Search NASA⌕ Search

SEARCH · Search NASA

Results for “carbonate solvent”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 127 records · Page 7

Regenerable solvents mediate accelerated low temperature CO 2 capture and carbon mineralization of ash and nano-scale calcium carbonate formation

The dual need to remove CO 2 from our emissions and treat alkaline industrial residues such as ash materials motivate the design of innovative pathways to simultaneously capture and convert CO 2 into mineralized carbonates. Direct carbon mineralization is one approach that addresses the need to simultaneously treat alkaline industrial residues and mineralize CO 2 emissions. Low CO 2 solubility in water and slow kinetics at ambient temperature have challenged the direct carbon mineralization of alkaline industrial residues. Here, to address these challenges, the use of CO 2 capture solvents that enhance CO 2 solubility and facilitate accelerated carbon mineralization of fly ash at temperatures below 90 °C is investigated. Calcium carbonate formation results in the inherent regeneration of the solvent. The carbon mineralization extents of non-calcium carbonate content in fly ash were 50% and 51% and in waste ash were 58% and 62% in 2.5 M sodium glycinate and 30 wt% MEA solutions, respectively. The experiments were performed at 50 °C for 3 hours with CO 2 partial pressure of 1 atm in a continuously stirred slurry environment with 15 wt.% solid. Furthermore, nanoscale CaCO 3 is successfully synthesized from dissolved calcium using CO 2 -loaded sodium glycinate and surfactants such as CTAB (Cetyl Trimethyl Ammonium Bromide). Surfactants such as CTAB bind to the calcium carbonate surface and regulate the growth of calcium carbonate particles. These innovative approaches demonstrate the feasibility of directly storing CO 2 in fly ash and waste ash as calcium carbonate and producing nanoscale calcium carbonate using regenerable CO 2 capture solvents.

42 ENGINEERING↗

Energy-efficient carbon capture from industrial point sources via commercially available green solvent and hollow fiber membrane contactors

Solvent-based absorption systems have emerged in the carbon capture space due to their high absorption capacities, reusability, and favorable energy requirements. Using diethyl sebacate as a solvent for pre- and post-combustion carbon capture has advantages over other solvents, including high hydrophobicity, low viscosity, low vapor pressure, high CO 2 solubility, high CO 2 selectivity, and being commercially available in large quantities. Despite these advantageous properties, the use of diethyl sebacate as a solvent for post-combustion carbon capture has not been studied in detail. To examine the capability of diethyl sebacate, a scalable, energy-efficient, hollow fiber membrane (microporous polypropylene and polyvinylidene fluoride) contactor (HFMC)-based process with low-cost and high surface area is investigated. A purity of 95.3 % CO 2 with 46 % recovery in one absorption stage was achieved, with a permeate flux over one magnitude greater than using a deep eutectic solvent in the same system. Technoeconomic analysis determined a ∼ 0.8 GJ per ton of CO 2 at a processing cost of ∼$93 per ton of CO 2 . Results from this work underscore the potential for utilizing green solvents in HFMC-based separation processes for effective carbon capture and provide a pathway towards practical deployment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Off-Design Load Analysis of sCO2 Bottoming Cycle for a Natural Gas Combined Cycle Power Plant with Carbon Capture

As an alternative to a steam cycle, a supercritical carbon dioxide (sCO2) power cycle can be considered. Able et. al performed an analysis of an sCO2 cycle in a 2x2-1 configuration; however, this study did not include carbon capture. Previous studies assumed an H-Frame turbine and added a solvent based 95% carbon capture system and performed a levelized cost of electricity (LCOE) optimization for the plant. Their results suggest a LCOE slightly better than when using a steam cycle. In the study, steam is still generated in the heat recovery sections for the solvent regeneration in the carbon capture stripper reboiler. H-Frame gas turbines are also assumed. This work starts with the optimal design from the mentioned work to analyze the off-design performance of the power plant from 100% down to 50% load. The main operational findings and plant-efficiency for off-load conditions while maintaining the target CO2 capture rate are presented. H-Frame gas turbine off-design performance and exhaust conditions to the heat recovery section are obtained from commercial software, Thermoflow®. The CO2 turbomachinery, heat exchangers and other unit operations are sized and implemented in an Aspen Plus® model. Using the gas turbine exhaust conditions as input, the sCO2 cycle is optimized by adjusting stream split ratios, sCO2 circulation flowrate and compressor speed for maximum efficiency. This is done while keeping the target 95% CO2 capture.

Chinen, Anderson Soares↗

Process for producing an activated carbon adsorbent with integral heat transfer apparatus

A process for producing an integral adsorbent-heat exchanger apparatus useful in ammonia refrigerant heat pump systems. In one embodiment, the process wets an activated carbon particles-solvent mixture with a binder-solvent mixture, presses the binder wetted activated carbon mixture on a metal tube surface and thereafter pyrolyzes the mixture to form a bonded activated carbon matrix adjoined to the tube surface. The integral apparatus can be easily and inexpensively produced by the process in large quantities.

Jones, Jack A.↗

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↗

Beta-Amino Carboxylate (BAC) non-aqueous physical solvents for enhanced CO2 separations in pre-combustion carbon capture, industrial CO 2 capture, and biogas upgrading processes

Novel beta-amino carboxylate (BAC) solvents have been synthesized and tested to efficiently capture carbon dioxide (CO 2 ) from process gas streams with CO 2 partial pressure intermediate between pre-combustion and post-combustion capture. The BAC solvents have molecular structures characterized by alkyl-substituted amides or esters containing a secondary amine functional group on the second carbon from the carbonyl carbon (referred to as the beta “β” carbon). The ester or amide functional group combined with optimal steric crowding around the amine nitrogen by proximate alkyl groups are tailored to modify the strength of CO 2 binding in the solvent. The solvents possess high CO 2 solubilities and high gas selectivity including good CO 2 /H 2 O selectivity and can be utilized for CO 2 absorption over a range of partial pressures. Due to low volatility, many of the solvents can be operated at or above ambient temperature which eliminates solvent chilling and allows regeneration using low grade waste heat. These novel solvents offer an opportunity for efficient carbon capture for a range of applications including biogas upgrading, hydrogen production, and pre-combustion carbon capture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Removing Biostatic Agents From Fermentation Solutions

Liquid carbon dioxide inexpensive solvent. Inexpensive process proposed for removing such poisons as furfural and related compounds from fermentation baths of biomass hydrolysates. New process based on use of liquid carbon dioxide as extraction solvent. Liquid CO2 preferable to such other liquid solvents as ether or methylene chloride.

Du Fresne, E. R.↗

Solvent-induced electrochemistry at an electrically asymmetric carbon Janus particle

Chemical doping through heteroatom substitution is often used to control the Fermi level of semiconductor materials. Doping also occurs when surface adsorbed molecules modify the Fermi level of low dimensional materials such as carbon nanotubes. A gradient in dopant concentration, and hence the chemical potential, across such a material generates usable electrical current. This opens up the possibility of creating asymmetric catalytic particles capable of generating voltage from a surrounding solvent that imposes such a gradient, enabling electrochemical transformations. In this work, we report that symmetry-broken carbon particles comprised of high surface area single-walled carbon nanotube networks can effectively convert exothermic solvent adsorption into usable electrical potential, turning over electrochemical redox processes in situ with no external power supply. The results from ferrocene oxidation and the selective electro-oxidation of alcohols underscore the potential of solvent powered electrocatalytic particles to extend electrochemical transformation to various environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mechanisms and Energetics of CO 2 Chemisorption in Choline-Based Eutectic Solvents

Understanding the influences of proton sharing and hydrogen transfer in amine and hydroxyl functionalized eutectic solvents is important for tuning CO 2 binding as they relate to the chemisorption capacity and energetics of solvent regeneration in carbon capture. In this study, we examine how the CO 2 binding mechanism and energetics vary in eutectic solvents composed of choline-based hydrogen-bond acceptors (HBAs) with amine and hydroxyl moieties and ethylene glycol (EG), propylene glycol (PG), 1,2-butanediol (BD), and monoethanolamine (MEA)-type hydrogen-bond donors (HBDs), through absorption–desorption experiments and spectral analysis, supported with density functional theory (DFT) calculations. While the HBD-CO 2 complex is the major and the thermodynamically more favored product of absorption in all of the examined eutectic solvents, this complexation is only possible proceeding a proton transfer from HBD to the HBA in diol-based systems (EG, PG, BD). The interplay between HBA-CO 2 and HBD-CO 2 speciation is governed by the HBD concentration, basicity, and steric effects, with increased HBD-CO 2 interactions in the presence of smaller HBDs (size: BD > PG > EG). On the other hand, in MEA-based systems, CO 2 readily binds to the amine followed by a proton transfer from the amine to the HBA as confirmed by DFT calculations. In this way, the MEA-CO 2 chemisorption capacities exceeded that of the conventional amine (up to 0.93 mol of CO 2 per mol of MEA versus 0.5). Furthermore, the increase in CO 2 capacities and enhanced binding in eutectics including MEA or the more basic HBAs also resulted in regeneration temperatures of 70 to 60 °C with calculated reaction energies of −82 to −57 kJ/mol, compared to 50 °C for others with weaker binding, following CO 2 absorption at 25 °C.

absorption↗

Solvent Dynamics Are Critical to Understanding Carbon Dioxide Dissolution and Hydration in Water

Simulations of carbon dioxide (CO 2 ) in water may aid in understanding the impact of its accumulation in aquatic environments and help advance technologies for carbon capture and utilization (via, e.g., mineralization). Quantum mechanical (QM) simulations based on static molecular models with polarizable continuum solvation poorly reproduce the energetics of CO 2 hydration to form carbonic acid in water, independent of the level of QM theory employed. Only with density-functional-theory-based molecular dynamics and rare-event sampling, followed by energy corrections based on embedded correlated wavefunction theory (in conjunction with density functional embedding theory), can a close agreement between theory and experiment be achieved. Such multilevel simulations can serve as benchmarks for simpler, less costly models, giving insight into potential errors of the latter. The strong influence of sampling/averaging over dynamical solvent configurations on the energetics stems from the difference in polarity of both the transition state and product (both polar) versus the reactant (nonpolar). When a solute undergoes a change in polarity during reaction, affecting its interaction with the solvent, careful assessment of the energetic contribution of the solvent response to this change is critical. Here, we show that static models (without structural sampling) that incorporate three explicit water molecules can yield far superior results than models with more explicit water molecules because fewer water molecules yield less configurational artifacts. Static models intelligently incorporating both explicit (molecules directly participating in the reaction) and implicit solvation, along with a proper QM theory, e.g., CCSD(T) for closed-shell systems, can close the accuracy gap between static and dynamic models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A simulation-based model studying monoethanolamine and aprotic heterocyclic anion ionic liquid (AHA-IL) mixtures for carbon capture

Capturing of waste CO 2 , particularly from large industrial point sources, is necessary for either permanent storage or CO 2 utilization. Amine solvents used for carbon capture have certain drawbacks, particularly the high energy required by the reboiler for solvent regeneration and degradation of the amine with absorption/regeneration cycling. These challenges may be overcome using ionic liquids (ILs) that can be tailored for operating under typical flue gas stream conditions (8–10% CO 2 , 18–20% H 2 O, 2–3% O 2 , and 67–72% N 2 ). ILs, however, oftentimes suffer from high viscosities, leading to diffusion limitations when compared to amine solvents. This work models the combinations of aprotic heterocyclic anion ILs (AHA-IL) with monoethanolamine (MEA) and studies the carbon capture effectiveness of these mixtures. Furthermore, this study found that all AHA-IL/MEA mixtures exhibited 32 % lower enthalpy of reaction (compared to MEA) and 64 % lower viscosity (compared to AHA-IL), which are desirable characteristics for CO 2 capture solvents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Technoeconomic and life cycle energy analysis of carbon fiber manufactured from coal via a novel solvent extraction process

Coal is a versatile energy resource and was a driver of the industrial revolution that transformed the economies of Europe and North America and the trajectory of civilization. In this work, a technoeconomic analysis was performed for a coal-to-carbon-fiber manufacture process developed at the University of Kentucky’s Center for Applied Energy Research. According to this process, coal, with decant oil as the solvent, was converted to mesophase pitch via solvent extraction, and the mesophase pitch was subsequently converted to carbon fiber. The total cost to produce carbon fibers from coal and decant oil via the solvent extraction process was estimated to be $\$$11.50/kg for 50,000-tow pitch carbon fiber with a production volume of 3750 MT/year. The estimated carbon fiber cost was significantly lower than the current commercially available PAN-based carbon fiber price ($\$$20–$\$$30/kg). With decant oil recycling rates of 50% and 70% in the solvent extraction process, the manufacturing cost of carbon fiber was estimated to be $\$$9.90/kg and $\$$9.50/kg of carbon fiber, respectively. A cradle-to-gate energy assessment revealed that carbon fiber derived from coal exhibited an embodied energy of 510 MJ/kg, significantly lower than that of conventionally produced carbon fiber from PAN. This notable difference is primarily attributed to the substantially higher conversion rate of coal-based mesophase pitch fibers into carbon fiber, surpassing PAN fibers by 1.6 times. These findings indicate that using coal for carbon fiber production through solvent extraction methods could offer a more energy-efficient and cost-competitive alternative to the traditional PAN based approach.

01 COAL, LIGNITE, AND PEAT↗

Pretreatment of Biomass by Selected Type-III Deep Eutectic Solvents and Evaluation of the Pretreatment Effects on Hydrothermal Carbonization

Hydrothermal carbonization (HTC) is a novel thermochemical conversion that converts wet biomass into energy dense solid fuel. Residual moisture under subcritical conditions reacts with a lignin-cellulose-hemicellulose matrix with the major reactions being identified as dehydration and decarboxylation. Among other reaction parameters (e.g., temperature, time, pressure), biomass morphology often plays a key role in HTC. The hypothesis of this study was enhancing the porous structure of biomass without significantly affecting biopolymer composition would augment hydrothermal carbonization (HTC). To prove the hypothesis, two type-III deep eutectic solvents (DESs), namely choline chloride:urea (ChCl:Urea, 1:2 mol/mol) and methyltriphenylphosphonium bromide:ethylene glycol (MTPB:EG, 1:4 mol/mol), were studied to pretreat loblolly pine at room temperature and ambient pressure for 1 h. DES pretreatment shows swelling of the biomass, increasing the surface fiber-to-fiber gap length by 52% and 185% for ChCl:Urea and MPTB:EG pretreatments, respectively. The total pore volume remained intact (2.6 × 10 –3 cm 3 /g), although new small pores evolved, and existing pores were abated with DES pretreatment. Hydrochars prepared from DES pretreated loblolly pine showed a high O/C and H/C ratio resulting in a significant increase of energy content (up to 42%) and a decrease of mass yield (up to 50 wt %), indicating an enhancement of HTC severity due to the alteration of surface morphology by DES. Finally, a preliminary process economics revealed that integrated DES pretreatment-HTC would increase fixed capital investment but decrease the cost of operation and manufacturing than the standalone HTC process.

09 BIOMASS FUELS↗

Microfluidic, One-Batch Synthesis of Pd Nanocrystals on N-Doped Carbon in Surfactant-Free Deep Eutectic Solvents for Formic Acid Electrochemical Oxidation

One of the grand challenges that impedes practical applications of nanomaterials is the lack of robust manufacturing methods that are scalable, cheap, and environmentally friendly. In this work, we address this challenge by developing a microfluidic approach that produces surfactant-free Pd nanocrystals (NCs) uniformly loaded on N-doped porous carbon in a one-batch process. The deep eutectic solvent (DES) prepared from choline chloride and ethylene glycol was employed as a novel synthesis solvent, and its extended hydrogen networks and abundant ionic species effectively stabilize Pd facets and confine nanocrystal sizes without using surfactants. The microreactors provide faster heat exchange and more uniform mass transport, which in combination with DES produced Pd NCs with better-defined shape and predominately exposed Pd (100) facet. Furthermore, we describe that the N-doped functional groups in porous carbon direct dense and uniform heterogeneous growth of Pd NCs in a one-batch process, thereby eliminating a separate catalyst deposition step that is often involved in conventional synthesis. The Pd NCs in the one-batch-produced Pd/C catalysts exhibited a size distribution of similar to ~13 ± 3.5 nm and a high ESCA of 46.0 m 2 /g and delivered 362 mA/mg for formic acid electrochemical oxidation with improved stability, demonstrating the unique potentials of microfluidic reactors and DES for the controllable and scalable synthesis of electrocatalyst materials for practical applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Direct Correlation of the Salt-Reduced Diffusivities of Organic Solvents with the Solvent’s Mole Fraction

We report that lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in organic solvents (especially propylene carbonate) has demonstrated extraordinary pseudocapacitive performance as an electrolyte in the supercapacitor configuration. However, the influence of the solvated ions on the diffusivity of the solvent molecules is yet to be understood. We examine the impact of LiTFSI on the diffusivity in five organic solvents: acetonitrile (ACN), tetrahydrofuran (THF), methanol (MeOH), dimethyl sulfoxide (DMSO), and propylene carbonate (PC) using a combination of neutron scattering, conductivity measurements, and molecular dynamics simulations. The extent of the diffusivity reduction in the concentration regime of ≤1 M directly correlates with the solvent mole fraction at which the solvation shells around Li + ions are of similar size in all the solvents, resulting in a universal ~50% reduction in the solvent diffusivity. These results provide guidance for formulation of the new electrolytes to enhance the performance of energy storage devices.

conductivity↗

Influence of solvents on electrochemical stability window of ionic liquid solutions

The electrochemical stability window (ESW) defines the voltage range within which an electrolyte remains stable against oxidation and reduction, serving as a key descriptor for ionic liquid (IL)-based systems. The ESWs of 15 ILs with diverse cation-anion combinations were systematically investigated, both in their neat forms and as binary mixtures with three representative solvents, i.e., propylene carbonate (PC), ethylene glycol (EG), and tetrahydrofuran (THF). Cyclic voltammetry on a glassy carbon electrode determined anodic and cathodic stability limits, revealing that ESW protection in IL-solvent mixtures strongly depends on solvent polarity, proticity, and IL compatibility. PC, with a high dielectric constant and aprotic character, broadened anodic limits and moderately stabilized cathodic limits. THF maintained compact interfacial structure, offering additional cathodic protection, whereas EG, being protic, reduced ESWs via proton-coupled electron transfer and hydrogen evolution. The solvent protection trend followed by PC > THF > EG, with bulky, hydrophobic cations ([HMIM] + , [BMPYRR] + ) and weakly coordinating anions ([NTF 2 ] - , [DCA] - , [DEP] - ) showing the highest ESW protection for 50 mol% IL in these solvents. Among the neat ILs, [EMIM][DEP], [HMIM][PF 6 ], and [BMPYRR][DCA] showed wide ESWs of ∼5.5 V. These results provide valuable insight into solvent-modulated electrochemical stability, enabling rational design of IL-based electrolytes for energy storage and electrosynthesis.

25 ENERGY STORAGE↗

Catalytic cathode for a lithium-oxygen battery

A metal-air battery includes an anode; a low-dimensional catalyst cathode; and an electrolyte; wherein: the low-dimensional catalyst cathode comprises a functional metal layer on a carbon support overcoated with a catalyst layer; the electrolyte comprises an aprotic solvent that is an ether-based solvent, a fluorinated ether-based solvent, an oligo (ethylene oxide) solvent, or a mixture of any two or more thereof; and the electrolyte is free of carbonate solvents.

25 ENERGY STORAGE↗