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At least 343 records · Page 19

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DOE OSTI2014

Scale Resistant Heat Exchanger for Low Temperature Geothermal Binary Cycle Power Plant

Phase 1 of the investigation of improvements to low temperature geothermal power systems was completed. The improvements considered were reduction of scaling in heat exchangers and a hermetic turbine generator (eliminating seals, seal system, gearbox, and lube oil system). A scaling test system with several experiments was designed and operated at Coso geothermal resource with brine having a high scaling potential. Several methods were investigated at the brine temperature of 235 ºF. One method, circulation of abradable balls through the brine passages, was found to substantially reduce scale deposits. The test heat exchanger was operated with brine outlet temperatures as low as 125 ºF, which enables increased heat input available to power conversion systems. For advanced low temperature cycles, such as the Variable Phase Cycle (VPC) or Kalina Cycle, the lower brine temperature will result in a 20-30% increase in power production from low temperature resources. A preliminary design of an abradable ball system (ABS) was done for the heat exchanger of the 1 megawatt VPC system at Coso resource. The ABS will be installed and demonstrated in Phase 2 of this project, increasing the power production above that possible with the present 175 ºF brine outlet limit. A hermetic turbine generator (TGH) was designed and manufacturing drawings produced. This unit will use the working fluid (R134a) to lubricate the bearings and cool the generator. The 200 kW turbine directly drives the generator, eliminating a gearbox and lube oil system. Elimination of external seals eliminates the potential of leakage of the refrigerant or hydrocarbon working fluids, resulting in environmental improvement. A similar design has been demonstrated by Energent in an ORC waste heat recovery system. The existing VPC power plant at Coso was modified to enable the “piggyback” demonstration of the TGH. The existing heat exchanger, pumps, and condenser will be operated to provide the required process conditions for the TGH demonstration. Operation of the TGH with and without the ABS system will demonstrate an increase in geothermal resource productivity for the VPC from 1 MW/(million lb) of brine to 1.75 MW/(million lb) of brine, a 75% increase.

15 GEOTHERMAL ENERGY↗

DOE OSTI2024

Impulse-driven release of gas-encapsulated drops

Gas-encapsulated drops, much like antibubbles, are drops enclosed in a bubble within a liquid. They show potential as payload carriers in fluid transport and mixing techniques where sound waves can be leveraged to induce the collapse of the gas core and the subsequent release of the drop. Here, the interaction of millimetre-sized gas-encapsulated drops with impulsive laser-induced shock waves is investigated to gain fundamental insights into the release process. Experimental synchrotron X-ray phase contrast imaging, which allows the drop dynamics to be visualised inside the encapsulating bubble, is complemented by numerical simulations to study the intricate physics at play. Three drop dynamical release regimes are discovered, namely the drop impact , partial deposition and jet impact regimes. The regime type is mainly dependent on the shape of the bubble interface impacting the drop and the associated Weber and Reynolds numbers. The drop dynamics of the drop impact and partial deposition regimes show similarities with the canonical configuration of drops impacting flat liquid surfaces, whereas the jet impact regime resembles binary drop collisions, which allows existing scaling laws to be applied to describe the underlying processes. The release of the drop is investigated numerically. The time evolution of the drop dissemination within the surrounding liquid discloses enhanced mixing for dynamics involving high Weber and Reynolds numbers such as the drop impact and jet impact regimes.

42 ENGINEERING↗

DOE OSTI2025

Physics or Knob‐Tuning? Tropical Anvil Peak Is Captured by GCMs

Tropical anvil clouds peak near 200 hPa and significantly impact Earth's climate, yet its physical realism in coarse‐resolution General Circulation Models (GCMs) remains debated. We examine anvil cloud formation by performing simulations with a GCM with a hierarchy of cloud fraction schemes ranging from a complex prognostic Tiedtke scheme to a simple binary scheme. All schemes consistently reproduce the anvil peak. The robust anvil peak arises because extremely cold temperatures at the upper troposphere facilitate frequent saturation events, producing clouds that disproportionately influence mean cloud fraction. Sensitivity experiments with enhanced evaporation of cloud condensate unexpectedly show increased anvil coverage, highlighting how slight evaporative moistening reinforces local saturation in cold upper‐tropospheric conditions. These results demonstrate that the tropical anvil cloud peak emerges from fundamental thermodynamic constraints, rather than specific cloud fraction parameterization choices.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2021

Estimating outflow masses and velocities in merger simulations: Impact of r -process heating and neutrino cooling

Here, the determination of the mass, composition, and geometry of matter outflows in black hole-neutron star and neutron star-neutron star binaries is crucial to current efforts to model kilonovae and to understand the role of neutron star merger in r-process nucleosynthesis. In this manuscript, we review the simple criteria currently used in merger simulations to determine whether matter is unbound and what the asymptotic velocity of ejected material will be. We then show that properly accounting for both heating and cooling during r-process nucleosynthesis is important to accurately predict the mass and kinetic energy of the outflows. These processes are also likely to be crucial to predict the fall-back timescale of any bound ejecta. We derive a model for the asymptotic velocity of unbound matter and binding energy of bound matter that accounts for both of these effects and that can easily be implemented in merger simulations. We show, however, that the detailed velocity distribution and geometry of the outflows can currently only be captured by full three-dimensional fluid simulations of the outflows, as nonlocal effect ignored by the simple criteria used in merger simulations cannot be safely neglected when modeling these effects. Finally, we propose the introduction of simple source terms in the fluid equations to approximately account for heating/cooling from r-process nucleosynthesis in future seconds-long three-dimensional simulations of merger remnants, without the explicit inclusion of out-of-nuclear statistical equilibrium reactions in the simulations.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2017

Experimental Capability for Preparation and Purification of Molten Salts to Support Advanced Reactor Concepts, Nuclear Hybrid Energy Systems and Dynamic Grid Energy Storage Concepts

High-temperature multi-fluid, multi-loop test facility to support thermal hydraulic, materials, and thermal energy storage research for nuclear and nuclear-hybrid applications is being developed at Idaho National Laboratory (INL). In its initial configuration, the facility will include a high-temperature helium loop, a liquid salt loop, and a hot water/steam loop. The three loops will be thermally coupled through an intermediate heat exchanger (IHX) and a secondary heat exchanger (SHX). Based on its relevance to advanced reactor systems, the new facility has been named the Advanced Reactor Technology Integral System Test (ARTIST) facility. The main objectives to be addressed with this facility include the characterization and performance evaluation of candidate compact heat exchangers at prototypical operating conditions, flow, and heat transfer issues related to core thermal hydraulics in advanced helium-cooled and salt-cooled reactors, and evaluation of corrosion behavior of new cladding materials and accident-tolerant fuels for light water reactors at prototypical conditions. Fluoride salt coolants are eutectic binary or tertiary mixtures of fluoride salts with melting points in the range of 320 to 500 deg. C. Fluoride high temperature reactors have reactor outlet temperatures of 600 deg. C or higher for high-efficiency power generation or process heat applications. To address research needs related to salt coolants experimental capability has been added to study thermodynamic properties such as melting point temperature, heat capacity, and thermal conductivity.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2023

Improved Particle Heat Transfer by way of Bimodal Particle Distributions for High Temperature Solar Thermal Energy

High temperature solar thermal facilities are looking to increase operating temperatures through novel heat transfer media, one such being solid particles. These particles operating at high temperatures will require transferring their thermal energy into another working fluid like supercritical carbon dioxide which can be used in advanced power cycles. Achieving high heat transfer between the particles and supercritical carbon dioxide is essential to high efficiency and low-cost operation. Therefore, optimizing the thermal conductivity of these particles is one potential way to ensure high performance. Traditionally, unimodal particle distributions have been employed in high temperature particle solar power plants. However, ambient temperature testing of bimodal particle distributions has revealed a superior thermal conductivity when compared to its unimodal counterpart at the same temperature. This data was obtained by certified, off-the-shelf instruments that can effectively simulate the conditions a particle would be exposed to in a high temperature solar thermal system. Data obtained in this way suggests that the increased thermal conductively imputed by a bimodal particle distribution is significant at working temperatures in solar facilities. Furthermore, the thermal conductivity of these bimodal particle distributions peaks when the best combination of large and small particles is applied. At high temperatures, binary particle distributions are compared to monodispersed distributions of larger particles where heat transfer is more prolific due to the increased surface radiation. Various thermal conductivity, porosity and heat exchanger models are explored in conjunction with data acquired up to 700 C.

Stout, Dallin (ORCID:0009000294586091)↗

NASA NTRS2016

Apatite-Melt Partitioning at 1 Bar: An Assessment of Apatite-Melt Exchange Equilibria Resulting from Non-Ideal Mixing of F and Cl in Apatite

The mineral apatite [Ca5(PO4)3(F,Cl,OH)] is present in a wide range of planetary materials. Due to the presence of volatiles within its crystal structure (X-site), many recent studies have attempted to use apatite to constrain the volatile contents of planetary magmas and mantle sources. In order to use the volatile contents of apatite to precisely determine the abundances of volatiles in coexisting silicate melt or fluids, thermodynamic models for the apatite solid solution and for the apatite components in multi-component silicate melts and fluids are required. Although some thermodynamic models for apatite have been developed, they are incomplete. Furthermore, no mixing model is available for all of the apatite components in silicate melts or fluids, especially for F and Cl components. Several experimental studies have investigated the apatite-melt and apatite-fluid partitioning behavior of F, Cl, and OH in terrestrial and planetary systems, which have determined that apatite-melt partitioning of volatiles are best described as exchange equilibria similar to Fe-Mg partitioning between olivine and silicate melt. However, McCubbin et al. recently reported that the exchange coefficients may vary in portions of apatite compositional space where F, Cl, and OH do not mix ideally in apatite. In particular, solution calorimetry data of apatite compositions along the F-Cl join exhibit substantial excess enthalpies of mixing. In the present study, we conducted apatite-melt partitioning experiments in evacuated, sealed silica-glass tubes at approximately 1 bar and 950-1050 degrees Centigrade on a synthetic Martian basalt composition equivalent to the basaltic shergottite Queen Alexandria Range (QUE) 94201. These experiments were conducted dry, at low pressure, to assess the effects of temperature and apatite composition on the partitioning behavior of F and Cl between apatite and basaltic melt along the F-Cl apatite binary join, where there is non-ideal mixing of F and Cl in apatite.

McCubbin, F. M.↗

DOE OSTI2023

Magnetically driven coupling in relativistic radiation-mediated shocks

ABSTRACT The radiation drag in photon-rich environments of cosmic explosions can seed kinetic instabilities by inducing velocity spreads between relativistically streaming plasma components. Such microturbulence is likely imprinted on the breakout signals of radiation-mediated shocks. However, large-scale, transverse magnetic fields in the deceleration region of the shock transition can suppress the dominant kinetic instabilities by preventing the development of velocity separations between electron–positron pairs and a heavy ion species. We use a 1D five-fluid radiative transfer code to generate self-consistent profiles of the radiation drag force and plasma composition in the deceleration region. For increasing magnetization, our models predict rapidly growing pair multiplicities and a substantial radiative drag developing self-similarly throughout the deceleration region. We extract the critical magnetization parameter σc, determining the limiting magnetic field strength at which a three-species plasma can develop kinetic instabilities before reaching the isotropized downstream. For a relativistic, single ion plasma drifting with γu = 10 in the upstream of a relativistic radiation-mediated shock, we find the threshold σc ≈ 10−7 for the onset of microturbulence. Suppression of plasma instabilities in the case of multi-ion composition would likely require much higher values of σc. Identifying high-energy signatures of microturbulence in shock breakout signals and combining them with the magnetization limits provided in this work will allow a deeper understanding of the magnetic environment of cosmic explosions like supernovae, gamma-ray bursts, and neutron star binary mergers.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2017

A New View on the Maximum Mass of Differentially Rotating Neutron Stars

We study the main astrophysical properties of differentially rotating neutron stars described as stationary and axisymmetric configurations of a moderately stiff Γ=2 polytropic fluid. The high level of accuracy and of stability of our relativistic multidomain pseudo-spectral code enables us to explore the whole solution space for broad ranges of the degree of differential rotation, but also of the stellar density and oblateness. Staying within an astrophysically motivated range of rotation profiles, we investigate the characteristics of neutron stars with maximal mass for all types of families of differentially rotating relativistic objects identified in a previous article. We find that the maximum mass depends on both the degree of differential rotation and the type of solution. It turns out that the maximum allowed mass can be up to 4 times higher than what it is for nonrotating stars with the same equation of state. Such values are obtained for a modest degree of differential rotation but for one of the newly discovered types of solutions. Since such configurations of stars are not that extreme, this result may have important consequences for the gravitational wave signal expected from coalescing neutron star binaries or from some supernova events.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2019

Autogenous healing of Engineered Cementitious Composites (ECC) based on MgO-fly ash binary system activated by carbonation curing

Developing self-healing of concrete cracks represents a critical approach for extending material longevity. If demonstrated on concretes with CO 2 stored through carbonation curing, self-healing can further mitigate infrastructure lifecycle emissions. In this study, the self-healing process is investigated on novel Engineered Cementitious Composites (ECC) based on binary blends of reactive MgO cement and siliceous fly ash activated by carbonation. The self-healing was observed under cyclic wetting and drying exposures and was characterized by measurements of resonance frequency, optical microscopy and X-ray computed microtomography (XCT). Thermogravimetric analysis, X-ray powder diffraction and scanning electron microscopy were employed to assist in identifying healing products and mechanisms. It was found that micro-cracks could be autogenously filled in 7 wet-dry cycles, as evidenced by over 95% recovery of resonance frequency and healed crack appearance under optical microscopic observation. Nevertheless, the composite mechanical performance, particularly tensile strength and ductility, did not fully recover with respect to the uncracked specimens. The inadequate post-healing mechanical properties were consistent with XCT observations that indicated low material densities in the cracked area. Based on the chemical and microstructural characterizations, it was determined that nesquehonite crystallites were responsible for the crack filling. Although the nesquehonite filled cracks will be less permeable to invasion of reactive fluids, novel strategies are needed to establish more robust healing capability to completely restore the crack bridging and composite tensile performance.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Impact of particle arrays on phase separation composition patterns

We examine the symmetry-breaking effect of fixed constellations of particles on the surface-directed spinodal decomposition of binary blends in the presence of particles whose surfaces have a preferential affinity for one of the components. Our phase-field simulations indicate that the phase separation morphology in the presence of particle arrays can be tuned to have a continuous, droplet, lamellar, or hybrid morphology depending on the interparticle spacing, blend composition, and time. In particular, when the interparticle spacing is large compared to the spinodal wavelength, a transient target pattern composed of alternate rings of preferred and non-preferred phases emerges at early times, tending to adopt the symmetry of the particle configuration. We reveal that such target patterns stabilize for certain characteristic length, time, and composition scales characteristic of the pure phase-separating mixture. To illustrate the general range of phenomena exhibited by mixture-particle systems, we simulate the effects of single-particle, multi-particle, and cluster–particle systems having multiple geometrical configurations of the particle characteristic of pattern substrates on phase separation. Our simulations show that tailoring the particle configuration, or substrate pattern configuration, a relative fluid-particle composition should allow the desirable control of the phase separation morphology as in block copolymer materials, but where the scales accessible to this approach of organizing phase-separated fluids usually are significantly larger. Limited experiments confirm the trends observed in our simulations, which should provide some guidance in engineering patterned blend and other mixtures of technological interest.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2003

Simulating the Effect of Space Vehicle Environments on Directional Solidification of a Binary Alloy

Space microgravity missions are designed to provide a microgravity environment for scientific experiments, but these missions cannot provide a perfect environment, due to vibrations caused by crew activity, on-board experiments, support systems (pumps, fans, etc.), periodic orbital maneuvers, and water dumps. Therefore, it is necessary to predict the impact of these vibrations on space experiments, prior to performing them. Simulations were conducted to study the effect of the vibrations on the directional solidification of a dendritic alloy. Finite element ca!cu!attie?ls were dme with a simd2titcr based on a continuum model of dendritic solidification, using the Fractional Step Method (FSM). The FSM splits the solution of the momentum equation into two steps: the viscous intermediate step, which does not enforce continuity; and the inviscid projection step, which calculates the pressure and enforces continuity. The FSM provides significant computational benefits for predicting flows in a directionally solidified alloy, compared to other methods presently employed, because of the efficiency gains in the uncoupled solution of velocity and pressure. finite differences, arises when the interdendritic liquid reaches the eutectic temperature and concentration. When a node reaches eutectic temperature, it is assumed that the solidification of the eutectic liquid continues at constant temperature until all the eutectic is solidified. With this approach, solidification is not achieved continuously across an element; rather, the element is not considered solidified until the eutectic isotherm overtakes the top nodes. For microgravity simulations, where the convection is driven by shrinkage, it introduces large variations in the fluid velocity. When the eutectic isotherm reaches a node, all the eutectic must be solidified in a short period, causing an abrupt increase in velocity. To overcome this difficulty, we employed a scheme to numerically predict a more accurate value for the rate of change of fraction of liquid as the liquid in an element solidifies. The new method enables us to contrast results of simulations in which the alloy is subjected to no gravity or a steady-state acceleration versus simulations when the alloy is subjected to vibration disturbances; therefore, the effect of vibration disturbances can be assessed more accurately. To assess the impact of these vibration-perturbations, transient accelerometer data from a space shuttle mission are used as inputs for the simulation model. These on-orbit acceleration data were obtained from the Microgravity Science Division at Glenn Research Center (GRC- MSD) and are applied to the buoyancy term of the momentum equation in a simulation of a Pb-5.8 wt. % Sb alloy that solidifies in a thermal gradient of 4000 K/m and a translation velocity of 3 p d s . Figure 2 shows the vertical velocity of a node that begins in the all-liquid region and subsequently solidifies; the vibrations are applied at 5000 seconds in this simulation. An important difficulty, common to all solidification models based on finite elements or 2 The magnitudes of the velocity oscillations that are vibration-induced are very small and acceptable. The biggest concern is whether the concentration of the liquid near the dendrite tips is distorted because of the vibration-induced perturbations. Results for this case show no concentration oscillations present in the all-liquid region.

Westra, D. G.↗

DOE OSTI2026

Axisymmetric hydrodynamics in numerical relativity: treating coordinate singularity, artificial heating and modeling MHD instabilities

Two-dimensional axisymmetric simulations of binary neutron star (BNS) merger remnant are a cheap alternative to 3D simulations. To maintain realism for secular timescales, simulations must avoid accumulated errors from drifts in conserved quantities and artificial heating, and they must model turbulent transport in a way that remains plausible throughout the evolution. It is also crucial to avoid numerical artifacts due to the polar coordinate axis singularity. Methods that behave well near the axis often break flux-conservative form of the hydrodynamic equations, resulting in significant drifts in conserved quantities. We present a flux-conservative scheme that maintains smoothness near the axis without sacrificing conservative formulation of the equations or incurring drifts in conserved global quantities. We compare the numerical performance of different treatments of the hydrodynamic equations when evolving a hypermassive neutron star resembling the remnant of a BNS merger. These simulations demonstrate that the new scheme combines the axis smoothness of non-conservative methods with the mass and angular momentum conservation of other conservative methods on $\sim 10^2$ ms timescales of viscous and neutrino-driven evolution. Because fluid profiles remain smooth in the remnant interior, it is possible to remove artificial heating by evolving the entropy density. We show how physical heating and cooling terms can be easily calculated from source terms of the conservative evolution variables and demonstrate our implementation. Finally, we discuss and implement improvements to the effective viscosity scheme to better model the effect of magnetohydrodynamic instabilities as the remnant evolves.

axisymmetry↗

DOE OSTI2018

Dynamic Process Intensification of Binary Distillation via Periodic Operation

This paper applies the concept of dynamic intensification (defined as changes to the dynamics, operation strategy, and/or control of a process that lead to a substantially more efficient processing path) to binary distillation columns. The resulting strategy consists of manufacturing a target product as a blend of two auxiliary products, both having lower energy demands than a reference value, which corresponds to producing the target product(s) in a column operating at steady state. Here, a discussion of the appropriate control structures and switching strategies between the two auxiliary products is provided. An extensive case study concerning the separation of a methanol–1-propanol mixture was carried out, demonstrating that energy savings in the order of 1.4% are possible with no disruption in product quality or production rate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2001

Vapor Growth of Binary and Ternary Chalcogenides in Preparation for Microgravity Experiments

In the bulk crystal growth of some technologically important semiconducting chalcopyrites, such as ZnTe, CdS, ZnSe and ZnS, vapor growth techniques have significant advantages over melt growth techniques due to the high melting points of these materials. The realization of routine production of high-quality single crystals of these semiconductors requires a fundamental, systematic and in-depth study on the PVT growth process and crystal growth by vapor transport in low gravity offers a set of unique conditions for this study. Previously, two reasons have been put forward to account for this. The first is weight-related reductions in crystal strain and defects. These are thought to be caused by the weight of the crystals during processing at elevated temperatures and retained on cooling, particularly for materials with a low yield strength. The second, and more general, reason is related to the reduction in density-gradient driven convection. The PVT crystal growth process consists of essentially three processes: sublimation of the source material, transport of the vapor species and condensation of the vapor species to form the crystal. The latter two processes can be affected by the convection caused by gravitational accelerations on Earth. Reductions in such convection in low gravity is expected to yield a nearly diffusion-limited growth condition which results in more uniform growth rates (on the microscopic scale) and hence greater crystalline perfection and compositional homogeneity. The reduction of convective contamination by performing flight experiments in a reduced gravity environment will help to understand the relation between fluid phase processes (growth parameters) and defect and impurity incorporation in grown crystals.

Su, C.↗

NASA NTRS2001

Vapor Growth of Binary and Ternary Chalcogenides in Preparation for Microgravity Experiments

Su, Ching-Hua↗

NASA NTRS2013

Uncertainty Determination for Aeroheating in Uranus and Saturn Probe Entries by the Monte Carlo Method

The 2013-2022 Decaedal survey for planetary exploration has identified probe missions to Uranus and Saturn as high priorities. This work endeavors to examine the uncertainty for determining aeroheating in such entry environments. Representative entry trajectories are constructed using the TRAJ software. Flowfields at selected points on the trajectories are then computed using the Data Parallel Line Relaxation (DPLR) Computational Fluid Dynamics Code. A Monte Carlo study is performed on the DPLR input parameters to determine the uncertainty in the predicted aeroheating, and correlation coefficients are examined to identify which input parameters show the most influence on the uncertainty. A review of the present best practices for input parameters (e.g. transport coefficient and vibrational relaxation time) is also conducted. It is found that the 2(sigma) - uncertainty for heating on Uranus entry is no more than 2.1%, assuming an equilibrium catalytic wall, with the uncertainty being determined primarily by diffusion and H(sub 2) recombination rate within the boundary layer. However, if the wall is assumed to be partially or non-catalytic, this uncertainty may increase to as large as 18%. The catalytic wall model can contribute over 3x change in heat flux and a 20% variation in film coefficient. Therefore, coupled material response/fluid dynamic models are recommended for this problem. It was also found that much of this variability is artificially suppressed when a constant Schmidt number approach is implemented. Because the boundary layer is reacting, it is necessary to employ self-consistent effective binary diffusion to obtain a correct thermal transport solution. For Saturn entries, the 2(sigma) - uncertainty for convective heating was less than 3.7%. The major uncertainty driver was dependent on shock temperature/velocity, changing from boundary layer thermal conductivity to diffusivity and then to shock layer ionization rate as velocity increases. While radiative heating for Uranus entry was negligible, the nominal solution for Saturn computed up to 20% radiative heating at the highest velocity examined. The radiative heating followed a non-normal distribution, with up to a 3x variation in magnitude. This uncertainty is driven by the H(sub 2) dissociation rate, as H(sub 2) that persists in the hot non-equilibrium zone contributes significantly to radiation.

Palmer, Grant↗

DOE OSTI2020

Adsorption of furan, hexanoic acid, and alkanes in a hierarchical zeolite at reaction conditions: Insights from molecular simulations

Hierarchical zeolites containing both micropores and mesopores are valuable catalysts for facilitating reactions of large molecules. Furan acylation by fatty acids is a promising reaction for valorizing biomass, and the self-pillared pentasil (SPP) zeolite was found to perform particularly well for this reaction. To better understand the distribution of molecules in hierarchical zeolites at the elevated temperature (T = 523 K) and the elevated pressure (p >1 bar) associated with typical reaction conditions, unary and binary adsorption were predicted using Monte Carlo simulations in the isothermal–isobaric Gibbs ensemble. Adsorption of six species (furan, hexanoic acid, -hexane, -decane, -tetradecane, and 3,6-diethyloctane) was investigated from vapor, liquid, and supercritical phases, and loadings into the micropores, onto the mesopore surface, and in the mesopore interior of SPP were obtained. As pressure increases, -alkanes fill the micropores before loading the surface and then the interior of the mesopore, while furan and hexanoic acid adsorb strongly to the mesopore surface due to hydrogen bonding interactions with surface silanols. Hydrogen bonding interactions also draw hexanoic acid molecules in the micropore region toward the pore mouths, so their carboxylic acid group forms H-bonds with silanols, while the alkyl tails interact with the micropore walls. Mesopore condensation is observed for molecules below their critical point, and occurs when the Gibbs free energy of transfer into the mesopore interior and onto the mesopore surface converge. When hexanoic acid adsorption occurs in the presence of alkane solvents, then the selectivity and spatial distribution of hexanoic acid in the micropores and on the surface can be tuned by adjusting the fluid pressure and the alkane length and/or branching.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗