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At least 37 records · Page 2

Solvent Hold Tank Sample Results for MCU-19-366- 367-368 (April 2019), MCU-19-469-470-471 (May 2019), MCU-19-524-525-526 (June 2019): Quarterly Report

A trend summary of three sets of Solvent Hold Tank (SHT) monthly samples MCU-19-366-367-368 (April), MCU-19-469-470-471 (May), and MCU-19-524-525-526 (June) are reported. Most of the conclusions are based on the June SHT sample (MCU-19-524-525-526). Analyses of the June SHT sample (MCU-19-524- 525-526) indicated that the Modifier (Cs-7SB) and the Extractant (MaxCalix) concentrations were below their nominal recommended concentrations (169,000 mg/L and 46,900 mg/L respectively) by 4% and 2% respectively but consistent with previously observed levels during normal runs. The Suppressor (N,N’,N”– tris(3,7-dimethyloctyl)guanidine or TiDG) concentration has decreased since the March 2019 measurement to 793 mg/L, which is above the minimum recommended concentration (479 mg/L). The Semi-Volatile Organic Analysis (SVOA) did not detect any impurities. However, the Fourier Transform Hydrogen Nuclear Magnetic Resonance (FT-HNMR) analysis detected presence of phthalates at a few ppm. The impurity concentration was highest in the April sample and consistently detected in the May and June samples (but always registered as a few ppm or less). Another impurity observed in the samples was mercury. Based on the June SHT sample, up to 25 ± 5 micrograms of mercury per mL of solvent was detected (as the average of the Direct Mercury Analysis (DMA) and X-Ray Fluorescence (XRF) methods). The higher mercury concentration in the solvent (as determined in the last three-monthly samples) is possibly due to the higher mercury concentration in Salt Batches 9 and 10. The gamma concentration (~2.90E4 dpm/mL) measured in the June 2019 SHT samples was consistent with previous values observed when the Modular Caustic-Side Solvent Extraction Unit (MCU) was operating continuously (for example, between December 2016 and January 2017). Statistical analysis of the different analytical methods detected a bias between the FT-HNMR and the High Performance Liquid Chromatography (HPLC) methods when measuring the MaxCalix and Modifier concentrations; the FT-HNMR gave a higher concentration possibly due to peak overlapping in the measured data. A bias was detected when measuring total mercury by the DMA method versus the XRF method with the XRF method reported higher mercury concentrations. The laboratory will continue to monitor the quality of the solvent for any new impurities or degradation of the solvent components.

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Efficient Fast Fractionation of Biomass Using a Diol-Based Deep Eutectic Solvent for Facilitating Enzymatic Hydrolysis and Obtaining High-Quality Lignin

Current DES pretreatment is often performed under relatively severe conditions with high temperature, long time, and high DES usage. This work studied a short-time diol DES (deep eutectic solvent) pretreatment under mild conditions to fractionate the bamboo, facilitate enzymatic hydrolysis, and obtain high-quality lignin. At an optimized condition of 130 °C for only 10 min, lignin and xylan removal reached 61.34% and 84.15 %, with residual glucan showing a ~90% enzymatic hydrolysis yield. Equally important, the dissolved lignin could be readily recovered with 97.51% yield, exhibiting 96.65 % β-O-4 preservation. The fractionation and lignin protection mechanisms were unveiled by XRD, FTIR, cellulose-DP, 2D HSQC NMR, 31 P NMR and GPC analysis. Finally, this study highlighted that short-time fractionation of bamboo can be achieved by a diol-based DES which is an ideal strategy to upgrade the lignocellulose biomass for high enzymatic hydrolysis yields and high-quality lignin stream.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Conclusions from 3 years of continuous capture plant operation without exchange of the AMP/PZ-based solvent at Niederaussem – insights into solvent degradation management

A many times heard mantra of solvent degradation management in amine-based post combustion capture is “keep the solvent clean” to minimize solvent consumption. It is assumed that the amine losses would decrease by the removal of metals, degradation products, and reactive trace components which are captured from the flue gas, like NO 2 (as potentially driving components of the amine degradation besides dissolved O 2 ). However, this theoretical hypothesis – based on results from laboratory experiments typically generated with fresh amines – disregards the complexity of the solvent matrix, interaction of potential metal catalysts with degradation products and oxidizing agents, and specific chemical requirements which must be fulfilled before a degradation mechanism can proceed. Degradation of the solvent CESAR1 (aqueous solution of 3.0 molar 2-amino-2-methylpropan-1-ol (AMP) and 1.5 molar piperazine (PZ)) is investigated in a unique long-time test campaign (testing time up to now 40 months; 24/7 operation) without replacement of the solvent inventory at the capture pilot plant at the lignite-fired power plant in Niederaussem. Three solvent management strategies with different effect mechanisms are investigated and evaluated: (a) removal of only anionic compounds and trace elements (within 75 days solvent inventory treated two times) and anionic as well as cationic compounds and trace elements (114 days, inventory treated four times) from the solvent by ion exchange, (b) adsorptive removal of trace elements from the solvent by active carbon in 35% of the operating time, and (c) removal of >80% NO 2 by flue gas pretreatment with thiosulfate/sulfite solution (dosing for 2,000 h). The results of the testing program clearly show that “solvent cleanliness” is not a well-defined parameter and that results from laboratory tests, tests without fully representative industrial flue gasses, and short-term testing of monoethanolamine cannot be generalized for other solvents and industrial application. Furthermore, these results showcase that specific degradation management considering solvent, capture plant and flue gas quality is reasonable. Overshooting efforts for solvent management are contra-productive and produce unnecessary waste streams, efficiency losses and costs.

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Improving Surface Quality of Titanium Electrodeposition from a Deep Eutectic Solvent with Organic and Inorganic Additives

Titanium electroreduction is desired for a variety of medical, electronic, and bonding applications but has not been possible until recently. Titanium electrodeposition with leveler and brightener additives in the deep eutectic solvent ethaline has been studied for effects on spectroscopic reflectance. Polymeric leveling agents and several small‐molecule brighteners produce level/bright films (respectively) with high values for both specular and diffuse reflectance. The application of these leveling and brightening agents can produce films with appearances and surface roughnesses that may be suitable for application in medical implants such as stents, corrosion protection of electronics for wearable technology, and as interlayers between dissimilar metals.

deep eutectic solvents↗

Toward a sustainable circular economy of multilayer plastic films: Life cycle and techno-economic assessment with a focus on end-of-life treatment and multiple recovery cycles

This study presents a life cycle assessment (LCA) and techno-economic analysis (TEA) of end-of-life technologies for treating polyethylene–polyamide barrier film waste, focusing on quality degradation across recovery cycles. Novel treatment methods are experimentally validated, while others are drawn from literature and industry consultations. A displacement approach, assuming no quality loss, is first applied. Results show that solvent-based recycling via the solvent-targeted recovery and precipitation (STRAP) process outperforms alternatives across environmental indicators, reducing global warming potential (GWP) by 40% compared to landfilling. Incineration performs worst in most categories, particularly eutrophication (80% higher than landfilling), due to nitrogen emissions. Experimentally validated downcycling (pelletizing) proves more economically viable. The assumption of infinite recoverability is overly optimistic. To address this, we propose a mathematical framework accounting for a finite number of recovery cycles. This refined model shows reduced GWP and cost savings for solvent recovery, making its benefits less pronounced than initially estimated. Sensitivity and uncertainty analyses reveal strong dependence on recovered material quality and solvent recovery efficiency, underscoring the need for optimized process design. Finally, hotspot analysis identifies greenhouse gas emissions from the polyamide supply chain as the dominant GWP contributor. In conclusion, the results underscore potential trade-offs across pathways and show that solvent-based recovery’s sustainability depends heavily on process conditions.

36 MATERIALS SCIENCE↗

Deep Eutectic Solvents for Efficient Fractionation of Lignocellulose to Produce Uncondensed Lignin and High-Quality Cellulose

Simultaneously inhibiting lignin condensation and cellulose degradation remains a major challenge for achieving holistic valorization of lignocellulose. Here, we developed a deep eutectic solvent (DES), composed of l-cysteine (Cys) and lactic acid (LA), to fractionate both uncondensed lignin and high-quality cellulose from eucalyptus wood by leveraging the unique properties of Cys, i.e., highly nucleophilic groups (–SH) and hydrogen bond acceptor/donor groups (–NH 2 and –COOH). The nucleophilic –SH in Cys effectively quenches the benzylic carbocations (C α + ions, formed at the benzylic sites of lignin) that lead to lignin condensation. This enables the high yield of uncondensed lignin (81%) with high retention of β–O–4 bonds (up to 90%). The separated uncondensed lignin is further depolymerized to prepare monophenols in a satisfactory 43% yield, equivalent to 73% of the theoretical yield. Moreover, the –NH 2 and –COOH groups in Cys form extensive hydrogen bonds with the hydroxyl groups in cellulose, thus decreasing the interaction energy of DES on cellulose. As a result, the cellulose achieves an astonishing 99% retention and maintains a high degree of polymerization of 1160. The obtained high-quality cellulose is further conversed into cellulose nanofibers for strong and transparent films. Furthermore, this study provides new insights into the efficient separation of uncondensed lignin and high-quality cellulose from lignocellulose by a novel DES system.

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Production of high-quality polyethylene (PE) films from post-consumer shrink wrap with solvent targeted recovery and precipitation (STRAP)

The solvent-targeted recovery and precipitation (STRAP™) process separates polymers from contaminants present in the feedstock. In this work, we demonstrate the recyclability of a post-consumer waste (PCW) shrink wrap that contains inks, adhesives, and paper using STRAP. We produced a clear rPE cast film from the PCR shrink wrap with no visual contamination from paper or inks. STRAP decreased the ash content from 0.96 wt% to 0.24 wt%. A techno-economic analysis (TEA) shows that a STRAP plant processing 50,000 metric tons annually of shrink wrap waste (purchased at $\$0.25$/kg) containing 85 wt% PE can achieve an IRR of 16.2% when selling rPE at $\$1.30$/kg, an IRR of 10.7% with an rPE price of $\$1.00$/kg, or an IRR of 3.79% with an rPE price of $\$0.70$/kg. Furthermore, the life cycle assessment (LCA) shows a 64% reduction in global warming potential (kg CO 2 equivalent) when compared to the production of virgin LDPE. As a result, this work shows how feedstocks with insoluble impurities can be recycled using STRAP on a large scale.

Radkevich, Elizaveta [University of Wisconsin-Madi↗

Unraveling the Crystallization Kinetics of 2D Perovskites with Sandwich-Type Structure for High-Performance Photovoltaics

2D perovskite solar cells with high stability and high efficiency have attracted significant attention. A systematical static and dynamic structure investigation is carried out to show the details of 2D morphology evolution. A dual additive approach is used, where the synergy between an alkali metal cation and a polar solvent leads to high-quality 2D perovskite films with sandwich-type structures and vertical phase segregation. Such novel structure can induce high-quality 2D slab growth and reduce internal and surface defects, resulting in a high device efficiency of 16.48% with enhanced continuous illumination stability and improved moisture (55-60%) and thermal (85°C) tolerances. Transient absorption spectra reveal the carrier migration from low n to high n species with different kinetics. An [PbI 6 ] 4- octagon coalescence transformation mechanism coupled with metal and organic cations wrapped is proposed. By solvent vapor annealing, a recrystallization and reorientation of the 2D perovskite slabs occurs to form an ideal structure with improved device performance and stability.

36 MATERIALS SCIENCE↗

Extraction, Scrub, and Strip Test Results for the IBC BOBCalix Solvent Samples

A second vendor for solvent extraction components has been chosen for use at the Salt Waste Processing Facility (SWPF). IBC Advanced Technologies (IBC) has provided samples of their BOBCalix, as well as complete solvent. These samples were tested for quality assurance purposes to ensure their use at SWPF is acceptable. Two Extraction, Scrub, and Strip (ESS) tests were performed on solvent samples from IBC. The purpose of testing these samples was to determine if the solvents are displaying the correct extraction and stripping behavior with cesium.

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Effect of Aromatic Solvents Residuals on Electron Mobility of Organic Single Crystals

Balanced electron and hole transport properties are essential for various organic electrical/optoelectrical applications such as organic solar cells, complementary circuits, and light-emitting transistors. However, the electron transport in organic semiconductor lags far behind the hole side, making it with vital significance to seek the factors that limit the electron mobility. Here, the authors demonstrate that the π-conjugated solvents, as essential components in the widely-used solution processing techniques, can significantly suppress the electron transport if they are not properly removed and trapped as residuals. Single crystals of typical p-type materials exhibit a transition from p-type behavior to ambipolar conductance via reducing the amount of solvent residuals, and the same effect is confirmed by varied p-type materials and solvents. The highest electron mobility reaches 0.027 cm 2 V –1 s –1 and 0.029 cm 2 V –1 s –1 for 6,13-bis(triisopropylsilylethynyl)pentacene and 5,15-bis(triisopropylsilylethynyl)tetrabenzoporphyrin, respectively. Finally, this work discloses the non-negligible existence of solvent residuals even in high quality, long-range ordered organic single crystals, and further provides efficient strategies to harvest the n-type behaviors of organic semiconductor materials.

36 MATERIALS SCIENCE↗

Life of Pennzane and 815Z-Lubricated Instrument Bearings Cleaned with Non-CFC Solvents

This report takes the form of two papers: (1) "Life of Pennzane and 815Z-Lubricated Instrument Bearings cleaned with Non-CFC Solvents" and (2) a published paper, entitled "Instrument bearing life with NON-CFC cleaners". Abstract for paper # 1 : Bearings used in spacecraft mechanisms have historically been cleaned with chlorofluorocarbon CFC-1 13 (Freon) solvents and lubricated with a perfluorinated polyalkylether (PFPE) oils like 815-Z. Little full-scale bearing life test data exists to evaluate the effects of the newer class environmental-friendly bearing cleaners or improved synthetic hydrocarbon space oils like Pennzane. To address the lack of data, a cooperative, bearing life test program was initiated between NASA, Lockheed Martin and MPB. The objective was to obtain comparative long-term, life test data for flight-quality bearings, cleaned with non-CFC solvents versus CFC-1 13 under flight-like conditions with two space oils. A goal was to gain a better understanding of the lubricant surface chemistry effects with such solvents. A second objective was to obtain well-controlled, full-scale bearing life test data with a relatively new synthetic oil (Pennzane), touted as an improvement to Bray 815Z, an oil with considerable space flight history. The second paper, which serves as an attachment, is abstracted below: Bearings used in spacecraft mechanisms have historically been cleaned with chlorofluorocarbon CFC-113 (Freon) solvents and lubricated with a perfluorinated polyalkylether (PFPE) oils like 815-Z. Little full-scale bearing life test data exists to evaluate the effects of the newer class environmental-friendly bearing cleaners or improved synthetic hydrocarbon space oils like Pennzane. To address the lack of data, a cooperative, bearing life test program was initiated between NASA, Lockheed Martin and MPB. The objective was to obtain comparative long-term, life test data for flight-quality bearings, cleaned with non-CFC solvents versus CFC-1 13 under flight-like conditions with two space oils. A goal was to gain a better understanding of the lubricant surface chemistry effects with such solvents. A second objective was to obtain well-controlled, full-scale bearing life test data with a relatively new synthetic oil (Pennzane), touted as an improvement to Bray 815Z, an oil with considerable space flight history.

Loewenthal, Stuart↗

Complementary roles for mechanical and solvent-based recycling in low-carbon, circular polypropylene

Plastic recycling presents a vexing challenge. Mechanical recycling offers substantial greenhouse gas emissions savings relative to virgin plastic production but suffers from degraded aesthetic and mechanical properties. Polypropylene, one of the most widely used and lowest-cost plastics, features methyl pendants along the polymer backbone, rendering it particularly susceptible to declining properties, performance, and aesthetics across a succession of mechanical recycles. Advanced processes, such as solvent-assisted recycling, promise near-virgin quality outputs at a greater energy and emissions footprint. Mechanical and advanced recycling are often presented as competing options, but real-world plastic waste streams are likely to require preprocessing regardless of whether they are routed to an advanced process. This study quantifies the life-cycle greenhouse gas implications of multiple recycling strategies and proposes a system in which mechanical and solvent-assisted recycling can be leveraged together to boost recycling rates and satisfy demand for a wider range of product applications. Polypropylene can be recovered from mixed-plastic bales produced at material recovery facilities and processed through mechanical recycling, with a varying fraction sent for further upgrading via solvent-assisted recycling to produce material approved for food packaging and other higher-quality applications. The resulting mechanically recycled rigid polypropylene reduces life-cycle greenhouse gas emissions by 80% relative to the same quantity of virgin material, while the upgraded higher-quality material achieves GHG savings of 30%.

36 MATERIALS SCIENCE↗

Expanding Parameter Space to Enable Low-Temperature Synthesis of Crystalline Indium Phosphide Quantum Dots

Established methods to synthesize indium phosphide quantum dots (QDs) require high temperatures (>180 °C) to make high-quality material for optoelectronic applications. Nonpolar solvent environments are overwhelmingly used in InP QD synthesis to reach the necessary high temperatures and for compatibility with the reactive precursors. In this study, we explored InP QD synthesis in polar aprotic solvent environments to dramatically decrease the temperature required for InP crystallization by imparting ionicity to the precursors and stabilizing charged reaction intermediates. A custom air-free 96- well plate setup was employed to identify key factors impacting low-temperature QD formation, including an increased percentage of polar solvent, carboxylic acid choice, and inclusion of polar additives. Guided by these insights, we developed a synthesis of crystalline, green-emitting InP QDs at 60 °C in a toluene-dimethylformamide mixture. Here's, the QDs withstood established Zn 2+ and HF surface treatments, which increased the photoluminescence quantum yield to 25%. Additionally, we demonstrated the rapid synthesis of quasi-wurtzite InP QDs at room temperature in a polar solvent environment using an acid-free indium myristate precursor.

absorption↗

High-purity Polypropylene from Disposable Face Masks via Solvent-Targeted Recovery and Precipitation

The high use of disposable face masks since the start of COVID-19 has globally generated 4.68–6.24 million tons per year of waste from personal protective equipment. Disposable face masks are generally disposed of in landfills. Polypropylene (PP) is the main component in face masks, which is one of the least recycled plastics but has a high market value. In this work, we extract high-quality PP from face masks using solvent-targeted recovery and precipitation (STRAP) with 90 wt% recovery. N,N-Dimethylacetamide removed the color from the recovered PP to produce a clear high-purity PP, as verified by CIELAB color space. The decolored PP shows similar thermochemical properties and color to virgin PP resin. Here, a techno-economic analysis of the process indicates that high-purity PP recovery can be economically viable at a scale of 5000 tons per year or higher.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Low-temperature electroplating of zirconium: Ionic mixture methods

Non-aqueous ionic mixture electroplating allows for room-temperature or near-room-temperature applications of thin metal films, typically metals for which aqueous solvents cannot be used. While there are many methods of plating zirconium, each has disadvantages that ionic liquid plating could correct. However, ionic liquid plating requires further research and development, as a new class of solvents were only developed a few years ago. Current ionic liquids cost several thousand dollars per liter, yet produce films with less than 90% surface coverage as well as deposition of salt species that enable interdiffusion through the Zr. Film coverage needs to be increased while maintaining approximate room temperatures and lower solvent costs. Current ionic liquid technology has suffered from poor surface wetting and limited Zr diffusivity leading to dendrite formation which inhibits total surface coverage. Zr electroplating can be improved by application of room-temperature ionic mixtures as the plating medium. We have successfully demonstrated the capability to plate high-quality metallic zirconium layers using deep eutectic solvents (DES) and DES-ionic liquid (IL) mixtures. Plating thicknesses of up to 6 microns have been achieved, and the coatings are conformal to the substrate and not dendritic, with low contamination from the plating solution. Our current method uses the DES ethaline (a 1:2 ratio of choline chloride and ethylene glycol) to complex zirconium (IV) ions (present via the addition of ZrF4). We pulse plate the Zr from a bath with an overabundance of LiF, in accordance with prior literature. We have also had success in mixing the DES with ILs, such as Triethylsulfonium bis(trifluoromethylsulfonyl)imide, 1-Butyl-3-methylpyridinium bis(trifluormethylsulfonyl)imide, Methyl-trioctylammonium bis(trifluoromethylsulfonyl)imide, and Diethylmethyl(2-methoxyethyl)ammonium bis(trifluoromethylsulfonyl)imide.

36 MATERIALS SCIENCE↗

Solvent-based plastic recycling technologies

Solvent-based recycling approaches are receiving industrial and academic interest for their ability to produce high-quality plastic resins from a variety of plastic waste sources without breaking the polymer chains. Here we highlight the development of solvent-based technologies, focusing on the underlying principles, techno-economic and life-cycle analyses, and commercialization. The basic steps in solvent-based recycling include plastic size reduction, plastic dissolution, filtration or centrifugation, and optional additional cleaning steps such as adsorption, precipitation and solvent removal. Impurities that build up in the solvent must also be removed. The goal of solvent-based technologies is to produce a high-quality resin without plastic contaminants or other added substances. Disadvantages of these solvent-based technologies are their physicochemical complexity and the difficulty in scaling up to achieve continuous operations with high polymer and solvent yields and throughputs. As a result, chemical engineering is thus critical in bringing solvent-based recycling technologies to market.

Chemical engineering↗

Crystal growth in fused solvent systems

The successful nucleation of bismuth germanate, B12GeO20 on a high quality seed and the growth of regions of single crystals of the same orientation of the seed are reported. Lead germanate, Pb5Ge3O11 was also identified as a ferroelectric crystal with large electrooptic and nonlinear optic constants. Solvent criteria, solvent/development, and crystal growth are discussed, and recommendations for future studies are included.

Ulrich, D. R.↗

Scalable aqueous-phase fabrication of reduced graphene oxide nanofiltration membranes by an integrated roll-to-roll (R2R) process

Economic fractionation of multicomponent biomass-derived streams is a key challenge in biobased fuels and chemicals production. Kraft black liquor (BL) is generated at ~1 billion tons/yr globally from biomass pulping and contains ~15wt% total solids including lignin, hemicellulose fragments, and inorganics. Membrane-based BL concentration is attractive but challenged by low solute rejections and poor stability in BL, which combines alkaline pH (~13), high dissolved solids content (15+ wt%) and high temperature (70–85°C). Here we discuss the scaled fabrication and characterization of reduced graphene oxide (rGO) nanofiltration membranes by slot die coating on a roll-to-roll (R2R) with integrated vacuum filtration. Here, we obtain high-quality 90×30 cm rGO membranes (referred to as “R2R-rGO membranes” in this work) with ~100 nm average thickness supported on porous poly(ethersulfone) (PES) sheets, and an effective area of 2700cm 2 . We present characterizations of their microstructure and uniformity as mapped over large areas by scanning electron microscopy (SEM), ellipsometry, adhesion test and X-ray photoelectron spectroscopy (XPS). The constructed ellipsometry model for the rGO membrane/PES substrate composite was successfully applied to 48 different locations of the R2R-rGO membranes. The R2R-rGO membranes showed >98% lignin rejection with a steady state flux of ~12 LMH at 50bar in a 15.7wt% total solids (TS) kraft BL stream at 72°C and 2–3 gal/min crossflow rates. Slot die coating on a R2R platform with integrated vacuum filtration can enable rapid fabrication of high-quality GO membranes at scale without organic solvents or volatile organic compounds.

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