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At least 19 records

Isotherm Modeling and Techno-Economic Analysis of Contactor Technologies for New Tetraamine-Appended MOF for NGCC Applications

Recently, a family of tetraamine-functionalized metal-organic frameworks (MOF) has been reported as promising sorbent materials for capturing CO2 from flue gas conditions relevant to natural gas combined cycle (NGCC) applications. The main advantages of these materials are their two-step cooperative CO2 adsorption, which gives rise to unusual two step-shaped CO2 adsorption profiles and their high thermal stability. This work presents the modelling of the two-transition isotherm of the tetraamine-appended MOF, N,N'-bis(3-aminopropyl)-1,4-diaminobutane (3-4-3)-appended Mg2(dobpdc), and the techno-economic analysis (TEA) of carbon capture processes utilizing this sorbent. Due to the unusual isotherm shapes of the experimental CO2 adsorption data for tetraamine-appended Mg2(dobpdc) and the strong nonlinearity of CO2 loading with respect to temperature and pressure, we tested two different models which use logistic functions for representing the different isotherm behaviors in the different pressure ranges. The first model uses the quadratic isotherm model in the low-pressure region, the Langmuir isotherm model in the middle pressure range, and the dual site Langmuir isotherm model in the high-pressure range. To model the transition between regions we used the arctangent functions independent of temperature and the thermal effect was accounted by using the Clausius-Clapeyron relation]. The second model is an extension of the weighted dual-site Langmuir isotherm model presented by Hughes et al.. In this extended model, the dual-site Langmuir isotherm is employed in the three transition regions, using temperature-dependent logistic functions to activate or deactivate the isotherm model in the low, middle, and high-pressure ranges. Both models fit the experimental data quite well with root mean squared errors (RMSE’s) of 0.41 and 0.17 for model 1 and model 2, respectively. Since model 2 resulted in a lower RMSE, it was leveraged for the development of the gas/solid contactor models used by the TEA. Specifically, two different contactor models, an axial-flow fixed bed and moving bed contactor, were developed as part of this work. These models are dynamic, pressure-driven, and consist of mass, energy, and momentum conservation equations. A kinetic model was also developed by performing parameter estimation using experimental fixed bed breakthrough data. These models are then used to simulate CO2 capture processes from the flue gas generated from a ~600 gross MW NGCC power plant. A cost model was developed which considers the capital cost of the reactors and the significant operating costs such as steam and electricity. Using NETL’s Framework for the Optimization and Quantification of Uncertainty of Uncertainty and Surrogates tool (FOQUS), which has the capability of linking models built using numerous modelling platforms with derivative-free optimization solvers, a techno-economic optimization of the carbon capture processes was performed which minimizes the cost of capture.

Caballero, Daison↗

From Langmuir isotherm to Brunauer–Emmett–Teller isotherm

Abstract Developed for multilayer adsorption, the Brunauer–Emmett–Teller ( BET) isotherm considers the adsorption of the first layer as an equilibrium chemical reaction between adsorbate molecules and adsorption sites and the adsorption of the second and subsequent layers as a condensation–evaporation process. Following the recent development of an activity‐based formulation for the Langmuir isotherm for monolayer adsorption, we present an activity‐based formulation for the BET isotherm in which species concentrations are replaced with species activities. Capturing the adsorbent surface heterogeneity for the adsorption of the first layer, the resulting thermodynamic BET isotherm is shown to accurately represent pure component adsorption isotherms over the relative pressure range of zero to unity or prior to the onset of capillary condensation. The thermodynamic BET isotherm should facilitate accurate estimation of monolayer adsorption capacity and the corresponding adsorbent surface area.

Vyawahare, Pradeep↗

Generalized Brunauer–Emmett–Teller Isotherm for Mixed-Gas Multilayer Adsorption Equilibria

Here, this work presents a rigorous thermodynamic framework to calculate mixed-gas multilayer adsorption equilibria from single-component isotherms and vapor–liquid equilibria. Named the generalized Brunauer–Emmett–Teller (gBET) isotherm, the newly formulated isotherm considers adsorbent surface heterogeneity, competitive adsorption on the monolayer, condensation–evaporation on the subsequent layers, and adsorbed phase nonideality for the monolayer and the subsequent layers. The monolayer adsorbed phase nonideality is tracked by using an area-based adsorption nonrandom two-liquid activity coefficient model. The adsorbed phase composition and corresponding nonideality in the subsequent layers are calculated at the dew point condition of the mixed gas with either an equation of state or an activity coefficient model for the vapor–liquid equilibria. The proposed model is validated with six single and three binary multilayer adsorption equilibrium systems, and the model results are compared against those from the classical BET isotherm for single-component adsorption and ideal adsorbed solution theory for mixed-gas adsorption equilibria.

09 BIOMASS FUELS↗

Numerical Model for Isothermal and Non-Isothermal Crystallization of Liquids and Glasses

A new numerical model of isothermal and non-isothermal first order phase transformations, such as the crystallization of liquids and glasses, is presented. This model computes directly the volume fraction transformed, taking into account time-dependent nucleation rates and cluster-size-dependent growth velocities. The model is applied to the crystallization of lithium disilicate glass, using the appropriate kinetic and thermodynamic parameters. The model is used (1) to determine the validity of common methods for computing the volume fraction transformed as a function of time in isothermal experiments when a time-dependent nucleation rate is expected, (2) to simulate non-isothermal differential scanning calorimetry (DSC) studies of glass devitrification as a function of scan rate, and (3) to compute the effect of preannealing on the DSC peak parameters. A novel behavior of the nucleation rate with scan rate is predicted, arising because the relaxation of the cluster distribution cannot be described by a single relaxation time. Comparisons of the calculations with experimental data on this glass demonstrate the validity of the model.

Kelton, K. F.↗

An energy model of droplet impingement on an inclined wall under isothermal and non-isothermal environments

The observation of spray-wall interaction is of great importance to understand the dynamics that occur during fuel impingement onto the chamber wall or piston surfaces in internal combustion engines. It is found that the maximum spreading length of an impinged droplet can provide a quantitative estimation of heat transfer and energy transformation for spray-wall interaction. Furthermore, it influences the air-fuel mixing and hydrocarbon and particle emissions at combusting conditions. In this paper, an analytical model of different droplet-wall impingement conditions is developed in terms of βm (dimensionless maximum spreading length, the ratio of maximum spreading length to initial droplet diameter) to understand the detailed impinging dynamic process. These conditions are grouped as: a single diesel droplet impinging on the wall with different inclined angles (α); cold wall - heated droplet and heated wall - cold droplet impingement when inclined angle of the wall is 0°, respectively. The analytical model is built up based on the energy conservation that considers kinetic energy, gravitation energy, and surface energy before impingement, as well as viscous dissipation, gravitation energy, adhesion energy, deformation energy, and heat energy after impingement. The experimental work of diesel droplet impinging on an inclined wall is performed at a certain range of the Weber number (We of 33 to 420) with various inclined angles (α of 0° to 45°), while for inclined angle is 0°, droplet and wall temperature are varied from 25°C to 150°C to study the effects of the inclined angle and temperature on the temporal evolution of the post-impingement characteristics (i.e. droplet spreading length, dynamic contact angle). The analytical model is validated and evaluated at the aforementioned experimental operating points. The validated model can be employed to predict maximum spreading length of the droplet impinged on the wall. It is further utilized to determine the transition from capillary regime to kinetic regime, then to viscous regime at different inclined angle of the wall.

42 ENGINEERING↗

Evaluation of residual stresses in isothermal friction stir welded 304L stainless steel plates

Friction stir welding was performed on 304L SS plates in order to heal simulated cracks created by electrical discharge machining. Two different tool temperatures (825 and 725 °C) were chosen for this study. Both neutron diffraction and X-ray diffraction techniques were employed to evaluate the residual stresses along two orthogonal reference directions, longitudinal (syy) and transverse (sxx). The former technique was also used to measure residual stresses at various depths. It was found that, at 1 mm depth from the top surface inside the stir zone (SZ), the longitudinal component was tensile in nature while the transverse component was compressive. The nature and magnitude of the residual stress fields, and the position of the peak residual stresses were found to vary with the weld depth. The SZ of the 725 °C weld exhibited higher peak stress than 825 °C weld mainly due to a lack of stress relief at the lower temperature.

Friction stir welding, Steel↗

Energy transfer by radiation in non-grey atomic gases in isothermal and non-isothermal slabs

A multiband model for the absorption coefficient of atomic hydrogen-helium plasmas is constructed which includes continuum and line contributions. Emission from 28 stronger lines of 106 that have been screened is considered, of which 21 are from hydrogen and 7 belong to helium, with reabsorption due to line-line, line-continuum overlap accurately accounted for. The model is utilized in the computation of intensities and fluxes from shock-heated slabs of 85% H2-15% He mixtures for slab thicknesses from 1 to 30 cm, temperature from 10,000 to 20,000 K, and for different densities. In conjunction with the multiband model, simple numerical schemes have been devised which provide a quick and comprehensive way of computing radiative energy transfer in nonisothermal and nongrey gases.

Poon, P. T. Y.↗

Experimentally Verified Alkane Adsorption Isotherms in Nanoporous Materials from Literature Meta-Analysis

Identification of independent experimental replicate measurements of well-defined physical properties provides a useful way to assess the reproducibility of literature reports of these properties. Prior meta-analysis of this kind for single-component adsorption of CO 2 and alcohols in nanoporous materials showed that ~20% of reported isotherms for these molecules were inconsistent with available replicate measurements. Here, we extend this analysis to the single-component adsorption of alkanes in nanoporous materials using a collection of 2998 experimental isotherms. Among these isotherms, 846 replicates were identified and analyzed. Many more replicates are available for CH 4 adsorption than for any other alkane. Our analysis finds that 15% of the replicate alkane isotherms are inconsistent with other replicate measurements. Furthermore, after discarding these outlier isotherms we report graphical and numerical consensus isotherms for 93 independent combinations of adsorbate, adsorbent, and temperature as well as an assessment of another 124 independent systems for which two replicate isotherms are available.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Isotherm Model for Moisture-Controlled CO 2 Sorption

Moisture-controlled sorption of CO 2 , the basis for moisture-swing CO 2 capture from air, is a novel phenomenon observed in strong-base anion exchange materials. Prior research has shown that Langmuir isotherms provide an approximate fit to moisture-controlled CO 2 sorption isotherm data. However, this fit still lacks a governing equation derived from an analytic model. As such, in this paper we derive an analytic form for an isotherm equation from a bottom-up approach, starting with a fundamental theory for an alkali liquid. In the range of interest relevant to CO 2 capture from air, an isotherm equation for an alkali liquid reduces to a simple analytic form with a single parameter, $K_{\text{eq}}$. In the limit $K_{\text{eq}} \gg 1$, a 2nd order approximation simplifies to a Langmuir isotherm that, however, deviates from experimental data. The isotherm theory for an alkali liquid has been generalized to a strong-base anion exchange material. In a strong-base anion exchange material, water concentration inside a sorbent, [H 2 O], is not large enough to be regarded as constant, which allows us to extend $K_{\text{eq}}$ to $K_{\text{eq(AEM)eff}} = K_{\text{eq(AEM)}} \times$ [H 2 O]$^{–n}$ according to the law of mass action. The final isotherm formula has been validated by experimental data from the literature. For a moisture-controlled CO 2 sorbent, $K_{\text{eq(AEM)eff}}$ varies significantly with moisture content of the sorbent. Depending on moisture level, the observed $K_{\text{eq(AEM)eff}}$ in a specific sorbent ranges from a few times to a few thousand times the value of $K_{\text{eq}}$ of a 2 mol L –1 alkali liquid.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Determining Kinetic Parameters for Isothermal Crystallization of Glasses

Non-isothermal crystallization techniques are frequently used to determine the kinetic parameters for crystallization in glasses. These techniques are experimentally simple and quick compared to the isothermal techniques. However, the analytical models used for non-isothermal data analysis, originally developed for describing isothermal transformation kinetics, are fundamentally flawed. The present paper describes a technique for determining the kinetic parameters for isothermal crystallization in glasses, which eliminates most of the common problems that generally make the studies of isothermal crystallization laborious and time consuming. In this technique, the volume fraction of glass that is crystallized as a function of time during an isothermal hold was determined using differential thermal analysis (DTA). The crystallization parameters for the lithium-disilicate (Li2O.2SiO2) model glass were first determined and compared to the same parameters determined by other techniques to establish the accuracy and usefulness of the present technique. This technique was then used to describe the crystallization kinetics of a complex Ca-Sr-Zn-silicate glass developed for sealing solid oxide fuel cells.

Ray, C. S.↗

Time-dependent water vapor desorption isotherm model of hardened cement paste

Highlights: • Short-term and long-term desorption isotherms of hardened cement paste are reviewed. • Water content at RH depends on both thermodynamic and microstructural equilibria. • An extended GAB equation is proposed to fit the cavitation drop during desorption. • A dynamic time-dependent sorption isotherm model is shown and used for simulations. • Numerical results capture anomalous drying in the same RH as seen experimentally. This study aims to enhance moisture transport modeling by elucidating the so-called anomalous water diffusion in cementitious materials. Water desorption isotherms are measured from samples at various drying stages using techniques with different durations to quantify the impact of the drying duration on the water sorption ability. A single water sorption isotherm does not solely give a relationship between the water content and relative humidity but also represents the state of microstructure. The continuous evolution of a desorption isotherm due to drying-induced microstructural rearrangement is demonstrated. For numerical modeling, the microstructural alteration can be explicitly considered through a dynamic desorption isotherm model, which governs the local thermodynamic equilibrium at the capillary meniscus. This approach is implemented into a multiphase transport code, whose ability to predict drying is validated using literature data. Finally, the effect of prolonged drying on the colloidal nature of the calcium-silicate-hydrate gel is discussed.

36 MATERIALS SCIENCE↗

Correlating isothermal compressibility to nucleon fluctuations in the inner crust of neutron stars

The question of how and which physical observables or thermodynamic parameters can best predict the onset of a possible phase transition in the inner crust of neutron stars remains largely unresolved. Here, using semiclassical Monte Carlo simulations, we investigate the isothermal compressibility and density fluctuations in a region of relevance to the dynamics of the inner crust. We show that the isothermal compressibility serves as a robust observable to characterize the transition from the nonuniform crust to the uniform core for proton fractions over 0.2. Moreover, we show explicitly how the two-component isothermal compressibility, computed using the Kirkwood-Buff theory, is directly connected to the fluctuations in the number density, recorded in the grand canonical ensemble by monitoring the number of particles in a small volume located at the center of the simulation box. That is, we compute mean-square particle fluctuations and compare them against the isothermal compressibility for different proton fractions. Although our results show that the mean-square particle fluctuations are proportional to the isothermal compressibility, the lack of a perfect correlation is attributed to the relatively small number of particles included in the simulations. The nonunity slope observed in the dimensionless isothermal compressibility—total nucleon fluctuation variance relationship suggests that the inner crust of neutron stars is composed of anisotropic and inhomogeneous matter.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Modified Isotherm Modeling to Predict Cs Exchange with Crystalline Silicotitanate in Tank Waste Simulants

The U.S. Department of Energy is working to expedite processing of Hanford tank waste supernate at the Hanford Waste Treatment and Immobilization Plant. To support this goal, Washington River Protection Solutions is designing a Tank Side Cesium Removal (TSCR) system for suspended solids and cesium (Cs/ 137 Cs) removal from Hanford tank waste supernate. The ion exchange media selected for Cs removal at TSCR is crystalline silicotitanate (CST) that is manufactured in a nearly spherical form by Honeywell UOP LLC (UOP; Des Plaines, IL) as product IONSIV® R9140-B (Na form). The Zheng Anthony Miller (ZAM) isotherm model (Zheng et al. 1997) is a multicomponent ion exchange model used to predict the exchange of Group I metals onto CST. The ZAM isotherm has historically been used to predict Cs distribution values from Hanford and Savannah River Site (SRS) tank waste simulants. Figure S.1 summarizes model predictions from the ZAM isotherm that indicate poor prediction of Cs distribution values for simple and complex simulants with the engineered form of CST, IONSIV® R9140-B, and IONSIV® R9120-B where the solid line indicates a perfect fit by the model. The dotted lines indicate ±20% error. Batch contact testing with Hanford tank waste complex and simple simulants was used in conjunction with SRS simulants to experimentally determine Cs distribution values using a modification to the original isotherm model. The experimentally determined maximum Cs capacity for IONSIV® R9140-B CST in both the simple and complex matrices was found to be 0.53±0.3 mmoles Cs/g of CST. This value is not drastically different from the maximum Cs capacity of 0.58 mmoles Cs/g TAM-5 reported by Zheng et al. (1997). However, it is important to note that TAM-5 (commercially IONSIV® IE-910) is a powder. Hamm et al. (2002) determined that a dilution factor was needed to account for the Zr(OH)2 binder in the engineered form of CST. Hamm et al. determined that a dilution factor of 0.68 was appropriate to account for binder contribution and correct overprediction of Cs exchange on the engineered form of CST in ZAM calculations. This reduced the total capacity from 0.58 mmol/g with TAM-5 to 0.39 mmol/g for the engineered form of CST (Hamm et al. 2002). Despite substituting the experimentally determined maximum Cs capacity of 0.55 mmoles Cs/g for the literature-reported capacity of 0.39 mmoles Cs/g, it was determined that additional modifications to the model’s equilibrium rate constants were necessary in refining the isotherm model. The modified model overpredicted K+ uptake by the CST when compared to digested CST results described by Campbell et al. (2019). The modified model was further revised to omit three of the five K+ exchange equilibrium reactions described by ZAM to reduce the additional K+ loading seen by the model. Figure S.2 summarizes the revised model isotherm predictions plotted against measured Kd values.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Thermomechanical and isothermal fatigue behavior of a (90)sub 8 titanium matrix composite

An experimental investigation was conducted to analyze the fatigue damage mechanisms operative in a 35 fiber volume percent (90 deg) titanium matrix composite (TMC) under 427 C isothermal and thermomechanical loading conditions. The thermomechanical fatigue (TMF) tests were performed with a temperature cycle from 200 to 427 C under closely controlled conditions to define both the deformation and fatigue life behavior. Degradation of the TMC's isothermal elastic moduli and coefficient of thermal expansion were monitored throughout the TMF tests. The results indicated TMF life trends which contrasted those established in a comparable (0 deg) system, as TMF loading of the (90 deg) TMC was not found to be 'life-limiting' in comparison to maximum temperature isothermal conditions. In-phase lives were very similar to those established under 427 C isothermal conditions. High stress isothermal fatigue at 427 C produced increased strain ratchetting and stiffness degradation relative to TMF conditions. Out-of-phase loadings produced TMF lives approximately an order of magnitude greater than the lives determined under isothermal and in-phase conditions. Extensive fractography and metallography were also performed. Two key issues were identified and appeared to dominate the fatigue damage and life of the (90 deg) TMC, namely, the weak fiber/matrix interface and environmental attack of the fiber/matrix interface via the exposed (90 deg) fiber ends.

Castelli, Michael G.↗