Vapor–Liquid Equilibrium and Excess Enthalpies: Measurements and Modeling for Process Industry

Helena Laavi

Vapor–Liquid Equilibrium and Excess Enthalpies: Measurements and Modeling for Process Industry

Julkaisun otsikon käännös: Höyry-nestetasapaino ja eksessientalpia: Mittauksia ja malleja prosessiteollisuuden tarpeisiin

Helena Laavi

Tutkimustuotos: Doctoral Thesis › Collection of Articles

Abstrakti

Tässä työssä mitattiin höyry-nestetasapainoja (VLE) ja eksessientalpioita (HE), joiden pohjalta laadittiin termodynaamisia malleja tutkituille kaksi-komponenttisysteemeille. Tutkitut systeemit ja näiden mallit ovat hyödyksi prosessiteollisuudelle. Höyry-nestetasapainojen mittaamiseen käytettiin staattista kokonaispainemittalaitteistoa, lasista kierrätysmittalaitteistoa ja headspace- mittalaitetta yhdistettynä kaasukromatografiin. Eksessientalpiat mitattiin sekoituskennolla varustetulla SETARAM C80 –virtauskalorimetril-lä, joka otettiin käyttöön tässä työssä. Anton Paarin DMA 512P –mallista tiheysmittaria käytettiin eksessitilavuuksien (VE) määrittämiseen. Eri VLE-mittausmenetelmien rinnakkainen käyttö mahdollisti laajemman mittausalueen ja paransi mittausten laatua. Tutkitut kaksi-komponenttisysteemit voitiin jakaa viiteen ryhmään. Systeemit muodostivat neljä ryhmää, joissa alkoholi oli toisena komponenttina ja toisena komponenttina oli joko alkaani, eetteri, esteri tai ketoni. Lisäksi viidenteen ryhmään kuuluivat komponenttiparit, joista toinen oli eetteri ja toinen nitriili. Komponenttien valinnoissa huomioitiin niiden merkitys prosessiteollisuudessa sekä ympäristöystävällisempien prosessien kehityksessä.Höyry-nestetasapainojen mittaustulokset mallinnettiin käyttämällä Hayden-O’Connell –menetelmää höyryfaasin fugasiteettien ja Wilson, NRTL, UNIQUAC tai UNIFAC-mallia nestefaasin aktiivisuuskertoimien määrittämiseen. Eksessientalpiat otettiin mukaan termodynaamiseen malliin, jota voitiin tämän ansiosta käyttää laajemmalla lämpötila- ja painealueella. Rinnakkaiset mittaukset tuottivat laadukasta tietoa aineominaisuuksista. Mittausten laatu tarkistettiin käyttämällä kolmea konsistessitestiä, joita kutsutaan pinta-alatestiksi, pistetestiksi ja äärettömän laimennoksen testiksi. Staattisella kokonaispainelaitteella saadut pTz-mittaustulokset redusoitiin pTxy-mittaustuloksiksi.

Julkaisun otsikon käännös	Höyry-nestetasapaino ja eksessientalpia: Mittauksia ja malleja prosessiteollisuuden tarpeisiin
Alkuperäiskieli	Englanti
Pätevyys	Tohtorintutkinto
Myöntävä instituutio	Aalto-yliopisto
Ohjaaja	Alopaeus, Ville, Vastuuprofessori Pokki, Juha-Pekka, Ohjaaja Uusi-Kyyny, Petri, Ohjaaja
Kustantaja	Aalto University
Painoksen ISBN	978-952-60-5271-7
Sähköinen ISBN	978-952-60-5272-4
Tila	Julkaistu - 2013
OKM-julkaisutyyppi	G5 Artikkeliväitöskirja

Tutkimusalat

höyry-nestetasapaino
eksessientalpia
eksessitilavuus
virtauskalorimetri

Pääsy asiakirjaan

http://urn.fi/URN:ISBN:978-952-60-5272-4

Siteeraa tätä

@phdthesis{bb4e65dbb08f4534b688dfff82b091ad,

title = "Vapor–Liquid Equilibrium and Excess Enthalpies: Measurements and Modeling for Process Industry",

abstract = "The purpose of this work was to examine vapor–liquid equilibria (VLE) together with excess enthalpies (HE) in order to formulate thermodynamic models for the studied systems to meet the needs of process industry. A static total pressure apparatus, a circulation still, and a headspace gas-chromatograph were used to obtain VLE data. A SETARAM C80 calorimeter with a flow mixing cell was implemented and used for HE measurements and an Anton Paar DMA 512P vibrating tube densimeter for excess volumes (VE). The parallel use of different VLE apparatuses widened the scope of the experiments and ensured the high quality of the VLE data. The studied binary systems consisted of a group of alcohols with alkanes, ethers, esters, and a ketone. Additionally, binary mixtures of ethers and nitriles were studied. The components were selected based on their relevance to chemical industry and to their potential for supporting the sustainable development of eco-friendlier chemical processes. The measured VLE data were modeled by using the Hayden–O{\textquoteright}Connell method with the chemical theory for the vapor phase fugacities and the Wilson model, NRTL, UNIQUAC, or UNIFAC model for the liquid phase activity coefficients. The inclusion of also HE data improved the model applicability beyond the original temperature and pressure ranges. The parallel thermodynamic measurements produced data of good quality. The consistency of the data was checked by applying the area test, the point test, and the infinite dilution test on the measured data. For the static total pressure apparatus, the method of Barker was used to reduct the pTz data to pTxy data.",

keywords = "vapor–liquid equilibrium, excess enthalpy, excess volume, flow calorimeter, circulation still, headspace, static total pressure apparatus, h{\"o}yry-nestetasapaino, eksessientalpia, eksessitilavuus, virtauskalorimetri, vapor–liquid equilibrium, excess enthalpy, excess volume, flow calorimeter, circulation still, headspace, static total pressure apparatus",

author = "Helena Laavi",

year = "2013",

language = "English",

isbn = "978-952-60-5271-7",

series = "Aalto University publication series DOCTORAL DISSERTATIONS",

publisher = "Aalto University",

number = "121",

address = "Finland",

school = "Aalto University",

}

TY - BOOK

T1 - Vapor–Liquid Equilibrium and Excess Enthalpies: Measurements and Modeling for Process Industry

AU - Laavi, Helena

PY - 2013

Y1 - 2013

N2 - The purpose of this work was to examine vapor–liquid equilibria (VLE) together with excess enthalpies (HE) in order to formulate thermodynamic models for the studied systems to meet the needs of process industry. A static total pressure apparatus, a circulation still, and a headspace gas-chromatograph were used to obtain VLE data. A SETARAM C80 calorimeter with a flow mixing cell was implemented and used for HE measurements and an Anton Paar DMA 512P vibrating tube densimeter for excess volumes (VE). The parallel use of different VLE apparatuses widened the scope of the experiments and ensured the high quality of the VLE data. The studied binary systems consisted of a group of alcohols with alkanes, ethers, esters, and a ketone. Additionally, binary mixtures of ethers and nitriles were studied. The components were selected based on their relevance to chemical industry and to their potential for supporting the sustainable development of eco-friendlier chemical processes. The measured VLE data were modeled by using the Hayden–O’Connell method with the chemical theory for the vapor phase fugacities and the Wilson model, NRTL, UNIQUAC, or UNIFAC model for the liquid phase activity coefficients. The inclusion of also HE data improved the model applicability beyond the original temperature and pressure ranges. The parallel thermodynamic measurements produced data of good quality. The consistency of the data was checked by applying the area test, the point test, and the infinite dilution test on the measured data. For the static total pressure apparatus, the method of Barker was used to reduct the pTz data to pTxy data.

AB - The purpose of this work was to examine vapor–liquid equilibria (VLE) together with excess enthalpies (HE) in order to formulate thermodynamic models for the studied systems to meet the needs of process industry. A static total pressure apparatus, a circulation still, and a headspace gas-chromatograph were used to obtain VLE data. A SETARAM C80 calorimeter with a flow mixing cell was implemented and used for HE measurements and an Anton Paar DMA 512P vibrating tube densimeter for excess volumes (VE). The parallel use of different VLE apparatuses widened the scope of the experiments and ensured the high quality of the VLE data. The studied binary systems consisted of a group of alcohols with alkanes, ethers, esters, and a ketone. Additionally, binary mixtures of ethers and nitriles were studied. The components were selected based on their relevance to chemical industry and to their potential for supporting the sustainable development of eco-friendlier chemical processes. The measured VLE data were modeled by using the Hayden–O’Connell method with the chemical theory for the vapor phase fugacities and the Wilson model, NRTL, UNIQUAC, or UNIFAC model for the liquid phase activity coefficients. The inclusion of also HE data improved the model applicability beyond the original temperature and pressure ranges. The parallel thermodynamic measurements produced data of good quality. The consistency of the data was checked by applying the area test, the point test, and the infinite dilution test on the measured data. For the static total pressure apparatus, the method of Barker was used to reduct the pTz data to pTxy data.

KW - vapor–liquid equilibrium

KW - excess enthalpy

KW - excess volume

KW - flow calorimeter

KW - circulation still

KW - headspace

KW - static total pressure apparatus

KW - höyry-nestetasapaino

KW - eksessientalpia

KW - eksessitilavuus

KW - virtauskalorimetri

KW - vapor–liquid equilibrium

KW - excess enthalpy

KW - excess volume

KW - flow calorimeter

KW - circulation still

KW - headspace

KW - static total pressure apparatus

M3 - Doctoral Thesis

SN - 978-952-60-5271-7

T3 - Aalto University publication series DOCTORAL DISSERTATIONS

PB - Aalto University

ER -

Vapor–Liquid Equilibrium and Excess Enthalpies: Measurements and Modeling for Process Industry

Abstrakti

Tutkimusalat

Pääsy asiakirjaan

Sormenjälki

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