Lithium Recovery from Low Temperature Geothermal Brines through Membrane Distillation and Manganese Oxide Sorption

Transcription

1 1 Lithium Recovery from Low Temperature Geothermal Brines through Membrane Distillation and Manganese Oxide Sorption Jay E. Renew, P.E. 1, Ryan Melsert 2, Tim Hansen 1, Jake Rajterowski 1, and Corey Tyree 1 1 Southern Research 2 Tesla Motors

2 Background Source: USDOE, electricity-generation Concern: Demand for Li is increasing worldwide. Li is utilized in electric vehicles, cell phones, electronics, and numerous military applications. Opportunity: Geothermal power is renewable form of energy utilized everywhere in the world. Geothermal fluids dissolve minerals and metals from rocks mining by nature [1]. Li recovery from geothermal fluids has been demonstrated at Salton Sea by Simbol Materials. 2

3 Background Low Temperature Geothermal Power Low-temperature geothermal fluids have temperatures < 150 o C. 3 Source: USDOE, /low-temperature-mineral-recovery-programfoa-selections Lower temperatures compared to conventional sources of geothermal energy. Potential exists for mineral extraction to supplement the development of low-temperature geothermal energy development. Li concentrations in lowtemperature brines can reach more than 100 ppm in the Great Basin (Nevada) [2].

4 Proposed Process 4

5 Simulated Brines for Si Removal Experiments 5 Component Low Strength Brine Concentration (mg/l) High Strength Brine Concentration (mg/l) Si Na 505-1,483 2,591-3,162 K Mg Ca

6 Si Removal - ph Adjusted to 9.0 and FeCl 3 Addition Temp. = 80 o C 6

7 Si Removal - ph Adjusted to 10.5 and FeCl 3 Addition Temp. = 80 o C 7

8 Si Removal - ph Adjusted to 9.0 and FeCl 3 Addition Temp. = 50 o C 8

9 Si Removal ph Adjusted to 10.5 and FeCl 3 Addition Temp. = 50 o C 9

10 Kinetics of Si removal. ph maintained at 9.0 and temperature maintained at 80 o C. Fe/Si molar ratio = 5.65 for low strength brine. No Fe addition for high strength brine. 10

11 Nanofiltration - Experimental Setup 11 Simulated Geothermal Brine Reservoir F1 V2 P2 Flat Sheet Membrane Module Pump V1 P1 Concentrate Side Permeate Side F1 Flowmeter P1 Pressure Gauge No. 1 P2 Pressure Gauge No. 2 V1 Valve No. 1 V2 Valve No. 2 Regulating Valve Permeate Collection Container

12 Simulated Brines for Nanofiltration Experiments 12 Component Low Strength Brine (mg/l) High Strength Brines (mg/l) High Strength Brine with Si (mg/l) Ca Cl 1,800 7,030 14,220 Li Mg Na 880 3,670 7,050 Si SO

13 Rejection Efficiency Nanofiltration Ca 2+ and Mg 2+ Rejection Efficiency % 90% 80% 70% Ca - High Strength Brine Ca - Low Strength Brine Mg - High Strength Brine Mg - Low Strength Brine Ca - High Strength Brine with Si Mg - High Strength Brine with Si 60% 50% 40% 30% 20% 10% 0% Mid-Point MWCO (Daltons)

14 Rejection Efficiency Nanofiltration Li + and Na + Rejection Efficiency % 90% 80% 70% Li - High Strength Brine Li - Low Strength Brine Na - High Strength Brine Na - Low Strength Brine Li - High Strength Brine w/si Na - High Strength Brine w/si 60% 50% 40% 30% 20% 10% 0% Mid-Point MWCO (Daltons)

15 Rejection Efficiency Nanofiltration SO 4 2- and Cl - Rejection Efficiency % 90% 80% 70% 60% Cl - High Strength Brine Cl - Low Strength Brine Sulfate - High Strength Brine Sulfate - Low Strength Brine Cl - High Strength Brine with Si Sulfate - High Strength Brine with Si 50% 40% 30% 20% 10% 0% Mid-Point MWCO (Daltons)

16 Membrane Distillation Experimental Setup 16 Distillate Simulated NF Permeate MD System Cold Cold HX Hot Hot Hot Hot HX Cold Cold Boiler Disposal Drain Cold Water Source

17 5 6 Concentration (mg/l) ,045 1,432 1,651 2,995 2,300 4,751 Membrane Distillation Low Strength Brine 17 10,000 1, Li Na Mg Ca Cl Brine Brine (after 3hrs) Brine (after 6.5 hrs)

18 9 Concentration (mg/l) ,875 2,825 3,068 4,345 4,979 7,204 Membrane Distillation Medium Strength Brine 18 10,000 1, Li Na Mg Ca Cl Brine Brine (after 3 hours) Brine (after 6.5 hours)

19 Concentration (mg/l) ,071 5,681 8,537 6,254 8,846 13,397 30,192 46,742 Membrane Distillation High Strength Brine ,000 10,000 1, Li Na Mg Ca Cl Brine Brine (after 3 hours) Brine (after 6.5 hours) Brine (after 10 hours)

20 Simulated Brines Utilized in Li Sorption Experiments 20 Component Low Strength (mg/l) Medium Strength (mg/l) High Strength (mg/l) Ca Cl - 4,751 7,204 46,742 Li Mg Na + 2,995 4,345 30,192 SO

21 Li Uptake (mg Li/g sorbent) Lithium Recovery with Li 1.6 Mn 1.6 O Low Strength Brine (1 g of sorbent/1,000 ml) Low Strength Brine (2 g of sorbent/1,000 ml) Medium Strength Brine (1 g of sorbent/1,000 ml) Medium Strength Brine (2 g of sorbent/1,000 ml) High Strength Brine (1 g / 50 ml, average of duplicates) 250,000 mg/l TDS brine (1 g / 50 ml, average of duplicates) Sorption Experiment

22 References Thomas, H., T.P. Reinhardt, and B. Segneri, Low Temperature Geothermal Mineral Recovery Program, in Thirty-Ninth Workshop on Geothermal Reservoir Engineering. 2015: Stanford, California. 2. Great Basin Groundwater Geochemical Database [cited 2014; Available from: se.html

23 Acknowledgements 23 This project is funded by the United States Department of Energy, Office of Energy Efficiency and Renewable Energy.