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.; Vu, D.T.; Miller, D.J.; Lira, C.T. "Phase equilibria for reactive distillation of diethyl succinate. Part I. System diethyl succinate + ethanol + water", in revision, Fluid Phase Equilibria, (2009).

Orjuela, A.; Yanez, A.J.; Rossman, P.K.; Vu, D.T.; 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", in revision, Fluid Phase Equilibria, (2009).

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

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 <a href = "http://www.egr.msu.edu/~lira/thermtxt.htm">www.egr.msu.edu/~lira/thermtxt.htm</a>. 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.; 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).

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).

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

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/.