Minerals Engineering 160 (2021) 106643

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Minerals Engineering
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Recovery lithium and potassium from lepidolite via potash calcination- T

leaching process
Yuqing Kuaia,b, Wengui Yaoa,b, Hongwen Maa, , Meitang Liua, Yuan Gaoa,b, Ruoyu Guoa,b
⁎

a
Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Solid Wastes, School of Materials Science and Technology, China University of Geosciences,
Beijing 100083, PR China
b
Blue Sky Technology Corporation, Beijing 100083, PR China

ARTICLE INFO ABSTRACT

Keywords: A new comprehensive way to extract lithium and potassium from lepidolite through calcination process with the
Lepidolite additive of K2CO3 has been proposed. By using flowing water vapor, the lepidolite concentrate mixed with
K2CO3 58.5% of K2CO3 could generate acid-soluble potassium aluminum silicate (KAlSiO4) and water-soluble lithium/
Lithium extraction potassium silicate (Li2SiO3/K2SiO3) at 850 °C for 2 h. Additionally, 80% of fluorine could be removed. The
Potassium extraction
reaction feasibility between lepidolite ore and K2CO3 was firstly evaluated through thermodynamic calculation.
Water leaching
The decomposition mechanism was explored through XRD and TG-DSC analysis. The experimental results reveal
that the decomposition of lepidolite undergoes following phase transformation: trilithionite phase → lepidolite
phase → KAlSi2O6 → KAlSiO4. As the desilication process proceeds, silicon is given off and forms lithium/
potassium silicate. Through a water leaching process, soluble Li2SiO3/K2SiO3 could be separated from KAlSiO4.
The extraction efficiency of Li and K could severally reach 95.52% and 95.70% from soluble silicates through
water leaching process, under the optimum conditions. Then the residue KAlSiO4 could be easily recovered by
acid solution. This new technique for processing lepidolite could make most of all of its components, as well as
being environmentally friendly.

1. Introduction
Lithium is the lightest alkali metal. Owing to its low thermal ex-
pansion coefficient, high specific heat characteristics and high elec-
trochemical potential (3.045 V), Li and compounds containing Li have
been widely used in the ceramic industry, and in the production of
glasses, lubricants and greases, pharmaceuticals and batteries
(Ebensperger et al., 2005; Meshram et al., 2014). Recently, due to the
great demand for primary and secondary batteries utilized in electronic
devices and electric vehicles, the global consumption of Li has rapidly
increased and now accounts for 56% of the global end-use market.
(USGS, Mineral Commodity Summaries, February 2019).
The enormous demand projection for Li has prompted the devel-
opment of potential lithium-containing minerals, such as spodumene
(LiAlSi2O6), petalite (LiAlSi4O10), lepidolite (K(Li,Al)3[(Al,Si)4O10]
(F,OH)2), eucryptite (LiAlSiO4), zinnwaldite (KLiFeAl[AlSi3O10]
(OH,F)2) and other economically valuable minerals (Choubey et al.,
2016; Tadesse et al., 2019). Normally, sulfuric acid or alkalines are both
exploited to destroy the silicate structure via a high-temperature
roasting process or hydrothermal method to release the lithium
(Swanson and Bailey, 1981; Brigatti et al., 2000; Choubey et al., 2016).
However, in the case of lepidolite and zinnwaldite, the presence of
fluorine renders the application of these ores more challenging.
At present, the studies on the extraction of Li from lepidolite mainly
divided into the following categories: vulcanization, carbonation,
chlorination, fluorination, and lime decomposition.
For vulcanization, there are three main methods. The first method is
sulfuric acid pyrolysis, in which lepidolite is treated with sulfuric acid
below 200 °C. After digestion, the soluble lithium sulfate could easily
dissolve by a water leaching process (Botton et al., 1965; Viecelia et al.,
2017, Viecelia et al., 2018a, Viecelia et al., 2018b; Samoilov et al.,
2018a). The second method is sulfuric acid roasting in which a highly
concentrated sulfuric acid used to roast with lepidolite at 200 °C, and
the maximum extraction efficiency of Li, Rb, and Cs reaches over 95%
(Zhang et al. 2019). Although the above two methods could easily di-
gest and decompose lepidolite, the acid-insoluble part like albite and
quartz remains in the acid solid waste causes serious environmental
concerns. Then, the sulfate roasting method is proposed, in which
K2SO4, Na2SO4, and FeSO4 are used as additives privately or synergis-
tically with CaO, CaCl2, CaSO4, or KOH when roasted with lepidolite

⁎
Corresponding authors.
E-mail address: mahw@cugb.edu.cn (H. Ma).

https://doi.org/10.1016/j.mineng.2020.106643
Received 16 April 2020; Received in revised form 24 July 2020; Accepted 16 September 2020
Available online 04 November 2020
0892-6875/ © 2020 Elsevier Ltd. All rights reserved.
Y. Kuai, et al. Minerals Engineering 160 (2021) 106643

(Yan et al., 2012a, 2012b; Luong et al., 2013, 2014; Vieceli et al., 2016;
Su et al., 2020). In addition to the processes described, Hien-Dinh et al.
(2015) also studied the calcination effect and mechanism of FeS-CaO-
lepidolite system on the Li extraction efficiency. However, the generally
produced double salt LiKSO4 is harmful to the recovery of lithium.
Besides, the rest of the fluorine, alumina, and silica exist in solid waste
is not concerned.
For carbonation, Mazza and Whittier (1960) was the first group to
use limestone as a fluxing agent to react with lepidolite. However, Li
recovery was relatively poor, reaching only 79.9%. Furthermore, this
method requires large amount of energy during calcination. More re-
cently, Samoilov et al. (2018b) has reported a new way to process le-
pidolite in which a soda melting procedure is introduced before treating
with sulfuric acid (93%). They also analysed the relationship between
the original lepidolite-soda charge (SiO2/(Na2O + K2O + Li2O)) with
the yielding of valuable elements. The results show that if the SiO2/
(Na2O + K2O + Li2O) = 2.9–3.0, and the silicon oxide content in
melt-granulate is 55%, 99% of Li and 97–99% each of aluminum, so-
dium, and potassium could be extracted. However, the usage of nu-
merous high concentrate sulfuric acid (0.6 ml/g granulate) is hard to
convert into industrial scale.
Yan et al. (2012d) also tested a chlorination roasting system using
lepidolite/NaCl/CaCl2 with a mass ratio of 1:0.6:0.4 in which the
mixture is ground and calcinated at 880 °C for 30 min. This allowed up
to 92.86% of Li to be extracted after water leaching. Nonetheless, the
complex chlorination roasting products in which consist of SiO2, CaF2,
CaSiO3, and aluminosilicates are useless.
In addition to the treatment of lepidolite with sulfuric acid, HF has
also been used to directly digest such lithium-containing silicate mi-
nerals (Guo et al., 2017; Rosales et al., 2014). Rosales et al. (2017)
dissolved lepidolite with HF (7% in volume concentration) using low
temperatures. Before Li recycled as LiF, the Al and Si are precipitated as
Na3AlF6 and K2SiF6, respectively. HF/H2SO4 mixed acid system pro-
posed by Guo et al. (2019). The introduction of H2SO4 not only ac- Scheme 1. The flow chart of the process of lepidolite-potash system.
celerated the dissolution but also reduced the dosage of HF. Through a
selective leaching process, 98% of Li, 90% of Rb and Cs, 91.7% of Al,
(Al2Si2O5(OH)4) according to our previous works (Yuan et al., 2018a,
and 66.7% of Si were recovered.
Yuan et al., 2018b; Ma et al., 2017). Compared with the above tech-
Alternatively, Yan et al. (2012c) used defluorinated lepidolite boiled
niques, the method proposed herein possesses the advantage of eco-
with lime-milk. This study revealed a relationship between lithium
friendliness, sustainability, high economic value, and maximizing the
extraction with defluorination efficiency. When the defluorination ef-
recovery of valuable components. In order to investigate the feasibility
ficiency of lepidolite is 42.3%, 98.9% of Li was extracted under the
and mechanism of the calcination process, thermodynamic calculation
optimum conditions (150 °C for 1 h, the liquid-solid ratio of 4:1, and the
and XRD/TG-DSC measurements were used. The optimum conditions of
proportion of the ingredients of 1:1). However, the existence of katoite,
the leaching process were also studied. Finally, the assessment of the
anorthite, albite, and calcium hydroxide in leaching residue is still an
leaching residue product was also given.
issue that needs to be solved.
Most of the methods described above predominately focus on the Li
extraction effects. While almost every process could allow more than 2. Experimental
90% of Li to be extracted, most of these methods did not consider the
disposal of residual, or the recovery of the huge amount of other in- 2.1. Materials
trinsic elements of silicate minerals, like aluminum and silicon.
Although HF has the ability to destroy the SieO bonds of silicate mi- The lepidolite concentrate used in this study was obtained from
nerals in which help to recover the Al and Si, the intense corrosion of Yichun, Jiangxi Province, China. The concentrate was processed by
HF make it difficult to expand to industrial scale because of the strin- ball-milling until over 90% of the particles were below 74 μm. The
gent anti-corrosion requirement of equipment. Thus, different from the chemical composition of the sample is listed in Table 1. The X-ray
HF digest approach, the potash (K2CO3) calcination process (as shown diffraction (XRD) pattern of the sample in Fig. 1 shows that the sample
in the Scheme 1) produces water-soluble alkaline silicates (K2SiO3, consists of the phases as trilithionite (KLi1.5Al1.5(Si3Al)O10F2 which
Li2SiO3) and acid-soluble alkali aluminosilicate (KAlSiO4). The soluble refer to RRUFF Project website), muscovite (KAl2(Si3Al)O10(OH)2),
alkaline silicates could be extracted easily through a water leaching albite (NaAlSi3O8) and quartz (SiO2). The mineral composition of le-
process. Then the silicon and the rest of fluorine in leaching liquor pidolite ore are 62.13% for trilithionite, 22.05% for muscovite, 13.98%
could be precipitated as CaSiO3, CaF2. The extraction of Li from alkali for albite and 1.73% for quartz. The mole factions of each mineral in
liquor could be implemented by any known method, notably by the lepidolite concentrate are 52.29% for trilithionite, 19.53% for musco-
addition of Na2CO3, but consider the difficulty of the separation be- vite, 18.29% for albite and 9.89% for quartz. The main crystal phase of
tween sodium and potassium in the next step, herein we would re- the concentrate is trilithionite which has the chemical formula,
commend using K2CO3 alternatively. Thus, the separated potassium (K0.856Na0.041)(Li1.597Fe0.016Mn0.049Ti0.003Al1.372)[Al0.510Si3.490O10]
carbonate can be reused in the calcination step. The acid-soluble (OH0.231F1.757). Anhydrous potassium carbonate (99%, analytical re-
KAlSiO4 could be the raw material for the preparation of kaolinite agent grade) was purchased from Beijing chemical works and deionized

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Y. Kuai, et al. Minerals Engineering 160 (2021) 106643

Table 1
Chemical composition of concentrated lepidolite (wt%).
Sample SiO2 TiO2 Al2O3 TFe2O3 MnO MgO CaO Na2O K2 O P2O5 Li2O F LOI Total

LY-19 53.81 0.04 25.50 0.77 0.50 0.02 0.22 1.76 7.58 0.28 3.38 5.34 3.29 100.2

from room temperature to 1000 °C under air atmosphere. Fourier

transform infrared (FT-IR) spectra were recorded on a Perkin Elmer
2000 spectrometer in the region from 4000 to 400 cm−1 by using po-
tassium bromide as a carrier.

3. Results and discussion

3.1. Theoretical analysis and feasibility

According to our previous research on the decomposition of K-

feldspar (Feng and Ma, 2004; Wang et al., 2006; Su et al., 2014), al-
kaline decomposition sintering method or alkali hydrothermal treat-
ment method was used to remove a certain amount of silicon and
generate water-soluble or acid-soluble compounds.
Therefore, based on our past experiences, we design an alkaline
calcination method to decompose lepidolite ore. The possible chemical
reactions of the lepidolite concentrate-K2CO3 system are listed below.

(K0.9)(Li1.6Al1.4)[Al0.50Si3.50O10](OH0.25F1.75) + 1.3K2CO3 + 0·.75H2O

(g) + 0.05O2(g) = 1.9KAlSiO4 + 0.8K2SiO3 + 0.8Li2SiO3 + 1.75HF↑
+1.3CO2↑ (1)

KAl2(Si3Al)O10(OH)2 + K2CO3 = 3KAlSiO4 + CO2↑+H2O↑ (2)

2NaAlSi3O8 + 4K2CO3 = 2KAlSiO4 + Na2SiO3 + 3K2SiO3 + 4CO2↑(3)

SiO2 + K2CO3 = K2SiO3 + CO2↑ (4)

The chemical formula of trilithionite is simplified in Eq. (1). The

Fig. 1. XRD pattern of the lepidolite concentrate. chemical formula for muscovite, albite, and quartz represent in their
theoretical chemical composition due to their relatively small amount
water was used in the leaching procedure. in the concentrate.
Based on Eqs. (1)–(4), the amount of the additive potassium car-
2.2. Methods bonate can be calculated through the modulus of Al, Si, Na, Li, K of
100 g of lepidolite concentrate. As listed in Table 2, the theoretical mass
The alkaline calcination experiment was carried out through a tube ratio of lepidolite concentrate: K2CO3 is 100: 58.53.
furnace with equipment that can generate vapor. The ground lepidolite The Gibbs free energy (ΔrGm) of Eqs. (1), (2), (3), and (4) are se-
ore was mixed with K2CO3 evenly at a mass ratio of 100:58.5, then parately calculated at a temperature of 823.15, 923.15, 973.15,
heated in the tube furnace under a water vapor atmosphere between the 1023.15, 1073.15, 1123.15, and1173.15 K according to the equation
temperature range of 500–900 °C for 30 to 120 min. The obtained (5) and (6). The ΣΔrGm values of all the reactions are given according to
calcined product was ground into a powder and then leached with Eq. (7) (Ma et al., 2006).
deionized water at a liquid-solid ratio of 3–9 in a water bath kettle for T T Cp
10–120 min. The leaching temperature from 30 to 90 °C was conducted f Gm = fH TS + Cp dT T dT
298 298 T (5)
through the water bath kettle, while the leaching temperature from 100
to 120 °C was performed in a hydrothermal autoclave. After leaching, r Gm = vi f Gm vi f Gm + RT ln Qa (6)
the mixture was separated through a three-step water washing cen-
trifugation. The solid products were dried in an oven at 105 °C for 24 h. r Gm = ni r Gm, i (7)
The centrifugal liquid was reserved to detect the amount of lithium and where vi and vj are coefficients of products and reactants in the equa-
potassium. tion, respectively; Qa represents the partial pressure of CO2, H2O, HF,
and O2; ni represents the molar fraction of the reactant. Since the cal-
2.3. Characterization cination process was conducted using a continuous flow of water vapor,

The chemical composition of concentrated lepidolite was de- Table 2

termined by X-ray fluorescence, excluding lithium and fluorine. The The calculation process of the addition amount of K2CO3.
content of Li from concentrated lepidolite and the leach liquor was n(K + Li + Na) n(Al) n(Si) sum
measured by ICP-AES (Thermofisher 7600). The determination of
fluorine content was measured via fluorine ion selective electrode. XRD Concentrate/100 g 0.444 0.500 0.896 \
n(K)/mol 0.056 \ 0.791 0.847
analysis was operated through an X-ray diffractometer (SmartLab, m(K2CO3)/g \ \ \ 58.53
Rigaku) with Cu Kα radiation at 40 kV and 40 mA. DSC-TGA was used
to study the thermal decomposition of concentrated lepidolite by an Where, n(K) means the modulus of the amount of potassium that needs to
SDT Q600 V20.9 Build 20 instrument at a heating rate of 10 °C/min supply; m(K2CO3) means the grams of the addition amount of K2CO3.

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Y. Kuai, et al. Minerals Engineering 160 (2021) 106643

Table 3
Thermodynamic data of reaction products and reactants.
Mineral, formula ΔfHθ kJ/mol Cp J/K mol Sθ J/K mol a b c D

(K0.856Na0.041)(Li1.597Fe0.016Mn0.049Ti0.003Al1.372)[Al0.510Si3.490O10](OH0.231F1.757)a −6041.08 334.4 313.0 131.1 421 69.1 0

KAl3Si3O10 (OH2)b −5976.56 321.98 292.00 756.4 −19.84 −21.7 −6979.2
NaAlSi3O8b −3935.49 204.79 207.4 452.0 −13.364 −12.759 −3953.6
SiO2 b −910.70 43.2 41.43 92.9 −0.642 −7.149 −716.1
O2 b 0 29.3 205.2 48.3 −0.691 4.992 −420.7
CO2 b −393.51 37.1 213.7 87.8 −2.644 7.064 −998.9
H2O b −241.81 33.6 188.8 40.1 8.656 4.875 −251.2
KAlSiO4 b −2122.89 118.5 136.0 242.0 4.482 −8.958 −1935.8
K2CO3 c −1150.18 114.2 155.50211998 97.906 92.048 −9.874 0
Na2SiO3 c −1561.43 111.8 113.8 130.29 40.166 −27.07 0
K2SiO3 c −1548.08 118.7 146.0 135.645 24.476 −21.548 0
Li2SiO3 c −1649.50 100.5 80.3 126.482 28.2 −30.543 0
HF(g) c −272.55 29.1 173.7 26.903 3.431 1.088 0

The data quote refer to a) Ogorodova et al., 2010; b) Holland and Powell, 2011; c) Ye and Hu, 2002; The heat capacitor polynomial from reference a) and b) is
Cp = a + bT*10-3 + cT−2*105 + dT−1/2 (J/K mol), for the data from reference c), Cp = a + bT*10-3 + cT−2*105 + d*10-6T−2 (J/K mol).

Table 4
Calculation results of ΣΔrGm (KJ·mol−1) for the thermal decomposition reactions of lepidolite concentrate sample.
T/K 823.15 923.15 973.15 1023.15 1073.15 1123.15 1173.15

ΔrGm(1) −253.45 −300.64 −323.85 −346.75 −369.29 −391.46 −413.22

ΔrGm(2) −198.61 −234.59 −252.27 −269.76 −287.04 −304.12 −321.00
ΔrGm(3) −195.41 −268.30 −304.14 −339.55 −374.53 −409.07 −443.16
ΔrGm(4) −42.97 −61.35 −70.38 −79.29 −88.09 −96.76 −105.32
ΣΔrGm −193.44 −233.63 −253.38 −272.89 −292.13 −311.07 −329.71

the particular partial pressure is hard to determine. Hence, the esti-

mated values of partial pressure for the thermodynamic calculation for
CO2, HF, and O2 are given as 1% each, for H2O the estimated value
could be 97%. All the thermodynamic data are listed in Table 3. Cal-
culation results can be referred to in Table 4. As shown in Table 4, the
ΔrGm of reaction (1), (2), (3), (4) and ΣΔrGm from 823.15 K to
1173.15 K are all negative, which means the reactions between lepi-
dolite concentrate and K2CO3 could take place above 823.15 K spon-
taneously.

3.2. Decomposition mechanism

The XRD patterns of the calcined product from 550 °C to 900 °C for
2 h are shown in Fig. 2. The results show that when the calcination
temperature is increased to 550 °C, the peak intensity of trilithionite
decreases sharply, and peaks corresponding to the trilithionite phase
gradually disappear and peaks associated with lepidolite (JCPDS No.
85-0912) phase form. Then the lepidolite phase disappears when the
temperature rises to 650 °C, with kalsilite and leucite these two new
phases emerge. As the temperature increases to 700 °C, the leucite
phase vanishes. Besides the main phase of kalsilite (JCPDS No. 76-
0635), there are three small peaks observed at 19.7°, 20.9° and
28.2°corresponding to the (2 0 0), (0 0 2) and (2 3 1) of KAlSiO4 (JCPDS
No. 33-0989), respectively. Increasing the temperature to 750 °C, the
phase of the calcined product is converted into potassium aluminum
silicate. Peaks corresponding to KAlSiO4 (JCPDS No. 33-0989) phase
are present between 800 °C and 900 °C, suggesting KAlSiO4 is stable Fig. 2. The XRD pattern of calcined product at different temperatures from
over this temperature range. However, due to the amorphous state of 550 °C to 900 °C for 2 h. The letter annotations in the pattern refer to different
K2SiO3, it is hard to detect this phase through XRD analysis. EDS ana- phase in JCPDS, a: Potassium aluminum silicate (JCPDS No. 33-0989); b:
lysis of the calcined product obtained at 850 °C for 2 h (Fig. S1) reveals Kalsilite (JCPDS No. 76-0635); c: Leucite (JCPDS No. 71-1147); d: Lepidolite
that the percentage of potassium oxide (54.7%) is higher than the (JCPDS No. 85-0912).
theoretical value of KAlSiO4 (29.7%). Indicating that the calcined
product KAlSiO4 is mixed or coated with K2SiO3 which has a higher derivative of weight loss and heat flow curves are presented in Fig. 3.
content of K2O (61.1%). There are four weight loss steps during the heating which correspond to
TG-DSC analysis of the lepidolite concentrate with the addition of 85.9–117.6 °C, 379–556.4 °C, 556.4–815.2 °C, and 815.2–996 °C re-
K2CO3 was tested to clarify the thermal behaviour during the heating spectively. The weight loss in the first step is 7.1%, the greatest change
process. The weight loss curve of the mixture together with its

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Y. Kuai, et al. Minerals Engineering 160 (2021) 106643

Fig. 3. TG-DSC curves of concentrated sample mixed with K2CO3.

of weight loss is at a temperature of 101.8 °C, and an endothermic peak

appears at around 107.8 °C which suggests the removal process of ab- Fig. 4. Effect of calcination temperature on the extraction efficiency of lithium
sorbed water from the surfaces of both raw materials. The 3% loss from and potassium.
379 to 556.4 °C is attributed to the release of carbon dioxide. The de-
rivative peak temperature at 508.5 °C and a small endothermic peak
Fig. 4, the extraction efficiency of both lithium and potassium starts to
found at 515.7 °C manifest that at this temperature range the con-
increase from 700 to 850 °C and is most optimum at 850 °C which
centrated sample starts reacting with K2CO3. During the next stage, one
indicates that the decomposition reactions could happen more thor-
weak and wide endothermic peak could be observed at about 670 °C,
oughly at a higher temperature. Furthermore, the defluorination effi-
besides two inflection points could be seen in the derivative curve.
ciency gradually increases with increasing temperature from 700 to
Together with the results in XRD analysis (Fig. 2), the thermal beha-
850 °C at the same dwelling time (Table 5.). Indicating that better de-
viour can be ascribed to the continued decomposition of lepidolite
fluorination efficiency has a positive influence on the leaching process.
between 550 °C to 650 °C and the desilication reaction of KAlSi2O6
The abnormally low extraction of lithium and potassium at 900 °C can
between 650 and 815.2 °C, the reduced amount of CO2 led to the mass
be attributed to the evaporation loss of them at this high temperature.
loss of 8.4%. The total amount of weight loss of CO2 is about 11.4%
The maximum extraction efficiency values of lithium and potassium are
which matches well with the theoretical weight loss (11.7%). The
95.32% and 41.02%, respectively.
weight loss during 815.2–996 °C can be associated with the de-
fluorination process which mainly occurs above 800 °C according to
Fig. S2. Hence, the above results confirm the possibility and feasibility 3.3.2. Effect of calcination time and defluorination
of this method which matches well with results of ΣΔrGm shown in In order to investigate the influence of the calcination dwell time,
Table 4. Theoretically, after the water leaching process, 100% of li- the calcination experiments were carried out at 850 °C for 0.5 h, 1 h,
thium and 49.11% of potassium can be recovered as silicate salts. To 1.5 h, and 2 h. The same leaching conditions were used described as the
gain the best leaching effect condition, several factors were tested same above. As can be seen in Fig. 5, the extraction of lithium exceeds
through the control variable method. 95%, as for potassium, the extraction efficiency remains constant.
Considering the defluorination effect which listed in Table 5, it is ob-
3.3. Investigation of optimal condition of extraction process vious that the defluorination efficiency increases with calcination time
at 850 °C, the defluorination percentage can reach 80.92%. It can also
3.3.1. Effect of calcination temperature
The effect of calcination temperature on the extraction efficiency of
lithium and potassium was studied. A series of calcination experiments
were carried out at 700 °C, 750 °C, 800 °C, 850 °C and 900 °C for 2 h
each. The defluorination percentage of all the calcined products are
summarized in Table 5. The calcined products were then leached using
the liquid-to-solid (L/S) ratio of 5:1, and leaching was performed at a
temperature of 70 °C for 60 min. The leaching results are shown in

Table 5
Effect of reaction temperature and time on defluorination percentage.
Temperature ( °C) Dwelling Time F (%) Defluorination percentage
(min) (%)

700 120 2.91 23.82

750 120 2.38 37.66
800 120 1.42 62.75
850 30 2.56 33.23
850 60 1.97 48.33
850 90 1.61 57.91
850 120 0.73 80.92
900 120 0.85 77.87
Fig. 5. Effect of calcination time on the extraction efficiency of lithium and
F(%) means the percentage of content of F in each calcined product. potassium.

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Y. Kuai, et al. Minerals Engineering 160 (2021) 106643

Fig. 6. Effect of calcination time on the extraction efficiency of lithium and Fig. 7. Effect of L/S ratio on the extraction efficiency of lithium and potassium.
potassium.

be concluded that about 33% of defluorination could result in a rela-

tively high extraction efficiency at 850 °C which conform to the con-
clusions of Yan et al. (2012c).

3.3.3. Effect of leaching temperature

The samples used in the next leaching experiments were gained
from calcining the product which was roasted at 850 °C for 2 h. The
effect of leaching temperature on elemental extraction was explored
from 30 to 120 °C for 1 h at an L/S ratio of 5:1 as shown in Fig. 6. The
extraction of Li and K slightly increases at ambient temperature
(30–60 °C) and then rapidly increases at elevated temperature
(60–70 °C). However, the behaviors between the extraction of Li and K
from 70 to 100 °C are different as shown in Fig. 6. The extraction of Li
remains around 95%, meanwhile, the extraction of K steadily increases
up to 100 °C. Beyond 100 °C, Fig. 6 shows the extraction of both Li and
K decreases. The dissolution of alkali metal silicates contains an ion
exchange process while producing a protective layer of the silanol
group on the surface and a nucleophilic depolymerization process
Fig. 8. Effect of leaching time on the extraction efficiency of lithium and po-
(Weldes and Lange, 1969). The elevated temperature from 30 to 100 °C
tassium.
promotes the ion exchange process of both silicates which leads to an
increasing extraction efficiency. Nevertheless, the higher temperature
and higher pressure can be harmful to the leaching out of alkali metal 3.3.5. Effect of leaching time
ions. In the case of the temperature greater than 100 °C the fast ion To investigate the effect of leaching time upon each elemental ex-
exchange process broke the balance between the ion exchange process traction, the experiments were performed under the optimum condition
and nucleophilic depolymerization stage. The protective layer of the described above. As demonstrated in Fig. 8, the leaching time has a
silanol group cannot go into the next stage dissolution process which prominent influence on the extraction of lithium. As time increases
hinders the further dissolution of alkali metal ions. from 10 min to 90 min, the lithium extraction efficiency continuously
increases from 38.66% to 98.68% and remains almost constant when
the time increases to 120 min. As for K, this presents a different be-
3.3.4. Effect of liquid-to-solid ratio havior. The extraction of K initially rises with increasing leaching time,
As it is displayed in Fig. 7, the effect of liquid-to-solid ratio on the but as the leaching time exceeds 90 min, the extraction effect decreases.
extraction efficiency of Li and K was studied from 3:1 to 9:1. A leaching This decrease can be caused by the absorption between potassium ions
temperature of 100 °C and a leaching time of 1 h were used. According and the siliceous gel. Although the lithium extraction efficiency is
to the trends observed in Fig. 7, the behavior of Li and K are similar. promoted with time, the difference between the extraction after 60 min
The extraction efficiency of Li increases from 58.50% to 95.52% with (95.52%) and after 100 min (98.68%) is negligible. On the other hand,
the increase of L/S ratio from 1:1 to 5:1. This then falls to 72.45% with the extraction efficiency of K after 60 min (47%) is greater than that
a L/S ratio of 7:1, while with a L/S ratio of 9:1 the extraction value after 100 min (40.03%). In consideration of the recovery of silicon, it is
slightly increases to 75.69%. By using more water, a large amount of better to use 60 min as the final optimized leaching time. Therefore, the
siliceous residue is formed after the alkali ions leaching out which is extraction rates of lithium and potassium from soluble silicates are
hard to dissolve in a diluted alkaline aqueous (Weldes and Lange, 95.52% and 95.70% under the optimum conditions, respectively.
1969). Therefore, the extraction of K (47.00%) is greatest when a L/S
ratio of 5:1 was used. This shows that the optimum L/S ratio for both Li
and K is 5:1.

6
Y. Kuai, et al. Minerals Engineering 160 (2021) 106643

Fig. 10. IR spectra of calcined product (850 °C, 2 h) and optimization leaching
products.

No obvious absorption bands could be observed in the rang

4000–1300 cm−1, which means the dehydration of the 850 °C-LP
product.

Fig. 9. XRD patterns of calcined product (850 °C, 2 h) and optimization

3.5. Comparison between the calcination mechanism of sulfate roasting and
leaching products. this method

As the most developed technique to promote the decomposition of

3.4. Analysis and characterization of optimization leaching product
lepidolite, the mechanism of sulfate roasting is to replace Li-ion with
alkali metal ion to form water-soluble sulfate. According to the HSC
3.4.1. XDR and XRF results
modeling results from Luong’s team, SO2/SO3 gases generated from
The product (850 °C-LP) obtained from using the optimized leaching
FeSO4 or FeS play the main role in the extraction of Li. (Luong et al.,
conditions and calcined product (850 °C-CP) obtained from heating at
2014; Hien-Dinh et al., 2015) During roasting, CaO, CaCl2, CaSO4, or
850 °C for 2 h were analyzed by using XRD (see Fig. 9) and XRF. The
KOH are employed as extra additives to enhance extraction efficiency.
characteristic diffraction peaks of 850 °C-LP can be assigned to the
The introduction of other additives improve the decomposition of le-
KAlSiO4 (JCPDS No. 33-0989). Except for the intensity of the diffraction
pidolite and prevent the production of LiKSO4, meanwhile grab the
peaks of 850 °C-LP is greater than that of 850 °C-CP. The KAlSiO4 phase
fluorine in the form of CaF2 or Ca4Si2O7F4. However, the quartz and
is not washable, and the removal of water-soluble lithium/potassium
albite in the ore still exist in the residue together with other alumino-
silicate leads to the exposure of the KAlSiO4 phase and this likely en-
silicates. (Yan et al., 2012a, 2012b; Luong et al., 2013) Furthermore,
hances the intensity of the diffraction peaks. The result of X-ray fluor-
taking into account the separation process of leaching liquor, the in-
escence spectrum analysis of 850 °C-LP is listed in Table 6. This analysis
troduction of the metal ion or chloride ion lead to more complicated
shows that 850 °C-LP consists of 25.39% K2O, 29.14% Al2O3, and
treatment process. Inspired by this thought, Su (2020) followed a po-
40.51% SiO2. The main components of 850 °C-LP are quite similar to
tassium-only strategy and study the effect of the mixture of K2SO4 and
the theoretical value of KAlSiO4 (the contents of K2O, Al2O3, and SiO2
KOH as roasting additives on lithium and potassium recovery. How-
are 29.78%, 32.23%, and 37.99%, respectively) which proves the fea-
ever, the calcined product consists of kalsilite, leucite, and LiKSO4
sibility of this process once again.
which further indicates that the potassium carbonate calcination
method is better than the sulfate roasting method. Our strategy is to
3.4.2. IR spectra gain the target products kalsilite, lithium metasilicate, and potassium
The FT-IR spectra of 850 °C-LP and 850 °C-CP are shown in Fig. 10. metasilicate by the control of the modulus of (K + Na + Li)/Si which
For both samples, the bands are mainly centered at about 473, 612, listed in table 2. The obtained calcined product could be separated
697, 991 and 1110 cm−1 which are quite similar to that of O1-phase of easily through a watering leaching process which is more advanced
KAlSiO4 (JCPDS No. 33-0989) reported by Mahloujifar and Mansournia than the sulfate roasting method. Furthermore, this calcination ac-
(2019). The bands located at 1110 cm−1, and 991 cm−1 can be as- company the water vapor flow is beneficial for the removal of fluorine.
signed to the asymmetric SieO stretching (Simonsen et al., 2009;
Becerro et al., 2009). The band related to symmetric SieO stretching is 4. Conclusion
located at 697 cm−1 (Novembre and Gimeno, 2017). The absorbance at
400–700 cm−1 reflects the bending modes of TeO (T = Si, Al) bonds. Based on the experience of the studies of the decomposition of K-

Table 6
Chemical composition of optimization leaching product (wt%).
Sample SiO2 TiO2 Al2O3 TFe2O3 MnO MgO CaO Na2O K2 O P2O5 LOI Total

850 °C-LP 40.51 0.01 29.14 0.84 0.12 0.12 0.51 0.17 25.39 0.04 2.16 99.36

7
Y. Kuai, et al.
feldspar, we designed a lepidolite-K2CO3 system. The thermodynamic
calculation manifests the feasibility of this process which allows the
formation of target products KAlSiO4, Li2SiO3, and K2SiO3 as well as the
removal of HF. The lepidolite concentrate decomposition mechanism is
a series of desilication reactions: trilithionite phase → lepidolite
phase → KAlSi2O6 → KAlSiO4. Maximum extraction of lithium
(95.52%) and potassium (95.70%) obtained from the soluble silicates at
the optimum leaching conditions (850 °C-CP leached at 100 °C for 1 h
using a liquid to solid ratio of 5:1). The leaching residue KAlSiO4 could
be the source of the production of kalinite and KNO3. The potassium
carbonate gained from the leaching liquor could cycle as the additives
in the calcination process. Therefore, this novel developed method
makes full use of all the valuable elements of lepidolite and sheds light
on the green comprehensive process of lithium-containing minerals.
CRediT authorship contribution statement
Yuqing Kuai: Software, Formal analysis, Investigation, Writing -
original draft, Visualization. Wengui Yao: Software, Project adminis-
tration. Hongwen Ma: Conceptualization, Software, Supervision.
Meitang Liu: Conceptualization. Yuan Gao: Software, Investigation.
Ruoyu Guo: Software, Investigation.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
The present work was supported by the Fundamental Research
Funds for the China Central Universities (2652017382).
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.mineng.2020.106643.
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