Lithium Recovery from Hydraulic Fracturing Flowback and Produced Water using a Manganese-Based Sorbent

• Author / Creator

  Seip, Adam

• Increased demand for lithium products for use in lithium ion batteries has led to a search for new lithium resources in recent years in order to meet projected future consumption. One such potential lithium resource is low lithium bearing brines that are discharged from hydraulically fractured oil and gas wells as flowback and produced water (FPW). In this way, hydraulic fracturing presents an opportunity to turn what is normally considered a wastewater into a lithium resource. In this research, two manganese-based adsorbents that are selective toward lithium were prepared using a co-precipitation method and were employed for lithium recovery from FPW. At optimized conditions, lithium uptake reached 18 mg g-1, with a 􏰀 80% lithium recovery within 30 minutes. The recovered lithium was isolated and concentrated to 15 mM in an acidic final product. The degree of sorbent loss during acid desorption of lithium were significantly higher for sorbents used to recover lithium from FPW as compared to recovery from a synthetic lithium-bearing brine (4.5% versus 0.8%); here, I propose that organic molecules present in the FPW reduce manganese in the sorbent structure during lithium sorption, leading to increased sorbent loss through reductive dissolution. Systematic characterization including wet chemical manganese valence measurements along with EXAFS and XPS show that tetravalent manganese in the sorbent is reduced during lithium sorption, and subsequently dissolves during acid desorption. Partial removal of these organic molecules by nanofiltration leads to decreased sorbent dissolution in acid. I show that dissolved organic molecules represent a critical control on the reductive dissolution of manganese-based lithium ion exchange sorbents.

• Subjects / Keywords

  • Reductive Dissolution
  • Ionic Sieve
  • Manganese Oxide
  • Hydraulic Fracturing
  • Hydrometallurgy
  • Lithium

• Graduation date

  Fall 2020

• Type of Item

  Thesis

• Degree

  Master of Science

• DOI

  https://doi.org/10.7939/r3-e1jv-cp06

• License

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