Advanced Biofuel Blends as Petroleum Diesel Replacements

The development of advanced biofuels as petroleum diesel replacements is carried out in a multidisciplinary project. The advanced fuels are renewable and avoid the limitations in purity, cold flow properties, and oxidative instability that challenge methyl ester based biodiesel. The advanced fuels promise cleaner combustion and a broader base of renewable resources as feedstocks than current biofuels. Collaboration with engine researchers will lead to optimum fuel compositions and engine performance.

Property Measurement and Prediction for Bio-derived Chemicals

Bio-derived chemicals and fuels typically have a significant oxygen content. Predictive models developed for petrochemicals often have difficulty accurately predicting properties. We are actively support collaborative efforts by providing estimations and measurements, including the use of molecular simulations.

Reactive Separations

Formation of chemical products from renewable resource-based feedstocks often results in a complex product mixture or dilute product streams. Novel separation and recovery schemes involving reactive separations reduce costs and enhance product purities. Systems under investigation include organic acid esters, polyols recovery, and acetal formation.

Reviewed Journal Publications

Orjuela, A.; Yanez, A.J.; Lira, C.T.; Miller, D.J. "Kinetics of mixed succinic acid/ acetic acid esterfication with Amberlyst 70 ion exchange resin as catalyst," accepted for publication in Chemical Engineering Journal (2012).

Orjuela, A.; Lira, C.T.; Miler, D.J. "A novel process for recovery of fermentation derived succinic acid: Conceptual design and preliminary economics," in preparation to Biosource Technology (2012).

Yang, X.; Lira, C.T.,"Adsorption of Benzaldehyde and Benzyl Alcohol from Supercritical Fluids onto Fluids onto Polymeric Resin"

Yang, X.; Lira, C.T., "Pore-size distributions using the ESD-SLD Approach,"

Hong, Xi; Lira, C.T.; Miller, D.J. "Kinetics of glycerol acetal formation from glycerol and 1,1- diethoxyethane," Submitted to Biomass and Bioenergy (2011).

Hassan, A.M.; Vu, D.T.; Elliott, J.R.; Miller, D.J.; Lira, C.T. "Application of SPEAD in press, IEC Res., 2011.

Orjuela, A.; Yanez, A.J.; Evans, J.; Hassan, A.M.; Miller, D.J.; Lira, C.T. "Phase Equilibria in Binary Mixtures with Monoethyl Succinate", submitted to Fluid Phase Equil.

Pappu, V.K.S.; Yanez, A.J.; Peereboom, L.; Muller, E.; Lira, C.T.; Miller, D.J. "A Kinetic Model of the Amberlyst-15 Catalyzed Transesterification of Methyl Stearate with n-Butanol" Bioresource Technology., in press, link

Orjuela, A.; Yanez, A.J.; Vu, D.T.;Bernard-Brunel, D.; Miller, D.J.; Lira, C.T. "Phase equilibria for reactive distillation of diethyl succinate. Part I. System diethyl succinate + ethanol + water", Fluid Phase Equil. 290, 63-67, (2010).

Orjuela, A.; Yanez, A.J.; Rossman, P.K.; Vu, D.T.; Bernard-Brunel, D.; Miller, D.J.; Lira, C.T. "Phase equilibria for reactive distillation of diethyl succinate. Part II. Systems diethyl succinate + ethyl acetate + water and diethyl succinate + acetic acid + water", Fluid Phase Equil. 290, 68-74, (2010).

Kolah, A.K.; Asthana, N.S.; Vu, D.T.; Lira C.T.; Miller, D.J. "Tri-ethyl Citrate Synthesis by Reactive Distillation," Ind.Eng.Chem. Res. 47,1017-1025, (2008).

Kolah, A.K.; Asthana, N.S.; Vu, D.T.; Lira, C.T.; Miller, D.J. "Reaction Kinetics for the Heterogeneously Catalyzed Esterification of Succinic Acid with Ethanol," Ind. Eng. Chem. Res., 47, 5313-5317 (2008).

Kolah, A.K.; Asthana, N.S.; Vu, D.T.; Lira, C.T.; Miller, D.J. "Reaction Kinetics of the Catalytic Esterification of Citric Acid with Ethanol", Ind. Eng. Chem. Res. 46, 3180-3187, (2007).

Yang, X.; Lira, C.T. "Theoretical Study of Adsorption on Activated Carbon from Supercritical Fluids by the SLD-ESD Approach," J. Supercritical Fluids 37, 191-200, (2006).

Asthana, N.S.; Kolah, A.K.; Vu, D.T.; Lira, C.T.; Miller, D.J. "A Kinetic Model for Esterification of Lactic Acid and Its Oligomers," Ind. Eng. Chem. Res. 45, 5251-5257 (2006).

Vu, D.T.; Lira, C.T.; Asthana, N,S; Kolah, A.K. Miller D.J. "Vapor-liquid equilibria in the systems Ethyl Lactate + Ethanol and Ethyl Lactate + Water," J. Chem. Eng. Data. 51, 1220-1225, (2006).

Asthana, N.; Kolah, A.; Vu, D. T.; Lira, C.T. ; Miller D.J. "A Continuous Reactive Separation Process for Ethyl Lactate Formation," J. Org. Process Res. Dev. 9, 599-607, (2005).

Baber, T.M.; Graiver, D. ; Lira, C. T. ; Narayan, R. "A Novel Application of Catalytic Ozone Chemistry for Improved Biodiesel Synthesis," Biomacromoles 6 (3), 1334-1344, (2005).

Guyer D.E; Saengcharoenrat, C; Lira, C.T. "Onion Flavor Recovery in the Process of Adsorption and Supercritical Carbon Dioxide Desorption," J. Food Process Eng. 28, 205-218, (2005).

Vu, D.T.; Kolah, A. ; Asthana, N.; Peereboom, L.; Lira, C.T.; Miller, D.J. "Oligomer distribution in concentrated lactic acid solutions," Fluid Phase Equilibria 236, 125-135 (2005).

Baber, T. M.; Vu, D.T.; Lira, C. T. "Liquid-Liquid Equilibrium of the Castor Oil plus Soybean Oil plus Hexane Ternary System," J. Chem. Eng. Data 47(6), 1502-1505, (2002).

Worden, R.M.; Briedis, D.; Lira, C.T. "Graduate Bridging and Continuing Education in ChE via the Internet," Chem. Engin. Ed. 35(4), 230, (2001).

Soule, A.D.; Smith, C.A.; Yang, X.N.; Lira, C.T. "Adsorption Modeling with the ESD Equation of State," Langmuir 17(10), 2950-2957, (2001).

Chen, J.H.; Wong, D.S.H.; Tan, C.S.; Subramanian, R.; Lira, C.T.; Orth, M. "Adsorption and Desorption of Carbon Dioxide onto and from Activated Carbon at High Pressures," Ind. Eng. Chem. Res. 36(7), 2808-2815, (1997).

Dron, A.; Guyer, D.E. ; Gage, D.A. ; Lira, C. T. "Yield and Quality of Onion Flavor Oil Obtained by Supercritical Fluid Extraction and Other Methods," J Food Process Eng. 20(2), 107-124, (1997).

Books, Chapters, Monographs

Miller, D.J.; Kolah, A.K.; Lira, C.T. " Reactive Distillation for the Biorefinery ,"Chapter 20, in Separation and Purification Technologies in Biorefineries; H.J. Huang and S. Ramaswamy, eds, New York, J.W. Wiley and Sons, (2012).

Wilkinson, Bruce W., Lira, Carl T., Bender, Timothy O, Ofoli, Robert Y., Manual on Laboratory Practice and Statistical Analysis (Student laboratory manual for CHE 316, junior-level experiential course), (January 2007).

Elliott, J.R.; Lira, C. T. "Introductory Chemical Engineering Thermodynamics," Documented at www.egr.msu.edu/~lira/thermtxt.htm. The text includes an assortment of authored computer programs distributed via the internet. Prentice-Hall:Upper Saddle River, NJ, (1999).

Conference Proceedings

Kolah, A.K.; Pappu, V.K.S; Lira, C.T.; Miller, D.J.; Dada, E.A.; Panchal, C.B.; Doctor, R.D.; Prindle, J.C.; "Heat Integrated Reactive Distillation for the Indirect Hydration of Cyclohexane to Cyclohexanol," (#709d). Proc. Annual Meeting of the AiChE, October 16-21, Minneapolis, MN (2011).

Pappu, V.K.S.; Kolah, A.K.; Lira,C.T.; Miller, D.J. "Methyl Stearate Transesterfication with n- Butanol: Process Intensification Using Distillation with External Side Reactors, " (#709a). Proc. Annual Meeting of the AiChE October 16-21, Minneapolis, MN, (2011).

Hong, X.; McGiveron,O. ;Lira, C.T.; Miller,D.J. "A Novel Reactive Distillation Approach for Producing 1,3-Dihydroxyacetone From Glycerol," Proc. Annual Meeting of the AIChE, October 16-21, Minneapolis, MN (2011).

Kolah, A.K.; Orjuela, A.; Hanna, N.; Lira, C.T., Miller D.J. "Reactive distillation for the biorefinary: pilot plant synthesis of succinic acid esters." A.I.Ch.E. Spring Conference, San Antonio, TX, USA, March 21-25, (2010).

Miller, D.J.; Orjuela, A.; Kolah, A.K.;Lira C.T."Reactive separation for the recovery and purification of organic acids." Proc. Corn Utilization and Technology Conference, Atlanta, Georgia, USA, June 7-9, 2010.

Orjuela, A.; Kolah, A.K.; Lira, C.T.;Miller, D.J."Esterification of succinic and acetic acid mixtures with ethanol by reactive distillation." A.I.Ch.E. Annual Conference, Salt Lake City, UT, USA, Nov 13-18, 2010.

Orjuela, A., A. Yanez-McKay, C.T. Lira, and D.J. Miller, "Enhanced recovery of organic acid monomers," Proc. 239th American Chemical Society National Meeting (Polymer Division paper #460), San Francisco, California, March 26- 28, 2010.

Orjuela, A.A. ; Kolah, A.; Lira, C.T.; Miller. D.J., "Esterfication of Succinic Acid and Acetic Acid Mixtures with Ethanol by Reactive Distillation," Proc. 2010 Annual Meeting of the American Insititute of Chemical Engineers, Salt Lake City, UT, November, 7-12,2010.

Kolah, A.K.; Orjuela, A.; Lira, C.T; Miller, D.J. "Reactive separations for esterification and purification of individual organic acids from mixed solutions" 31st Symposium on Biotechnology for Fuels and Chemicals. May 3-6,. San Francisco, CA. USA, (2009).

Orjuela, A.; Miller, D.J.; Lira, C.T.; Vu, D.T.; Yanez, A.J.; "Phase Equilibria for the System Diethyl Succinate - Ethanol - Water", presented at the 8th World Congress of Chemical Engineering, Aub 23-17, Montréal, Quebec, Canada, (2009).

Orjuela, A.; Vu, D.T.; Bernard-Brunel, D.; Evans, J.R.; Kolah, A.K.; Yanez, A.J.; Peereboom, L.; . Miller, D.J.; Lira C.T. "Phase Equilibria for Reactive Distillation of Diethyl Succinate", presented at the Seventeenth Symposium on Thermophysical Properties, June 21-26, Boulder, CO, (2009).

Vu, D.T.; Bernard-Brunel, D.; Hassan, A.M.; Elliott, J.R.; Miller D.J.; Lira C.T. "Vapor Pressures of Oxygenated Compounds using a Step Potential Perturbation Method", presented at the Seventeenth Symposium on Thermophysical Properties, June 21-26, Boulder, CO, (2009).

Hong, X.; Kolah, A.K.; Lira, C.T.; Miller, D.J. "An Improved Approach to Make Cyclic Acetals From Glycerol", presented at the AIChE Annual Meeting, Nov 8-13, Knoxville, TN, USA, (2009).

Orjuela, A; Kolah, A.K.; Hong, X; Lira, C.T.; Miller, D.J. "Reactive Distillation in a Mixed Acid Esterification Process for Biobased Chemicals Production", presented at the AIChE Annual Meeting, Nov 8-13, Knoxville, TN, USA, (2009).

Peereboom, L.; Bernard-Brunel, D.; Kolah, A.; Asthana, N.; Lira, C.T.; Miller, D.J. Reactive Distillation for Chemical Products from Ethanol. Proc. Corn Utilization and Technology Conference, Kansas City, MO, June 2-4, 2008.

Vu, D.T.; Lira, C.T.; Elliott J.R.; Asthana, N.S.; Kolah, A.K.; Miller D.J. "Vapor Pressure Predictions of Oxygenated Compounds" Midwest Thermodynamics and Statistical Mechanics Conference, Iowa State University, Ames, IA, Jun 6-8, (2007).

Miller, D.J., Kolah, A., Asthana, N., Lira, C.T., "Reactive Distillation: A Versatile Unit Operation for the Biorefinery," Proc. CHEMCON 2007, Indian Institute of Chemical Engineers Annual Meeting, Kolkata, India, December 28, 2007.

Asthana N.S.; Kolah, A.K.; Vu, D.T.; Lira, C.T.; Miller, D.J. "Continuous Esterification of Citric Acid: Formation of Tri-ethyl Citrate", Gordon Research Conference on Green Chemistry, Magdalen College, Oxford University, UK, Aug. 27-Sept. 1, (2006).

Asthana N.S.; Kolah, A.K.; Vu, D.T.; Lira, C.T.; Miller, D.J. "Process For Continuous Esterification of Citric Acid", Presentation at 28th Symposium on Biotechnology, Nashville, Tennessee, April 30-May 3, (2006).

Asthana, N.S.; Kolah, A.K.; Vu, D.T.; Lira, C.T.; Miller, D.J. "Continuous Process for Esterification of Bio-based Organic Acid: Esterification of Citric acid to Triethyl Citrate" at 10th Annual Conference on Green Chemistry & Engineering, Washington DC, June 26-30, (2006).

Vu, D.T.; Lira, C.T.; Elliott, J.R.; Asthana, N.; Kolah, A.K.; Miller, D.J.; "Phase Equilibria for Bio-derived Chemicals", Midwest Thermodynamics and Statistical Mechanics Conference 2006, University of Akron, Ohio, May 25-26, (2006).

Vu, D.T.; Lira, C.T.; Elliott, J.R.; Asthana, N.; Kolah, A.K.; Miller, D.J.; "Phase Equilibria for Bio-Derived Chemicals", Annual Meeting-American Institute of Chemical Engineers, San Francisco, CA, Nov. 12-17, (2006).

Miller, D.J.; Asthana, N.S.; Lira, C.T.; Kolah, A.K.; Vu, D.T.; "Formation of Organic Acid Esters via Reactive Distillation," 38th Central Regional Meeting of the American Chemical Society, Frankenmuth, MI, May 16-20, (2006).

Asthana, N.; Kolah, A.; Vu, D.T.; Lira, C.T.; Miller, D.J. "Reactive Distillation for the Biorefinery: Production of Organic Acid Esters," Proc. 230th ACS National Meeting, Washington, DC, Aug 28 - Sept 1, Prepr. Am. Chem. Soc., Div. Fuel Chem. 50(2), 683, (2005).

Asthana, N.; Kolah, A.; Vu, D.T.; Lira, C.T.; Miller, D.J. "Factors Influencing the Kinetics of Lactic Acid Esterifiecation: Ethyl Lactate by Reactive Distillation," Proc. IICHE-AICHE Joint Conference 2004, Mumbai, India, December 27-30, (2004).

Other Works

Asthana, N.; Kolah, A.; Vu, D.T.; Lira, C.T.; Miller, D.J."Process for reactive distillation esterification.",US7667068, 2010.

Asthana, N.; Kolah, A.; Vu, D.T.; Lira, C.T.; Miller, D.J."Process for production of organic acid esters." US7652167, 2010.

Orjuela, A.; Lira, C.T.; Miller, D.J. "An Improved Process for Organic Acid Recovery from Fermentation Solutions," US Patent application filed 12/2009.

Miller, D.; Lars, P.; Kolah, A.; Asthana, N.; Lira, C.T.; "Process for production of composition useful as a fuel, US7321052, (2008).

Asthana, N.; Miller, D.J.; Lira, C.T.; Bittner, E. "Process for Producing Mixed Esters of Fatty Acids as Biofuels," US Patent Application 20090126262, filed 11/20/07.

Runge Kutta Integration: A spreadsheet that will perform integration of up to 20 simultaneous ordinary differential equations. Used in support of ChE804. Available at http://www.egr.msu.edu/~lira/supp/.