Dynamic Adsorption of CO2 from Methane: Studies on Mass and Heat Transfer

Three‐dimensional computational fluid dynamics studies related to dynamics adsorption of CO₂ from natural gas is found to be limited. 3D analyses for dynamics adsorption are substantially crucial to give a better prediction on the adsorption process by considering the actual fluid flow behavior within the packed‐bed porous media. A kinetic adsorption model has been integrated in a commercial fluid dynamics simulator to simulate the 3D hydrodynamics and adsorption phenomenon in a zeolite‐filled packed column for a CO₂‐methane separation system. The effects of various parameters such as Reynolds number, CO₂ feed concentration, feed temperature, and column dimension on CO₂ adsorption efficiency have been investigated. A correlation for adsorption efficiency based on the CO₂ concentration profiles has been developed and validated.     

Simultaneous optimization of CO2 emissions reduction strategies for effective carbon control in the process industries

Concerns about global warming have led governments to regulate CO₂ emissions, including through emissions caps, trading and penalties, thus creating economic incentives to reduce CO₂ emissions. This paper presents a mathematical model based on a MINLP formulation to address the problem of CO₂ emissions from large-scale sites in the process industries. The proposed approach considers the interactions between process units, associated heat exchanger networks and the site utility system. The CO₂ emissions reduction strategies considered include retrofit of heat exchanger networks (HENs), operational optimization of the utility system and fuel switching. The mathematical model captures interactions between the HEN and the utility system; the optimization explores these interactions systematically within a superstructure of CO₂ reduction options. The optimization objective is to determine suitable CO₂-mitigation options for a given emissions reduction target and available capital for investment, taking carbon trading issues into account. The proposed approach is applied to a published industrial case study; the results demonstrate the applicability of the approach to finding cost-effective solutions for CO₂ emissions reduction. Results show that the best solution CO₂ emissions reduction is affected by carbon trading. Therefore, opportunities to sell CO₂ allowances, if practically achievable, play an important role in the process economics.     

Uncertainty quantification via bayesian inference using sequential monte carlo methods for CO2 adsorption process

This work presents the uncertainty quantification, which includes parametric inference along with uncertainty propagation, for CO₂ adsorption in a hollow fiber sorbent, a complex dynamic chemical process. Parametric inference via Bayesian approach is performed using Sequential Monte Carlo, a completely parallel algorithm, and the predictions are obtained by propagating the posterior distribution through the model. The presence of residual variability in the observed data and model inadequacy often present a significant challenge in performing the parametric inference. In this work, residual variability in the observed data is handled by three different approaches: (a) by performing inference with isolated data sets, (b) by increasing the uncertainty in model parameters, and finally, (c) by using a model discrepancy term to account for the uncertainty. The pros and cons of each of the three approaches are illustrated along with the predicted distributions of CO₂ breakthrough capacity for a scaled‐up process. © 2016 American Institute of Chemical Engineers AIChE J, 62: 3352–3368, 2016     

Mathematical modeling of extraction of egg yolk oil with supercritical CO2

Extraction of egg yolk oil (EYO) from egg yolk powder (EYP) with supercritical CO₂ was performed on a laboratory apparatus. Solubility of EYO in supercritical CO₂ was measured. The external diffusion and the equilibrium between solid and fluid phases were experimentally found to be the controlling steps during the extraction process. Based on this mechanism, a mathematical model for this extraction process was developed. The model parameters, adsorption equilibrium constant (k_p), EYO concentration in solid controlling the transition in the equilibrium (x_k) and the overall volumetric mass transfer coefficient (K_fa_p), were obtained by simulation. The simulation results indicated that x_k is 0.56, K_fa_p is directly proportional to CO₂ flow rate with an exponent of 0.548, and the adsorption heat of EYO is 6–9 kJ mol⁻¹. The model was verified by concentration profiles of solid. The extraction process of EYO with supercritical CO₂ was conducted on a pilot plant and the developed model could predict satisfactorily the process.     

A study of methodologies for CO2 storage capacity estimation of coal

Carbon dioxide (CO₂) capture and storage (CCS) in unmineable coal seams is regarded as one of the possible approaches to mitigate the ever increasing CO₂ concentration in the atmosphere resulting from human activities since the Industrial Revolution. Injection of CO₂ into unmineable coal seams not only provides a solution for long term storage of CO₂ but it also provides the added advantage of enhancing coalbed methane recovery. Adsorption is the main trapping mechanism for CO₂ storage in coal seams where it constitutes to about 95–98% of total storage. Other trapping mechanisms include gas trapped within the matrix structure, free gas and CO₂ trapped as a solute in the pore water. Coal is usually highly heterogeneous and contains pores of different sizes: micropores, mesopores and macropores. The physical properties such as permeability, which usually changes with depth and the degree of cleating, complicates the storage capacity estimation process. Injection of highly dense phase CO₂ may offer higher storage capacity because of its higher density compared to gaseous CO₂. However, there is a lack of verified CO₂ storage capacity estimation methodology for coalbeds. Computing storage potential of CO₂ is not straightforward due to the highly variable coal properties even in the same coal seam. Therefore, in this paper a statistical framework for estimating the CO₂ storage capacity in coal seams is presented with the emphasis on highly dense CO₂ conditions. The approach is based on earlier studies, which utilise important in situ parameters to estimate storage capacity in coal seams. These parameters include volatile matter content, moisture, ash, pressure and temperature. Furthermore, several widely used adsorption models for single- and multi-component gas are reviewed. The ability of the various models in predicting the adsorption capacity for different coal types and under various in situ conditions was examined. Dataset consists of adsorption data representing 69 coal types having vitrinite reflectance ranging from 0.25% to 3.86%. Results of analyses of this dataset showed that better estimation can be obtained by expressing adsorption capacity as a power function of pressure rather than assuming a linear relationship between adsorption capacity and pressure while keeping other important parameters unchanged.     

Hydrogen Production by Sorption‐Enhanced Steam Glycerol Reforming: Sorption Kinetics and Reactor Simulation

Sorption‐enhanced glycerol reforming, an integrated process involving glycerol catalytic steam reforming and in situ CO₂ removal, offers a promising alternative for single‐stage hydrogen production with high purity, reducing the abundant glycerol by‐product streams. This work investigates this process in a fixed‐bed reactor, via a two‐scale, nonisothermal, unsteady‐state model, highlighting the effect of key operating parameters on the process performance. CO₂ adsorption kinetics was investigated experimentally and described by a mathematical reaction‐rate model. The integrated process presents an opportunity to improve the economics of green hydrogen production via an enhanced thermal efficiency process, the exothermic CO₂ adsorption providing the heat to endothermic steam glycerol reforming, while reducing the capital cost by removing the processing steps required for subsequently CO₂ separation. The operational time of producing high‐purity hydrogen can be enhanced by increasing the adsorbent/catalyst volume ratio, by adding steam to the reaction system and by increasing the inlet reactor temperature. © 2012 American Institute of Chemical Engineers AIChE J, 59: 2105–2118, 2013     

A new approach to quantify the microporosity of activated carbons by analysing the N2/77 K and CO2/273 K adsorption data by the simplex flexible method

A mathematical model has been applied to N₂/77 K and CO₂/273 K adsorption isotherms for a series of activated carbons prepared by carbonising olive stones in N₂ and then activating them in CO₂ to six different levels of burn-off in the range 8–80%. Narrow and wide micropore volumes of activated carbons were calculated from the Dubinin-Radushkevich and Dubinin-Astakhov equations considering one, two and three micropore size distributions in each sample, and allowing a variation of the micropore volume and characteristic energy of each distribution with the burn-off. The flexible simplex method was applied to obtain the parameters of each distribution in the mathematical model. Generally, it was found that increasing the number of micropore size distributions above two did not significantly improve fits. Each isotherm was fitted using six parameters at most. However, various constraints were imposed, and the parameters were estimated from each isotherm using non-linear, least-squares regression analysis. The results obtained confirm the valuable use of CO₂/273 K adsorption to quantify the narrow microporosity of activated carbons. Differences between N₂/77 K and CO₂/273 K adsorption in microporous activated carbons were due to the wide microporosity. An agreement between micropore volumes obtained from CO₂/273 K adsorption and that corresponding to one of the two distributions of micropores obtained from N₂/77 K adsorption was obtained. The Dubinin-Radushkevich equation was more successful than the Dubinin-Astakhov equation in the quantification of the microporosity with N₂/77 K and CO₂/273 K. On the other hand, the exponent n of the Dubinin-Astakhov equation was better correlated with the burn-off of the carbons than with the parameter B.     

Study of the CO2 adsorption isotherms on El Hicha clay by statistical physics treatment: microscopic and macroscopic investigation

ABSTRACT

CO₂ introduction in deep aquifers based on adsorption phenomena represents geological tanks that reduce CO₂ emission. Thus, investigating carbon dioxide adsorption on rocks is becoming more interesting. In our work, carbon dioxide adsorption on El Hicha clay is extensively studied. Experimental data for CO₂ adsorption on this clay are given for the first time. All the corresponding parameters are simulated and interpreted using the multilayer model with two interaction energies. The effect of the key parameters involved in the adequate model on the isotherm curves are thus elucidated and interpreted. The formulation of this model is based on statistical physic formalism. Several hypotheses involving some physicochemical parameters which describe perfectly the adsorption process are used.

The characteristic parameters of the adsorption isotherm such as the number of carbon dioxide molecules per site (n), the receptor site densities (N_M), the number of adsorbed layers (N_L) and the energetic parameters (-ε₁) and (-ε₂) are estimated for the studied systems by a nonlinear least square regression. These parameters are discussed and interpreted considering their temperature dependence. In order to provide new macroscopic interpretations of adsorption mechanisms, three thermodynamic functions are also determined such as the entropy, the internal energy and the free enthalpy of Gibbs from experimental data. Thus, we prove theoretically and experimentally that CO₂ adsorption on El Hicha clay is feasible, spontaneous and exothermic in nature.     

Correlation of adsorption equilibria of CO2 on activated carbon

Adsorption isotherms of CO₂ on three types of activated carbon were measured over wide temperature range, from 298‡K to 194.5‡K. The adsorption equilibria were correlated according to the Dubinin-Radushkevich equation. The correlations for the carbons in temperature indifferent characteristic curve were yielded by the use of pressure variable density of adsorbed phase in deriving adsorption volume. The pressure variable density, which is the density of saturated liquid CO₂ under given equilibrium adsorption pressure, was determined from reduced density correlation and empirical vapor pressure function of CO₂. Density and vapor pressure of quasi-liquid state CO₂ at below the triple point were evaluated by extrapolation of the correlations.     

In-situ temperature-depth profile evaluation of South African unmineable coal seams to determine CO2 sequestration potential

This study aimed to investigate the sorption behaviour of South African coal seams with relation to the effect of temperature during CO₂ sequestration. The excess adsorption isotherms of CO₂ adsorption were undertaken using a high-pressure volumetric system for four coals of different coal rank (denoted by Somkele [SK], anthracite KZN [AN], Tshikondeni [TD], and Syferfontein [SF]). The volumetric pressure step method was conducted at increments of system temperature of 35, 45, 55, and 65°C for pure CO₂ adsorption at incremental pressures up to 93 bar. The results showed that high temperatures have a very significant negative effect on the amount of CO₂ adsorbed on the coal samples. The high-rank coal samples (SK and AN) demonstrated elevated CO₂ adsorption capacity across all tested temperatures due to their high vitrinite content. The medium-rank coals (TD and SF) exhibited comparatively lower CO₂ adsorption capacity, attributed to the presence of adsorption hindrances such as higher ash content and volatile and mineral matter. The isosteric heat of adsorption revealed an increasing trend with coverage for all coal samples, with higher rank coals displaying greater slopes. The determined range of the isosteric heat of adsorption, spanning from 10 to 59 kJ/mol, indicated that the adsorption process is primarily of a physisorption nature. Three theoretical models (Langmuir, Freundlich, and Temkin) were evaluated and fitted to the sorption experimental data. The Temkin model exhibited superior fitting compared to the Langmuir and Freundlich isotherms. The Temkin isotherm parameters suggest that the adsorption of CO₂ onto coal is a physisorption process.     

Prediction of ethane and CO2 solubilities in heavy norma paraffins using generalized-parameter soave and peng-robinson equations of state

A study was made of the abilities of the Soave and Peng-Robinson equations to represent the phase behavior of ethane + n-paraffin and CO₂ + n-paraffin systems. These equations are capable of describing the phase behavior of such systems; however, the level of precision obtained varies with the degree of complexity used in representing the interaction parameters in the mixing rules employed. For ethane/C0₂ with n-paraffins extending from C₃ to n-C₄₄, an uncertainty of about 1 % is obtained for bubble point pressures (or about 0.005 mole fraction for solubilities) when two system-specific interaction parameters per isotherm are used. Simple generalized correlations are presented for the equation-of-state interaction parameters which allow prediction of the bubble point pressures with an expected uncertainty of about 5.7% (0.014 in mole fraction).     

Numerical modelling of rotating packed beds used for CO2 capture processes: A review

Over the last decades, renewable and clean energy sources are being rigorously adopted along with carbon capture technologies to tackle the increasing carbon dioxide (CO₂) concentration level in the environment. CO₂ capture is a quintessential option for tackling global warming issues. In this context, the present paper has reviewed the process intensification equipment called a rotating packed bed (RPB), which is highly industry applicable due to high gravity (HiGee) force. This facilitates strong mass transfer characteristics, a compact design, and low energy consumption. In this review, the current research scenario of RPBs using numerical, computational fluid dynamics (CFD), and mathematical modelling, along with different machine learning approaches in the CO₂ capture process, has been reviewed. The different geometry designs, hydrodynamic characteristics, performance parameters, research methods, and their effects on CO₂ removal efficiency have been discussed. Furthermore, the latest experimental studies are also summarized, especially in the absorption and adsorption domain. Finally, recommendations have been given to support the RPBs in different industrial and commercial applications of CO₂ removal.     

Rigorous treatment of adsorption data for multicomponent predictions

Three considerations in the rigorous treatment of adsorption data for multicomponent adsorption equilibria are discussed below: (1) choice of pure-component model for the ideal adsorbed solution theory; (2) variable sensitivity analysis for the choice of independent variable sets; and (3) the error-in-variables method for binary interaction parameters. The O’Brien and Myers model gave better agreement with adsorption data than the Langmuir model for single components. However, in the prediction of binary and ternary component adsorption equilibria, IAS theory combined with the O’Brien and Myers model did not show any improvement over the IAS theory with Langmuir model. Sensitivity analysis showed that large sensitivities of dependent variables to independent variables can give large deviations in the prediction of binary component adsorption. This motivated the use of the error-in-variables method, which was shown to be superior to conventional least-squares in calculating the Wilson binary parameters for the prediction of ternary component equilibria with O₂-N₂-CO adsorption data on zeolite 10X. Smaller deviations in the predictions of total amount of adsorption were found from the parameters regressed by EVM, but the errors in the prediction of mole fraction were not reduced significantly compared to the traditional least squares approach.     

Tackling increased CO2 concentration in feeds for existing acid gas removal units: A simulation study based on a customized CO2 kinetics model

A Middle East-based amine sweetening unit, with an overall capacity of about 2.2 BSCFD of gas, is among the world’s largest process plants and currently processes sour gas with 10 mol% of hydrogen sulfide (H₂S) and carbon dioxide (CO₂) put together. Current expectation is that acid gas contents in the feed may increase beyond the design limit of the plant. The present work is an effort to quantify the effects of the feed gas CO₂ increase on the plant and to proffer solutions to handle these effects efficiently. We revised the kinetics of amine-based CO₂ absorption correlation of an existing model using real-data-driven parameters re-estimation. Evolutionary technique that employs particle swarm optimization algorithm is used for this purpose. The new CO₂ kinetic model is inserted in a first-principle process simulator, ProMax® V4.0, in order to analyze various solutions necessary to mitigate the operational challenges due to increased feed CO₂. The process plant with present design and operating conditions is determined to handle up to 8.45 mol% CO₂ contents in the sour gas feed. Further results revealed that methyldiethanolamine, diethanolamine, and dimethyl ether propylene glycol (DEPG) could not handle this high feed CO₂ challenge, even at maximum (design) steam and solvent usage. However, diglycolamine exclusively renders the solution as it treats high CO₂ feed gas efficiently with allowable utility consumption, while satisfying the constraints imposed by product gas specifications.     

Evaluating isotherm models for the prediction of flue gas adsorption equilibrium and dynamics

We evaluated isotherm models for the precise prediction of adsorption equilibrium and breakthrough dynamics. Adsorption experiments were performed using pure N₂, CO₂ and their binary mixture with an activated carbon (AC) material as an adsorbent. Both BET and breakthrough measurements were conducted at various conditions of temperature and pressure. The corresponding uptake amount of pure component adsorption was experimentally determined, and parameters of the four different isotherm models, Langmuir, Langmuir-Freundlich, Sips, and Toth, were calculated from the experimental data. The predictive capability of each isotherm model was also evaluated with the binary experimental results of binary N₂/CO₂ mixtures, by means of sum of square errors (SSE). As a result, the Toth model was the most precise isotherm model in describing CO₂ adsorption equilibrium on the AC. Based on the breakthrough experimental result from the binary mixture adsorption, non-isothermal modeling for the adsorption bed was performed. The breakthrough results with all of the isotherm models were examined by rigorous dynamic simulations, and the Toth model was also the most accurate model for describing the dynamics.     

Parameter estimation in multiple contact CO2 miscibility simulation with uncertain experimental core flooding data

CO₂ flooding, which is an efficient method of enhanced oil recovery, is a very complicated process involving phase behavior. To understand the performance of CO₂ flooding and provide accurate data for designing reservoir development, a comprehensive investigation of the phase behavior of CO₂ miscible flooding and an accurate compositional reservoir simulation needs to be conducted. In PVT modeling, an effective and more physically reasonable equation of state model was achieved and the feasibility of CO₂ miscible flooding was determined by multiple contact minimum miscibility pressure (MCMMP) calculation. Furthermore, compositional reservoir simulation studies for predicting CO₂ miscible performance were designed and constructed with core flooding data. By matching with laboratory core flooding data, we can estimate parameters with uncertainty. The objective of this study was to find a work flow for parameter estimation in CO₂ miscible flooding process that can be used to design and optimize field CO₂ miscible floods.     

Adsorption of CO2 from dry gases on MCM-41 silica at ambient temperature and high pressure. 2: Adsorption of CO2/N2, CO2/CH4 and CO2/H2 binary mixtures

Adsorption equilibrium capacity of CO₂, CH₄, N₂, H₂ and O₂ on periodic mesoporous MCM-41 silica was measured gravimetrically at room temperature and pressure up to 25 bar. The ideal adsorption solution theory (IAST) was validated and used for the prediction of CO₂/N₂, CO₂/CH₄, CO₂/H₂ binary mixture adsorption equilibria on MCM-41 using single components adsorption data. In all cases, MCM-41 showed preferential CO₂ adsorption in comparison to the other gases, in agreement with CO₂/N₂, CO₂/CH₄, CO₂/H₂ selectivity determined using IAST. In comparison to well known benchmark CO₂ adsorbents like activated carbons, zeolites and metal-organic frameworks (MOFs), MCM-41 showed good CO₂ separation performances from CO₂/N₂, CO₂/CH₄ and CO₂/H₂ binary mixtures at high pressure, via pressure swing adsorption by utilizing a medium pressure desorption process (PSA-H/M). The working CO₂ capacity of MCM-41 in the aforementioned binary mixtures using PSA-H/M is generally higher than 13X zeolite and comparable to different activated carbons.     

On the modelling of multidisciplinary electrochemical systems with application on the electrochemical conversion of CO2 to formate/formic acid

This paper presents a model-based approach on the analysis of complex multidisciplinary electrochemical processes, with implementation on a reactor for the electrochemical conversion of CO₂ to formate/formic acid. The process is regarded as a system of interacting physical and electrochemical mechanisms. A process model is developed by combining individual mathematical sub-models of the mechanisms, organised at groups of compartments following the physical process structure. This approach results in a generic reconfigurable model that can be used as a part of integrated systems, and to test design modifications. The approach is demonstrated on an electrochemical cell, where CO₂ is converted to formate/formic acid. The model captures the molar transportation under electric field, the two-phase flow effects, and the key electrochemical reactions. The model is calibrated and validated against experimental data obtained from a continuous flow cell. The key parameters affecting the process performance are discussed through scale-up analysis.     

CO2 Adsorption Kinetics of K2CO3/Activated Carbon for Low‐Concentration CO2 Removal from Confined Spaces

K₂CO₃ supported on activated carbon (K₂CO₃/AC) is a promising means to remove low‐concentration CO₂ from confined spaces. In this removal process, physical adsorption plays an important role but it is difficult to quantify the amount of CO₂ adsorbed when both H₂O and CO₂ are present. The linear driving force mass transfer model is adopted to study the CO₂ adsorption kinetic characteristics of K₂CO₃/AC by analyzing the experimental data. The effect of K₂CO₃ and H₂O on the adsorption of CO₂ in K₂CO₃/AC was also evaluated. K₂CO₃ loaded on the support is found to increase the mass transfer resistance but decrease the activation energy required for the physical adsorption process. The presence of water vapor is disadvantageous to achieve high physical adsorption capacity since it enhances the chemical sorption in the competitive dynamic sorption process.