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Minerals Engineering 202 (2023) 108284

Contents lists available at ScienceDirect

Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

High recovery of lithium from coal residue by roasting and sulfuric

acid leaching
Yu Xie a, 1, Chenquan Ni a, 1, Zhengwei Han a, Hui Zhong b, *, Zhiguo He a, c, *, Wei Sun a
a
School of Minerals Processing and Bioengineering, Central South University, Changsha 410083, China
b
School of Life Sciences, Central South University, Changsha 410083, China
c
Aerospace Kaitian Environmental Technology Co., Ltd., Changsha 410100, China

A R T I C L E I N F O A B S T R A C T

Keywords: As the price and demand for lithium metal continue to rise, super-enriched lithium coal is expected to become a
Coal-serial lithium extracting new resource to obtain lithium, but there are little research studies on methods for extraction process and
Sulfuric acid leaching mechanism. In this study, a lithium-rich coal residue was leached with H2SO4 after roasting activation without
Low-temperature roasting
any additive. The properties and morphology of raw ore, calcined samples and leaching residue were charac­
Kaolinite
terized by proximate analyses, XRF, ICP-OES, XRD and SEM-ESD. The major chemical compositions were Al2O3
(26.46 %), SiO2 (41.35 %), C (9.43 %) and the valuable lithium content was 550 mg/kg. The main phase
compositions of the raw coal residue are kaolinite, quartz, anatase, gypsum and muscovite. The highest leaching
efficiency of lithium was achieved under conditions of calcination at 500 ◦ C, leaching reaction time of 40 min, in
15 % wt/v sulfuric acid concentration at a leaching temperature at 90 ◦ C. The occurrence at lithium was closely
associated with the kaolinite. The mechanism of roasting activation is that kaolinite loses its structural hydroxyl
group and transforms into metakaolinite, and the exposed lithium can undergo ion exchange and minerals
dissolution reaction with sulfuric acid.

1. Introduction Coal and its by-products are known to contain many trace elements
(such as rare earth elements, gallium), sometimes in high concentrations
In the last week of June of 2022, the price of battery grade lithium (Xu et al., 2004; Li et al., 2013; Lewińska-Preis et al., 2009; Qin et al.,
carbonate in China rose to 473,500 yuan/ton, a 65 % increase so far in 2018). In recent years, researchers have noticed the enrichment of
2022, up 700 % from 65,500 yuan/ton in the same period of last year. lithium in coal. The average grade of lithium in coal is 20–30 ppm (Sun
The reason of rising lithium prices is the imbalance between supply and et al., 2012), but some coal mines have lithium grade of hundreds of
demand, as rising demand for electric vehicles, while supply continues ppm or even thousands of ppm have been reported in recent years,
to tighten (Martin et al., 2017; Mo and Jeon, 2018). At present, lithium which is expected to become a new lithium resource (Sun et al., 2010;
annual consumption of resources is estimated at 300,000 tons and is Sun et al., 2012; Chen et al., 2015; Sun et al., 2013). Extraction of
increasing rapidly. The main lithium sources are from hard rock (mainly lithium from fly ash has long been studied by many researchers (Li et al.,
pegmatite deposits) and salt lake brine (Kesler et al., 2012; Tabelin et al., 2020; Li et al., 2017; Xu et al., 2021; Qin et al., 2015). Fly ash is the
2021). The total amount of lithium (about 14 m tons) in traditional product of coal combustion and the main chemical composition is Al2O3
resource is increasingly inadequate for sustaining for future market and SiO2 and sum of which can reach 80 %. The phase is composed of
demand in the long run (Gil-Alana and Monge, 2019; Liu et al., 2021). mullite, quartz, corundum and aluminate glass. Lithium mainly exists in
Seawater is a huge reservoir of lithium resources, with reserves of the stable glass phase, and is very difficult to free lithium from those
lithium reaching 260 billion tons. But the concentration of lithium in minerals. Given the occurrence of lithium in fly ash, it is necessary to
seawater is only 0.17 mg/L, which is too low, and the extraction method break the mineral phase through high temperature roasting, strong acid/
is still not economic (Zhao et al., 2019; Li et al., 2021). Therefore, it is alkali and additives to achieve lithium extraction, which is energy-
very necessary to find new potential lithium resources. intensive and high-cost process. Hence, the method of extracting

* Corresponding authors at: School of Minerals Processing and Bioengineering, Central South University, Changsha 410083, China (Z.H.).
E-mail addresses: [email protected] (H. Zhong), [email protected] (Z. He).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.mineng.2023.108284
Received 31 August 2022; Received in revised form 29 July 2023; Accepted 30 July 2023
Available online 5 August 2023
0892-6875/© 2023 Elsevier Ltd. All rights reserved.
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Y. Xie et al. Minerals Engineering 202 (2023) 108284

lithium from coal fly ash is not economic and not suitable for direct Table 1
extraction from coal. Leaching experimental conditions.
Although there are many studies on the occurrence of lithium in coal Number Calcination H2SO4 Leaching Leaching
(Sun et al., 2012; Yuan et al., 2019; Chelgani, 2021; Wang et al., 2008), temperature concentration temperature time (min)
little research has involved on the direct extraction of lithium from coal (◦ C) (wt/v %) (◦ C)
(Zhang et al., 2020). To some extent, the understanding on the occur­ 1 300, 400, 500, 15 90 40
rence state of lithium in coal is the prerequisite of lithium extraction. 600, 700, 800,
The lithium in coal is mainly related to minerals matter, mostly adsorbed 900
2 500 5, 10, 15, 20, 30 90 40
by aluminosilicate (clay minerals) (Qin et al., 2015). The Li-bearing clay 3 500 15 20, 40, 60, 70, 40
minerals include montmorillonite (Amer, 2008), diaspore (Gu et al., 80, 90
2020), bentonite (Büyükburç et al., 2006); smectite and illite (Castor 4 500 15 90 10, 20, 30,
and Henry, 2020). These minerals have strong ion adsorption and 40, 50, 60
lithium will not be easily exchanged. Calcination and acid leaching are
employed to extract lithium from those clay-type lithium resource. As
for coal-serial lithium, roasting is a proper pretreatment mean for Table 2
extracting lithium. One reason is to remove excess carbon, and the other Determined feed analysis of the raw coal residue (wt.%).
is to destroy the carrier mineral of lithium and release the lithium. Moisture Volatile Fixed carbon Ash content Total
Calcination and acid leaching tests were performed to extract lithium on
3.54 7.37 9.87 79.22 100.00
the Baker seam coal of the Illinois Basin and the lithium recovery rate
was 70–80 % under optional conditions (Zhang et al., 2020). The
dehydration and disintegration of kaolinite as well as dehydroxylation crystallization of samples.
and expansion of muscovite/illite are the leaching mechanism. A few
studies have reported the direct extraction of lithium from coal, but 2.2. Leaching experiments
lithium is recovered as an associated element, and the recovery effi­
ciency is not high (Tabelin et al., 2021; Zhang and Honaker, 2020). The Coal residue particles were roasted at different temperatures for 60
development of efficient extraction processes for lithium recovery from min, and then the leaching experiments were conducted under different
coal will effectively alleviate the increasingly urgent demand for lithium sulfuric acid concentrations. Specifically, 3 g homogenized roasted
supply, and provide raw material for the sustainable development of the sample and 15 mL sulfuric acid were added into the beaker. After the
new energy industry, and realize the high-value expansion of the coal beaker was sealed, it was stirred and leached in a magnetic stirring water
industry chain. bath at constant temperature between 20 and 90 ◦ C. When leaching
This paper studied a lithium-rich coal residue with high ash content process finished, the ore pulp was vacuum filtered immediately by
and low calorific value, which was activated by roasting at low tem­ Buchner funnel filter. The filter residues were cleaned for three times
perature without any additive, followed by sulfuric acid leaching for and dried at 80 ◦ C for 24 h. The filtrate was collected to measure the Li
lithium extraction. The occurrence of lithium in the coal residue, the content. The detailed experimental conditions were listed in Table 1.
activation mechanism of roasting and leaching, as well as leaching ki­ Sulfuric acid with analytical grade (AG) were provided by Kemiou
netic analysis were preliminarily discussed. This study provides a good Chemical Reagent Limited Company. All water used was ultra-pure
reference for lithium extraction research on lithium-rich coal. deionized water (18.2 MΩ/cm). The element concentration in the
filtrate was measured by ICP-OES. The calculation formula of leaching
2. Materials and methods efficiency was according to equation (1):
c* V
2.1. Raw materials and characterization methods η= × 100% (1)
m*w
The coal residue used in this experiment came from Guangxi prov­ Where η is leaching efficiency (%), c is ion concentration in filtrate
ince, China. The coal residue was crushed and ground to particles, 80 % (g/L), V is the volume of filtrate (L), m is the weight of the coal residue
of passing the 74 μm. The particles were dried at 80 ◦ C for 24 h and then used (g) and w is the contents of Li in the coal residue (wt.%). Each test
homogenized for the characterization testing and leaching studies. The was conducted at least three times, and the mean value was used as the
particles were pretreated in the muffle furnace at different temperatures final result. The standard deviation of each test was calculated and
under air atmosphere before investigating leaching. presented as error bars.
Proximate analyses of the raw coal residue were conducted following
the GB/T 212-2008 standard. The main compositions and contents of 3. Results and discussion
chemical elements of coal residue were determined by X-ray fluores­
cence spectrometer (XRF) (Axiosm AX, Malvern Panaly-tical. B. V, 3.1. Chemical and mineral composition
Netherlands). The trace elements were analyzed by the inductively
coupled plasma-optical emission spectroscopy (ICP-OES) (SPECTRO Feed analysis in Table 2 shows that the coal residue in this study has
BLUE SOP, Spike Analytical Instruments, Germany). Before the ICP-OES high ash content (79.22 %) and low fixed carbon value (9.87 %) that
analysis, the coal residue was first ashed under the procedures of GB/T even cannot be used as power coal. Such residue is regarded as waste so
212-2008 standard and then digested in perchloric, sulfuric, nitric and will be stacked and occupy wasted land.
hydrofluoric acids. The residue was diluted to volume by 1 % dilute The main chemical composition of the coal residue is shown in
nitric acid (Rodushkin et al., 2000; Low and Zhang, 2012). Table 3. Al2O3 and SiO2 are the major chemical composition, which
The phase composition and phase transformation of the raw coal count for 67.8 %, followed by SO3, Fe2O3, CaO, TiO2, K2O and Na2O, etc.
residue, calcined minerals and leaching residues were investigated by The content of Al2O3 (26.46 %) is too low to satisfy the requirement for
means of X-ray diffraction (XRD, Cu Kα radiation, λ = 0.15406 nm), extraction of Al as well as the standard of kaolin clay. The weight ratio of
scanning electron microscope and energy dispersive spectrometer (SEM- Al2O3:SiO2 is 0.64, indicating there are other SiO2-containing minerals
EDS, MIRA4 LMH, TESCAN, Chech). The XRD analysis was character­ other than kaolinite.
ized by a X-Pert3 Powder, Panalytical B.V. with a scanning range of 2θ = The trace elemental concentrations in the coal residue are listed in
5◦ –80◦ to gain the information about the phase composition and Table 4. Lithium was the highest valuable element, which was 550 mg/

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Y. Xie et al. Minerals Engineering 202 (2023) 108284

Table 3
Main chemical composition of the coal residue.
Components Al2O3 SiO2 Fe2O3 SO3 CaO K2O Na2O TiO2 MgO

wt % 26.46 41.35 3.98 7.31 2.83 0.90 0.61 1.61 0.53

Table 4
Trace elemental concentration of the coal residue.
Elements Li Ga Nd Ce Er La V Cr Zr

wt mg/kg 550 33 71 23 17 12 400 620 360

Fig. 2. Effect of calcination temperature on the leaching behavior of Li from

coal residue.

calcined products. As shown in Fig. 2., the Li leaching increased with the
calcination temperature and reached the highest at 500 ◦ C. Higher
calcination temperatures decreased the lithium extraction. The leaching
efficiency of raw coal residue and calcined product at 300 ◦ C did not
Fig. 1. XRD patterns of the raw coal residue and calcined products at different
exceed 5 %, suggesting there has little Li dissolved by sulfuric acid and Li
temperature.
is stable in the coal residue. Kaolinite has good acid and alkaline resis­
tance under normal temperature and pressure, and the integrity of
kg in the coal residue, nearly 20 times higher than the average Li content
crystal form can be maintained when the roasting temperature is below
in coal. It also exceeds the economic grade of 80 mg/kg and industrial
400 ◦ C. Therefore, it may be difficult to release lithium from the coal
grade of 120 mg/kg for Chinese coals suggested by Sun (Sun et al.,
residue under this condition, resulting in little lithium leaching.
2012). Ga content in this residue was 33 mg/kg, far higher than the
There is a huge increasement of lithium extraction at different
average Ga content in Chinese coal (6.52 mg/kg), and reached the in­
leaching temperature for the coal residue calcined at 400 ◦ C and 500 ◦ C,
dustrial grade of Ga in coals (30 mg/kg) in China (Sun et al., 2012). The
and the leaching efficiency is 34.19 % and 99.64 %, respectively. The
coal residue also contained rare earth elements (such as Nd, Ce, Er, La),
extraction of Li for calcined product at 400 ◦ C may attribute to the
but the concentrations were too low and had little economic value.
combustion of carbon and part of kaolinite that intensity of kaolinite
As shown in Fig. 1, the main phase compositions of the raw coal
peak decreases compared to the calcined sample of 300 ◦ C. Apart from
residue are kaolinite, quartz, anatase, gypsum, and muscovite. The ex­
that, the leaching increase for coal residue calcined at 500 ◦ C is corre­
istence of quartz is consistent with previous analysis of weight ratio of
sponding to the almost all phase of kaolinite disappeared.
Al2O3:SiO2. The first and second highest peak are the characteristic peak
The lithium extraction declines as the calcination temperature in­
of kaolinite of (0 0 1) and (0 0 2), indicating it is the main phase in the
crease. There is a slight decrease in leaching efficiency at 600 ◦ C and
coal residue. As the calcination temperature increases, the intensity of
significant drop for 700 and 800 ◦ C. When the roast temperature reaches
kaolinite peak is weakening gradually. The kaolinite peak nearly dis­
900 ◦ C, the lithium extraction is less than 20 %. When the roasting
appears at 500 ◦ C and totally cannot be observed when the calcination
temperature exceeds 600 ◦ C, the leaching of Li gradually decreases,
temperatures are greater than 500 ◦ C. It is known from the literatures
which may be related to the formation of new phase, trolleite, which
(Qiao et al., 2008; Claverie et al., 2015; Yuan et al., 2017) that meta­
turns Li into structural Li and cannot be leached by sulfuric acid.
kaolinite will be formed when the calcination temperature is higher than
It is worth noting that the leaching temperature greatly influenced on
600 ◦ C. The gypsum has the same trend as the kaolinite. The anatase,
the extraction of Li. Under the optimal roasting temperature of 500 ◦ C,
quartz and muscovite have little change in this study’s temperature
when the leaching temperature was 30 ◦ C, only 29.39 % of the lithium
range. According to the literature, these minerals can exist stably below
leached. When the leach temperature was to 60 ◦ C, the of lithium
900 ◦ C. Noticeably, there is a new phase, trolleite, when the calcination
extracted increased to 40.78 %, but at a leaching temperature of 90 ◦ C,
temperature is above 600 ◦ C.
the lithium extraction increases rapidly to 99.64 % of the lithium
extracted.
3.2. Effect of calcination temperature on Li leaching
3.3. Effect of acid concentration and temperature on Li leaching
The coal residue calcined at different temperature for 60 min were
leached for 40 min in 15 % wt/v H2SO4 with a L/S ratio of 5 mL/g. The The coal residue calcined at 500 ◦ C for 60 min were leached for 40
leaching temperature of 30, 60 and 90 ◦ C were investigated for raw and min at different H2SO4 concentrations with a L/S ratio of 5 mL/g. The

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Y. Xie et al. Minerals Engineering 202 (2023) 108284

Fig. 3. Effect of acid concentration on the leaching behavior of Li from coal Fig. 5. XRD patterns of calcined sample at 500 ◦ C and its acid leaching residue
residue calcined at 500 ◦ C. at 90 ◦ C.

3.4. Effect of reaction time on Li leaching

The coal residue calcined at 500 ◦ C for 60 min were leached for
different reaction time in 15 % wt/v H2SO4 concentrations with a L/S
ratio of 5 mL/g at 90 ◦ C. The Li that leached increased with the extension
of reaction time. In the first ten minutes of leaching, 54.56 % leached.
When the leaching time is extended to 30 min, the extent of lithium
extracted increased rapidly to 95.83 %. As the leaching time was
extended to 40 min, the amount of of lithium extracted was close to 100
%.

3.5. Characterization of the leached residue

Fig. 5 is the XRD patterns of calcined example at 500 ◦ C and its acid
leaching residue at 90 ◦ C. As shown in Fig. 5, XRD peaks are basically the
same before and after leaching, indicating that the main phases do not
dissolve during leaching process or the leaching process involves sul­
furic acid reacting with amorphous materials (such as metakaolinite).
To further clarify the mechanism of lithium leaching process, SEM-
EDS images of raw coal residue, calcined sample at 500 ◦ C and its acid
Fig. 4. Effect of reaction time on the leaching behavior of Li from coal residue
leaching residue are shown in Fig. 6. As shown in Fig. 6(a), the stratified
calcined at 500 ◦ C.
structures can be clearly seen and indicate the mineral is kaolinite. The
main elements obtained from EDS test are Al, O and Si and the Al/Si
influences of leaching temperature of 20 ◦ C, 40 ◦ C, 60 ◦ C, 70 ◦ C, 80 ◦ C
atomic ratio is 0.77, which is lower than the Al/Si atomic ratio of pure
and 90 ◦ C was also investigated. As shown in Fig. 3, the Li extraction
kaolinite. It may be that this particle is impure and contains other silicon
increased with the increase of sulfuric acid concentration. When the
containing minerals. After calcination, the contents of main elements is
leaching temperature is 90 ◦ C and sulfuric acid is not added, the lithium
as same as the raw coal residue and Al/Si ratio increase into 0.94. The
extraction is 12.23 %. This part of lithium belongs to water-soluble
compact lamellar structure of kaolinite begins to dissociate and the
lithium, which may come from the decomposed organic matter after
monolithic metakaolinite can be clearly seen in Fig. 6(b). This process is
calcination. Many studies have reported that lithium could occurs in
due to the release of hydroxyl groups and the collapse of layers in clay
organic matter in coal (Qin et al., 2015). When the concentration of
minerals. In the previous water leaching test of roasted residue, the
sulfuric acid is 5 %, the lithium extraction rises sharply to 79.39 %. The
lithium extraction was 14.23 %, which may come from the interlayer
lithium extraction rises slowly at increasing sulfuric acid concentrations.
lithium released after calcination of kaolinite.
The extraction of lithium is close to 100 % when the acid concentration
After H2SO4 leaching, the edges and angles of the monolayer struc­
is 15 % and higher (see Fig. 4).
ture of metakaolinite gradually disappear and change to amorphous
Like what was reported previously (Li et al., 2020; Xu et al., 2021;
morphology, implying that extraction of lithium is accompanied by
Zhang et al., 2020), the leaching temperature is one of most important
dissolution of metakaolinite minerals. The Al/Si atomic ratio of leached
factors affecting the extraction for liquid–solid interface reaction. In this
slag decreased from 0.94 to 0.334, indicating that Al in metakaolinite is
study, the leaching efficiency increases substantially from 20 to 90 ◦ C,
dissolved by H2SO4 during leaching, while the pure kaolinite is acid
namely, lithium extraction from 20.58 % to 99.64 % under the optimal
resistant and will not be dissolved by sulfuric acid. The leached lithium
acid concentration. On the one hand, a higher leaching temperature
is likely come from the reaction between metakaolinite and sulfuric
means more H+ in the solution; on the other hand, high temperature will
acid, resulting in the dissolution of lithium in lattices.
accelerate the movement of ions (H+ going inside and Li+ going outside)
in the solution, which was confirmed in the later kinetic analysis.

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Y. Xie et al. Minerals Engineering 202 (2023) 108284

Fig. 6. SEM-EDS images of raw coal residue (a), calcined sample at 500 ◦ C (b) and its acid leaching residue (c).

fitting results in Fig. 7, the extraction of lithium is more accurately fitted

Table 5
by the diffusion model compared to the chemical reaction model.
R2 of lithium leaching in SCM models at different temperature.
Therefore, lithium extraction was mainly controlled by the diffusion rate
Temperature (◦ C) R2 of solid film. From the results of SEM, the solid layer are mainly
1 2 aluminosilicate minerals and still existed after the acid leaching and this
2
1 − (1 − α)3 1−
3
α − (1 − α)3 may be the resistance hindering the lithium diffusion.
Activation energies for lithium extracting from roasted ore by sul­
60 ◦ C 0.7521 0.9537
furic acid are calculated using the Arrhenius equation:
70 ◦ C 0.9011 0.9982
80 ◦ C 0.9407 0.9988 − Ea
90 ◦ C 0.8969 0.9823 k = Aexp( ) (4)
RT
This equation could also be written as follows:
3.6. Leaching kinetic analysis
Ea 1
lnk = lnA − (5)
Kinetic modeling is a useful method to understand the reaction rates R T
and mechanism of the leaching process. The dissolution of lithium from
calcined samples in the H2SO4 solution is a liquid–solid process occur­
ring on the interface of the two phases. The shrinking core model (SCM)
is often used to describe liquid–solid reactions (Vegliò et al., 2001). The
rate-controlling step is determined by the slowest step. If the reaction
rate is controlled by the surface chemical reaction, the equation can be
expressed as follows:

(2)
1
1 − (1 − α)3 = Kc t
Where ɑ is the lithium extraction; t is leaching time (min); Kc is the
chemical reaction rate constants. Similarly, if the reaction rate is
controlled by diffusion through the solid layer, the equation can be
expressed as follows:
2
(3)
2
1− α − (1 − α)3 = Kd t
3
where Kd is the diffusion rate constants.
Due to the linear relationship between the left-hand side of the
equation and time, it is easy to judge the model accuracy through the
value of the R2.
The leaching kinetics of lithium was investigated at the temperature
ranging from 60 to 90 ◦ C. As indicated by the R2 values in Table 5 and Fig. 8. Arrhenius fitting straight line of lithium extraction during acid leaching.

Fig. 7. Fitting of lithium leaching at 60–90 ◦ C by different models.

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Y. Xie et al. Minerals Engineering 202 (2023) 108284

Fig. 9. The mechanism of roasting activation and leaching by H2SO4.

Where Ea is the activation energy, k the rate constant, A the fre­ Acknowledgement
quency factor, T the temperature (in Kelvin), and R is the gas constant.
According to Equation (5), plotting the logarithm of k at different The authors gratefully acknowledge the financial support of National
temperatures versus 1/T, as shown in Fig. 8, the result showed a good Key Research & Development Project of China (No. 2021YFC2903203-
linear relationship. Based on the slope of the fitted curve, the activation 02), Research on Key Technologies of Exploration and Development of
energy is 75.32 kJ/mol. Coal-serial Mineral Resources (ZMKJ-2021-ZX03).

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