Measurement and Calculation for CO2 Solubility and Kinetic Rate in Aqueous Solutions of Two Tertiary Amines

AbstractAbsorbing CO2 with amine solutions is one of the most promising methods of CCS and has been widely applied. In order to improve efficiency and reduce costs, new solvents need to be selected. In this work, two amine solvents, N,N-dimethylethanolamine(DMEA) and Triethylene diamine (TEDA), have been characterized, with the use of gas- liquid reactor for CO2 solubility and kinetic rate measurements. Solubility of CO2 has been measured for amine concentrations of 1.0, 2.5 and 4.0mol/L at temperatures of 313.2K, 343.2K, 373.2K, and 393.2K while partial pressure of CO2 varies from 1 to 300kPa. The e-NRTL model has been used for these amine-water-CO2 systems in order to calculate CO2 solubility. Meanwhile the thermo-regulated constant interfacial area Lewis-type cell was also operated to obtain absorption kinetic data for CO2 absorption in 0.5M and 1.0M amine solutions

Inhibition of calcium carbonate crystal growth by organic additives using the constant composition method in conditions of recirculating cooling circuits

The cooling circuits used in power plants are subject to mineral crystallization which can cause scaling on the surfaces of equipment and construction materials reducing their heat exchange efficiency. Precipitated calcium carbonate is the predominant mineral scale commonly observed in cooling systems. Supersaturation is the key parameter controlling the nucleation and growth of calcite in these systems. The present work focuses on the precipitation of calcite using the constant composition method at constant supersaturation, through controlled addition of reactants to a semi-batch crystallizer, in order to maintain constant solution pH. The determination of the thermodynamic driving force (supersaturation) was based on the relevant chemical equilibria, total alkalinity and calculation of the activity coefficients. Calcite crystallization rates were derived from the experiments performed at supersaturation levels similar to those found in industrial station cooling circuits. Several types of seeds particles were added into the aqueous solution to mimic natural river water conditions in terms of suspended particulate matters content, typically: calcite, silica or illite particles. The effect of citric and copolycarboxylic additive inhibitors added to the aqueous solution was studied. The calcium carbonate growth rate was reduced by 38.6% in the presence of the citric additive and a reduction of 92.7% was observed when the copolycarboxylic additive was used under identical experimental conditions. These results are explained by the location of the adsorbed inhibitor at the crystal surface and by the degree of chemical bonding to the surface

Performance of green antiscalants and their mixtures in controlled calcium carbonate precipitation conditions reproducing industrial cooling circuits

Cooling circuits in many industrial sectors are faced with daily issues of scaling. One preventive treatment consists in injecting a polymer additive in the circuit to inhibit precipitation of calcium carbonate. Among the used additives, very few are “green” and the efficiency of new candidates are difficult to test directly in industrial conditions. The present study compared performance between two “green” polymer additives, polyaspartic acid (PASP) and polyepoxysuccinic acid (PESA), versus a traditional gold-standard, homopolymer of acrylic acid (HA) in a laboratory scale set-up designed to be representative of an industrial circuit. Results showed that HA and PASP are both inhibitors of calcium carbonate crystal growth. This inhibition resulted from adsorption of polymer additive molecules on the crystal surface, as confirmed by adsorption measurement. Under the same conditions, PESA additive, showed a high rate of calcium ion complexation and a very low inhibition rate. But, PESA was shown to be a nucleation delayer. Mixing PESA and PASP can gave nucleation retardation of about 19 h, which approximates the 24 h water residence time in industrial cooling circuits, as well as almost 90% calcium carbonate crystal growth inhibition. This synergy offers promising prospects for preventive scaling treatmen

Modeling and optimization of CO2 capture processes by chemical absorption

Les procédés de captage de CO2 par absorption chimique engendrent une importante pénalité énergétique sur la production électrique des centrales à charbon, constituant un des principaux verrous technologiques au déploiement de la filière. L'objectif de cette thèse est de développer et valider une méthodologie à même d'évaluer précisément le potentiel d'un procédé de captage aux amines donné. La phénoménologie de l'absorption chimique a été étudiée en détail et représentée par des modèles à l'état de l'art. Le modèle e-UNIQUAC a été utilisé pour décrire les équilibres chimiques et de phases des solutions électrolytiques et les paramètres du modèle ont été régressés pour quatre solvants. Un modèle hors-équilibre a été utilisé pour représenter le transfert couplé de matière et de chaleur, accéléré par les réactions chimiques. Les modèles ont été validés avec succès sur des données expérimentales d'un pilote industriel et d'un pilote de laboratoire. L'influence des phénomènes sur les efficacités de séparation a été explicitée afin d'isoler les phénomènes les plus impactants. Une méthodologie a alors été proposée pour évaluer la pénalité énergétique, incluant les consommations thermiques et électriques, liée à l'installation d'un procédé de captage sur une centrale à charbon supercritique. Une méthode d'estimation du coût de l'électricité est proposée pour quantifier les dépenses opératoires et d'investissement d'un tel procédé. L'environnement de simulation et d'évaluation de procédés obtenu a ensuite été couplé à une méthode d'optimisation afin de déterminer les paramètres opératoires et les dimensions des équipements maximisant les performances énergétiques et économiquesCO2 capture processes by chemical absorption lead to a large energy penalty on efficiency of coal-fired power plants, establishing one of the main bottleneck to its industrial deployment. The objective of this thesis is the development and validation of a global methodology, allowing the precise evaluation of the potential of a given amine capture process. Characteristic phenomena of chemical absorption have been thoroughly studied and represented with state-of-the-art models. The e-UNIQUAC model has been used to describe vapor-liquid and chemical equilibria of electrolyte solutions and the model parameters have been identified for four solvents. A rate-based formulation has been adopted for the representation of chemically enhanced heat and mass transfer in columns. The absorption and stripping models have been successfully validated against experimental data from an industrial and a laboratory pilot plants. The influence of the numerous phenomena has been investigated in order to highlight the most limiting ones. A methodology has been proposed to evaluate the total energy penalty resulting from the implementation of a capture process on an advanced supercritical coal-fired power plant, including thermal and electric consumptions. Then, the simulation and process evaluation environments have been coupled with a non-linear optimization algorithm in order to find optimal operating and design parameters with respect to energetic and economic performance

Contacteurs membranaires pour l’intensification de séparations gaz-liquide

National audienc

Use of meta models for process simulation

International audienc

Modélisation et optimisation des procédés de captage de CO2 par absorption chimique

CO2 capture processes by chemical absorption lead to a large energy penalty on efficiency of coal-fired power plants, establishing one of the main bottleneck to its industrial deployment. The objective of this thesis is the development and validation of a global methodology, allowing the precise evaluation of the potential of a given amine capture process. Characteristic phenomena of chemical absorption have been thoroughly studied and represented with state-of-the-art models. The e-UNIQUAC model has been used to describe vapor-liquid and chemical equilibria of electrolyte solutions and the model parameters have been identified for four solvents. A rate-based formulation has been adopted for the representation of chemically enhanced heat and mass transfer in columns. The absorption and stripping models have been successfully validated against experimental data from an industrial and a laboratory pilot plants. The influence of the numerous phenomena has been investigated in order to highlight the most limiting ones. A methodology has been proposed to evaluate the total energy penalty resulting from the implementation of a capture process on an advanced supercritical coal-fired power plant, including thermal and electric consumptions. Then, the simulation and process evaluation environments have been coupled with a non-linear optimization algorithm in order to find optimal operating and design parameters with respect to energetic and economic performancesLes procédés de captage de CO2 par absorption chimique engendrent une importante pénalité énergétique sur la production électrique des centrales à charbon, constituant un des principaux verrous technologiques au déploiement de la filière. L'objectif de cette thèse est de développer et valider une méthodologie à même d'évaluer précisément le potentiel d'un procédé de captage aux amines donné. La phénoménologie de l'absorption chimique a été étudiée en détail et représentée par des modèles à l'état de l'art. Le modèle e-UNIQUAC a été utilisé pour décrire les équilibres chimiques et de phases des solutions électrolytiques et les paramètres du modèle ont été régressés pour quatre solvants. Un modèle hors-équilibre a été utilisé pour représenter le transfert couplé de matière et de chaleur, accéléré par les réactions chimiques. Les modèles ont été validés avec succès sur des données expérimentales d'un pilote industriel et d'un pilote de laboratoire. L'influence des phénomènes sur les efficacités de séparation a été explicitée afin d'isoler les phénomènes les plus impactants. Une méthodologie a alors été proposée pour évaluer la pénalité énergétique, incluant les consommations thermiques et électriques, liée à l'installation d'un procédé de captage sur une centrale à charbon supercritique. Une méthode d'estimation du coût de l'électricité est proposée pour quantifier les dépenses opératoires et d'investissement d'un tel procédé. L'environnement de simulation et d'évaluation de procédés obtenu a ensuite été couplé à une méthode d'optimisation afin de déterminer les paramètres opératoires et les dimensions des équipements maximisant les performances énergétiques et économique

Applications des contacteurs membranaires gaz-liquide pour l'industrie électrique

National audienc

Ab-initio process synthesis using evolutionary programming

International audienceProcess synthesis methods enable the determination of unit operations and their interconnection into a process owsheet, with associated design and operating parameters, and responding to given objectives. Modern methods are optimization-based, using for example Mixed Integer Non-Linear Programming (MINLP) formulation to optimize a process superstructure. Finding an adequate denition of the search space is a non-trivial problem in such approaches, especially when the number of possible combinations is high due to the process complexity, and is mostly driven by expertise (e.g. heuristics). Consequently, an inductive bias is intrinsically introduced due to restriction of a limited search space, such as the choice of a superstructure representing a limited set of process alternatives. In this work, an evolutionary method is proposed to generate several process architectures based on a set of available unit operations (and associated models) as elementary building blocks. The procedure is here called ab-initio process synthesis since it does not require any pre-dened process structure. The developed method relies on the use of an Evolutionary Programming (EP), mimicking natural evolution at species-level, for the automatic construction of a process by using mutation operators to choose, assemble and connect elementary building blocks (i.e. unit operations). A Non-Linear Programming (NLP) is used for process evaluation, by simultaneously solving balances and optimizing process degrees of freedom. The method is implemented in a newly developed tool called PSEvo (Process Synthesis by Evolution). An application to a typical reaction-separation problem is presented, using various problem denitions and evolution control parameters, which demonstrates the method capability to generate optimal processes. The possible uses and the challenges of ab-initio process synthesis are nally discussed