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Circular Economy Approaches
Abstract: In view of the increasing demand for lithium and the unequal distribution of lithium
deposits worldwide, local deposits such as the zinnwaldite deposit at Zinnwald/Cínovec are
increasingly coming into focus. It could be shown that especially the direct carbonation process with
supercritical CO2 represents a promising approach for a technical implementation due to the low
chemical consumption as well as the high selectivity for lithium. Moreover, besides primary ore
(zinnwaldite), the method is also suitable for recovering lithium carbonate from black mass, the
lithium-containing fraction from lithium ion battery recycling.
Introduction
As an energy-critical element, lithium, the lightest metal, has evolved into a strategic raw material [1].
Since it is currently regarded as irreplaceable in the most important fields of application, e.g., for the
storage of energy in electric vehicles and mobile electrical devices, in the glass, enamel, and ceramics
industries, as lubricant, in pharmaceutical products, and in aluminum production, a steadily increasing
demand of 8–11 % per year is expected [2]. Scenarios even suggest that a supply bottleneck could
already occur in 2025, since the demand of lithium for energy storage will increase from actually
39 % to approx. 70 % in 2025 [3,4].
The most important lithium derivative is lithium carbonate, Li2CO3 (40,44 % Li2O) with a market
share of 46%. After 5500 USD/t Li2CO3 in October 2015, the price increased to 14000 USD/t Li2CO3
(+254 %) in August 2017. Some scenarios even predict an increase for Li2CO3 from the current
market price to 25500 USD/t in 2020 [5].
Lithium compounds find widespread applications in secondary batteries (rechargeable batteries) as
cathode materials (e.g. LiFePO4, LiCoO2, LiMn2O4, LiNixCoyMnzO2) as well as in primary batteries
(single-discharge batteries) as anode materials [6]. Nevertheless, lithium cannot be limited to primary
and secondary battery production. Lithium compounds are also used in the glass, enamel and ceramic
industries, as lubricants, in pharmaceutical products or in aluminum production (Figure 1).
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70 E-Mobility and Circular Economy
Lithium from secondary sources had no significant impact on the total supply so far. Indeed, some
scenarios agree on the importance of lithium recycling, predicted to attain relevance in about 2030
and is forecasted to substitute up to 25 % of the supply in 2050 [7]. The greatest potential lies in
recycling lithium containing batteries. In all other applications, the light metal dissipates. However,
the methods presently employed, aim at recovering particularly cobalt and nickel. Since previous
recycling processes aim at recovering more valuable cathode materials cobalt and nickel, domestic
lithium deposits may become increasingly important.
Lithium mobilisation of untreated zinnwaldite concentrate by sc-CO2/H2O digestion typically did not
exceed 5 % (150 bar, 150 °C, 24 h), though.
Results of thermal treatment of zinnwaldite, showed that the main decomposition products above
900 °C are β-spodumene (LiAlSi2O6), leucite (KAlSi2O6), hematite (Fe2O3) and magnetite (Fe3O4).
The formation of new mineral phases, particularly of the lithium containing β-spodumene, which is
known to be readily soluble in mineral acids, is the basis of subsequent leaching with carbon dioxide
[11]
.
Direct carbonation of sintered material with the same digestion parameters is significantly more
promising (Lithium mobilisation rate ~40 %). The major issue was to increase the lithium yield to a
level, which enables this process to become economically viable. Therefore, a variety of influencing
parameters to carbonation efficiency were studied and optimised. These main investigated variables
are: i) carbonation time, ii) CO2 pressure, iii) particle size, iv) carbonation temperature and v) liquid
to solid weight ratio which where optimised by design of experiments (DoE) and sequential
experimental design.
Promising digestion parameters were found in a dual digestion procedure (Solid to liquid ratio 1:30,
3 h, 100 bar, 18 μm (d50), 230 °C). The overall lithium mobilisation rates of this sequence were 71 %
at a constant content of approx. 325 mg/L Li.
The direct carbonation process is predominantly selective for alkali metal cations. The higher the
radius of the cation, the lower the mobilisation efficiency. The yields of K+ (138 pm, 18 %) and Rb+
(152 pm, 4 %) are significantly below Li+ (76 pm).
Prior to Li2CO3 precipitation, the lithium containing leach liquor (Lithium content between
200−400 mg/L) requires concentration for ensuing product precipitation to about 7 g/L Li+. Such
concentrations are typically done by evaporation. Exploring potentially more energy-efficient
alternatives for low concentrated solutions led to membrane processes as method for leach liquor
concentration [12].
Materials Science Forum Vol. 959 71
primary and secondary raw materials. Residues and by-products are fed to other production processes,
thus almost entirely implementing the zero-waste principle, yet on a technically feasible basis.
The COOL process (CO2 leaching) not only allows for recycling Li2CO3,[18] it generates almost no
waste, since the calcination by-products can be further processed to geopolymers for instance (e.g.
for use in construction materials industry). Iron oxide can be separated by magnetically and processed
separately (Figure 2).
Figure 2. Flow sheet for the production of lithium carbonate from zinnwaldite concentrate or from
spent lithium batteries by direct carbonation [9,9,18,19].
The design of integrated processes complying with the zero-waste principle (the target of waste-free
production describes an ideal state) represents a particular procedural challenge. The lithium recovery
process presented here fulfils these criteria. It becomes clear, that modern resources chemistry can
significantly contribute to solve contemporary and future challenges.
These modern, future-oriented process concepts are no longer assignable to any classical discipline.
In fact, these highly interdisciplinary approaches profit from overcoming classical boundaries and
from combining chemistry, process engineering, hydro- and pyrometallurgy, silicate technology and
others.
The advantages are:
1. Lithium ores are processed in one process chain.
2. Process simplification through high input variability
− Suitability for all siliceous lithium ores proven
− No separate processing of different siliceous lithium ores required. Mixed ores (such
as from pegmatitic deposits) need no upstream separation, but are processed as they
are.
3. Lithium recycling is possible
− Recycling in primary product quality → genuine recycling
− Lithium recycling in front of classic pyrometallurgy → As a result, no change to
existing processes and markets is necessary
4. Utilisation options for by-components
− H2SiF6: production of hydrofluoric acid (HF)
− SiO2 & Al2O3: geopolymers, glass and ceramics industry
− Fe2O3/Fe3O4 iron compounds
− Utilisation options for by-components
5. The hybrid process does not generate CO2 for the production of Li2CO3, it consumes CO2
with negligible use of chemicals.
Materials Science Forum Vol. 959 73
Follow-up activities aim at a detailed economic analysis. In addition, the sintering process will be
investigated with particular consideration of mineral phase formation to increase the subsequent
lithium mobilisation, respectively decrease the liquid to solid ratio.
Acknowledgements
Financial support by the German Federal Ministry of Education and Research (BMBF, grant number
03WKP18A) and the German Research Foundation (DFG, grant number INST 267/125-1 FUGG) is
gratefully acknowledged. Further thanks are expressed to Dr. Andreas Massanek, Mineralogical
Collection of Freiberg University of Mining and Technology for providing lithium mineral samples.
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