Dissertations / Theses on the topic 'Ethanolamines. Carbon dioxide. Mass transfer'

Thesis (Honors)--Ohio State University, 2007.
Title from first page of PDF file. Document formatted into pages: contains vii, 28 p.; also includes graphics. Includes bibliographical references (p. 26-28). Available online via Ohio State University's Knowledge Bank.

Acoustic agitation of a carbon dioxide/water mixture in a 1 dm3 cylindrical, high-pressure reactor led to the simultaneous formation of carbon dioxide/water (C/W) and water/carbon dioxide (W/C) emulsions, with the dispersed phase occupying up to 10% of the volume. These emulsions were stable for several minutes. Inclusion of 1% of the non-ionic surfactant Tween 80 led to the generation of C/W emulsions which were stable for over 1 hour after ceasing sonication, in which all of the carbon dioxide present in the system comprised the dispersed phase. The mixing capacity of pulsed ultrasound was assessed by studying the mass transfer of benzaldehyde across the carbon dioxide/water interface, leading to determination of the system mixing time. A model for mass transfer with a fast chemical reaction, namely the hydrolysis of benzoyl chloride, was used to separate the mass transfer and kinetic effects, and to identify those reactions that would most significantly benefit from ultrasound-induced emulsification. For the first time, the Barbier synthesis was shown to occur in a carbon dioxide/water mixture as solvent, leading to moderate to high yields. Moreover, it was possible to recover the homoallylic alcohol product directly from the carbon dioxide phase in which it was preferentially partitioned.

The purpose of this research was to determine the solubility of apricot (Prunus armeniaca L.) oil in supercritical carbon dioxide (SC-CO2), effects of parameters (particle size, solvent flow rate, pressure, temperature and co-solvent (ethanol) concentration) on extraction yield and to investigate the possibility of fractionation. Solubility, increased with pressure and increased with temperature above the crossover pressure, which was found between 200 and 300 bar, and decreased with temperature below the crossover pressure. Appropriate models were fitted to data. Extraction of apricot kernel oil occurred in two extraction periods as fast and slow extraction periods. Most of the oil was extracted in the fast extraction period and the oil recovered in the slow extraction period was negligible. Extraction yield increased with decrease in particle size and recovery of more than 99 % of the oil was possible if particle diameter decreased below 0.425 mm. Extraction rate increased with increase in flow rate, pressure, temperature and ethanol concentration. The volume mass transfer coefficient in the fluid phase changed between 0.6 and 3.7 /min, whereas the volume mass transfer coefficient in the solid phase changed between 0.00009 and 0.00048 /min. Extraction yield at 15 min for particle diameter smaller than 0.85 mm was formulated as a function of solvent flow rate, pressure, temperature, and ethanol concentration by using Response Surface Methodology. According to the model yield was highest (0.26 g /g) at 4 g/min flow rate, 60 oC, 450 bar and 3 % ethanol concentration. Fractionation was not possible at significant levels.

The growth of microalgae has the potential to be extremely useful for the production of a wide range of products or for specific processes, such as capture and cycling of CO₂. The fast micro-algal growth rates and ability to grow on agriculturally poor land and in waste water means that bio-production using algae has many advantages over traditional agricultural processes for certain applications. The raceway pond is the most common reactor used for the growth of microalgae, due to low capital costs, low operating costs, higher energy efficiency, improved net energy recovery and ease of installation. Low carbon dioxide mass transfer, which limits algal growth and productivity, is currently one of the largest issues in photo bioreactors of all forms. The microalgae within these systems only obtain carbon from the dissolved inorganic carbon and hence sufficient carbon dioxide mass transfer is one of the most important design parameters for any photobioreactor. This is particularly evident in raceway ponds as they have a lower volumetric mass transfer rate than other photobioreactors and are typically mass transfer limited. [Please note: the full text of this thesis has been deferred until 30 September 2017]

The Fe(II) regeneration process is an important aspect of Alternate Anode Reaction Technology (AART) using Fe(II)/Fe(III)-SO2 reactions for copper hydrometallurgy; however little has been done to study it specifically. The process regenerates Fe(II) via Fe(III) reduction by SO2(aq), catalyzed by activated carbon particles. To better understand and improve the process, two studies have been conducted with respect to variable factors and their affects on the regeneration. A study of fundamental kinetics confirms that the regeneration reaction is mass transfer-controlled, requiring adsorption of reactants onto the catalyst surface for reaction. The reaction rate is limited by the diffusivity of Fe(III). Initial Fe(III) concentration and carbon particle size are determined to be the most influential factors on the rate under the condition studied. Furthermore, it is observed that flow rate may inhibit the reaction by reducing ion diffusivity. A rate expression for the regeneration is derived and experimentally validated, and the Fe(III) diffusivity is determined to be 1.1x10-7 cm2/s. An optimization problem is also developed and solved for the process, constrained by the requirement that negligible SO2 could be present in the process effluent. Before optimization, a relationship is developed between regeneration rate and variable factors. Again, carbon size and initial Fe(III) are the most influential factors on the regeneration rate, related to it linearly; temperature is significant with a squared relationship to the rate; initial SO2 is insignificant. Optimal conditions are found with minimum carbon particle size, maximum initial Fe(III) concentration, and moderate temperature.
Master of Science

Thesis (PhD)--Stellenbosch University, 2014.
ENGLISH ABSTRACT: The reactive absorption rate of CO2 into non-aqueous solvents containing the primary amine, mono-ethanolamine (MEA) is recognised as a suitable method for measuring the effective interfacial mass transfer area of separation column internals such as random and structured packing. Currently, this method is used under conditions where the concentration of MEA in the liquid film is unaffected by the reaction and the liquid phase reaction is, therefore, assumed to obey pseudo first order kinetics with respect to CO2. Under pseudo first order conditions, the effect of surface depletion and renewal rates are not accounted for. Previous research indicated that the effective area available for mass transfer is also dependent upon the rate of surface renewal achieved within the liquid film. In order to study the effect of surface depletion and renewal rates on the effective area, a method utilising a fast reaction with appreciable depletion of the liquid phase reagent is required. The homogeneous liquid phase reaction kinetics of CO2 with MEA n-Propanol as alcoholic solvent was investigated in this study. A novel, in-situ Fourier Transform Infra-Red (FTIR) method of analysis was developed to collect real time concentration data from reaction initiation to equilibrium. The reaction was studied in a semi-batch reactor set-up at ambient conditions (T = 25°C, 30°C and 35°C, P = 1 atm (abs)). The concentration ranges investigated were [MEA]:[CO2] = 5:1 and 10:1. The concentration range investigated represents conditions of significant MEA conversion. The reaction kinetic study confirmed the findings of previous research that the reaction of CO2 with MEA is best described by the zwitterion reactive intermediate reaction mechanism. Power rate law and pseudo steady state hypothesis kinetic models (proposed in literature) were found to be insufficient at describing the reaction kinetics accurately. Two fundamentally derived rate expressions (based on the zwitterion reaction mechanism) provided a good quality model fit of the experimental data for the conditions investigated. The rate constants of the full fundamental model were independent of concentration and showed an Arrhenius temperature dependence. The shortened fundamental model rate constants showed a possible concentration dependence, which raises doubt about its applicability. The specific absorption rates (mol/m2.s) of CO2 into solutions of MEA/n-Propanol (0.2 M and 0.08 M, T = 25°C and 30°C, P = ±103 kPa) were investigated on a wetted wall experimental setup. The experimental conditions were designed for a fast reaction in the liquid film to occur with a degree of depletion of MEA in the liquid film. Both interfacial depletion and renewal of MEA may be considered to occur. The gas phase resistance to mass transfer was determined to be negligible. An increase in liquid turbulence caused an increase in the specific absorption rate of CO2 which indicated that an increase in liquid turbulence causes an increase in effective mass transfer area. Image analysis of the wetted wall gas-liquid interface confirmed the increase in wave motion on the surface with an increase in liquid turbulence. The increase in wave motion causes an increase in both interfacial and effective area. A numerical solution strategy based on a concentration diffusion equation incorporating the fundamentally derived rate expressions of this study is proposed for calculating the effective area under conditions where surface depletion and renewal rates are significant. It is recommended that the reaction kinetics of CO2 with MEA in solvents of varying liquid properties is determined and the numerical technique proposed in this study used to calculate effective area from absorption rates into these liquids. From the absorption data an effective area correlation as a function of liquid properties may be derived in future.
AFRIKAANSE OPSOMMING: Die reaktiewe absorpsie van CO2 in nie-waterige oplossings van die primêre amien, monoetanolamien (MEA) word erken as ‘n geskikte metode om die effektiewe massaoordragsarea van gepakte skeidingskolomme te bepaal. Tans word die metode gebruik onder vinnige pseudo eerste orde reaksietoestande met betrekking tot CO2. Die pseudo eersteorde aanname beteken dat die konsentrasie van MEA in die vloeistoffilm onbeduidend beïnvloed word deur die reaksie en effektief konstant bly. Onder pseudo eerste orde toestande word oppervlakverarming- en oppervlakvernuwingseffekte nie in ag geneem nie, juis as gevolg van die konstante konsentrasie van MEA in die vloeistoffilm. Daar is voorheen bevind dat oppervlakverarming en oppervlakvernuwing ‘n beduidende invloed het op die beskikbare effektiewe massaoordragsarea. Hierdie invloed kan slegs bestudeer word met ‘n vinnige reaksie in die vloeistoffilm wat gepaard gaan met beduidende oppervlakverarming van die vloeistoffase reagens. Die homogene vloeistoffase reaksiekinetika van CO2 met MEA in die alkohol oplosmiddel, n- Propanol, is in hierdie studie ondersoek. ‘n Nuwe, in-situ Fourier Transform Infra-Rooi (FTIR) metode van analiese is ontwikkel in hierdie ondersoek. Die reaksie is ondersoek in ‘n semienkelladings reaktor met MEA wat gevoer is tot die reaktor om met die opgeloste CO2 te reageer. Die FTIR metode meet spesiekonsentrasie as ‘n funksie van tyd sodat die konsentrasieprofiele van CO2, MEA en een van die soutprodukte van die reaksie gebruik kan word om verskillende reaksiesnelheidsvergelykings te modelleer. Die reaksie is ondersoek onder matige toestande (T = 25°C, 30°C and 35°C, P = 1 atm (abs)). Die konsentrasiebereik van die ondersoek was [MEA]:[CO2] = 5:1 en 10:1. Hierdie bereik is spesifiek gebruik sodat daar beduidende omsetting van MEA kon plaasvind. Die reaksiekinetieka studie het, ter ondersteuning van bestaande teorie, bevind dat die reaksie van CO2 met MEA in nie-waterige oplosmiddels soos alkohole, beskyf word deur ‘n zwitterioon reaksiemeganisme. Die bestaande reaksiesnelheids modelle (eksponensiële wet en pseudo gestadigde toestand hipotese) kon nie die eksperimentele data met genoegsame akuraatheid beskryf nie. Twee nuwe reaksiesnelheidsvergelykings, afgelei vanaf eerste beginsels en gebaseer op die zwitterioon meganisme, word voorgestel. Hierdie volle fundamentele model het goeie passings op die eksperimentele data getoon oor die volledige temperatuur en konsentrasiebereik van hierdie studie. Die reaksiekonstantes van die fundamentele model was onafhanklik van konsentrasie en tipe oplosmiddel en het ‘n Arrhenius temperatuurafhanklikheid. Die verkorte fundamentele model se reaksiekonstantes het ‘n moontlike konsentrasieafhanlikheid gewys. Dit plaas onsekerheid op die fundamentele basis van hierdie model en kan dus slegs as ‘n eerste benadering beskou word. Die spesifieke absorpsietempos (mol/m2.s) van CO2 in MEA/n-Propanol oplossings (0.2 M en 0.08 M MEA, T = 25°C and 30°C, P = ±103 kPa) is ondersoek met ‘n benatte wand (‘wetted wall’) eksperimentele opstelling. Die eksperimentele toestande is gekies sodat daar ‘n vinnige reaksie in die vloeistoffilm plaasgevind het, met beide beduidende en nie-beduidende MEA omsetting. Die doel met hierdie eksperimentele ontwerp was om die invloed van intervlakverarming en intervlakvernuwing op die spesifieke absorpsietempo te ondersoek. Gas fase weerstand was nie-beduidend onder die eksperimentele toestande nie. Beide intervlakverarming en intervlakvernuwing gebeur gelyktydig en is waargeneem vanuit die eksperimentele data. ‘n Beeldverwerkingstudie van die gas-vloeistof intervlak van die benatte wand het bevind dat daar ‘n toename in golfaksie op die vloeistof oppervlak is vir ‘n toename in vloeistof turbulensie. Hierdie golfaksie dra by tot oppervlakvernuwing en ‘n toename in effektiewe massaoordragsarea. ‘n Numeriese metode word voorgestel om die effektiewe area van beide die benatte wand en gepakte kolomme te bepaal vanaf reaktiewe absorpsietempos. Die metode gebruik die fundamentele reaksiesnelheidsvergelykings, bepaal in hierdie studie, in a konsentrasie diffusievergelyking sodat oppervlakverarming en vernuwing in ag geneem kan word. Daar word voorgestel dat die reaksiekinetika van CO2 met MEA in oplossings met verskillende fisiese eienskappe (digtheid, oppervlakspanning en viskositeit) bepaal word sodat die numeriese metode gebruik kan word om ‘n effektiewe area korrelasie as ‘n funksie van hierdie eienskappe te bepaal.

In this diploma work, the absorption of CO₂ in different liquid solutions was studied by gas absorption in a randomly packed column. To characterize the absorption a few experiments with SO₂ absorption were made.The report has resulted due to the large amounts of carbon dioxide released into the atmosphere, mainly from fossil-fired power plants. To reduce these emissions, carbon dioxide can be separated from flue gas by different techniques such as CO₂ absorption with ammonia. The work consists of a theoretical and a laboratory part of measurements and calculations. In the experimental part a system of absorption and associated test equipment was constructed. Different liquid solutions of pure water, potassium carbonate solution and ammonia in various concentrations were used to catch carbon dioxide by countercurrent absorption. Also SO₂ was absorbed in the potassium carbonate solution to determine the gas film constant. The absorption efficiency of CO₂ ranged from a few percent in the experiment with water to up to 7% with potassium carbonate solution. The CO₂ absorption of ammonia varied with concentration and gave a separation of between 12 and 94%. Ammonia tests were made at both 10 and 20 °C. In general, a higher CO₂-capture at 20 °C was obtained as confirmed by theory.

I detta examensarbete har absorptionseffektivitet av CO₂ hos olika vätskelösningar undersökts genom gasabsorption i en slumpmässigt packad kolonn. För att karakterisera absorptionen absorberades även SO₂ i några experiment.

Rapporten är utförd med anledning av de stora mängder koldioxid som släpps ut i atmosfären, främst från fossileldade kraftverk. För att minska dessa utsläpp kan koldioxiden avskiljas från rökgaserna genom olika tekniker t.ex. genom CO₂-absorption med ammoniak.

Arbetet består av en teoridel och en laborativ del med mätningar och beräkningar. I den experimentella delen konstruerades ett system med en absorptionskolonn och tillhörande mätutrustning. Olika vätskelösningar bestående av rent vatten, kaliumkarbonatlösning och ammoniak i olika koncentrationer användes till att ta upp koldioxid genom motströms absorption. Även SO₂ absorberades i kaliumkarbonatlösning för att bestämma gasfilmkonstanten. Absorptionsgraden av CO₂ varierade från några få procent i försöket med vatten upp till 7 % med kaliumkarbonatlösningen. CO₂-absorptionen av ammoniak varierade med koncentrationen och gav en avskiljning på mellan 12 och 94 %. Ammoniakförsöken gjordes med både vid 10 och 20 °C. Generellt erhölls en bättre CO₂-avskiljning vid 20°C, vilket bekräftas av teorin.

In this diploma work, the absorption of CO2 in different liquid solutions was studied by gas absorption in a randomly packed column. To characterize the absorption a few experiments with SO2 absorption were made.The report has resulted due to the large amounts of carbon dioxide released into the atmosphere, mainly from fossil-fired power plants. To reduce these emissions, carbon dioxide can be separated from flue gas by different techniques such as CO2 absorption with ammonia. The work consists of a theoretical and a laboratory part of measurements and calculations. In the experimental part a system of absorption and associated test equipment was constructed. Different liquid solutions of pure water, potassium carbonate solution and ammonia in various concentrations were used to catch carbon dioxide by countercurrent absorption. Also SO2 was absorbed in the potassium carbonate solution to determine the gas film constant. The absorption efficiency of CO2 ranged from a few percent in the experiment with water to up to 7% with potassium carbonate solution. The CO2 absorption of ammonia varied with concentration and gave a separation of between 12 and 94%. Ammonia tests were made at both 10 and 20 °C. In general, a higher CO2-capture at 20 °C was obtained as confirmed by theory.
I detta examensarbete har absorptionseffektivitet av CO2 hos olika vätskelösningar undersökts genom gasabsorption i en slumpmässigt packad kolonn. För att karakterisera absorptionen absorberades även SO2 i några experiment. Rapporten är utförd med anledning av de stora mängder koldioxid som släpps ut i atmosfären, främst från fossileldade kraftverk. För att minska dessa utsläpp kan koldioxiden avskiljas från rökgaserna genom olika tekniker t.ex. genom CO2-absorption med ammoniak. Arbetet består av en teoridel och en laborativ del med mätningar och beräkningar. I den experimentella delen konstruerades ett system med en absorptionskolonn och tillhörande mätutrustning. Olika vätskelösningar bestående av rent vatten, kaliumkarbonatlösning och ammoniak i olika koncentrationer användes till att ta upp koldioxid genom motströms absorption. Även SO2 absorberades i kaliumkarbonatlösning för att bestämma gasfilmkonstanten. Absorptionsgraden av CO2 varierade från några få procent i försöket med vatten upp till 7 % med kaliumkarbonatlösningen. CO2-absorptionen av ammoniak varierade med koncentrationen och gav en avskiljning på mellan 12 och 94 %. Ammoniakförsöken gjordes med både vid 10 och 20 °C. Generellt erhölls en bättre CO2-avskiljning vid 20°C, vilket bekräftas av teorin.

Aqueous-biphasic organometallic catalysis is, as illustrated by the industrial hydroformylation of propene and butene, one of the most promising ways to overcome the intrinsic problem of catalyst separation in organometallic catalysis. However, for poorly water-soluble substrates, mass transfer limitations bring the reaction rate below any that could be economically viable, greatly limiting the scope of this elegant technology. We have studied three different strategies to overcome this limitation. We developed additives that speed up the reaction whilst retaining fast phase separation and good metal retention. Evidence suggests that those additives affect the reaction by forming emulsions with poor stability under the reaction conditions These emulsions increase the interfacial surface area but break after settling for a short time. We also developed ligands that allow the catalyst to be reversibly transported between an aqueous and an organic phase upon addition and removal of carbon dioxide. This allows the reaction to be carried out under homogeneous conditions, only limited by intrinsic kinetics, and the catalyst to be separated by aqueous extraction triggered by carbon dioxide. The catalyst can be returned to a fresh organic phase by flushing out the carbon dioxide. By applying this methodology for the hydroformylation of medium chain length alkenes, very high reaction rates were obtained and the catalyst could be recycle three times with excellent retention of activity and low metal leaching. This methodology could also be reversed with the reaction being carried out in an aqueous phase in the presence of carbon dioxide and extracting the catalyst into an organic solvent using nitrogen flushing. Finally, we briefly investigated the use of an oscillatory baffled reactor as a mean for mass transfer improvement for aqueous-biphasic hydroformylation. This new type reactor did not improve the performance of the system under the investigated conditions, but may require less energy input for equivalent agitation and mixing.

La digestion anaérobie par voie sèche est un procédé de valorisation des déchets organiques qui est défini par une teneur en matière sèche supérieure à 15%. Ce procédé est particulièrement adapté aux déchets ligno-cellulosiques puisqu’il ne nécessite qu’un ajout limité en eau. Cependant, la digestion anaérobie est inhibée pour des teneurs en matière sèche élevées, due à une diminution des transferts gaz-liquide au sein du milieu qui provoquerait des accumulations locales de produits inhibiteurs comme les gaz dissous. L’objectif de cette thèse est donc de comprendre le rôle des gaz dissous dans la digestion anaérobie par voie sèche à l’échelle microscopique et mésoscopique. Les principaux résultats montrent que l’hydrogène inhibe spécifiquement l’hydrolyse de la matière ligno-cellulosique à l’échelle microscopique. Cette inhibition est réversible en ajoutant du dioxyde de carbone, par consommation de l’hydrogène, avec cependant des effets rémanents inhibiteurs visibles sur la méthanogenèse et la dégradation de l’acétate. A l’échelle mésoscopique, la diminution des transferts de matière inhiberait l’hydrolyse, par l’accumulation locale d’hydrogène. De plus, un gradient de concentration d’hydrogène se met en place et serait responsable du gradient de concentration des acides gras volatils au sein du milieu. De plus, l’ajout de dioxyde de carbone à l’échelle mésoscopique avec un transfert gaz-liquide limitant augmente la concentration en acides gras volatils et baisse le pH du milieu, ce qui indique le rôle important du dioxyde de carbone dans la diminution des performances de la digestion anaérobie pour de fortes teneurs en matières sèches
Dry anaerobic digestion is a method of organic waste treatment and conversion to bioenergy, defined by a total solid content over 15%. This process is particularly suitable for lignocellulosic residues since the quantity of water to be added for the process is rather limited. However, dry anaerobic digestion processes is inhibited for a high total solid content, due to a decrease of the gas-liquid transfer within the medium, which may cause local accumulations of inhibitory byproducts, such as dissolved gases. This thesis aims to better understand the role of dissolved gas in dry anaerobic digestion at microscopic and mesoscopic scale. It was shown that hydrogen can inhibit specifically the hydrolysis step of lignocellulosic residues at microscopic level. This inhibition was reversible after addition of carbon dioxide, with remaining inhibitory effect on the acetate degradation and methanogenesis. At mesoscopic scale, the decrease of the mass transfer inhibits the hydrolysis, by dissolved hydrogen accumulation. Moreover, a local hydrogen concentration gradient was present and seems responsible for a concentration gradient of volatile fatty acids in the medium. Moreover, adding carbon dioxide at mesoscopic scale, with a limited gas-liquid transfer, increased the volatile fatty acids concentration and decreased the pH, which showed the important role of carbon dioxide in the inhibition of anaerobic digestion under high dry matter content

L'utilisation du CO2 comme matière première pour la synthèse de produits à haute valeur ajoutée, comme les carbonates cycliques, est aujourd'hui l'une des alternatives proposées dans la réduction des émissions gazeuses à effet de serre. Ce travail de thèse vise à comprendre et concevoir un procédé de valorisation de CO2 à partir de la modélisation de la thermodynamique et des cinétiques de transfert de matière et de réactions, qui sont engendrées dans la synthèse de carbonates cycliques à partir des époxydes et un composé hétérocyclique comme catalyseur. Grâce à ce nouveau système, les carbonates cycliques très utilisés dans l'industrie de polymères, cosmétique ou pharmaceutique, sont obtenus avec de bons rendements, dans des conditions opératoires douces et en absence de solvants. Des propriétés thermodynamiques telles que la solubilité et la constante de Henry ont été estimées pour les systèmes binaires CO2/époxyde. L'étude du transfert de matière sans ou avec réactions a permis de déterminer respectivement le coefficient de transfert de matière en phase liquide et le régime de la réaction. Des suivis cinétiques ont été réalisés afin de proposer un modèle cinétique capable de représenter la réaction et d'estimer les paramètres cinétiques. Ces derniers ont été utilisés pour la conception préliminaire et la simulation du procédé de production du carbonate d' épichlorohydrine sur Aspen Hysys
Today, the utilisation of CO2 as raw material for the synthesis of high-value added products like cyclic carbonates, is one of the alternatives used for reducing greenhouse gases. This thesis aims to understand and design a CO2 valorisation process by modelling the thermodynamic and the mass transfer/reaction kinetics generated during the cyclic carbonates synthesis from CO2, epoxides and a heterocyclic compound as catalyst. By using this new catalytic system, cyclic carbonates, which are used in the polymeric, pharmaceutic or cosmetic industry, can be produced with good yields at low temperatures and pressures and without any solvent. Thermodynamic properties as solubility and Henry's law constant have been estimated for CO2/epoxide binary systems. Mass transfer occurring without and with reaction has been studied in order to determine respectively the liquid volumetric mass transfer coefficient and the reaction regime. A kinetic study has been performed to propose a model able to represent the reaction and to estimate the kinetic parameters. This information has been used in the design and the simulation of the production process of epichlorohydrin carbonate on Aspen Hysys

La micro-oxygénation des vins, par la dispersion de bulles d’oxygène, est une pratique de plus en plus utilisée dans le domaine de l’œnologie. Cette technique n’est pas toujours convenablement maitrisée par manque de connaissances scientifiques sur les paramètres régissant le transfert de l’oxygène. La recherche s'est focalisée sur l'étude des coefficients de transfert en fonction des composés du vin (CO2, éthanol, sucrose, consommateurs d’oxygène) et des conditions opératoires (type de diffuseur, température, rapport entre hauteur et diamètre du contenant de liquide). Les résultats montrent que lors de la micro-oxygénation, le dioxyde de carbone dissous et le sucrose ont une incidence négative sur le transfert alors que la présence d’éthanol améliore le transfert. En ce qui concerne les conditions opératoires, l’augmentation de débit de gaz et l’augmentation de rapport entre la hauteur et le diamètre de la cuve de micro-oxygénation joue positivement sur le transfert d’oxygène La surface spécifique des bulles et le coefficient de transfert de matière ont pu être dissociés pour les vins. La nature tensio-active des composés du vin semble être un élément important sur le transfert de matière. Les connaissances acquises ont été appliquées à la micro-oxygénation au cours de deux étapes de l'élaboration des vins : la fermentation alcoolique avec la maitrise de l’apport d’oxygène et la simulation de la technique d’élevage en barrique par micro-oxygénation couplée à l’ajout de copeaux de bois. Une nouvelle approche concerne l'étude d'un contacteur membranaire qui permet le transfert d’oxygène par diffusion
Micro-oxygenation of the wines, by the dispersion of oxygen bubbles, is a practice increasingly used in oenology. This technique is not always suitably controlled for lack of scientific knowledge on the parameters governing the transfer of oxygen. Research was focused on the study of transfer coefficients in function of wine components (CO2, ethanol, sucrose, consuming oxygen) and of operating conditions (type of diffuser, temperature, relationship between height and diameter of the container of liquid). The results show that during micro-oxygenation, the dissolved carbon dioxide and the sucrose have a negative incidence on the transfer whereas the presence of ethanol improves the transfer. As operating conditions are concerned, the increase in gas output and the increase in micro-oxygenation tank height/diameter ratio positively influence oxygen transfer. For wines, the specific surface of the bubbles and the mass transfer coefficient could be dissociated. The surfactant nature of wine components seems to be the most important factor in mass transfer. The knowledge so acquired was applied to micro-oxygenation during two stages of wine making: alcoholic fermentation with the oxygen yield control and the simulation of ageing technique in barrels coupled with the wood chips addition. A new approach relates to the study of a membrane contactor application allowing the oxygen transfer by diffusion

L'extraction d'un constituant d'un mélange gazeux peut être réalisée par couplage des phénomènes de diffusion et réaction à travers une membrane. Ce mode de transport a été appliqué à des membranes échangeuses d'ions dont les contre-ions, appelés transporteurs, réagissent réversiblement avec le substrat pour former un ou des complexes. Cette étude théorique a été appliquée au transport facilité du dioxyde de carbone par les ions éthylènediamines à travers différentes membranes échangeuses de cations (permion et nafion)

To screen amine solvents for application in CO2 capture from coal-fired power plants, the equilibrium CO2 partial pressure and liquid film mass transfer coefficient were characterized for CO2-loaded and highly concentrated aqueous amines at 40 – 100 °C over a range of CO2 loading with a Wetted Wall Column (WWC). The acyclic amines tested were ethylenediamine, 1,2-diaminopropane, diglycolamine®, methyldiethanolamine (MDEA)/Piperazine (PZ), 3-(methylamino)propylamine, 2-amino-2-methyl-1-propanol and 2-amino-2-methyl-1-propanol/PZ. The cyclic amines tested were piperazine derivatives including proline, 2-piperidineethanol, N-(2-hydroxyethyl)piperazine, 1-(2-aminoethyl)piperazine, N-methylpiperazine (NMPZ), 2-methylpiperazine (2MPZ), 2,5-trans-dimethylpiperazine, 2MPZ/PZ, and PZ/NMPZ/1,4-dimethylpiperazine (1,4-DMPZ). The cyclic CO2 capacity and heat of CO2 absorption were estimated with a semi-empirical vapor-liquid-equilibrium model. 5 m MDEA/5 m PZ, 8 m 2MPZ, 4 m 2MPZ/4 m PZ and 3.75 m PZ/3.75 m NMPZ/0.5 m 1,4-DMPZ were identified as promising solvent candidates for their large CO2 capacity, fast mass transfer rate and moderately high heat of absorption. The speciation in 8 m 2MPZ and 4 m 2MPZ / 4 m PZ at 40 °C at varied CO2 loading was investigated using quantitative 1H and 13C nuclear magnetic resonance (NMR) spectroscopy. In 8 m 2MPZ at 40 °C over the CO2 loading range of 0 – 0.37 mol CO2/mol alkalinity, more than 75% of the dissolved CO2 exists in the form of unhindered 2MPZ monocarbamate, and the rest is in the form of bicarbonate and dicarbamate; 19% - 56% of 2MPZ is converted to 2MPZ carbamate at 0.1 - 0.37 mol CO2/mol alkalinity. A rigorous thermodynamic model was developed for 8 m 2MPZ in the framework of the Electrolyte Nonrandom Two-Liquid (ENRTL) model. At 40 °C, the reaction stoichiometry for 2MPZ and CO2 is around 2 at lean loading but diminishes to 0 at rich loading. Bicarbonate becomes the major product at CO2 loading greater than 0.35 mol/mol alkalinity. The predicted heat of CO2 absorption is 75 kJ/mol at 140 °C and decreases with temperature when CO2 loading is above 0.25. The mass transfer rate data for 8 m 2MPZ was represented with a rate-based WWC model created in Aspen Plus®. The reaction rate was described with termolecular mechanism on an activity basis. With minor CO2 loading adjustment and regression of pre-exponential kinetic constants and diffusion activation energy, a majority of the measured CO2 fluxes in the WWC experiments were fitted by the model within ±20% over 40 – 100 °C and 0.1 – 0.37 mol CO2/mol alkalinity. The diffusion activation energy for 8 m 2MPZ at the rich loading is about 28 kJ/mol. The activity-based reaction rate constant at 40 °C for 2MPZ carbamate formation catalyzed by 2MPZ is 1.94×1010 kmol/m3•s. The calculated liquid film mass transfer coefficients are in close agreement with the experimental values. The liquid film mass transfer rate is dependent on the diffusion coefficients of amine and CO2 to the same extent at lean loading and 40 °C. The sum of the powers for the two diffusivities is approximately equal to 0.5 over the loading range of 0 – 0.4 mol CO2/mol alkalinity. The sum of the powers for the dependence of the liquid film mass transfer coefficient on the carbamate formation rate constants (k2MPZ-2MPZ and k2MPZCOO--2MPZ) approaches 0.5 at very lean loading at low temperature, but it decreases as CO2 loading and temperature is increased. At 100 °C, the physical liquid film mass transfer coefficient is the most important factor that determines the liquid mass transfer rate. The pseudo-first order region shifts to higher range of physical liquid film transfer coefficient as temperature increases.
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This work evaluates stripper performance for CO₂ capture using seven potential solvent formulations and seven stripper configurations. Equilibrium and rate models were developed in Aspen Custom Modeler (ACM). The temperature approach on the hot side of the cross exchanger was varied between 5 - 10°C. The results show that operating the cross exchanger at a 5°C approach results in 12% energy savings for a 7m MEA rich solution of 0.563 mol/mol Alk and 90% CO₂ removal. For solvents with [Delta]H[subscript abs] < 60 kJ/gmol CO₂, stripping at 30 kPa is more attractive than stripping at 160 kPa. Normal pressure (160 kPa) favors solvents with high heats of desorption. The best solvent and process configuration, matrix with MDEA/PZ, offers 22% and 15% energy savings over the baseline and improved baseline, respectively, with stripping and compression to 10 MPa. The energy requirement for stripping and compression to 10 MPa is about 20 % of the power output from a 500 MW power plant with 90% CO2 removal. Rate model results show that a 'short and fat' stripper requires 7 to 15% less equivalent work than a 'tall and skinny' one. The optimum stripper design could be one that operates between 50% and 80% flood at the bottom. Stripping at 30 kPa and 160 kPa require 230 s and 115 s of effective packing volume to get an equivalent work 4% greater than the minimum. Stripping at 30 kPa with [Delta]T = 5°C was controlled by mass transfer with reaction in the boundary layer and diffusion (88% resistance at the rich end and 71% resistance at the lean end) and mass transfer with equilibrium reactions (84% resistance at the rich end and 74% resistance at the lean end) at 160 kPa. The model was validated with data obtained from pilot plant experiments at the University of Texas with 5m K⁺/2.5m PZ and 6.4m K⁺/1.6m PZ under normal pressure and vacuum conditions using Flexipac AQ Style 20 structured packing. Foaming was experienced during tests. The effective packing height was 5.09m for 5m K⁺/2.5m PZ and 6.47m for 6.4m K⁺/1.6m PZ.
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