Effect of ship tilting and motion on amine absorber with structured‐packing for CO2 removal from natural gas

A gas‐liquid Eulerian porous media computational fluid dynamics (CFD) model was developed for an absorber with structured packing to remove CO₂ from natural gas by mono‐ethanol‐amine (MEA). The three‐dimensional geometry of the amine absorber with Mellapak 500.X was constructed to investigate the effect of the tilting and motion experienced on ships and barges for offshore plants. The momentum equation included porous resistance, gas‐liquid momentum exchange, and liquid dispersion to replace structured‐packing by porous media. The mass equation involved mass transfer of CO₂ gas into MEA solution, and one chemical reaction. Parameters of the CFD model were adjusted to fit experimental data measured in the CO₂‐MEA system. As the tilting angle increased, the liquid holdup and effective interfacial area decreased and CO₂ removal efficiency was lowered. The uniformity of liquid holdup deteriorated by 10% for a 3° static tilting, and a rolling motion with 4.5° amplitude and 12 s period, respectively. © 2015 American Institute of Chemical Engineers AIChE J, 61: 4412–4425, 2015     

Chemical Absorption of Carbon Dioxide into Aqueous PEO Solution of Monoethanolamine

Abstract

Carbon dioxide was absorbed into aqueous polyethylene oxide (PEO) solution containing monoethanolamine (MEA) in a flat‐stirred vessel to investigate the effect of non‐Newtonian rheological behavior of PEO on the rate of chemical absorption of CO₂, where the reaction between CO₂ and MEA was assumed to be a first‐order reaction with respect to the molar concentration of CO₂ and MEA, respectively. The liquid‐side mass transfer coefficient (k_L), which was obtained from the dimensionless empirical equation containing the properties of viscoelasticity of the non‐Newtonian liquid, was used to estimate the enhancement factor due to chemical reaction. PEO with elastic property of non‐Newtonian liquid made the rate of chemical absorption of CO₂ accelerate compared with Newtonian liquid based on the same viscosity of the solution.     

Experimental study on the solvent regeneration of a CO2‐loaded MEA solution using single and hybrid solid acid catalysts

The performance of a hybrid solid acid catalyst consisting of a physical mixture of γ‐Al₂O₃ and H‐ZSM‐5 in terms of the rate and heat duty for solvent regeneration (i.e., CO₂ stripping) of a CO₂‐rich MEA solution was compared with the individual performance of γ‐Al₂O₃, H‐ZSM‐5, and H‐Y solid acid catalysts using MEA (2–7 mol/L), with initial CO₂ loading of 0.5 mol CO₂/mol MEA at 378 K. It was observed that any catalyst significantly decreased the energy required for CO₂ regeneration. The performance of the catalysts investigated ranked as follows: γ‐Al₂O₃/H‐ZSM‐5 = 2/1 > γ‐Al₂O₃ > H‐ZSM‐5 > H‐Y if the process is in the lean CO₂ loading region whereas it was H‐ZSM‐5 > γ‐Al₂O₃/H‐ZSM‐5 = 2/1 > γ‐Al₂O₃ > H‐Y if the process is in the rich CO₂ loading region. These results highlight the joint dependence on Brønsted/Lewis acidity and mesopore surface area of heat duty for solvent regeneration. © 2015 American Institute of Chemical Engineers AIChE J, 62: 753–765, 2016     

Dew‐point measurements for water in compressed carbon dioxide

When transporting CO₂ for sequestration, it is important to know the water dew point in order to avoid condensation that can lead to corrosion. A flow apparatus to measure the water content at saturation in a compressed gas has been constructed. A saturator humidifies the flowing gas by equilibrating it with liquid water. Then, a gravimetric hygrometer measures the water mole fraction of the humid gas. Dew‐point data for H₂O in CO₂ on six isotherms between 10 and 80 °C at pressures from 0.5 to 5 MPa are reported. The uncertainties in water content at the dew point (expanded uncertainty with coverage factor k = 2) are on average 0.3%, significantly smaller than in any previous work. The data have been analyzed to extract the interaction second virial coefficient; the values are consistent with the theoretical estimates of Wheatley and Harvey but have a much smaller uncertainty. Published 2015 American Institute of Chemical Engineers AIChE J, 2015 © 2015 American Institute of Chemical Engineers AIChE J, 61: 2913–2925, 2015     

Investigation mechanism of DEA as an activator on aqueous MEA solution for postcombustion CO2 capture

In this work, Diethanolamine (DEA) was considered as an activator to enhance the CO₂ capture performance of Monoethanolamine (MEA). The addition of DEA into MEA system was expected to improve disadvantages of MEA on regeneration heat, degradation, and corrosivity. To understand the reaction mechanism of blended MEA‐DEA solvent and CO₂, ¹³C nuclear magnetic resonance (NMR) technique was used to study the ions (MEACOO^‐, DEACOO^–, MEA, DEA, MEAH⁺, DEAH⁺, , ) speciation in the blended MEA‐DEA‐CO₂‐H₂O systems with CO₂ loading range from 0 to 0.7 mol CO₂/mol amine at the temperature of 301 K. The different ratios of MEA and DEA (MEA: DEA = 2.0:0, 1.5:0.5, 1.0:1.0, and 0:2.0) were studied to comprehensively investigate the role of DEA in the system of MEA‐DEA‐CO₂‐H₂O. The results revealed that DEA performs the coordinative role at the low CO₂ loading and the competitive role at high CO₂ loading. Additionally, the mechanism was also proposed to interpret the reaction process of the blended solvent with CO₂. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2515–2525, 2018     

Absorption of CO2 into aqueous solutions of MEA and AMP in a wetted wall column with film promoter

The process for removing CO₂ from a gas mixture can be achieved by absorption into amines through of different conventional techniques. But, the report of mass transfer parameters that can be used for process design is limited. Thus, a study of CO₂ absorption process into monoethanolamine (MEA), 2-amino-2-methyl-1-propanol (AMP) and their respective blend were developed with the aim of evaluating the absorption performance and of determining a design parameter for a single-amine absorption system. The experimental tests were carried out in a wetted wall column employing a film promoter, a thin stainless steel woven. The experimental device was operated in countercurrent and the different tests were developed at 298 K, atmospheric pressure, a constant gas load (10% CO₂) and three different liquid loads. The results show that the interfacial area is influenced by increasing the liquid load. The K_Ga values of MEA and the blend based on it are higher in relation to AMP. Moreover, the results of the thermodynamical-kinetic parameter show that this absorption process is independent of liquid load, characteristic of rapid chemical reactions. The K_Ga value for the different MEA:AMP mixtures shows that it increases when the MEA proportion is increased in the blend.     

Improving uncertainty evaluation of process models by using pedigree analysis. A case study on CO2 capture with monoethanolamine

This article aims to improve uncertainty evaluation of process models by combining a quantitative uncertainty evaluation method (data validation) with a qualitative uncertainty evaluation method (pedigree analysis). The approach is tested on a case study of monoethanolamine based postcombustion CO₂ capture from a coal power plant. Data validation was used to quantitatively assess the uncertainty of the inputs and outputs of the MEA model. Pedigree analysis was used to qualitatively assess the uncertainty in the current knowledge base on MEA carbon capture systems, the uncertainty in the MEA process model, and the uncertainty of the MEA model results. The pedigree review was done by 13 international experts in the field of postcombustion carbon capture with chemical solvents.The data validation showed that our MEA model is accurate in predicting specific reboiler duty, and CO₂ stream purity (4% and 1% difference respectively between model and pilot plant results), but in first instance it was less accurate in predicting liquid over gas ratio, and cooling water requirement (54% and 23% difference respectively between model and pilot plant results). The pedigree analysis complemented these results by showing that there was fairly high uncertainty in the thermodynamic, and chemistry submodels, as reflected in the low pedigree scores on most indicators. Therefore, the model was improved to better resemble pilot plant results.The results indicate that using a pedigree approach improved uncertainty evaluation in three ways. First, by highlighting sources of uncertainty that quantitative uncertainty analysis does not take into account, such as uncertainty in the knowledge base regarding a specific phenomenon. Second, by providing a systematic approach to uncertainty evaluation, thereby increasing the awareness of modeller and model user. And finally, by presenting the outcomes in easy to understand numerical scores and colours, improving the communication of model uncertainty. In combination with quantitative validation efforts, the pedigree approach can provide a strong method to gain deep insight into the strengths and weaknesses of a process model, and to communicate this to policy and decision-makers.     

Cover Chem. Eng. Technol. 2/2015

CO₂ Capture in a Bubble‐Column Scrubber Bubble columns are widely used in industry, such as on operations of reaction, fermentation, crystallization, desorption, and absorption. They can be operated in batch, continuously, or in semi‐batch, as well as in two or three phases. With the advantages of easy operation, simple structure, high mass transfer efficiency, high absorption factor, and low energy consumption, bubble columns have attracted wide attention in the industry. In recent years, as the carbon dioxide capture, storage, and regeneration are urgent issues, CCS and CCU have been used as the key point to solve greenhouse effect. This plays a great role in CO₂ capture and storage in thermal power plants, in which the CCS capture and regeneration account for 70 % of the power generation cost. How to achieve effective capture and regeneration has become a topical subject in the energy saving and carbon reduction. Among various technologies of CO₂ capture, absorption is the most mature, and MEA is used most widely. Although the capture of acid gases is still dominated by filling towers, many recent studies have confirmed the advantages of bubble towers that prevail over filling towers or other appliances. Thus, bubble columns have been adopted as the absorber and MEA as the absorbent for the new attempt of CO₂ capture. The operation variables include CO₂ concentration, pH, temperature, air flow rate, available gas‐liquid flow rate ratio, absorption efficiency, absorption velocity, overall mass transfer coefficient, and absorption factor, which are the important parameters for the design and operation of absorber. This study adopts the Taguchi experiment design to obtain the priority of parameter type and the optimal parameters of bubble towers for CO₂ capture, so as to achieve energy saving and carbon reduction. DOI: 10.1002/ceat.201400240 CO₂ Capture Using Monoethanolamine in a Bubble‐Column Scrubber Pao‐Chi Chen*, Yi Xin Luo, Pao Wein Cai Chem. Eng. Technol. 2015 , 38 (2), 274–282.     

Mass transfer investigation and operational sensitivity analysis of amine-based industrial CO2 capture plant

In this article, the industrial process of CO₂ capture using monoethanolamine as an aqueous solvent was probed carefully from the mass transfer viewpoint. The simulation of this process was done using Rate-Base model, based on two-film theory. The results were validated against real plant data. Compared to the operational unit, the error of calculating absorption percentage and CO₂ loading was estimated around 2%. The liquid temperature profiles calculated by the model agree well with the real temperature along the absorption tower, emphasizing the accuracy of this model. Operational sensitivity analysis of absorption tower was also done with the aim of determining sensitive parameters for the optimized design of absorption tower and optimized operational conditions. Hence, the sensitivity analysis was done for the flow rate of gas, the flow rate of solvent, flue gas temperature, inlet solvent temperature, CO₂ concentration in the flue gas, loading of inlet solvent, and MEA concentration in the solvent. CO₂ absorption percentage, the profile of loading, liquid temperature profile and finally profile of CO₂ mole fraction in gas phase along the absorption tower were studied. To elaborate mass transfer phenomena, enhancement factor, interfacial area, molar flux and liquid hold up were probed. The results show that regarding the CO₂ absorption, the most important parameter was the gas flow rate. Comparing liquid temperature profiles showed that the most important parameter affecting the temperature of the rich solvent was MEA concentration.     

Mean‐squared‐error‐based method for parameter ranking and selection with noninvertible fisher information matrix

Two approaches are developed to rank and select model parameters for estimation in complex models when data are limited, the Fisher information matrix (FIM) is noninvertible, and accurate predictions are desired at key operating conditions. These approaches are evaluated using synthetic data sets in a linear regression example to examine the influence of several factors including: the quality of initial parameter guesses, uncertainty ranges for initial parameter values, noise variances, and the operating region of interest. It is shown that using a reduced FIM with full rank leads to more reliable model predictions for a variety of cases than the alternative approach using the pseudoinverse of the FIM. The proposed reduced‐FIM methodology also provides better predictions than related techniques that do not consider the operating region where reliable predictions are required. The methodology is illustrated using a nonlinear differential equation model of a polymer film casting process. © 2015 American Institute of Chemical Engineers AIChE J, 62: 1112–1125, 2016     

Advanced solution methods for microkinetic models of catalytic reactions: A methanol synthesis case study

Microkinetic models, combined with experimentally measured reaction rates and orders, play a key role in elucidating detailed reaction mechanisms in heterogeneous catalysis and have typically been solved as systems of ordinary differential equations. In this work, we demonstrate a new approach to fitting those models to experimental data. For the specific example treated here, by reformulating a typical microkinetic model for a continuous stirred tank reactor to a system of nonlinear equations, we achieved a 1000‐fold increase in solution speed. The reduced computational cost allows a more systematic search of the parameter space, leading to better fits to the available experimental data. We applied this approach to the problem of methanol synthesis by CO/CO₂ hydrogenation over a supported‐Cu catalyst, an important catalytic reaction with a large industrial interest and potential for large‐scale CO₂ chemical fixation. © 2013 American Institute of Chemical Engineers AIChE J, 60: 1336–1346, 2014     

Study of parametric sensitivity in an autothermal nylon 6 reactor

The parametric sensitivity of an industrial autothermal nylon 6 reactor was studied. The sensitivities of the temperature maxima with respect to various parameters of the model are computed numerically. The sensitivity peaks were found to occur (almost) at the same value of the input parameter, thus confirming the generalized nature of the thermal parametric sensitivity criterion. It is shown that this criterion can easily be used to find safer regions of operation of the reactor. The variation of the number‐average chain length of the product, μ_nf, with the variation of input parameter, W₀, was also studied. A methodology was suggested to obtain the desired ranges of operation of the reactor which represent an optimal balance between the thermal sensitivity and the sensitivity of μ_nf. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 333–343, 1999     

Modeling of CO2 sorption on coal

This paper discusses moderate pressure CO₂ sorption behavior of Illinois coals. The results fit the Langmuir and Dubinin–Astakhov (D–A) sorption models satisfactorily although the fit is better for D–A equation. Since factors like swelling of coal with CO₂ sorption and CO₂ dissolution in coal matrix contribute to uncertainties in estimating the void volume in and around the sample, an attempt was made to account for these by modifying the conventional adsorption equation. Re-fitting the experimental data using the modified equation results in improved fit for both models. The adsorption capacities of coals tested, as predicted by the equations, also reduce by 7% to 32%. The effect of volumetric uncertainty is more in lower rank coals than the higher rank ones. Furthermore, it explains the excess sorption behavior observed by others when extrapolated beyond the experimental pressure range.     

Very small-scale,segregating-fluidized-bed experiments: A dataset for CFD-DEM validation and uncertainty quantification

Fluidization experiments were conducted on a small scale and with a rapid response (short duration) to enable corresponding simulations at low-computational cost. Rise times are reported for four or fewer polyethylene particles (intruders) in an air-fluidized bed of ~5000 group D glass beads. Experimental inputs were completely characterized—particle properties, system dimensions and operating conditions—which is necessary for validating computational fluid mechanics (CFD)-discrete element method (DEM) including a comprehensive uncertainty quantification (UQ) analysis. Input uncertainties are reported as bounds or cumulative distribution functions of measured values. The staggering number of simulations required to complete a UQ analysis (~O[10⁴] simulations corresponding to ~5 uncertain inputs) motivates this study. These segregating-bed experiments are designed to permit analogous CFD-DEM simulations to complete in less than a day on a single (~2.5 GHz) computational processor unit (CPU). Segregation times are reported for several operating conditions, intruder sizes, and initial configurations, providing a rich dataset for numerical model testing, validation and UQ.     

Absorption of carbon dioxide into aqueous blends of 2-amino-2-methyl-1-propanol and monoethanolamine

This work presents an investigation of CO₂ absorption into aqueous blends of 2-amino-2-methyl-1-propanol (AMP) and monoethanolamine (MEA). The acid gas mass transfer has been modeled using equilibrium-mass transfer-kinetics-based combined model to describe CO₂ absorption into the amine blends according to Higbie's penetration theory. The effect of contact time and relative amine concentration on the rate of absorption and enhancement factor were studied by absorption experiment in a wetted wall column at atmospheric pressure. The model was used to estimate the rate coefficient of the reaction between CO₂ and monoethanolamine at 313 K from experimentally measured absorption rates. A rigorous parametric sensitivity test has been done to identify the key systems’ parameters and quantify their effects on the mass transfer using the mathematical model developed in this work. The model predictions have been found to be in good agreement with the experimental rates of absorption of CO₂ into (AMP+MEA+H₂O).     

A systematic approach to assessing measurement uncertainty for CO2 emissions from coal-fired power plants - Missing contributions from the Theory of Sampling (TOS)

An augmented measurement uncertainty approach for CO₂ emissions from coal-fired power plants with a focus on the often forgotten contributions from sampling errors occurring over the entire fuel-to-emission pathway is presented. Current methods for CO₂ emission determination are evaluated in detail, from which a general matrix scheme is developed that includes all factors and stages needed for total CO₂ determination, which is applied to the monitoring plan of a representative medium-sized coal-fired power plant. In particular sampling involved significant potential errors, as identified and assessed by the Theory of Sampling (TOS), which also shows how these can be eliminated and/or minimised. Since coal-related CO₂ emission calculations not only require analytical results of the carbon content of coal itself but also of the by-products fly ash and bottom ash, sampling procedures of these three materials were also given full attention. A systematic error (bias) is present in the current sampling approach, which increases the present uncertainty estimate unnecessarily. For both primary sampling and analytical sample extraction steps, random variations, which hitherto only have been considered to a minor extent, have now also been fully quantified and included in the overall uncertainty. Elimination of all identified sampling errors lead to modified CO₂ determination procedures, which indicate that the actual CO₂ emission is approximately 20,000 t higher than the present estimate. Based on extensive empirical sampling experiments, a fully comprehensive uncertainty estimate procedure has been devised. Even though uncertainties increased (indeed one particular factor is substantially higher, the so-called “emission factor”), the revised CO₂ emission budget for the case plant complies with the official pre-determined uncertainty levels maxima in the EU guidelines.     

Experimental studies and modeling of CO2 solubility in high temperature aqueous CaCl2, MgCl2, Na2SO4, and KCl solutions

The phase equilibria of CO₂ and aqueous electrolyte solutions are important to various chemical‐, petroleum‐, and environmental‐related technical applications. CO₂ solubility in aqueous CaCl₂, MgCl₂, Na₂SO₄, and KCl solutions at a pressure of 15 MPa, the temperatures from 323 to 423 K, and the ionic strength from 1 to 6 mol kg^?1 were measured. Based on the measured experimental CO₂ solubility, the previous developed fugacity‐activity thermodynamic model for the CO₂‐NaCl‐H₂O system was extended to account for the effects of different salt species on CO₂ solubility in aqueous solutions at temperatures up to 523 K, pressures up to 150 MPa, and salt concentrations up to saturation. Comparisons of different models against literature data reveal a clear improvement of the proposed PSUCO2 model in predicting CO₂ solubility in aqueous salt solutions. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2286–2297, 2015     

The influence of random packed column parameters on the liquid holdup and interfacial area

Carbon dioxide capture via solvent absorption in packed columns has emerged as a potential technology to mitigate coal-fired power plant CO₂ emissions. Parameters, including packing types, solvent properties, and operating conditions, could potentially affect the packed column CO₂ capture efficiency. To understand the importance of those parameters and help packed column optimization, a design of experiments (DoEs) method was proposed to generate input parameter matrix. Combined with multiphase computational fluid dynamics (CFD), the random packed column parameter influence on the liquid holdup and interfacial area can be efficiently investigated. Surrogate-based sensitivity analysis shows that the solvent flow rate and contact angle are key factors dictating liquid holdup and interfacial area. On the other hand, solvent viscosity has a marginal impact on the interfacial area. The sensitivity scores were calculated for each input parameter to guide the selection of dimensionless numbers for the liquid holdup and interfacial area correlation development.     

Ni‐Al2O3/Ni‐foam catalyst with enhanced heat transfer for hydrogenation of CO2 to methane

Monolithic Ni‐Al₂O₃/Ni‐foam catalyst is developed by modified wet chemical etching of Ni‐foam, being highly active/selective and stable in strongly exothermic CO₂ methanation process. The as‐prepared catalysts are characterized by x‐ray diffraction scanning electron microscopy, inductively coupled plasma atomic emission spectrometry, and H₂‐temperature programmed reduction‐mass spectrometry. The results indicate that modified wet chemical etching method is working efficiently for one‐step creating and firmly embedding NiO‐Al₂O₃ composite catalyst layer (～2 μm) into the Ni‐foam struts. High CO₂ conversion of 90% and high CH₄ selectivity of >99.9% can be obtained and maintained for a feed of H₂/CO₂ (molar ratio of 4/1) at 320°C and 0.1 MPa with a gas hourly space velocity of 5000 h^?1, throughout entire 1200 h test over 10.2 mL such monolithic catalysts. Computational fluid dynamics calculation and experimental measurement consistently confirm a dramatic reduction of “hotspot” temperature due to enhanced heat transfer. © 2015 American Institute of Chemical Engineers AIChE J, 61: 4323–4331, 2015     

The analysis of solubility,absorption kinetics of CO2 absorption into aqueous 1‐diethylamino‐2‐propanol solution

In this present work, the CO₂ absorption performance of aqueous 1‐diethylamino‐2‐propanol (1DEA2P) solution was studied with respect to CO₂ equilibrium solubility, absorption kinetics, and absorption heat. The equilibrium solubility of CO₂ in 2M 1DEA2P solution was measured over the temperature range from 298 to 333 K and CO₂ partial pressure range from 8 to101 kPa. The absorption kinetics data were developed and analyzed using the base‐catalyzed hydration mechanism and artificial neural network models (radial basis function neural network [RBFNN] and back‐propagation neural network [BPNN] models) with an acceptable absolute average deviation of 10% for base‐catalyzed hydration mechanism, 2.6% for RBFNN model and 1.77% for BPNN model, respectively. The CO₂ absorption heat of 1DEA2P was estimated to be ?43.6 kJ/mol. In addition, the ions (1DEA2P, 1DEA2PH⁺, , CO₃^2?) speciation plots of the 1DEA2P‐CO₂‐H₂O system were developed to further understand the reaction process of 1DEA2P with CO₂. Based on a comparison with conventional amines (e.g., MEA, DEA, MDEA) and alternative amines (i.e., 1DMA2P and 4‐(diethylamino)?2‐butanol [DEAB]), 1DEA2P exhibited good performance with respect to CO₂ equilibrium solubility, reaction kinetics, and CO₂ absorption heat. Meanwhile, the overall evaluation of 1DEA2P for application in CCS in terms of absorption and desorption is presented, giving helpful information for the screening of these novel amines. © 2017 American Institute of Chemical Engineers AIChE J, 63: 2694–2704, 2017