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Lively, Ryan P.

Publications and source records attributed to Lively, Ryan P..

At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Development of Novel Materials for Direct Air Capture of CO 2 : MIL-101(Cr)-Amine Sorbents Evaluation Under Realistic Direct Air Capture Conditions (Final Report)

The overarching goal of this project is to evaluate the CO 2 adsorption properties of a small family of metal-organic framework (MOFs) materials functionalized with amines at sub-ambient conditions. Our goal is to develop capabilities to measure CO 2 adsorption at conditions more relevant to the weather of the planet. For this purpose, Georgia Tech is constructing a “sub-ambient adsorption facility” in partnership with ZCP Sorbent Development, LLC, aimed specifically at rapidly and deeply characterizing the performance of DAC candidate materials in this important operational range (adsorption at -20 to 20 °C and RH of 0-100%). Here, we use the sub-ambient lab instrumentation designed or adapted to study the behavior of the pristine metal organic framework (MOF) MIL-101(Cr) and the MOF in the presence of amines ranging from small molecules (e.g. TREN, tris(2-aminoethylamine)) to oligomers (e.g. PEI, poly(ethyleneimine)). Any DAC sorbent must be amenable to deployment in practical contactors for gas-solid contacting (traditional pellet-based fixed beds are impossible at scale). To this end, we developed and tested these DAC materials in the forms of composite polymer/MOF fibers and custom 3D-printed monolith structures containing MOF DAC sorbents. The proposed studies advance these materials from technology readiness level (TRL) 2 to TRL 3.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2022

Theoretical Pathway toward Improved Reverse Osmosis Membrane Selectivity for Neutral Solutes: Inspiration from Gas Separations

We report highly rigid membrane materials with tailored structures have exhibited permeabilities and selectivities that exceed the polymer upper bound in gaseous and organic solvent separations for challenging mixtures containing species that are similar in size and shape. One potential question is whether such membrane materials can maintain meaningful guest diffusivities in situations where the microporous spaces are essentially full of guest molecules. Here, we use a simplified transition state theory approach to estimate the diffusivity of water and small organics within a microporous membrane. The transition state theory model is parameterized using experimental values from zeolites and carbon molecular sieve materials found in the literature. We demonstrate the differences in transport and Maxwell–Stefan diffusivities based on guest species loading with different isotherm behaviors. These calculations theorize a path forward for highly selective reverse osmosis membranes for aqueous phase separations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Unblocking a rigid purine MOF for kinetic separation of xylenes

The separation of xylene isomers still remains an industrially challenging task. Here, we synthesized and studied porous purine-based metal–organic frameworks (MOFs) for their potential in xylene separations. In particular, Zn(purine)I showed excellent para-xylene/ortho-xylene separation capability with a diffusion selectivity of 6 and high equilibrium adsorption selectivity as indicated by coadsorption experiments. This high selectivity is attributed to the shape and size of the channel aperture within the rigid framework of Zn(purine)I.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Achieving order of magnitude increases in CO 2 reduction reaction efficiency by product separations and recycling

CO 2 reduction reaction (CO 2 RR) systems are the heart of many proposed e-refinery schemes. There have been few studies on the separation systems that will be needed to complement CO 2 RR reactors. Here, we show that by strategic use of downstream separations and recycling of unreacted CO 2 , the efficiency of CO 2 RR can be significantly improved without changes in the electrochemical reactor.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Positive Power with Negative Emission Flexible NGCC Enable by Modular Direct Air Capture (Final Report)

The primary project objective was to synthesize a retrofit design of a natural gas combined cycle plant (Fseries gas turbines in 2x1 configuration) to integrate post-combustion (PCC) and direct air carbon capture (DAC) systems that could produce power with negative emissions across a wide range of loads, see table below. The IP-LP crossover and LP steam system of the NGCC were reconfigured to enable 97% CO2 capture in the PCC system at all loads, and heat integration with the DAC reduced the parasitic load of carbon capture by recovering the heat of condensation of the steam. Similar results were found for Hseries gas turbines.

03 NATURAL GAS↗
DOE OSTI2022

How Reproducible are Surface Areas Calculated from the BET Equation?

Abstract Porosity and surface area analysis play a prominent role in modern materials science. At the heart of this sits the Brunauer–Emmett–Teller (BET) theory, which has been a remarkably successful contribution to the field of materials science. The BET method was developed in the 1930s for open surfaces but is now the most widely used metric for the estimation of surface areas of micro‐ and mesoporous materials. Despite its widespread use, the calculation of BET surface areas causes a spread in reported areas, resulting in reproducibility problems in both academia and industry. To prove this, for this analysis, 18 already‐measured raw adsorption isotherms were provided to sixty‐one labs, who were asked to calculate the corresponding BET areas. This round‐robin exercise resulted in a wide range of values. Here, the reproducibility of BET area determination from identical isotherms is demonstrated to be a largely ignored issue, raising critical concerns over the reliability of reported BET areas. To solve this major issue, a new computational approach to accurately and systematically determine the BET area of nanoporous materials is developed. The software, called “BET surface identification” (BETSI), expands on the well‐known Rouquerol criteria and makes an unambiguous BET area assignment possible.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Co-transport of water and p-xylene through carbon molecular sieve membranes

Carbon molecular sieve (CMS) materials are a potential candidate for scalable and high-performance reverse osmosis membranes due to their impressive chemical and thermal stabilities. Moreover, they have the potential to enable impressive rejections of small neutral solutes from water based on their known ability to separate small organic molecules. CMS has been extensively examined for gas and organic solvent separations, but the transport of organic and aqueous mixtures through CMS microstructures is poorly understood. In this work, we investigated the sorption, diffusion, and permeation behavior of organic compounds and water in poly(vinylidene fluoride)(PVDF)-derived CMS (PVDF-CMS). Experimental observations of diffusion, sorption, and permeation shows how the properties of penetrants such as polarity and molecular size affect the transport rates and selectivity. These basic transport and sorption parameters are utilized in sorption-diffusion models to permeation rates of water-organic mixtures in CMS membranes. The transport of water and p-xylene in CMS was experimentally confirmed to follow the sorption-diffusion mechanism. The sorption-diffusion model ideal permselectivity indicates that the CMS is p-xylene selective over water. Water/p-xylene mixture permeation experiments revealed an increased selectivity of p-xylene over water, thus providing tentative evidence for a competitive sorption-selective separation mechanism. Furthermore, this work suggests that CMS membranes exhibit organic-permeable separation properties in water/organic separations. The results presented here highlight the potential for the removal of dilute organics in water via CMS pervaporation membranes.

02 PETROLEUM↗
DOE OSTI2022

Tailoring the Structure of Carbon Molecular Sieves Derived from an Aromatic Polyamide

Energy-efficient and selective separation technologies are required to reclaim aqueous waste streams for reuse. Carbon molecular sieves (CMS) are one material capable of separating organic solvent and gaseous mixtures due to the presence of permanent, rigid, and molecular sieving pores and could potentially be used in aqueous separations. Here, a novel CMS material is derived from an aromatic polyamide precursor with tailored fabrication techniques. Structural characteristics of this CMS have been probed with various analyses and are potentially ideal for selective separations as adsorbents. In this work, elemental analyses provide insight about the potential chemical structures of CMS materials that result from degradation mechanisms. Gravimetric sorption data is used to estimate sorption, diffusion, and permeability selectivity with water and N, N-dimethylformamide. While challenges to the development and implementation of such carbonaceous materials remain, highly selective materials are critical starting points for enabling ultra-challenging separation processes of the future.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Accelerating Solvent Selection for Type II Porous Liquids

Type II porous liquids, comprising intrinsically porous molecules dissolved in a liquid solvent, potentially combine the adsorption properties of porous adsorbents with the handling advantages of liquids. Previously, discovery of appropriate solvents to make porous liquids had been limited to direct experimental tests. We demonstrate an efficient screening approach for this task that uses COSMO-RS calculations, predictions of solvent pK a values from a machine-learning model, and several other features and apply this approach to select solvents from a library of more than 11,000 compounds. Additionally, this method is shown to give qualitative agreement with experimental observations for two molecular cages, CC13 and TG-TFB-CHEDA, identifying solvents with higher solubility for these molecules than had previously been known. Ultimately, the algorithm streamlines the downselection of suitable solvents for porous organic cages to enable more rapid discovery of Type II porous liquids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Research needs targeting direct air capture of carbon dioxide: Material & process performance characteristics under realistic environmental conditions

The extraction of CO 2 from ambient air, or direct air capture (DAC), is a crucial negative CO 2 emissions technology with great potential for contributing to the mitigation of global warming and climate change. Furthermore, nearly all published research on DAC has been conducted under indoor temperature conditions, i.e. 20 to 30 °C. In contrast, the future global implementation of DAC requires it to be operational across a wide expanse of geographical areas, of which the local temperatures can vary between -30 to 50 °C. Similarly, the absolute humidity can vary from ~0 to 84 g/m 3 in various locations. Due to the massive amount of air that would be processed, it may be impractical to preheat or dehumidify the air before the CO 2 separation. Therefore, it is important to develop DAC materials with good performance at realistic outdoor conditions, especially at sub-ambient conditions, i.e. -30 to 20 °C. In addition to material development, system-level studies at sub-ambient conditions are also needed for the DAC processes to reach optimal designs, which may be very different from those at ambient conditions. In this perspective article, we first assess the literature to identify the technical gaps that need to be filled for DAC to be applicable at realistic outdoor conditions. We then suggest additional research directions needed for DAC to be viable under varied conditions from the perspectives of materials and system designs. For materials, we discuss the expected physical and chemical property changes for the sorbents when the temperature or humidity reaches extremes within their range, and how that will impact performance. Similarly, for system design, we indicate how varied conditions will impact performance and how these changes will impact process optimization.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2021

Assessing the physical potential capacity of direct air capture with integrated supply of low-carbon energy sources

Direct Air Capture (DAC) is a negative emission technology that can remove up to 10–20 Gt of CO 2 per year. However, to achieve this potential, DAC systems must be coupled to suitable locally available energy sources and sited near geological storage. Here this study explores the potential of low-carbon energy sources to supply power and heat to the DAC process in a dedicated, self-sufficient system tailored for each energy source. Solar, geothermal, woody biomass, wind, and nuclear energy sources are assessed for their global energy supply potential and possible land use requirements. While the options differ in area requirement and regional efficacy, we estimate that all the regionally specific technologies considered can supply energy to achieve significant removal of carbon dioxide from the atmosphere globally. The amount of energy physically available from solar, offshore wind, and woody biomass converts to a removal potential of 160–971, 45–150, and 2–5 Gt CO 2 /year, respectively. Thus, negative emission targets can be reached by utilizing a moderate fraction of the overall potential of several different low-carbon energy sources for DAC while the magnitude of the potential changes significantly according to the source of energy.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗