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Chemical-Free Lithium Separation from High-Salinity Brines Using Model-Informed and Machine Learning-Optimized Multi-Column Zwitterionic Chromatography

Direct Lithium Extraction (DLE) technologies often struggle to produce high-purity lithium salts from high-salinity brines, as current approaches require chemical-based elution, regeneration, and precipitation steps, resulting in significant environmental footprints. A novel salt fractionation approach using carboxybetaine resin, known as zwitterionic chromatography (ZIC), has demonstrated that lithium ions can be separated from divalent cations under high-salinity conditions using only water as eluent, with no regeneration required. To enable continuous and scalable deployment of this approach, we developed a chemical-free Multi-column Zwitterionic Chromatography (MZC) process and its theoretical and process models. To predict and optimize this nontraditional separation system, we introduced a novel anti-Langmuir isotherm, and the isotherm parameters were estimated through a machine learning-driven optimization based on artificial neural network ensembles with numerical feasibility assessment. Using machine learning-driven optimization, the MZC process achieved 98.0% lithium recovery, 99.5 % Li/(Li + Mg + Ca) purity, a 31.3% productivity increase, and a 33% reduction in water use compared to batch operation. The proposed MZC process enables lithium separation at $0.6-1.2 kg-1 Li, with costs dominated by resin manufacturing, while offering lower separation costs and carbon footprint compared with conventional carbonation. Overall, these findings position the MZC process as an effective polishing step within scalable and sustainable lithium production pipelines.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Novel Zwitterionic Chromatography Approach to Separate Lithium from Unconventional Resources

Lithium (Li) is a key element for clean energy technologies, and, accordingly, the global lithium demand has been increasing rapidly. Therefore, to meet the Li demand and maintain supply chain stability, it is critical to develop efficient lithium extraction technologies that allow exploitation of unconventional lithium resources, such as geothermal brines and inland brine streams. However, the recovery of Li from these resources is challenging due to low Li concentration, low ratios of Li/Na, Li/Mg, or Li/Ca, and complex feed compositions. To address this, we introduced a new Direct Lithium Extraction (DLE) process using Zwitterionic Chromatography (ZIC) to separate Li from other salts. Since salts are partitioned on ZIC under water elution, no reagent chemicals are needed, and the Li separation is not limited by the adsorption capacity. We prepared 13 different zwitterionic (ZI) resins to investigate the salt retention on various ZI groups and then screened out promising sorbents for efficient Li separation. It was found that salt retention was synergistically affected by the pore size and ZI configurations. Using carboxybetaine (QAC3CA) sorbents, multicomponent separations showed that Li can be partitioned from divalent salts or Na with selectivities of 1.8 or 1.9, respectively. Although the selectivity is relatively low, in real brine tests, Li was separated from Ca and Mg with 79.2 % yield, showing the potential for a continuous process to achieve high productivity and high yield. Simulation studies suggest the salt elution mechanism is related to the hydration reaction energy and the effective hydrated radius of cations.

critical minerals↗

Novel Zwitterionic Chromatography to Separate Lithium from Unconventional Resources

Since lithium (Li) is a key element for clean energy technologies, the global lithium demand is anticipated to increase rapidly. As a result, efficient lithium extraction technologies that allow the exploitation of unconventional lithium resources, such as geothermal brines and inland brine streams, are essentially needed to meet the Li demand and keep supply chains stable. However, because of low Li concentration, low ratio of Li/Mg or Li/Ca, and complex feed compositions in these feedstocks, using conventional hydrometallurgy or current Direct Lithium Extraction (DLE) processes are often chemical-intensive, requiring substantial amounts of reagent chemicals to recover Li at scale, resulting in large chemical footprints. Therefore, we developed a novel Zwitterionic Chromatography (ZIC) process to separate Li from these resources. Because Li can be partitioned from divalent salts on ZIC under water elution without using chemicals, exploiting the unconventional resources via a ZIC approach can be environmentally benign and sustainable. In this work, we will present the development of the ZIC process for DLE applications. Simulation studies for the Li separation mechanism in ZIC and the demonstration of a continuous ZIC process to separate Li from domestic inland brine and mining wastewater will be presented. Finally, the chemical and energy footprints of ZIC in comparison to other DLE processes will be discussed.

09 BIOMASS FUELS↗

"Lignin First" Catalytic Biomass Fractionation: Cooperative Research and Development (Final Report)

In this work, a continuous zwitterionic chromatography using simulated moving beds will be conducted to separate Li and Mg from brines. The existing program that ExxonMobil is carrying out with Clariant and Genomatica is consistent with all pioneer cellulosic fuels plants inasmuch as biomass enters the facility and is processed, in its entirety, through at least the hydrolysis step of biochemical conversion. This approach creates significant operating challenges as biomass can vary widely in composition and mechanical properties across and within a given biomass type. The proposed program involves a first step fractionation using solvolysis and reductive catalysis to generate a lignin oil containing well-defined monomers, dimers, and oligomers and a delignified cellulose/ hemicellulose pulp. The amount of lignin oil vs pulp and the type of monomers produced are expected to vary with biomass type due to differences in lignin composition and chemistry.

09 BIOMASS FUELS↗

Separation of Lithium and Magnesium from Brines Using Zwitterionic Simulated Moving Beds: Cooperative Research and Development (Final Report)

The purpose of this work was to separate lithium and magnesium from lithium-containing brines by applying a zwitterionic simulated moving bed (zSMB) system that NLR developed. This work was needed to validate lithium and magnesium separation for future development at scale. Below is a summary of the tasks outlined in the Statement of Work and the results that were generated.

36 MATERIALS SCIENCE↗

Deep eutectic solvents as green and sustainable diluents in headspace gas chromatography for the determination of trace level genotoxic impurities in pharmaceuticals

Genotoxic impurities (GTIs) are potential carcinogens that need to be controlled down to ppm or lower concentration levels in pharmaceuticals under strict regulations. The static headspace gas chromatography (HS-GC) coupled with electron capture detection (ECD) is an effective approach to monitor halogenated and nitroaromatic genotoxins. Deep eutectic solvents (DESs) possess tunable physico-chemical properties and low vapor pressure for HS-GC methods. In this study, zwitterionic and non-ionic DESs have been used for the first time to develop and validate a sensitive analytical method for the analysis of 24 genotoxins at sub-ppm concentrations. Compared to non-ionic diluents, zwitterionic DESs produced exceptional analytical performance and the betaine: 7 (1,4- butane diol) DES outperformed the betaine: 5 (1,4-butane diol) DES. Limits of detection (LOD) down to the 5-ppb concentration level were achieved in DESs. Wide linear ranges spanning over 5 orders of magnitude (0.005–100 µg g –1 ) were obtained for most analytes with exceptional sensitivities and high precision. The method accuracy and precision were validated using 3 commercially available drug substances and excellent recoveries were obtained. Finally, this study broadens the applicability of HS-GC in the determination of less volatile GTIs by establishing DESs as viable diluent substitutes for organic solvents in routine pharmaceutical analysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Changes in environmental and engineered conditions alter the plasma membrane lipidome of fractured shale bacteria

ABSTRACT Microorganisms that persist in fractured shale reservoirs cause several problems including secreting foul gases and forming biofilms. Current biocontrol measures often fail due to limited knowledge of their in situ activities. The plasma membrane protects the cell, mediates many of its critical functions, and responds to intracellular cues and ecological perturbations through physicochemical modifications. As such, it provides valuable insight into the physiological adaptation of microorganisms in disturbed environmental systems. Here, we (i) demonstrate how changes in salinity and hydraulic retention time (HRT) influence the plasma membrane intact polar lipid (IPL) chemistry of model bacterium, Halanaerobium congolense WG10, and mixed microbial consortia enriched from shale-produced fluids and (ii) elucidate adjustments in membrane IPL chemistry during biofilm growth relative to planktonic cells. We incubated H. congolense WG10 in chemostats under three salinities (7%, 13%, and 20% NaCl), operated under three HRTs (19.2, 24, and 48 h), and in drip flow biofilm reactors under the same salinity gradients. Also, mixed microbial consortia in produced fluids were enriched in triplicate chemostat vessels under three HRTs (19.2, 24, and 72 h) and biofilm reactors. Lipids were analyzed by ultra high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). Our results show that phosphatidylglycerols, cardiolipins, and phosphatidylethanolamines were predominantly enriched in planktonic H. congolense WG10 cells grown at hypersalinity (20%) compared to optimum (13%). In addition, several zwitterionic phosphatidylcholines and phosphatidylethanolamines were higher in abundance during biofilm growth. These observations suggest that microbial adaptation and biofilm formation in fractured shale are enabled by strategic plasma membrane IPL chemistry adjustments. IMPORTANCE Microorganisms inadvertently introduced into the shale reservoir during fracturing face multiple stressors including brine-level salinities and starvation. However, some anaerobic halotolerant bacteria adapt and persist for long periods of time. They produce hydrogen sulfide, which sours the reservoir and corrodes engineering infrastructure. In addition, they form biofilms on rock matrices, which decrease shale permeability and clog fracture networks. These reduce well productivity and increase extraction costs. Under stress, microbes remodel their plasma membrane to optimize its roles in protection and mediating cellular processes such as signaling, transport, and energy metabolism. Hence, by observing changes in the membrane lipidome of model shale bacteria, Halanaerobium congolense WG10, and mixed consortia enriched from produced fluids under varying subsurface conditions and growth modes, we provide insight that advances our knowledge of the fractured shale biosystem. We also offer data-driven recommendations for improving biocontrol efficacy and the efficiency of energy recovery from unconventional formations.

03 NATURAL GAS↗