LITHIUM EXTRACTION FROM BRINE WITH ION EXCHANGE RESIN AND FERRIC PHOSPHATE by HIROKI FUKUDA B.Eng., Waseda University, Japan, 2017 A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF APPLIED SCIENCE in THE FACULTY OF GRADUATE AND POSTDOCTORAL STUDIES (Materials Engineering) THE UNIVERSITY OF BRITISH COLUMBIA (Vancouver) July 2019 © Hiroki Fukuda, 2019 The following individuals certify that they have read, and recommend to the Faculty of Graduate and Postdoctoral Studies for acceptance, a thesis/dissertation entitled: Lithium extraction from brine with ion exchange resin and ferric phosphate submitted by Hiroki Fukuda in partial fulfillment of the requirements for the degree of Master of Applied Science in Materials Engineering Examining Committee: David Dreisinger, Materials Engineering Supervisor David Dixon, Materials Engineering Supervisory Committee Member Berend Wassink, Materials Engineering Supervisory Committee Member Daan Maijer (Chair), Materials Engineering Additional Examiner Additional Supervisory Committee Members: Supervisory Committee Member Supervisory Committee Member - ii - Abstract Lithium is an essential metal for our society. Notably, increasing energy storage system will necessitate much more lithium in the future. This study focused on brine deposit while lithium exists in hard rocks as well. Conventionally, solar evaporation has been used to concentrate lithium from brine, but it takes more than one year. Thus, a more rapid process is desired for the accelerating demand. Here, two types of adsorbent, ion exchange (IX) resin and heterosite ferric phosphate (FP), were studied in order to extract lithium selectively from brine rapidly. First, more than thirty IX resins were tested in lithium chloride solution. Out of the thirty, sulfonate, iminodiacetate and aminomethylphosphonate resins succeeded in extracting lithium with the value of 16.3–32.9 mg-Li/g. However, no resins could adsorb lithium from a mixed brine solution which contains other interfering cations like sodium. An aluminum loaded resin was also tested since some past studies had reported lithium selectivity with this material. Its adsorption density was 6.6 mg-Li/g and was higher than any other resins tested for the mixed brine in this study. Nevertheless, the overall results showed that the IX resins were not so suitable for lithium extraction from a mixed brine. Then, heterosite FP was investigated as an alternative adsorbent. The FP can adsorb lithium selectively with the addition of a reducing agent to form lithium iron phosphate. This study used thiosulfate (TS) and sulfite (SF) individually as a reducing agent. The maximum adsorption density was 45.9 mg-Li/g by SF reduction at 65 °C, which is almost the same as the theoretical value of 46.0 mg-Li/g. The maximum selectivity over sodium was 2541 by SF reduction at 45 °C. Additionally, it was confirmed that the FP could be recycled by persulfate oxidation without degradation. Finally, the kinetics was studied and fit using pseudo first-order and shrinking sphere model. The two models fit the experimental results and indicated that the lithium extraction - iii - reaction was chemical reaction controlled. Since the FP method was found to be promising, it is highly recommended that it should be developed further by using natural brine sources. - iv - Lay Summary Mobile phones and electric cars always have a battery. Some kinds of battery contain lithium (Li) and are called lithium batteries. As we buy a new mobile phone with better quality and buy an electric car for an eco-friendly lifestyle, Li demand has been increasing. However, with a conventional method using solar heat, it may take more than one year to concentrate lithium from brines, which are saltwater and primary lithium sources. More rapid technologies are required to meet the rapidly increasing demand. This work investigated two extraction techniques using a solid adsorbent with experimental results for speedy lithium recovery. The extraction of lithium was demonstrated as a potential pathway to rapid lithium recovery from saltwater solution. - v - Preface This thesis is original, unpublished, independent work by the author, Hiroki Fukuda. - vi - Table of Contents Abstract ......................................................................................................................................... iii Lay Summary ................................................................................................................................ v Preface ........................................................................................................................................... vi Table of Contents ........................................................................................................................ vii List of Tables ................................................................................................................................. xi List of Figures ............................................................................................................................. xiii Nomenclature ............................................................................................................................. xxi Acknowledgements .................................................................................................................. xxiv Chapter 1. Introduction .......................................................................................................... 1 Chapter 2. Literature Review ................................................................................................. 2 2.1. Lithium Chemistry ............................................................................................................ 2 2.1.1. Electrochemical Properties of Lithium ...................................................................... 2 2.1.2. Lithium Ion Battery.................................................................................................... 3 2.1.3. Eh-pH Diagram .......................................................................................................... 4 2.2. Lithium Market ................................................................................................................. 8 2.2.1. Supply/Demand and Price .......................................................................................... 8 2.2.2. Products and Applications ....................................................................................... 10 2.3. Lithium Deposits ............................................................................................................. 13 2.3.1. Overview .................................................................................................................. 13 2.3.2. Ore Deposits............................................................................................................. 16 2.3.3. Brine Deposits .......................................................................................................... 17 - vii - 2.4. Processes for Lithium Production ................................................................................... 19 2.4.1. Overview .................................................................................................................. 19 2.4.2. Process of Ore Deposits ........................................................................................... 20 2.4.3. Process of Brine Deposits ........................................................................................ 21 2.4.4. Process for Lithium Hydroxide Production ............................................................. 31 2.5. Lithium Extraction Technologies .................................................................................... 33 2.5.1. Overview .................................................................................................................. 33 2.5.2. Phosphate Precipitation ............................................................................................ 35 2.5.3. Ion Exchange Resin ................................................................................................. 36 2.5.4. Al/Mn/Ti-based Adsorbent ...................................................................................... 42 2.5.5. Solvent Extraction .................................................................................................... 43 2.5.6. Membrane Technologies .......................................................................................... 44 2.5.7. Ferric Phosphate Reduction ..................................................................................... 45 2.6. Summary and Objectives ................................................................................................ 56 Chapter 3. Experimental Methods ....................................................................................... 59 3.1. Preparation ...................................................................................................................... 59 3.1.1. Materials .................................................................................................................. 59 3.1.2. Apparatus ................................................................................................................. 63 3.2. Procedures for Lithium Extraction with Ion Exchange Resin ........................................ 64 3.2.1. Preparation of Ion Exchange Resin .........................................................................