roasted in an
electrical muffle furnace (Hangzhou Zhuochi Co.,Ltd) at 1050 °C for Residue Filtrate
30 min for crystal transformation. The obtained β-spodumene was then
used for autoclave process. The sodium carbonate autoclave process was Heating
carried out in a 1 L stainless steel autoclave which was equipped with a
heating system, an internal cooling coil and a variable speed stirrer Lithium carbonate
(WDF-1, Weihai Automatically-controlled Reactor Co., Ltd). 20 steel balls
(ϕ10 mm) were put into the autoclave to enhance the agitation in this
experiment. Fig. 1. Schematic of laboratory process for preparation of lithium carbonate from
spodumene.
The autoclave was charged with Na2CO3 solution and β-spodumene,
and then sealed and heated at 5 °C/min to the temperature specified for
the test. The system was allowed to react under constant temperature
for the specified time. At the end of the experiment, the autoclave was
cooled by circulating cold water through the cooling coil and the slurry 3. Results and discussion
in the reactor was discharged.
The reacted slurry was then put into a 2 L reactor equipped with an 3.1. Autoclaving carbonation
agitator, and water was added into the slurry to adjust the liquid-to-
solid ratio to 8. For carbonation reaction, carbon dioxide gas was In order to obtain the optimal conditions for preparation of lithium
sparged into the slurry at a flow rate of 0.5 l/min for 120 min to ensure carbonate from spodumene, the effects of different variables on the
that almost all lithium carbonate in the slurry converted to lithium lithium carbonate conversion efficiencies were evaluated. The main
bicarbonate. After the carbonation reaction, the slurry was filtered. variables studied were ratio of liquid to solid, ratio of lithium to
The residue on the filter was washed with dilute sulfuric acid solu- sodium, agitation, temperature and time of reaction. The results
tion and distilled water, and finally analyzed by atomic absorption obtained are summarized as the follows.
spectroscopy (AAS, Beijin Puxi General Instrument Co., Ltd., TAS990F)
and X-ray diffraction (XRD, Rigaku, D/max-7500). Because the
β-spodumene is inactive to sulfuric acid at room temperature, 3.1.1. Effect of liquid-to-solid ratio
the residue was washed with a dilute sulfuric acid solution and water for The effect of liquid-to-solid ratio on the lithium carbonate
many times before analysis, which should not remove lithium from the conversion efficiency was studied in the range from 2 to 5 (milliliter
un-reacted β-spodumene in the residue. Thus the lithium carbonate of solution per gram of solid), maintaining the sodium-to-lithium
conversion efficiency was calculated according to the lithium content in ratio at 1.5, stirring speed at 350 rpm, reaction temperature 230 °C
the washed residue. and reaction time 90 min.
The lithium bicarbonate rich filtrate was heated to 90 °C in a 2 L In order to evaluate the experimental error, each experiment was
reactor equipped with an agitator and maintained at this temperature replicated for five times. The average conversion efficiency and
for 120 min to drive off CO2. The resulting slurry was filtered and standard deviation was calculated and the results are presented in
lithium carbonate was obtained. The contents of impurities in the Fig. 2, where it can be seen from the error bars that the largest
lithium carbonate were determined by atomic absorption spectros- standard deviation is about ±1.6%.
copy and inductively coupled plasma (ICP, Perkin Elmer, Optima As can be seen in Fig. 2, increasing the liquid-to-solid ratio from 2
3000) analysis. The test work flowsheet is shown in Fig. 1. to 4, an obvious increase in the lithium carbonate conversion
efficiency is obtained. The efficiency reaches up to about 96% when
the liquid-to-solid ratio of 4 is used. Since lithium carbonate is slightly
soluble in water at high temperature (Somers, et al., 1971), this may
be partially explained by the fact that more lithium carbonate layer
Table 1 covering the spodumene particles in the slurry can dissolve with
Elemental analysis results of spodumene concentrate.
increasing liquid-to-solid ratio. As a result, the mass transfer between
Element Content, % Element Content, % the spodumene particles and sodium carbonate solution is strength-
Li 2.81 Na 0.395
ened and thus the reaction (1) can proceed more smoothly.
K 0.255 Ca 0.112 However, a further increase in the ratio from 4 to 5 does not lead to
Mg 0.063 Al 13.4 a substantial increase in the efficiency. Consequently, according to
Fe 0.358 P 0.057 these data, the autoclave process should be carried out at the liquid-
S 0.111 Ba 0.001
to-solid ratio of 4.
Y. Chen et al. / Hydrometallurgy 109 (2011) 43–46 45

100 100
Conversion efficiency, % 98

Conversion efficiency, %
95
96

94
90
92

90 85

88
80
86
2.0 2.5 3.0 3.5 4.0 4.5 5.0 -50 0 50 100 150 200 250 300 350 400
Liquid-to-solid ratio Stirring speed, rpm

Fig. 2. Effect of liquid-to-solid ratio on the conversion efficiency of lithium carbonate. Fig. 4. Effect of stirring speed on the conversion efficiency of lithium carbonate.
Conditions: sodium-to-lithium ratio 1.5, stirring speed 350 rpm, reaction temperature Conditions: reaction temperature 230 °C, Na/Li 1.25, liquid-to-solid ratio 4 and reaction
230 °C and reaction time 90 min. time 90 min.

This increase in conversion efficiency can be attributed to two


3.1.2. Effect of sodium-to-lithium ratio factors. First, it is postulated that higher stirring speed makes the
According to the reaction (1), the sodium carbonate consumption spodumene particles ground by the stainless steel ball in the reactor
must affect the lithium carbonate conversion. The effect of sodium-to- much more effectively, which strips the lithium carbonate layer
lithium (Na/Li) ratio on the conversion efficiency was preliminarily covering the spodumene particles and thus strengthen the mass
evaluated in the range from 0.8 to 1.6, maintaining the liquid-to-solid diffusion process in the particles (internal diffusion). In addition, it is
ratio at 4, stirring speed at 350 rpm, reaction temperature 230 °C and obvious that high speed can lead to suspension of the solid particles in
reaction time 90 min. The results are presented in Fig. 3. the sodium carbonate solution and thus improve the diffusion across
As can be seen in Fig. 3, when Na/Li ratio is no more than 1, the the hydrodynamic boundary layer around the spodumene particles
conversion efficiency is below 80%, which is due to lack of sodium (Fernández et al., 1999; Lee, 2004).
carbonate in the slurry. With the increase of Na/Li ratio from 0.8 to
1.25, the conversion efficiency increases dramatically. When a Na/Li 3.1.4. Effect of reaction temperature
ratio of 1.25 is used, a lithium carbonate conversion efficiency of about To study the effect of reaction temperature on the lithium
96% can be obtained. As can be expected, a further increase in Na/Li carbonate conversion efficiency, the experiments were conducted in
ratio from 1.25 to 1.6 has little influence on the conversion efficiency. the range of 150 to 250 °C. In these experiments the liquid-to-solid
ratio was maintained at 4, the Na/Li was 1.25, stirring speed 300 rpm
3.1.3. Effect of agitation and reaction time 90 min.
The effect of stirring speed on the lithium carbonate conversion Fig. 5 shows the conversion efficiency as a function of the reaction
efficiency was studied in experiments conducted at 230 °C, 1.25 of temperature in the range of 150 to 250 °C, where it can be seen that
Na/Li, 4.0 of liquid-to-solid ratio and 90 min of reaction time. The with an increase in the reaction temperature from 150 to 225 °C, the
stirring speed was varied from 0 to 350 rpm. The results are shown in conversion efficiency increases significantly. The efficiency is about
Fig. 4, where it can be seen that the conversion efficiency of lithium 96% when the reaction temperature is 225 °C. But further increasing
carbonate increases with the stirring speed increasing from 150 to the temperature does not result in a clear increase in the efficiency.
300 rpm. The conversion efficiency reaches up to about 96% at
300 rpm of stirring speed. But further increase in the stirring speed 3.1.5. Effect of reaction time
seems to have little influence on the conversion efficiency. The effect of reaction time on the lithium carbonate conversion
efficiency was investigated in the range from 10 to 120 min. During
100
100
Conversion efficiency, %

90
Conversion efficiency, %

95
80

90 70
60
85 50
40
80 30
20
75
0.8 1.0 1.2 1.4 1.6 140 160 180 200 220 240 260
Na/Li ratio Temperature, ºC

Fig. 3. Effect of Na/Li on the conversion efficiency of lithium carbonate. Conditions: Fig. 5. Effect of reaction temperature on the conversion efficiency of lithium carbonate.
liquid-to-solid ratio 4, stirring speed 350 rpm, reaction temperature 230 °C and Conditions: liquid-to-solid ratio 4, Na/Li 1.25, stirring speed 300 rpm and reaction time
reaction time 90 min. 90 min.
46 Y. Chen et al. / Hydrometallurgy 109 (2011) 43–46

98
A
A--Analcime
97
Conversion efficiency, %
Q--Quartz

96

Intensity
A
A
95

94 Q

A A A A
93 AA
QA AA
A A
92
0 20 40 60 80 100 120 0 10 20 30 40 50 60 70 80 90
Reaction time, min 2 , degree

Fig. 6. Effect of reaction time on the conversion efficiency of lithium carbonate. Fig. 7. XRD pattern of the residue.
Conditions: liquid-to-solid ratio 4, Na/Li 1.25, stirring speed 300 rpm and reaction
temperature 225 °C.

these experiments, the liquid to solid ratio was maintained at 5, the 3.3. Characterization of the residue
Na/Li was 1.25, stirring speed 300 rpm and reaction temperature
225 °C. Since the heating rate of the autoclave process was 5 °C/min To verify whether the lithium extraction proceeded according to
and at the end of the experiment, the reactor was hardly cooled down reaction (1), the residue obtained after autoclave process and
to room temperature at once, lithium carbonate conversion should carbonation reaction was characterized by XRD. Fig. 7 shows the
occur during the heating and cooling process. So it must be noted that XRD pattern of the residue obtained after autoclave process at 225 °C
the reaction time is actually nominal reaction time. for 60 min and carbonation reaction.
The results are presented in Fig. 6, where it seems that the As can be seen in Fig. 7, there are just analcime and quartz detected
conversion efficiency increases from about 92% to 97% with increasing in the residue. Since analcime has only one crystal water (Tu et al.,
the reaction time from 10 to 120 min. However, considering the 2003; Yang, 2004), the chemical reaction (1) can be rewritten as
experimental deviation shown in Fig. 2, the optimal reaction time can follow:
not be determined according to these results. Consequently, the
experiments conducted at the reaction times of 30 min and 60 min β  Li2 O·Al2 O3 ·4SiO2 þ Na2 CO3 þ H2 O
were repeated for five times, respectively. The results show that the ¼ Li2 CO3 þ Na2 O·Al2 O3 ·4SiO2 ·H2 O ð4Þ
average conversion efficiencies are 92.7% and 95.8%, respectively.
Combined with the experimental deviations and the conversion 4. Conclusion
efficiency obtained at the liquid-to-solid ratio of 4 presented in Fig. 2,
these results suggest that a conversion efficiency of not less than 94% An autoclave process for preparation of lithium carbonate from
can be obtained at the reaction time of 60 min. spodumene was proposed and the autoclave process conditions were
initially optimized. The results show that the lithium carbonate
3.2. Precipitation of lithium carbonate conversion efficiency is not less than 94% under the obtained optimal
conditions. The purity of the obtained lithium carbonate reaches up to
The lithium bicarbonate rich filtrate prepared under above optimal 99.6%. This is higher than that obtained by sulfuric acid process, which
conditions was used for preparation of lithium carbonate. It was heated can be mainly attribute to the fact that the lithium carbonate does not
at 90 °C for 1 h to eliminate CO2 and then filtered. To determine the content any sulfate.
recovery and purity of the resulting lithium carbonate, the obtained
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