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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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Implementation and evaluation of multi-dual mode counter-current chromatography in the CUP Modeler software

Counter-current chromatography (CCC) is a separation technique that utilizes immiscible solvent pairs as stationary and mobile phases, which imparts numerous benefits compared to solid-liquid chromatography including the ability to treat either the more-dense or less-dense solvent layer as the mobile phase. Multi-dual mode (MDM) is a CCC elution mode capable of improving the separation of closely eluting compounds by alternating upper- and lower-layer solvent flows in opposing directions within the same separation. While some effort has been made to model MDM, implementation of these models in experimental design has yet to be widely adopted. Accordingly, we further developed our previously published cell utilized partitioning (CUP) model to include MDM predictions with CCC and packaged the full suite of CUP modeling capabilities into a user-friendly, open-source tool called the CUP Modeler. The mathematical model for MDM CCC was derived and validated with experimental separation of ethyl guaiacol (EG) and ethyl phenol (EP), two compounds that co-elute in our previously demonstrated reductive catalytic fractionation (RCF) lignin monomer isolation method. The developed MDM model provided insights into the effect of multiple operating parameters - including stationary phase retention, flow rate, column efficiency, feed concentration ratio, selectivity factor, and solute distribution ratios - on the separation yields, productivity, and purities. Our model agreed with prevailing understanding of MDM but also revealed new insights including that the ideal distribution ratios for co-eluting solutes to be separated by MDM is between 1.1 and 1.5, with the lower value ideally close to 1.25. Overall, this work provides fundamental insights for MDM process design and enables broader adoption of general liquid-liquid chromatography with a new, open-source user-friendly interface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Task 2.3: Continuous Counter-Current Chromatography

This task in the Separations Consortium focuses on the development of counter-current chromatography (CCC), which is an advanced liquid-liquid chromatography method. Today, CCC is primarily practiced in batch mode operation, but continuous operation will be required for at-scale deployment in a biorefinery setting. In this task, we are developing a continuous CCC process in collaboration with a company that builds CCC units. This work will be demonstrated on the biorefining challenge of lignin valorization. Specifically, we demonstrate use of continuous CCC for both monomer-monomer and monomer-oligomer separations in multiple lignin streams of relevance to the biorefining industry. Breakthroughs in this area would be useful for BETO goals in both sustainable aviation fuel and biochemicals production, including directly contributing to BETO's 2030 lignin valorization goal. Our approach includes developing new computational modeling approaches to optimize both batch and continuous CCC processes, experimental work to determine optimal solvent systems for multiple lignin streams sourced from BETO-funded projects and industrial collaborators, and techno-economic analysis and life cycle assessment to identify the most impactful areas to ultimately enable this approach in the biorefinery. This task overall will enable high-resolution, multi-component, continuous separations at scale, demonstrated on a grand challenge biorefining problem.

BIOMASS FUELS↗

Separation of rare earth element radioisotopes by reverse-phase high-speed counter-current chromatography

Analytical scale purification of rare earth element (REE) radioisotopes is typically accomplished using cation-exchange resins (e.g. AG 50W-X8) and high-performance liquid chromatography (HPLC). Despite the variety of improvements made since the development of this separation process in the 1950s, nearest neighbor separations remain a challenge, as does the issue of irreversible sample adsorption. Herein, we report a study that evaluates the potential of high-speed counter-current chromatography (HSCCC) as an alternative method for purifying REE elements, with specific reference to separations of fission product REE of interest to nuclear forensics. Complementary HSCCC REE separation experiments, one spiked with radiotracer and REE fission product activity, allowed for in depth analysis of resulting fractions from both an elemental (inductively coupled plasma atomic emission spectroscopy, ICP-AES) and radiological (gamma-ray spectrometry, beta counting) purity perspective. The highly reproducible nature of separation profiles generated from HSCCC instruments was leveraged to simplify work-up of samples containing radioisotopes. Subsequent radioanalytical evaluation revealed minimal carryover of Eu into neighboring Sm and Tb fractions (as indicated by presence of 150Eu), and trace contamination of the Tb fraction with Y (as indicated by presence of 91Y). Subtle differences in stationary phase retention across the two columns were reflected in significant variations in decontamination factors of duplicate parallel separations. Furthermore, these differences paired with obtained distribution of radioisotopes provided valuable insights into future improvements. Collectively, this study represents a significant step forward in development of HSCCC technology for task specific REE radioisotope purification.

07 ISOTOPE AND RADIATION SOURCES↗

147 Nd Quantification Using HSCCC-Purified Samples

Quantifying the fission product 147 Nd in nuclear debris samples is an important component of post-detonation nuclear forensics. The most accurate quantifications are obtained when Nd is purified from all other fission products, actinides, activation products, and environmental matrix contained within the debris. In this study, a recently developed method for Nd purification was tested, purifying 147 Nd from solutions of mixed fission products using high-speed counter-current chromatography (HSCCC). Importantly, the new method allowed for faster elution of Nd from the column as compared with established high performance liquid chromatography (HPLC) methods, and resulted in accurate/precise 147 Nd quantification by gamma-ray spectrometry. While the up-front equipment costs associated with HSCCC may be higher, its operational costs are on par with those of HPLC (solvents, extractants, power). Gas-flow proportional beta decay counting revealed contamination from the nearest neighbor lanthanide 143 Pr (a gamma-silent radioisotope) in the HSCCC-purified samples, but the activity contribution from 147 Nd could still be quantified. Remarkably consistent elution profiles were observed for the HSCCC method, spanning rare earth element (REE) loadings of more than 10 orders of magnitude (tracer to mmol quantities). In conclusion, the reliability and speed of the new method suggest utility for the rapid separation and quantification of 147 Nd in unknown samples.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Extraction, purification, and reuse of dyes from coloured polyester textiles

The removal of dyes from coloured textile waste represents a sustainable approach to textile recycling, enabling the recovery of valuable chemical, and material resources that would otherwise be discarded. Up to 40% of the greenhouse gas emissions from textiles originate from dye production, making efficient recycling of dyes a major opportunity for curbing emissions and minimizing waste in both textile manufacturing and recycling. Here, in this study, we demonstrate a process for the extraction, purification, and reuse of mixed dyes from polyester textiles using bio-based, non-hazardous solvents selected on the basis of computational predictions for polyester and dye solubilities. Extracted dyes are purified to individual compounds using counter-current chromatography and analysed via liquid chromatography-mass spectrometry. Post-extraction characterization of the extracted dyes and polymer substrate confirms dye colour retention and polyester fabric property preservation. Dye recycling is demonstrated by redyeing colour-free fabrics with the recovered dyes. We further show a potential process configuration for dye removal using a flow-through reactor packed with a textile substrate. The proposed dye removal process produces reusable, recyclable dyes, and dye-free fabrics, thus facilitating textile recycling.

36 MATERIALS SCIENCE↗

Ni Mediated Carboxylation and Oxidation of PE to C12/C14 Fatty Acids: Cooperative Research and Development Final Report, CRADA Number CRD-22-22451

Given its chemical structure, polyethylene (PE) waste may be a viable feedstock for the production of linear fatty alcohols (FALCs), a major surfactant produced either from palm kernel oil, vegetable oils, or via synthetic pathways that are associated with high carbon footprint. The BOTTLE Consortium will collaborate with Procter & Gamble (P&G) to develop FALCs from waste PE feedstocks.

09 BIOMASS FUELS↗