Rosendahl, Lasse

Rudolf, Andreas

Toor, Saqib Sohail

English

    Aalborg UniversitetThermodynamic modelling of CatLiq® biomass conversion processToor, Saqib Sohail; Rosendahl, Lasse; Rudolf, AndreasPublication date:2010Document VersionAccepted author manuscript, peer reviewed versionLink to publication from Aalborg UniversityCitation for published version (APA):Toor, S. S., Rosendahl, L., & Rudolf, A. (2010). Thermodynamic modelling of CatLiq® biomass conversionprocess. Poster presented at International Conference on Renewable Resources and Biorefineries, Düsseldorf,Germany.General rightsCopyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright ownersand it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights.            ? Users may download and print one copy of any publication from the public portal for the purpose of private study or research.            ? You may not further distribute the material or use it for any profit-making activity or commercial gain            ? You may freely distribute the URL identifying the publication in the public portal ?Take down policyIf you believe that this document breaches copyright please contact us at vbn@aub.aau.dk providing details, and we will remove access tothe work immediately and investigate your claim.Downloaded from vbn.aau.dk on: November 29, 2020Thermodynamic modeling of CatLiq® biomass conversion processToor, S. S.1, Rosendahl, L.1, Rudolf, A.21Department of Energy Technology, Aalborg University, DK-9220 Aalborg, Denmark2SCF Technologies A/S, Smedeholm 13B, DK-2730 Herlev, DenmarkIntroductionProcess:A second generation catalytic liquefaction process for the production of bio-oil.Raw Material:DDGS (Dried Distilled Grain with Solubles), a byproduct in first generation ethanol production.Process conditions:280-350 oC and 225-250 bar, in the presence of homogeneous (K2 CO3 ) and a heterogeneous (Zirconia) catalyst.Products:Main components are bio-oil, H2 O, CO2 , and water- soluble organic compounds. Capacity:10-20 L/h of wet biomass pilot plant with fixed-bed reactor.ResultsAimMeasurement and Prediction of bubble point pressures of  selected model system to investigate phase boundaries of the CatLiq® process.ExperimentThe experimental study was carried out in a mercury free JEFRI-DBR high pressure PVT phase behavior system using composition of (7.0% CO2 + 84.8% H2 O + 0.1% Ethanol + 0.1% Acetic acid + 8.0% Octanoic acid) as a model system for CatLiq® process.ConclusionExperimental and predicted data shows that the capability of the PSRK model is reasonably good in predicting the phase behaviour of such a model system for CatLiq® process.This modelling work is useful for the CatLiq® process design, development and optimization, which provides a general thermodynamic approach on how to model biomass conversion processes.AcknowledgementThe authors would like to thank the SCF Technologies A/S for giving the opportunity to perform this research. Thanks are also due to Tor Austad and Sivert  for his help in the experimental work at the Department of Petroleum Engineering, Stavanger University, Norway.Figure 2. JEFRI-DBR mercury free PVT systemFigure 4. Measured and predicted phase boundaries for the model systemFigure 1. CatLiq® process schemeDDGS Oil + water soluble organic  compoundsCatLiq® bio-oilOil productGasHeatingHeatingCoolingPre-conversionFeed pumpFeed heaterCoolerReactorTrim heaterPressure reductionSeparatorCirculation pumpThermodynamic modelThe results were correlated with PSRK model proposed by Holderbaum and Gmehling, which is predictive Soave-Redlich-Kwong EOS with the modified Huron-Vidal first-order (MHV1) mixing rule of Michelsen coupled with the UNIFAC model.Figure 3. The proposed algorithm for bubble pressure calculationYesNoNo YesSpecify liquid mole fractionxi and TGuess bubble-pointpressure, PCalculate φiL(T, P, xi ) for all components using  ZL through PSRKyi ´=yi (φiL/φiV)For all componentsComputed bubble-point pressure and vapor compositions are correct∑yi ´=1Calculate φiV(T, P, yi ) for all components using  ZV through PSRKIs yi ´=yi For allComponents?   y=yi ´ for all  Components?P=P∑yi ´Guess set of Ki for all components yi =Ki xiBubble point Pressure at 50oC80,5580,680,6580,780,7580,880,8580,980,950 50 100 150 200 250P(bar)Vt (cc)PB = 190.88 barBubble point Pressure at 60oC80,680,88181,281,481,681,80 50 100 150 200 250 300 350P(bar)Vt (cc)PB = 224.48 barBubble point Pressure at 40oC80,180,280,380,480,580,680,70 50 100 150 200 250P(bar)Vt (cc)PB = 156.73 barBubble point Pressure at 75oC8181,281,481,681,88282,20 50 100 150 200 250 300 350P(bar)Vt (cc)PB = 258.97 barTable 1. Experimental and PSRK-estimated bubble point pressures for model systemaRelative Deviation (%) = (Pexp – Pcal)/Pexp×100bAverage Absolute Deviation (%) = (∑ │error %│) /number of data pointsT/oC Pexp/bar Pcal/bar Rel. Dev. (%)a40 156.73 138.53 11.612350 190.88 169.22 11.347460 224.48 202.08 9.978675 258.97 253.85 1.9770AAD %b 8.72886305010015020025030030 40 50 60 70 80T(oC)P(bar)Exp. Bubble points (VLL to LL)Pred. (PSRK model, VLL to LL)LLVLLReferencesHolderbaum, T., Gmehling, J., 1991. PSRK: A group contribution equation of state based on UNIFAC. Fluid Phase Equilibria 70, 251-265.Michelsen, M.L., 1990. A modified Huron-Vidal mixing rule for cubic equations of state. Fluid Phase Equilibria 60, 213-219.Sandler, S. I., Orbey, H., 1998. Modeling Vapor- Liquid Equilibria- Cubic Equations of State and Their Mixing rules. Cambridge University Press ISBN: 0- 521-62027-9 (hb).Bruusgaard, H., Beltrán, G.J., Servio, P., 2008. Vapor-liquid water-hydrate equilibrium data for the system N2 + CO2 + H2 O. Journal of Chemical and Engineering Data 53, 2594-2597.Beltrán, G.J., Servio, P., 2008. Equilibrium studies for the system Methane + Carbon Dioxide +Neohexane + Water. Journal of Chemical and Engineering Data 53, 1745-1749.

Thermodynamic modelling of CatLiq® biomass conversion process

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Thermodynamic modelling of CatLiq® biomass conversion process

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