Phase Equilibrium Measurements and Modeling for Alkanolamine Systems

Anne Penttilä

Phase Equilibrium Measurements and Modeling for Alkanolamine Systems

Julkaisun otsikon käännös: Alkanoliamiini systeemien faasitasapainojen mittaaminen ja mallittaminen

Anne Penttilä

Tutkimustuotos: Doctoral Thesis › Collection of Articles

Abstrakti

Hiilidioksidin talteenottoa tutkittiin tässä työssä mittaamalla ja mallittamalla alkanoliamiini systeemejä ja kehittämällä täysin uusia malleja prosessin suunnittelutarkoitukseen. Henryn laki hiilidioksidille vesipohjaisessa amiiniliuoksessa on välttämätön, kun hiilidioksidin talteenottoprosesseja mallitetaan. Hiilidioksidin fysikaalista liukoisuutta vesipohjaiseen amiiniliuokseen ei kuitenkaan voida suoraan mitata ja siksi se saadaan typpioksiduulin fysikaalisesta liukoisuudesta samaa liuokseen käyttämällä N2O - CO2 analogia. Tässä työssä kehitettiin uusi malli Henryn laille, joka kuvaa typpioksiduulin liukoisuutta binäärisiin ja ternäärisiin vesipohjaisiin amiiniliuoksiin (monoetanoliamiini MEA, dietanoliamiini DEA, diisopropanoliamiini DIPA, N-metyylidietanoliamiini MDEA ja 2-amino-2-metyyli-1-propanoli AMP) lämpötilan ja amiinipitoisuuden funktiona. Mallin parametrit optimoitiin 992 mitattuun pisteeseen aina 393 K asti. Uutta mallia verrattiin myös muihin kirjallisuudesta löydettyihin malleihin. Tässä työssä kehitetty malli kuvasi kokeellisia pisteitä paremmin kuin kirjallisuuden mallit. Lämpöstabiileja suoloja muodostuu hiilidioksidin talteenottoprosesseissa, kun happi on läsnä systeemissä. Lämpöstabiileja suoloja ei ole tutkittu paljon kirjallisuudessa ja siksi tämä työ laajennettiin kattamaan myös amiinien hajoamistuotteita. 2-hydroksietyyliammonium asetaattia (2-HEAA), joka on lämpöstabiili suola mutta myös tislautuva ioninen neste, valmistettiin MEA:sta ja etikkahaposta (HAc) ja se puhdistettiin tislaamalla vakuumissa. Höyry-neste tasapainoja mitattiin staattisella kokonaispainemittalaitteistolla. Kiinteä-neste tasapainoja ja puhtaiden komponenttien sulamispisteitä mitattiin joko visuaalisella menetelmällä tai DSC:llä (Differential Scanning Calorimetry). Tiheyttä mitattiin DMA HP:lla, joka oli yhdistetty DMA 5000 M tiheysmittariin. Lisäksi, höyrynpainetta mitattiin Vigreaux -tyyppisellä tislauskolonnilla. 2-HEAA:n tutkiminen osoitti, että lämpöstabiilien suolojen vaikutus faasitasapainoihin voidaan ottaa huomioon, kun mallitetaan hiilidioksidin talteenottoprosesseja. Uusi malli kehitettiin myös H2O + DIPA liuoksen tiheydelle lämpötilan ja koostumuksen funktiona, sillä kyseiselle systeemille ei löytynyt yleistä mallia kirjallisuudesta. Lisäksi tioli + hiilivety systeemien höyry-neste tasapainoja mallitettiin NRTL, Wilson ja UNIQUAC aktiivisuuskerroin malleilla. Myös ennustavia UNIFAC ja COSMO SAC malleja käytettiin.

Julkaisun otsikon käännös	Alkanoliamiini systeemien faasitasapainojen mittaaminen ja mallittaminen
Alkuperäiskieli	Englanti
Pätevyys	Tohtorintutkinto
Myöntävä instituutio	Aalto-yliopisto
Valvoja/neuvonantaja	Alopaeus, Ville, Vastuuprofessori Uusi-Kyyny, Petri, Ohjaaja
Kustantaja	Aalto University
Painoksen ISBN	978-952-60-5995-2
Sähköinen ISBN	978-952-60-5996-9
Tila	Julkaistu - 2014
OKM-julkaisutyyppi	G5 Artikkeliväitöskirja

Tutkimusalat

Henryn laki
hiilidioksidi
typpioksiduuli
höyry-neste tasapaino
kiinteä-neste tasapaino
amiinit

Pääsy asiakirjaan

http://urn.fi/URN:ISBN:978-952-60-5996-9

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@phdthesis{3e6ff2359a5246d8ae15cb970403d5f8,

title = "Phase Equilibrium Measurements and Modeling for Alkanolamine Systems",

abstract = "CO2 capture was investigated in this work by measuring and modeling alkanolamine systems and by developing entirely new models for process design purposes. The Henry's law constant of CO2 in aqueous amine solutions is necessary when modeling CO2 capture processes. However, the physical solubility of CO2 in aqueous amine solutions cannot be measured directly and therefore it is derived from the Henry's law constant of N2O in the same solutions by employing the N2O - CO2 analogy. In this work a new model was developed for the Henry's law constant of N2O in aqueous binary and ternary amine solutions (monoethanolamine MEA, diethanolamine DEA, diisopropanolamine DIPA, N-methyldiethanolamine MDEA, and 2-amino-2-methyl-1-propanol AMP) as a function of temperature and amine concentration. The parameters of the new expression were fitted to 992 data points up to 393 K. The new model was also compared with the models found in the literature. The model developed in this work describes the experimental data better than the models found in the literature.Heat stable salts are formed in CO2 capture processes when oxygen is present in a system. Heat stable salts have not been studied much in the literature and thus this work was extended to cover amine degradation products. 2-hydroxyethylammonium acetate (2-HEAA), which is a heat stable salt but also a distillable protic ionic liquid, was prepared from MEA and acetic acid (HAc) and it was purified by distilling under vacuum. Vapor-liquid equilibrium was measured with a static total pressure apparatus. Solid-liquid equilibrium and the melting point of pure compounds were measured either with a visual method or with a Differential Scanning Calorimeter. Density was measured with a DMA HP connected to a DMA 5000 M densimeter. In addition, vapor pressure was measured using a Vigreaux type distillation column. The research of 2-HEAA indicated that the effect of heat stable salts on phase equilibria can be taken into consideration when modeling CO2 capture processes. A new model was also developed for the density of aqueous DIPA solution as a function of both temperature and composition since no general model for aqueous DIPA solution was found in the literature. In addition, vapor-liquid equilibrium data of thiol + hydrocarbon systems were modeled with the NRTL, Wilson and UNIQUAC activity coefficient models. Also predictive UNIFAC and COSMO SAC models were used.",

keywords = "Henry's law, carbon dioxide, nitrous oxide, vapor-liquid equilibrium, solid-liquid equilibrium, amines, Henryn laki, hiilidioksidi, typpioksiduuli, h{\"o}yry-neste tasapaino, kiinte{\"a}-neste tasapaino, amiinit, Henry's law, carbon dioxide, nitrous oxide, vapor-liquid equilibrium, solid-liquid equilibrium, amines",

author = "Anne Penttil{\"a}",

year = "2014",

language = "English",

isbn = "978-952-60-5995-2",

series = "Aalto University publication series DOCTORAL DISSERTATIONS",

publisher = "Aalto University",

number = "200",

address = "Finland",

school = "Aalto University",

}

TY - BOOK

T1 - Phase Equilibrium Measurements and Modeling for Alkanolamine Systems

AU - Penttilä, Anne

PY - 2014

Y1 - 2014

N2 - CO2 capture was investigated in this work by measuring and modeling alkanolamine systems and by developing entirely new models for process design purposes. The Henry's law constant of CO2 in aqueous amine solutions is necessary when modeling CO2 capture processes. However, the physical solubility of CO2 in aqueous amine solutions cannot be measured directly and therefore it is derived from the Henry's law constant of N2O in the same solutions by employing the N2O - CO2 analogy. In this work a new model was developed for the Henry's law constant of N2O in aqueous binary and ternary amine solutions (monoethanolamine MEA, diethanolamine DEA, diisopropanolamine DIPA, N-methyldiethanolamine MDEA, and 2-amino-2-methyl-1-propanol AMP) as a function of temperature and amine concentration. The parameters of the new expression were fitted to 992 data points up to 393 K. The new model was also compared with the models found in the literature. The model developed in this work describes the experimental data better than the models found in the literature.Heat stable salts are formed in CO2 capture processes when oxygen is present in a system. Heat stable salts have not been studied much in the literature and thus this work was extended to cover amine degradation products. 2-hydroxyethylammonium acetate (2-HEAA), which is a heat stable salt but also a distillable protic ionic liquid, was prepared from MEA and acetic acid (HAc) and it was purified by distilling under vacuum. Vapor-liquid equilibrium was measured with a static total pressure apparatus. Solid-liquid equilibrium and the melting point of pure compounds were measured either with a visual method or with a Differential Scanning Calorimeter. Density was measured with a DMA HP connected to a DMA 5000 M densimeter. In addition, vapor pressure was measured using a Vigreaux type distillation column. The research of 2-HEAA indicated that the effect of heat stable salts on phase equilibria can be taken into consideration when modeling CO2 capture processes. A new model was also developed for the density of aqueous DIPA solution as a function of both temperature and composition since no general model for aqueous DIPA solution was found in the literature. In addition, vapor-liquid equilibrium data of thiol + hydrocarbon systems were modeled with the NRTL, Wilson and UNIQUAC activity coefficient models. Also predictive UNIFAC and COSMO SAC models were used.

AB - CO2 capture was investigated in this work by measuring and modeling alkanolamine systems and by developing entirely new models for process design purposes. The Henry's law constant of CO2 in aqueous amine solutions is necessary when modeling CO2 capture processes. However, the physical solubility of CO2 in aqueous amine solutions cannot be measured directly and therefore it is derived from the Henry's law constant of N2O in the same solutions by employing the N2O - CO2 analogy. In this work a new model was developed for the Henry's law constant of N2O in aqueous binary and ternary amine solutions (monoethanolamine MEA, diethanolamine DEA, diisopropanolamine DIPA, N-methyldiethanolamine MDEA, and 2-amino-2-methyl-1-propanol AMP) as a function of temperature and amine concentration. The parameters of the new expression were fitted to 992 data points up to 393 K. The new model was also compared with the models found in the literature. The model developed in this work describes the experimental data better than the models found in the literature.Heat stable salts are formed in CO2 capture processes when oxygen is present in a system. Heat stable salts have not been studied much in the literature and thus this work was extended to cover amine degradation products. 2-hydroxyethylammonium acetate (2-HEAA), which is a heat stable salt but also a distillable protic ionic liquid, was prepared from MEA and acetic acid (HAc) and it was purified by distilling under vacuum. Vapor-liquid equilibrium was measured with a static total pressure apparatus. Solid-liquid equilibrium and the melting point of pure compounds were measured either with a visual method or with a Differential Scanning Calorimeter. Density was measured with a DMA HP connected to a DMA 5000 M densimeter. In addition, vapor pressure was measured using a Vigreaux type distillation column. The research of 2-HEAA indicated that the effect of heat stable salts on phase equilibria can be taken into consideration when modeling CO2 capture processes. A new model was also developed for the density of aqueous DIPA solution as a function of both temperature and composition since no general model for aqueous DIPA solution was found in the literature. In addition, vapor-liquid equilibrium data of thiol + hydrocarbon systems were modeled with the NRTL, Wilson and UNIQUAC activity coefficient models. Also predictive UNIFAC and COSMO SAC models were used.

KW - Henry's law

KW - carbon dioxide

KW - nitrous oxide

KW - vapor-liquid equilibrium

KW - solid-liquid equilibrium

KW - amines

KW - Henryn laki

KW - hiilidioksidi

KW - typpioksiduuli

KW - höyry-neste tasapaino

KW - kiinteä-neste tasapaino

KW - amiinit

KW - Henry's law

KW - carbon dioxide

KW - nitrous oxide

KW - vapor-liquid equilibrium

KW - solid-liquid equilibrium

KW - amines

M3 - Doctoral Thesis

SN - 978-952-60-5995-2

T3 - Aalto University publication series DOCTORAL DISSERTATIONS

PB - Aalto University

ER -

Phase Equilibrium Measurements and Modeling for Alkanolamine Systems

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