ORIGINAL PAPER
Recovery of lithium from waste liquid of rock salt brine using aluminum hydroxide precipitation method
1
107 Geological and Mineral Exploration Institute
2
Yangtze Normal University
These authors had equal contribution to this work
Submission date: 2024-03-31
Final revision date: 2024-09-11
Acceptance date: 2024-11-19
Publication date: 2024-12-17
Gospodarka Surowcami Mineralnymi – Mineral Resources Management 2024;40(4):47-69
KEYWORDS
lithium recoverywaste liquid of rock salt brinealuminum hydroxide precipitation methodthermodynamic analysis
TOPICS
ABSTRACT
An integrated process consisting of Li+ precipitation by Al(OH)3, roasting, water leaching, evaporation, and Li2CO3 precipitation was used to recycle Li+ from the waste liquid of rock salt brine (0.099 g/L Li+). Waste liquid from rock salt brine was discharged wastewater after NaCl crystallization and the removal of impurities in the salt manufacturing plant of the good rock salt mine. The influences of Al3+/Li+ mole ratio, Na+/Al3+ mole ratio, precipitation temperature, and time on the recovery of Li+ were investigated during Li+ precipitation by Al(OH)3 stage. The results showed that the optimal condition was Al3+/Li+ mole ratio = 2.5, Na+/Al3+ mole ratio = 2.2, precipitation temperature of 60℃ (333.15 K) for more than 20 min, whose recovery of Li+ reached 97.25%. The thermodynamic analyses of the simulated Li+–Al+–Mg2+–Cl––H2O system were conducted to construct the potential-pH (φ-pH) diagrams. The results showed that the pH value should be located in the LiCl · 2Al(OH)3 · 2H2O salt region with no formation of Mg(OH)2, which started at pH = ~6.5 and ended at pH from 10.09 to 8.55 as the temperature changed. Subsequently, the Li+ precipitate was roasting for the transformation of insoluble LiCl · 2Al(OH)3 · xH2O salt to soluble LiCl, followed by the water leaching to obtain the enriched Li+ solution (1.951 g/L Li+) with Li+ recovery of 85.52%. To meet the requirement of Li2CO3 precipitation, the enriched Li+ solution was evaporated, and Na2CO3 was added to precipitate the Li2CO3 product after SO42–, Ca2+, and Mg2+ removal. The total recovery of Li+ was 66.69% after the experimental process, and the purity of Li2CO3 product was 99.3%, which can be regarded as industrial-grade Li2CO3. In conclusion, the success in lithium recovery using the aluminum hydroxide precipitation method provided a new perspective for preparing Li2CO3 from the waste liquid of rock salt brine, which could be considered as a newly developing lithium resource to meet the dramatically increasing demand for lithium in new energy vehicle industry.
ACKNOWLEDGEMENTS
Project Supported by Technology Project of Chongqing Planning and Natural Resources Bureau (Grant No. KJ-2023008) and Scientific and Technological Research Program of Chongqing Municipal Education Commission (Grant No. KJQN202101434 and Grant No. KJQN202301423). Thanks to school funding of Yangtze Normal University.
CONFLICT OF INTEREST
The Authors have no conflicts of interest to declare.
METADATA IN OTHER LANGUAGES:
Polish
Odzysk litu z cieczy odpadowej solanki kamiennej metodą wytrącania wodorotlenkiem glinu
odzysk litu, ciecz odpadowa solanki z soli kamiennej, metoda wytrącania wodorotlenkiem glinu, analiza termodynamiczna
Do recyklingu Li+ z cieczy odpadowej solanki kamiennej zastosowano zintegrowany proces obejmujący wytrącanie Li+ przez Al(OH)3, prażenie, ługowanie wodą, odparowywanie i wytrącanie Li2CO3 (0,099 g/l Li+). Płyn odpadowy z solanki soli kamiennej odprowadzano do ścieków po krystalizacji NaCl i usunięciu zanieczyszczeń w zakładzie produkcji soli kopalni soli kamiennej Dobra. Badano wpływ stosunku molowego Al3+/Li+, stosunku molowego Na+/Al3+, temperatury i czasu wytrącania na odzysk Li+ podczas wytrącania Li+ w etapie Al(OH)3. Wyniki wykazały, że optymalnymi warunkami był stosunek molowy Al3+/Li+ = 2,5, stosunek molowy Na+/Al3+ = 2,2, temperatura wytrącania 60℃ (333,15 K) przez ponad 20 min, przy czym odzysk Li+ osiągnął 97,25%. Przeprowadzono analizy termodynamiczne symulowanego układu Li+–Al+–Mg2+–Cl––H2O w celu skonstruowania wykresów potencjał-pH (φ-pH). LiCl · 2Al(OH)3 · 2H2O obszar soli bez tworzenia Mg(OH)2, który rozpoczął się przy pH = ~6,5 i zakończył przy pH od 10,09 do 8,55 wraz ze zmianą temperatury. Następnie osad Li+ prażono w celu przekształcenia nierozpuszczalnej soli LiCl · 2Al(OH)3 · xH2O w rozpuszczalny LiCl, a następnie ługowano wodą w celu uzyskania wzbogaconego roztworu Li+ (1,951 g/L Li+) z uzyskiem Li+ wynoszącym 85,52 %. Aby spełnić wymagania dotyczące wytrącania Li2CO3, wzbogacony roztwór Li+ odparowano i dodano Na2CO3 w celu wytrącenia produktu Li2CO3 po usunięciu SO42–, Ca2+ i Mg2+. Całkowity odzysk Li+ po procesie eksperymentalnym wyniósł 66,69%, a czystość produktu Li2CO3 wyniosła 99,3%, co można uznać za Li2CO3 klasy przemysłowej. Podsumowując, sukces w odzyskiwaniu litu metodą wytrącania wodorotlenkiem glinu otworzył nową perspektywę przygotowania Li2CO3 z cieczy odpadowej solanki z soli kamiennej, który można uznać za nowo rozwijające się źródło litu w celu zaspokojenia dramatycznie rosnącego zapotrzebowania na lit w przemyśle pojazdów wykorzystujących nowe źródła energii.
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