Comparison of three different bioleaching systems for Li recovery from lepidolite
Bioleaching kinetics
Comparison of Li bioleaching by three various types of organisms (Fig. 1) revealed that the leaching kinetics in systems with yeast R. mucilaginosa was the fastest. Presence of Li in solution was detected at 6th day of the process. After initial faster bioleaching within first 6 days (285.5 µg l−1), there was a gradual decrease of Li concentration in solution due to Li bioaccumulation into the biomass up to 13th day and later stable Li concentration in range of 240–250 µg l−1 was observed suggesting that the rate of bioleaching and bioaccumulation were equal.
Figure 1
Kinetics of Li bioleaching from lepidolite by consortium of A. ferrooxidans and A. thiooxidans (bacteria), A. niger (fungi) and R. mucilaginosa (yeast) (A), long-term kinetics of Li bioleaching by bacteria (B) (fungi: initial ore concentration 10 g l−1, t = 21 °C, pH = 5.1, statically, standard medium, yeast: 10 g l−1, t = 21 °C, pH = 5.1, shaking 160 rpm, rich medium and bacteria: 10 g l−1, t = 30 °C, pH = 1.5, statically, poor medium).
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The lowest amount of Li was bioleached by fungi A. niger. Under this bioleaching conditions Li was for the first time observed in solution after 26 days of the process. Its concentration gradually increased later on. Again bioaccumulation was observed affecting the amount of Li in the solution.
In the case of bacteria, medium composition was the most important for Li bioleaching. In nutrient rich medium for acidophilic chemoautotrophic acidithiobacilli which contained energy sources (Fe2+ ions and S0) no Li bioleaching was observed during the whole process time. However, in the medium with limited amount of nutrients and energy sources containing just sulphuric acid and elemental sulphur, Li+ ions presence was observed at 21st day for the first time. Bacteria were probably forced to utilize nutrients necessary for their life directly in the leached material. During the first 77 days the lithium bioleaching kinetics was very slow but this stage was followed by the sharp increase of bioleaching rate (400 times increase of the bioleaching rate was observed) resulting in 11 mg l−1 of solubilised Li at the end of the bioleaching experiments (after 336 days). The rapid change in the bioleaching rate might be attributed to the changes of mineral structure due to bacterial activity. No Li was found in control experiments using the media without microorganisms addition.
Kinetic analysis
To kinetically interpret the heterogeneous non-catalytic reaction for lepidolite bioleaching the shrinking core model (SCM) was used. The assumptions to use the model are based on the three facts—(i) mixed lepidolite particles are considered as nonporous particles, (ii) ore grains gradually shrank and (iii) the product layers form around the unreacted grains20. The development and verification of the model were previously described in details by several authors20,21.
Experimental data obtained for all three studied bioleaching systems were substituted into both equations of SCM model. In the case of bacterial bioleaching a plot of 1−(1−X)1/3 versus time (Fig. 2) was found a straight line suggesting that chemical reaction and outer diffusion are the rate controlling steps of the process of bacterial bioleaching. Changes of rate constant, kr, (apparent from slopes of the plots) can be visible, as well. The linear relationship was obtained in the initial stage of bioleaching (R2 = 0.9944) and later at the day 77 the rate of the process changed but still showed the good fitting obtained by plotting 1−(1−X)1/3 versus time (R2 = 0.9991). This changes are very well visible also in the previous Fig. 1 showing the increase of Li+ ion concentration within the experimental period.
Figure 2
Plot of 1−(1−X)1/3 versus time for Li recovery by consortium of bacteria (initial ore concentration 10 g l−1, t = 30 °C, pH = 1.5, statically, poor media).
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However, the SCM model did not fit to the bioleaching data of two other bioleaching systems, using fungi and yeasts. Obviously, parallel bioaccumulation of Li+ ions into the biomass was responsible for considerably different bioleaching behaviour.
Changes of pH
Conditions of bioleaching experiments (pH, medium composition) were adjusted according the type of the microorganism used. Independently of conditions, the decrease of pH (Fig. 3) was recorded in all three bioleaching system. The most obvious decrease in pH occurred in bioleaching by microscopic fungi A. niger, with a pH decrease from 5.1 to 3 within first 12 days, followed by slow decrease to 2.5 until the end of the experiment. According to various authors22,23, it can be suggested that organic acids, considered the main fungal bioleaching agents, were produced. In the control medium a small increase in pH (from 5.2 to 5.6) was observed.
Figure 3
Changes of pH during bioleaching of lepidolite by consortium of A. ferrooxidans and A. thiooxidans (bacteria), A. niger (fungi) and R. mucilaginosa (yeast) (fungi: initial ore concentration 10 g l−1, t = 21 °C, pH = 5.1, statically, standard medium, yeast: 10 g l−1, t = 21 °C, pH = 5.1, shaking 160 rpm, rich medium and bacteria: 10 g l−1, t = 30 °C, pH = 1.5, statically, poor medium).
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A similar pattern was also observed in bacterial bioleaching, in which fast decrease of pH to 1.2 was observed during first 7 days followed by slow decrease to 0.9. Later the pH was stable in range of 0.9–1.2. Probably bacteria A. thiooxidans were mainly responsible for such pH decrease. In the control without bacteria addition the pH initially decreased from 1.5 to 1.3 and later increased and remained at 1.5.
As shown in Fig. 3 fast pH decrease was observed during first 6 days of bioleaching with yeast R. mucilaginosa from initial 5.1 to 4.1. Later pH did not change until 20th day followed by slow decrease to 3.5 at 30th day. In control media, without microorganisms, pH value slowly increased from initial 5.1 to final 5.5.
Bioleaching mechanisms
According to obtained results different mechanisms can be suggested for lepidolite bioleaching by biological systems studied. Mechanisms of Li bioleaching from lepidolite by A. niger fungus may be attributed to combination of biochemical (due to organic acids production) and biomechanical (due to hyphae penetration) leaching mechanisms. Significant drop of pH values indicates increased concentration of organic acids in the media as the result of high metabolic activity of the A. niger cell what was confirmed by various authors studying bioleaching by the microscopic fungi14,22,23,24,25. However, lepidolite interpenetration by A. niger hyphae growing along cleavages was observed by SEM analysis of solid residue after bioleaching, as well (Supplementary Information, Fig. S1), suggesting that direct biomechanical deterioration of lepidolite was also a part of the whole lithium extraction mechanism. However, according to Gadd26 the biochemical activities of microorganisms play more significant role than mechanical degradation.
Mechanisms of lepidolite bioleaching by bacteria is unknown. However, from abovementioned results it is obvious that no other substance except H+ ions contributed to the dissolution of Li+ ions. These results suggested that Li in lepidolite was dissolved by acid. Probably the mechanisms suggested by Liu et al.20 for leaching of lepidolite in sulphuric acid may be applied to bioleaching by acidophilic bacteria with sulphuric acid as a main bioleaching agent, as well. The main reaction of mixed alkali metal bioleaching may be expressed as follows:
$$ {text{M}}_{{2}} {text{O }} + {text{ H}}_{{2}} {text{SO}}_{{4}} = {text{ M}}_{{2}} {text{SO}}_{{4}} + {text{ H}}_{{2}} {text{O}} $$
(1)
where M presents alkali metals. Metallic elements from lepidolite are dissolved to form metal sulphates and mixed alums in the solution resulting just in partial lepidolite dissolution20. Overal reaction of lepidolite bioleaching in sulphuric acid produced by bacteria may be adopted from Onalbaeva et al.11:
$$ {text{3Li}}_{{2}} {text{O}}cdot{text{2K}}_{{2}} {text{O}}cdot{text{5Al}}_{{2}} {text{O}}_{{3}} cdot{1}0{text{SiO}}_{{2}} cdot{text{2SiF}}_{{4}} + { 2}0{text{H}}_{{2}} {text{SO}}_{{4}} = {text{ 3Li}}_{{2}} {text{SO}}_{{4}} + {text{ 2K}}_{{2}} {text{SO}}_{{4}} + {text{ 5Al}}_{{2}} left( {{text{SO}}_{{4}} } right)_{{3}} + {text{ 11SiO}}_{{2}} + {text{ H}}_{{2}} {text{SiF}}_{{6}} + {text{ 18H}}_{{2}} {text{O }} + {text{ 2HF}} $$
(2)
$$ {text{3Li}}_{{2}} {text{O}}cdot{text{2K}}_{{2}} {text{O}}cdot{text{5Al}}_{{2}} {text{O}}_{{3}} cdot{text{12SiO}}_{{2}} cdot{text{4H}}_{{2}} {text{O }} + { 2}0{text{H}}_{{2}} {text{SO}}_{{4}} = {text{ 3Li}}_{{2}} {text{SO}}_{{4}} + {text{ 2K}}_{{2}} {text{SO}}_{{4}} + {text{ 5Al}}_{{2}} left( {{text{SO}}_{{4}} } right)_{{3}} + {text{ 12SiO}}_{{2}} + {text{ 24H}}_{{2}} {text{O}} $$
(3)
Also Guo et al.27observed that increased H+ concentration catalysed the process of Li leaching from lepidolite via accelerating the protonation of the crystal lattices.
X-ray diffraction analysis
XRD analysis was applied in this study for phase identification and structural changes evaluation of samples before and after bioleaching in all three studied systems. Significant differences in mineralogical composition of leaching residue among the three studied bioleaching systems are visible from XRD spectra comparison (Supplementary Information, Fig. S2) suggesting that different mechanisms can be responsible for bioleaching. While bacterial bioleaching led to the disappearing of muscovite phase from XRD spectrum, the fungal bioleaching led to the appearance of new silicate phase (SiO2) and muscovite was found a dominant phase. According to Liu et al.20 presence of quartz in the spectrum at the end of the process may correspond with alkali metal dissolution from the silicate lattice. Phase changes were observed also after bioleaching by yeast R. mucilaginosa. Reallocation and significant decrease of diffraction peaks intensity was observed and similarly as in case of microscopic fungi muscovite has become a dominant phase while polylithionite phase significantly weakened. Based on the results, it can be suggested that the bioleaching mechanisms of lepidolite by fungi and yeast may be similar, however, in the case of bacteria the mechanisms might be significantly different. Further experiments are necessary to understand the mechanisms behind the lepidolite bioleaching.
Li distribution
Bioaccumulation of lithium into the biomass was observed when heterotrophic microorganisms A. niger and R. mucilaginosa were used (Fig. 4A). No bioaccumulation was found when bioleaching by consortium of acidophilic bacteria was studied. It can be suggested that the process of Li recovery by A. niger and R. mucilaginosa is a combination of two basic processes – initial bioleaching (metal solubilisation) followed by rapid bioaccumulation (intracellular lithium accumulation). It is possible that lithium bioaccumulation could significantly contribute to its solubilisation as released Li+ cations were fast accumulated in the cells and thus “pulled” the equilibrium resulting in the increased efficiency of the Li dissolution.
Figure 4
Distribution of Li between solution and biomass during bioleaching of lepidolite (A) and efficiency of the lepidolite bioleaching (B) by consortium of A. ferrooxidans and A. thiooxidans (bacteria), A. niger (fungi) and R. mucilaginosa (yeast) (fungi: initial ore concentration 10 g l−1, t = 21 °C, pH = 5.1, statically, standard medium, yeast: 10 g l−1, t = 21 °C, pH = 5.1, shaking 160 rpm, rich medium and bacteria: 10 g l−1, t = 30 °C, pH = 1.5, statically, poor medium).
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The highest amount of lithium was accumulated by R. mucilaginosa cells, representing 92% of the total amount of Li recovered from the ore. In the case of microscopic fungi A. niger, produced biomass accumulated 77% of the total solubilised Li. Distribution of Li between solution and biomass of particular microorganisms is shown in Fig. 4A. It is obvious that in both cases (fungi and yeast) bioaccumulation is dominant process of Li recovery and just small amount of Li+ ions remain in solution.
Bioleaching efficiency
The bioleaching efficiency is given as a sum of two processes – Li dissolution and its accumulation in the biomass. The final bioleaching yields for consortium of A. ferrooxidans and A. thiooxidans, fungi A. niger and R. mucilaginosa were found to be 8.8%, 0.2% and 1.1%, respectively. The results suggested that the most efficient among all three studied systems was the consortium of acidophilic bacteria A. ferrooxidans and A. thiooxidans (Fig. 4B) with the final bioleaching yield of almost 9%. On the other hand, very long time (336 days) was necessary for the process. Reichel et al.15 found 11% Li recovery from zinnwaldite using consortium of sulphur-oxidising bacteria, however, authors reported just 14 days for observed Li bioleaching efficiency although they do not found clear explanation of higher bioleaching efficiency in comparison with chemical leaching.
The lowest bioleaching yield was observed when A. niger was used. Rezza et al.13,14 used A. niger for Li bioleaching from spodumene with highest recovery of 0.75 mg l−1 of lithium, they do not reported any bioaccumulation.
Composition of medium had very strong effect on bioleaching efficiency by R. mucilaginosa as in nutrient rich medium due to significantly higher biomass production majority of Li has accumulated into the biomass resulting in 3 times higher final Li recovery. There were also morphological differences observed between yeasts cultivated in nutrient rich and poor environments with spherical shape and thin exopolymer layer of 0.48 µm for yeast from nutrient rich media in comparison with oval cells and thick exopolymer layer (1.8 µm) when cultivated in nutrient poor medium17.
Despite of quite low bioleaching efficiency there is clearly visible potential of all three biological systems for Li recovery from hard rocks. Even with low Li concentration in solution after bioleaching, the lithium concentration in the leaching solution resembles the lithium concentration of sea water (0.1–0.2 mg l−1) and brines (0.1–2 g l−1) considered for economic recovery28,29. That shows that the leaching solution is generally suitable for further processing15.
Due to the expensive separation of Li from leaching liquor, the conventional processing routes are likely not economic. However, ability of fungus A. niger and especially yeast R. mucilaginosa represent advantageous route of Li recovery after bioleaching. Thermal, chemical or microbiological process can be used to Li extraction from the biomass later on.
Metabolic activity and hyphae penetration of microscopic fungi and yeasts resulted in significant structural changes of mineral enhancing the access of lithium by bioleaching agent. Maybe the combination of heterotrophic microorganisms (microscopic fungi or yeast) bioleaching leading to mineral structure changes with consequent bacterial bioleaching could bring better results in the future. More
