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Lively, Ryan P.

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

At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Exploitation of Pore Structure for Increased CO 2 Selectivity in Type 3 Porous Liquids

CO 2 capture requires materials with high adsorption selectivity and an industrial ease of implementation. To address these needs, a new class of porous materials was recently developed that combines the fluidity of solvents with the porosity of solids. Type 3 porous liquids (PLs) composed of solvents and metal–organic frameworks (MOFs) offer a promising alternative to current liquid carbon capture methods due to the inherent tunability of the nanoporous MOFs. However, the effects of MOF structural features and solvent properties on CO 2 –MOF interactions within PLs are not well understood. Herein experimental and computational data of CO 2 gas adsorption isotherms were used to elucidate both solvent and pore structure influences on ZIF-based PLs. The roles of the pore structure including solvent size exclusion, structural environment, and MOF porosity on PL CO 2 uptake were examined. A comparison of the pore structure and pore aperture was performed using ZIF-8, ZIF-L, and amorphous-ZIF-8. Adsorption experiments here have verified our previously proposed solvent size design principle for ZIF-based PLs (1.8× ZIF pore aperture). Furthermore, the CO 2 adsorption isotherms of the ZIF-based PLs indicated that judicious selection of the pore environment allows for an increase in CO 2 selectivity greater than expected from the individual PL components or their combination. This nonlinear increase in the CO 2 selectivity is an emergent behavior resulting from the complex mixture of components specific to the ZIF-L + 2'-hydroxyacetophenone-based PL.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

CO 2 Uptake and Stability Enhancement in Vinyltrimethoxysilane‐Treated SBA‐15 Solid Amine‐Based Sorbents

Abstract Silica‐supported amine absorbents, including materials produced by tethering aminosilanes or infusion of poly(ethyleneimine), represent a promising class of materials for CO 2 capture applications, including direct air and point source capture. Various silica surface treatments and functionalization strategies are explored to enhance stability and CO 2 uptake in amine‐based solid sorbent systems. Here, the synthesis and characterization of novel vinyltrimethoxysilane‐treated Santa Barbara Amorphous‐15 (SBA‐15) supports and the corresponding enhancement in CO 2 uptake compared to various SBA‐15‐based control supports are presented. The relationship between CO 2 diffusion and amine efficiency in these systems is explored using a previously reported kinetic model. The synthesized materials are characterized with CO 2 and H 2 O isotherms, diffuse reflectance infrared Fourier transform spectroscopy, 1 H T 1 – T 2 relaxation correlation NMR, and rapid thermal cycling experiments. The novel support materials are shown to enable high amine efficiencies, approaching a fourfold improvement over standard SBA‐15‐supported amines, while simultaneously exhibiting excellent stability when cycled rapidly under humid conditions. As the poly(ethyleneimine) loadings are held constant across the various samples, enhancements in CO 2 uptake are attributed to differences in the way the poly(ethyleneimine) interacts with the support surface.

Vallace, Anthony↗
DOE OSTI2024

“Hybridizing heat-integrated 3D printed modules with mass manufacturable, low pressure drop fiber sorbents” (Final Report)

The overall objective of this proposal was to research, develop, and evaluate a modular direct air capture (DAC) system that is simple and scalable. This system was based on the adsorption of CO 2 into commercial polyamines supported by porous fiber sorbents, which can be produced at kilometer per hour scales using our pre-pilot spinning line. We have housed these fiber materials in novel 3D printed modular housing systems that provide easy-to-manufacture and localized heat integration and flow control. This hybridization of fiber sorbent technology with modular housing provided several advantages that led to lower air pressure drops, higher sorbent productivity, as well as ease of manufacturing and assembly unrivaled by existing and emerging heat integrated contactor designs. The modular housing was fabricated with the following features, at a minimum: (i) a tapered air intake to reduce pressure drop related to entrance effects, (ii) a structured network of heat transfer channels to enable localized cooling and heating during adsorption and desorption, respectively, and (iii) low pressure drop supports for the fiber sorbents. This hybrid manufacturing approach provides a facile method for taking fiber sorbents from lab scale to pilot scale as it dramatically simplifies the fabrication of heat integrated contactor structures.

42 ENGINEERING↗
DOE OSTI2023

Structure–Transport Relationships of Water–Organic Solvent Co-transport in Carbon Molecular Sieve (CMS) Membranes

We explore the effects of the carbon molecular sieve (CMS) microstructure on the separation performance and transport mechanism of water–organic mixtures. Specifically, we utilize PIM-1 dense films and integrally skinned asymmetric hollow fiber membranes as polymer precursors for the CMS materials. The PIM-1 membranes were pyrolyzed under several different pyrolysis atmospheres (argon, carbon dioxide, and diluted hydrogen gas) and at multiple pyrolysis temperatures. Detailed gas physisorption measurements reveal that membranes pyrolyzed under 4% H 2 and CO 2 had broadened ultramicropore distributions (pore diameter <7 Å) compared to Ar pyrolysis, and pyrolysis under CO 2 increased ultramicropore volume and broadened micropore distributions at increased pyrolysis temperatures. Gravimetric water and p-xylene sorption and diffusion measurements reveal that the PIM-1-derived CMS materials are more hydrophilic than other CMS materials that have been previously studied, which leads to sorption-diffusion estimations showing water-selective permeation. Water permeation in the vapor phase, pervaporation, and liquid-phase hydraulic permeation reveal that the isobaric permeation modes (vapor permeation and pervaporation) are reasonably well predicted by the sorption-diffusion model, whereas the hydraulic permeation mode is significantly underpredicted (>250×). Conversely, the permeation of p-xylene is well predicted by the sorption-diffusion model in all cases. The collection of pore size analysis, vapor sorption and diffusion, and permeation in different modalities creates a picture of a combined transport mechanism in which water–under high transmembrane pressures–permeates via a Poiseuille-style mechanism, whereas p-xylene solutes in the mixture permeate via sorption-diffusion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Data-driven predictions of complex organic mixture permeation in polymer membranes

Membrane-based organic solvent separations are rapidly emerging as a promising class of technologies for enhancing the energy efficiency of existing separation and purification systems. Polymeric membranes have shown promise in the fractionation or splitting of complex mixtures of organic molecules such as crude oil. Determining the separation performance of a polymer membrane when challenged with a complex mixture has thus far occurred in an ad hoc manner, and methods to predict the performance based on mixture composition and polymer chemistry are unavailable. Here, we combine physics-informed machine learning algorithms (ML) and mass transport simulations to create an integrated predictive model for the separation of complex mixtures containing up to 400 components via any arbitrary linear polymer membrane. We experimentally demonstrate the effectiveness of the model by predicting the separation of two crude oils within 6-7% of the measurements. Integration of ML predictors of diffusion and sorption properties of molecules with transport simulators enables for the rapid screening of polymer membranes prior to physical experimentation for the separation of complex liquid mixtures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Evaluating degradation of CO 2 adsorbents in flue gas from bioenergy with carbon capture and storage

For this work, the potential degradation of CO 2 adsorbents in Bioenergy with Carbon Capture and Storage (BECCS) was investigated through direct exposure to biomass combustion flue gas. Pre- and post-exposure characterization after 6–12 hours of exposure provided valuable insight into how common adsorbents would realistically perform in a BECCS process. The stability of zeolites and robust ZIFs was confirmed, but some unanticipated degradation mechanisms of less-stable MOFs and amine-based materials were also revealed, including pore fouling and chemical poisoning. The results emphasize the need for stability evaluations of adsorbents in comprehensive flue gas mixtures and suggest relationships between sorbent structure and degradation mechanism and extent.

09 BIOMASS FUELS↗
DOE OSTI2023

Dynamic study of direct CO 2 capture from indoor air using poly(ethylenimine)-impregnated fiber sorbents

Supported amine adsorbents are promising materials for direct air capture (DAC) of CO 2 due to their high CO 2 capacity and relatively low energy requirement for regeneration. For a DAC process, it is essential to properly define operating parameters to achieve high sorbent productivity (amount of CO 2 captured per unit quantity of sorbent material over unit time). It is furthermore essential to understand the kinetic behavior of the process under the influence of various operating conditions such as the inlet air velocity, sorbent composition, and humidity to select an effective range of operating conditions to maximize sorbent productivity. Here, the dynamic behavior of a DAC process is probed using a fixed fiber sorbent contactor containing poly(ethylenimine) (PEI)-impregnated composite silica/cellulose acetate (CA) fibers. Throughout this study, experiments are conducted using both simulated air (398 ppm CO 2 balanced by N 2 ) and real indoor air (~400–500 ppm CO 2 ). The experimental behavior of the fibers using simulated air and indoor air is compared, and the influence of the inlet air velocity on the breakthrough behavior is assessed. By changing operating conditions, the impact on the fiber sorbent productivity (mmol CO 2 g fiber –1 h –1 ) is quantified to identify conditions that could favor high rates of CO 2 removal. The kinetics of steam-assisted CO 2 desorption are studied, identifying achievable desorption times. Productivities of 1.2 mmol CO 2 g fiber –1 h –1 are obtained using an inlet air velocity of 1.1 m s –1 . Performance trends show that further increasing the inlet air velocity will likely lead to even higher productivities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Kinetic model describing self-limiting CO 2 diffusion in supported amine adsorbents

A reaction–diffusion shrinking core model describing the decay in diffusivity of supported amine sorbents upon CO 2 sorption under both simulated direct air capture and point source capture conditions is described. The decay in CO 2 diffusivity is associated with crosslinking in the aminopolymer samples and general pore blockage in the amino-silane derived samples, which occurs as CO 2 is adsorbed. The model is used to extract four kinetic parameters that govern the CO 2 uptake kinetics and working capacity: an apparent reaction rate constant, an initial effective diffusivity, and two dimensionless decay parameters. Ideally, an initially reaction limited system would allow for direct determination of the intrinsic reaction rate constant; however, sorption experiments suggest mass transfer resistances related to gas mixing, external boundary layers and intraparticle diffusion are present. Reaction rate constants are determined and agree well with theoretical values predicted with the Eyring equation parameterized using density functional theory energies from literature sources. The kinetic performance is expressed as the average effective diffusivity as a function of average conversion, which can be correlated to the dispersion of sorption sites on the support and the morphology of the active sorbent phase. Four supports are impregnated or grafted with amines, SBA-15, single-walled zeolite nanotubes (ZNT), Syloid SiO 2 , and γ-Al 2 O 3 . Due to its pore structure, γ-Al 2 O 3 supported amines can be modeled at the μm scale or at the nm scale, where the shell balance is on the μm-sized macroporous particle aggregate or on the nm-sized amine film on the surface of the Al 2 O 3 nanoparticles, which comprise the spherical particle aggregates. Faster diffusion rates are maintained under 400 ppm rather than 10% CO 2 due to a slower reaction rate giving a slower decay in diffusivity. In conclusion, this work provides a first principles kinetic analysis of CO 2 sorption where previous models are semi-empirical and use arbitrary kinetic parameters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Selective permeation up a chemical potential gradient to enable an unusual solvent purification modality

The need for energy-efficient recovery of organic solutes from aqueous streams is becoming more urgent as chemical manufacturing transitions toward nonconventional and bio-based feedstocks and processes. In addition to this, many aqueous waste streams contain recalcitrant organic contaminants, such as pharmaceuticals, industrial solvents, and personal care products, that must be removed prior to reuse. We observe that rigid carbon membrane materials can remove and concentrate organic contaminants via an unusual liquid-phase membrane permeation modality. Surprisingly, detailed thermodynamic calculations on the chemical potential of the organic contaminant reveal that the organic species has a higher chemical potential on the permeate side of the membrane than on the feed side of the membrane. This unusual observation challenges conventional membrane transport theory that posits that all permeating species move from high chemical potential states to lower chemical potential states. Based on experimental measurements, we hypothesize that the organic is concentrated in the membrane relative to water via favorable binding interactions between the organic and the carbon membrane. The concentrated organic is then swept through the membrane via the bulk flow of water in a modality known as “sorp-vection.” We highlight via simplified nonequilibrium thermodynamic models that this “uphill” chemical potential permeation of the organic does not result in second-law violations and can be deduced via measurements of the organic and water sorption and diffusion rates into the carbon membrane. Moreover, this work identifies the need to consider such nonidealities when incorporating unique, rigid materials for the separations of aqueous waste streams.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Interpreting inorganic compositional depth profiles to understand the rate-limiting step in vapor phase infiltration processes

Vapor phase infiltration (VPI) is a post-polymerization modification technique that infuses inorganics into polymers to create organic–inorganic hybrid materials with new properties. Much is yet to be understood about the chemical kinetics underlying the VPI process. The aim of this study is to create a greater understanding of the process kinetics that govern the infiltration of trimethyl aluminum (TMA) and TiCl 4 into PMMA to form inorganic-PMMA hybrid materials. To gain insight, this paper initially examines the predicted results for the spatiotemporal concentrations of inorganics computed from a recently posited reaction–diffusion model for VPI. This model provides insight on how the Damköhler number (reaction versus diffusion rates) and non-Fickian diffusional processes (hindering) that result from the material transforming from a polymer to a hybrid can affect the evolution of inorganic concentration depth profiles with time. Subsequently, experimental XPS depth profiles are collected for TMA and TiCl 4 infiltrated PMMA films at 90 °C and 135 °C. The functional behavior of these depth profiles at varying infiltration times are qualitatively compared to various computed predictions and conclusions are drawn about the mechanisms of each of these processes. TMA infiltration into PMMA appears to transition from a diffusion-limited process at low temperatures (90 °C) to a reaction-limited process at high temperatures (135 °C) for the film thicknesses investigated here (200 nm). While TMA appears to fully infiltrate these 200 nm PMMA films within a few hours, TiCl 4 infiltration into PMMA is considerably slower, with full saturation not occurring even after 2 days of precursor exposure. Infiltration at 90 °C is so slow that no clear conclusions about mechanism can be drawn; however, at 135 °C, the TiCl 4 infiltration into PMMA is clearly a reaction-limited process, with TiCl 4 permeating the entire thickness (at low concentrations) within only a few minutes, but inorganic loading continuously increasing in a uniform manner over a course of 2 days. Near-surface deviations from the uniform-loading expected for a reaction-limited process also suggest that diffusional hindering is high for TiCl 4 infiltration into PMMA. In conclusion, these results demonstrate a new, ex situ analysis approach for investigating the rate-limiting process mechanisms for vapor phase infiltration.

36 MATERIALS SCIENCE↗