Phase equilibria of aqueous bio-component mixtures with different solvents for the design of a liquid-liquid extraction unit

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School of Chemical Engineering | Doctoral thesis (article-based) | Defence date: 2019-01-25
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Date

2018

Department

Kemian tekniikan ja metallurgian laitos
Department of Chemical and Metallurgical Engineering

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Mcode

Degree programme

Language

en

Pages

67 + app. 69

Series

Aalto University publication series DOCTORAL DISSERTATIONS, 243/2018

Abstract

The aim of this thesis was the investigation of various solvents for the liquid-liquid extraction of furfural from aqueous solutions, which are present in bio-refineries. Additionally, the potential of the solvents for the separation of acetic acid, also present in these mixtures, was tudied. Different separation methods are often studied and analysed through process simulations, which require accurate models for the studied systems. When experimental data is not available, predictive models fill this need, but a better fit can be achieved through measured data and accurately regressed parameters for a suitable thermodynamic model. This work measured liquid-liquid equilibria (LLE) for such applications for various systems over a wide range of temperatures. The measured data, along with available excess enthalpy and vapor-liquid equilibria data, was then used for regression of UNIQUAC-HOC binary interaction parameters, which allows not only for accurate LLE analysis and extraction unit simulation, but also for the simulation of distillation systems for the purification of these mixtures. The solvents studied were compared through the distribution factor and through their selectivity towards component separation. The comparisons were carried out for ternary systems with furfural, solvent and water, as well as systems with acetic acid. Additional data was also measured for quaternary systems involving both components. The work also takes into account the remaining traces of solvent in the raffinate through selectivity analysis. This study suggests that, out of the tested solvents, furfural and acetic acid can be most efficiently separated by cyclopentyl methyl ether when either of the products is desired. The next most suitable solvents are methyl isobutyl ketone and tert-amyl methyl ether, which provide good results for both components. The measured methyl tertbutyl ether data is limited by its low boiling point, but it separates furfural and HAc effectively at lower temperatures. 2-methyl tetrahydrofuran and tert-amyl alcohol provide inferior results.

Tässä väitöskirjassa tutkittiin erinäisiä liuottimia furfuraalin neste-neste uuttoon biojalostamoilla esiintyvistä vesiliuoksista. Lisäksi tutkittiin valittujen liuottimien kykyä erottaa biojalostamoiden vesiliuoksissa esiintyvää etikkahappoa. Erilaisia erotustapoja vastaaville liuoksille tutkitaan usein erilaisten prosessisimulointien avulla. Tällaiset simuloinnit tarvitsevat tarkkoja termodynaamisia malleja. Jos tarjolla ei ole kokeellista data, voidaan käyttää ennustavia malleja, mutta parhaan ja luotettavimman tuloksen antavat kokeelliseen dataan pohjautuviin parameterihin perustuvat termodynaamiset mallit. Tässä työssä mitattiin neste-neste tasapainoa useille eri seoksille laajalla lämpötila-alueella. Mitattua dataa, sekä kirjallisuudesta saatua eksessientalpia- ja neste-höyry ta-sapainodataa käytettiin UNIQUAC-HOC mallin vuorovaikutusparametrien regressointiin. Tällä tavoin regressoidut parametrit mahdollistavat uuttolaitteistojen simuloinnin lisäksi tislauskolonnien simuloinnin, jolloin voidaan tutkia myös uuton tuotevirtojen puhdistuksen vaatimia yksikköoperaatiota. Tutkittuja liuottimia vertailtiin komponenttikohtaisten jakautumiskertoimien ja selektiivisyyksien kautta. Vertailussa käytettiin kolmen komponentin seoksia (furfuraali+vesi+liuotin tai etikkahappo+vesi+liuotin) sekä nelikomponenttiseoksia (furfuraali+etikkahappo+vesi+liuotin). Lisäksi otettiin huomioon raffinaattiin jäävä liuotinmäärä. Tutkimuksessa havaittiin, että tutkituista liuottimista parhaiten furfuraalia ja etikkahappoa erottaa syklopentyylimetyylieetteri. Seuraavaksi parhaan tuloksen antoivat metyyli-isobutyyli ketoni ja tert-amyylimetyylieetteri, joilla molemmilla erotuskyky on hyvä. Mitattua metyyli tertbutyylieetterin dataa rajoittaa sen matala kiehumispiste, mutta erotuskyky on matalissa lämpötiloissa hyvä. 2-metyylitetrahydrofuraani ja tertamyyli alkoholi suoriutuivat erotuksesta heikoiten.

Description

Supervising professor

Alopaeus, Ville, Prof., Aalto University, Department of Chemical and Metallurgical Engineering, Finland

Thesis advisor

Pokki, Juha-Pekka, Dr., Aalto University, Department of Chemical and Metallurgical Engineering, Finland

Keywords

liquid-liquid equilibria, aqueous bio-component mixtures

Other note

Parts

  • [Publication 1]: Männistö, Mikael; Pokki, Juha-Pekka; Creati, Arianna; Voisin, Arthur; Zaitseva, Anna; Alopaeus, Ville. Ternary and Binary LLE Measurements for Solvent (4-Methyl-2-pentanone and 2-Methyl-2-butanol) + Furfural + Water between 298 and 401 K. Journal of Chemical & Engineering Data, 2016, volume 61, issue 2, pp. 903–911.
    DOI: 10.1021/acs.jced.5b00738 View at publisher
  • [Publication 2]: Männistö, Mikael; Pokki, Juha-Pekka; Haapaniemi, Hele; Alopaeus, Ville. Quaternary, Ternary, and Binary LLE Measurements for 2-Methoxy-2-methylpropane + Furfural + Acetic Acid + Water at Temperatures between 298 and 307 K. Journal of Chemical & Engineering Data, 2016, volume 61, issue 7, pp. 2458-2466.
    DOI: 10.1021/acs.jced.6b00149 View at publisher
  • [Publication 3]: Männistö, Mikael; Pokki, Juha-Pekka; Haapaniemi, Hele; Alopaeus, Ville. Quaternary, ternary and binary LLE measurements for 2-Methoxy-2-methylbutane + Furfural + Acetic acid + Water at temperatures between 298 and 341 K. Journal of Chemical & Engineering Data, 2016, volume 61, issue 11, pp. 3730-3739.
    DOI: 10.1021/acs.jced.6b00150 View at publisher
  • [Publication 4]: Männistö, Mikael; Pokki, Juha-Pekka; Fournis, Ludivine; Alopaeus, Ville. Ternary and Binary LLE measurements for Solvent (2-Methyltetrahydrofuran and Cyclopentyl methyl ether) + Furfural + Water between 298 and 343 K. The Journal of Chemical Thermodynamics, 2016, volume 110, pp. 127-136.
    DOI: 10.1016/j.jct.2017.02.016 View at publisher
  • [Publication 5]: Männistö, Mikael; Pokki, Juha-Pekka; Alopaeus, Ville. Quaternary, ternary and binary LLE measurements for Solvent (2-Methyltetrahydrofuran and Cyclopentyl methyl ether) + Acetic Acid + Furfural + Water between 298 and 343 K. The Journal of Chemical Thermodynamics, 2016, volume 119, pp. 61-75.
    DOI: 10.1016/j.jct.2017.12.015 View at publisher

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https://urn.fi/URN:ISBN:978-952-60-8334-6

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[diss] Kemian tekniikan korkeakoulu / CHEM