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.

Aqueous Phase Hydrogenation of Organic Acids

Organic acids constitute an important class of feed materials for renewable resource-based chemicals production. Hydrogenation over supported metal catalysts in aqueous solutions produces the corresponding alcohols that have important industrial uses. Substrates investigated include lactic, succinic, propanoi, and various amino acids; the corresponding alcohols can retain the stereochemistry found in the parent acid.

Hydrogenolysis of Carbohydrate Feedstocks

Carbohydrate feedstocks such as glucose or xylose can be hydrogenated to sugar alcohols and further cracked to value-added polyols such as ethylene glycol, propylene glycol, and glycerol. Catalysts, solvents, and reaction conditions play a key role in product distribution. Modeling of three phase reactors for polyol hydrogenolysis is a key focus of the project.

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).

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).

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).

Jere, F.T.; Jackson, J.E.; Miller, D.J. "Kinetics of the Aqueous Phase Hydrogenation of L-Alanine to L-Alaninol," I&EC Research 43, 3297, (2004).

Dhale, A.D.; Myrant, L.K.; Chopade, S.P.; Jackson J.E.; Miller, D.J. "Propylene Glycol and Ethylene Glycol Recovery from Aqueous Solution via Reactive Distillation," Chem. Eng. Sci. 59, 2881, (2004).

Chopade, S.; Dhale, A.; Kiesling, C.; Clark, A.; Jackson, J.E.; Miller, D.J. "Vapor-Liquid-Liquid Equilibrium (VLLE) and Vapor Pressure Data of the Systems 2-Methyl-1,4-Dioxolane (2MD) + Water and 2,4-Dimethyl-1,4-Dioxolane (24DMD) + Water," J. Chem. Eng. Data 48, 44, (2003).

Jere, F. T.; Miller, D. J.; Jackson, J. E. "Surprisingly facile, stereoretentive aqueous phase catalytic hydrogenation of amino acids to amino alcohols," Org. Lett. 5(4), 527, (2003).

Reviews

Miller, D.J.; Jackson, J.E. "NSF Workshop Final Report: Catalysis for Biorenewables Conversion," available in hardcopy and at www.egr.msu.edu/apps/nsfworkshop.

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).

Farrugia, J.; Jackson, J.E.; Miller, D.J. "Aqueous Phase Catalytic Hydrogenation of alpha-substituted Organic Acids," Proc. 19th North American Meeting of the Catalysis Society; Philadelphia, PA, May 22-27, (2005).

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).

Chen, Y.; Jackson, J.E.; Miller, D.J. "Aqueous-Phase Catalytic Hydrogenation of Organic Acids and Their Mixtures," Proc. AICHE 2005 Annual Meeting, Cincinnati, Ohio, October 30 - November 4, (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).

Asthana, N.; Zhang, Z.; Miller, D.J. "Solid Acid Catalysed Esterification of Amino Acids and other Bio-Based Acids," Organic Reactions & Catalysis Society: Proceedings Twentieth Conference on Catalysis of Organic Reactions, Charleston, South Carolina, April, 2004.

Zacher, A.H.; Frye, Jr. J.G.; Werpy, T.A.; Miller, D.J. "Catalytic Hydrogenolysis of 5-Carbon Sugar Alcohols," Organic Reactions & Catalysis Society: Proceedings Twentieth Conference on Catalysis of Organic Reactions, Charleston, South Carolina, April, 2004.

West, J.; Miller, D.J.; Briedis, D.; "Involving Constituencies in Curriculum Redesign," Proc. of the 2004 ASEE Conference and Exposition, Salt Lake City, UT, June 20-23, 2004.

Other Works

Zacher, A.; Frye, J.; Miller, D.J.; Werpy, T. "Hydrogenolysis of Six-carbon Sugars and other Organic Compounds," U.S. Patent #6,841,085 (January 11, 2005).

Werpy, T.A.; Frye, J.G.; Zacher, Jr. A.H.; Miller, D.J. "Hydrogenolysis of 5-carbon sugars, sugar alcohols and compositions for reactions involving hydrogen," U.S. Patent #6,677,385 (January 13, 2004).

Miller, D.J.; Jackson, J.E.; Chopade, S.; Dhale, A.; Kiesling, C.; Clark, A.; Jackson, J.E. "Process for the Recovery of a Polyol from an Aqueous Solution," U.S. Patent #6,713,640 (March 30, 2004).