Source: MICHIGAN STATE UNIV submitted to NRP
BIO-DERIVED FUELS AND CHEMICALS: FACILITATING DEVELOPMENT THROUGH PROPERTY CHARACTERIZATION
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
COMPLETE
Funding Source
HATCH
Reporting Frequency
Annual
Accession No.
0217111
Grant No.
(N/A)
Cumulative Award Amt.
(N/A)
Proposal No.
(N/A)
Multistate No.
(N/A)
Project Start Date
Dec 1, 2008
Project End Date
Nov 30, 2013
Grant Year
(N/A)
Program Code
[(N/A)]- (N/A)
Recipient Organization
MICHIGAN STATE UNIV
(N/A)
EAST LANSING,MI 48824
Performing Department
Chemical Engineering
Non Technical Summary
One thrust of this project concerns measurement and prediction of properties such as vapor pressure, surface tension and cold flow behavior to facilitate blending and increased adoption of biofuels. Another thrust focuses specifically on measurement and correlation of vapor-liquid, liquid-liquid, and solid-liquid solubilities for mixtures related to the succinic acid platform, to facilitate development of bioderived chemicals from succinic acid.
Animal Health Component
(N/A)
Research Effort Categories
Basic
(N/A)
Applied
(N/A)
Developmental
(N/A)
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
5111510202050%
5111899202050%
Knowledge Area
511 - New and Improved Non-Food Products and Processes;

Subject Of Investigation
1510 - Corn; 1899 - Oilseed and oil crops, general/other;

Field Of Science
2020 - Engineering;
Goals / Objectives
1) Characterize boiling points, surface tensions, cold flow properties of biofuel components snd their mixtures. 2) Develop and extend molecular simulation predictions for properties of biofuel components and bioderived chemicals. 3) Measure and develop correlations for vapor-liquid, liquid-liquid, and liquid-solid behavior for support of the succinic acid platform and reactive distillation as a method of upgrading for products such as diethyl succinate. 3) Disseminate information through publications and meetings.
Project Methods
Bioderived fuels and chemicals have more oxygen content in the molecular structure compared to petroleum-derived products. Most correlations in the literature for pure component properties are challenged by the oxygen content, and also when multiple functional groups exist on the same molecule. In this work, we will use traditional methods and correlations as appropriate and also develop new methods using molecular simulations for predition/correlation of vapor pressures and surface tensions, and cold flow properties of fuels. We will measure and correlate mixture phase equilibria related to the succinic acid platform.

Progress 12/01/08 to 11/30/13

Outputs
Target Audience: Academic Professionals Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? This project has supported students to educate them for careers working with upgrading bioderived compounds. How have the results been disseminated to communities of interest? Peer-reviewed publications. What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? We have publishd information regarding biofuel blends and methods for upgrading bioderived products.

Publications

  • Type: Book Chapters Status: Awaiting Publication Year Published: 2014 Citation: Lown, A.L.; Peereboom, L.; Mueller, S.A.; Anderson, J.E.; Miller, D.J.; Lira, C.T. Cold Flow Properties for Blends of Biofuels with Diesel and Jet Fuels, Fuel, 117PA, 544-551, (2014). doi: 0.1016/j.fuel.2013.09.067
  • Type: Book Chapters Status: Published Year Published: 2013 Citation: 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, (2013)
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Orjuela, A.; Orjuela, A.; Lira, C. T.; Miller, D. J., A novel process for recovery of fermentation-derived succinic acid: Process design and economic analysis. Bioresource Technology, 139, 235-241. doi:10.1016/j.biortech.2013.03.174, (2013)
  • Type: Journal Articles Status: Published Year Published: 2013 Citation: Hong, X.; McGiveron, O.; Kolah, A.K.; Orjuela, A.; Peereboom, L.; Lira, C.T.; Miller, D.J. Reaction Kinetics of glycerol acetal formation via transacetalization with 1,1-diethoxyethane, Chemical Engineering Journal, 222, 374-381 (2013). doi: 10.1016/j.cej.2013.02.023


Progress 01/01/12 to 12/31/12

Outputs
OUTPUTS: Experiments have been conducted on mixed acid esterifications showing that a universal rate constants are capable of representing data when the hydroxyl concentration is used rather than the molecular concentration. Reactive distillation with side reactors for transesterification have been studied. Work is ongoing to develop surrogate models for diesel and jet fuels that can be used for blends with biofuel components. Existing surrogate models are not able to represent the cold flow properties simultaneously with the distillation curve. PARTICIPANTS: Graduate Student: Anne Lown. Collaborator: Tom Bruno (NIST). TARGET AUDIENCES: Academic Professionals PROJECT MODIFICATIONS: Not relevant to this project.

Impacts
The ability to model esterifications with universal rates provides an mechanism to predict reaction rates. The development of surrogate fuel compositions will further enable knowledge for blending of fuels.

Publications

  • Windom, B.; Huber, M.L.; Bruno, T.J.; Lown, A.L.; Lira, C.T. "Measurements and Modeling Study on a High-Aromatic Diesel Fuel," Energy and Fuel, 26(3), 1787-1797, (2012). doi: 10.1021/ef201861b
  • Orjuela, A.; Yanez, A. J.; Santhanakrishnan, A; Lira, C. T.; Miller, D. J. "Kinetics of mixed succinic acid/acetic acid esterification with Amberlyst 70 ion exchange resin as catalyst" Chem. Eng. J. 188, 98-107, (2012). doi: 10.1016/j.cej.2012.01.103
  • Hassan, A.M; Vu, D.T.; Bernard-Brunel, D.; Elliott, J.R.; Miller, D.J; Lira, C.T, "Application of SPEAD to bioderived esters and acetals" Ind. Eng. Chem. Res. 51(8), 3209-3214, (2012). doi: 10.1021/ie2009058
  • Orjuela, A.; Kolah, A.; Hong, Xi; Lira, C.T.; Miller, D.J. "Diethyl Succinate Synthesis by Reactive Distillation," Sep. and Pur. Tech. 88, 151-162 (2012). doi: 10.1016/j.seppur.2011.11.033


Progress 01/01/11 to 12/31/11

Outputs
OUTPUTS: I attended the annual Hatch meeting this fall at Oklahoma State University. We have advanced capabilities for property prediction using molecular simulation, and we have shown that proper fitting of molecular potentials is necessary for good transferability of group parameters. A publication on the work is in revision and two more publications are in preparation. We have investigated cold flow properties of biofuel/petroluem fuel blends. We find that cloud points change in a rather systematic way depending on functional group. We have collaborated with NIST on a surrogate compositions for diesel fuels. PARTICIPANTS: Carl T. Lira TARGET AUDIENCES: Not relevant to this project. PROJECT MODIFICATIONS: Not relevant to this project.

Impacts
The annual meeting provides valuable exchange of information about trends and current projects of others.

Publications

  • Orjuela, A.; Kolah, A.; Lira, C. T.; Miller, D. J., Mixed Succinic Acid/Acetic Acid Esterification with Ethanol by Reactive Distillation. Ind. Eng. Chem. Res. 2011, 50, (15), 9209-9220. doi: 10.1021/ie200133w
  • Orjuela, A.; Yanez, A. J.; Peereboom, L.; Lira, C. T.; Miller, D. J., A novel process for recovery of fermentation-derived succinic acid. Separation and Purification Technology 83, (0), 31-37, (2011). doi: 10.1016/j.seppur.2011.08.010
  • Orjuela, A.; Yanez, A.J.; Evans, J.; Hassan, A.M.; Miller, D.J.; Lira, C.T. Phase Equilibria in Binary Mixtures with Monoethyl Succinate, Fluid Phase Equil., 309, 121-127, (2011). doi: 10.1016/j.fluid.2011.06.020
  • 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., 102, 4270-4272 (2011) DOI: 10.1016/j.biortech.2010.12.006.


Progress 01/01/10 to 12/31/10

Outputs
OUTPUTS: During this reporting period, we have: (1) Improved the capabilities of the SPEAD method for simulation of vapor pressures and densities. (2) Measured phase equilibria for systems related to the recovery of succinic acid; (3) Improved ebulliometer designs. PARTICIPANTS: Carl T. Lira, Alvaro Orjuela TARGET AUDIENCES: Professionals interested in green biofuels and biochemical production. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
Our improved understanding of capabilities and limitations of the SPEAD method will enable us to address improvements. We have found that esters are challenging to model without systematic deviations as a function of vapor pressure. We are working to incorporate charges into the model. The improved model will be useful for prediction and modeling of biofuel properties. Our method for separation and recovery of succinic acid as diethyl succinate will be ecomomically competitive with petroleum feedstocks.

Publications

  • Miller, D.J.; Asthana, N.; Kolah, A.; Vu, D.T.; Lira, C.T. "Process for reactive esterification distillation," US Patent 7,667,068, Feb. 23, (2010).
  • Miller, D.J.; Asthana, N.; Kolah, A.; Lira C.T. "Process for Production of Organic Acid Esters", U.S. Patent 7,652,167, Jan 26, (2010).
  • Orjeula, A; Orjeula, A.P.; Kolah, A,K.; Lira, C.T.; Miller, D.J.; "Esterification of Succinic and Acetic Acid Mixtures with Ethanol by Reactive Distillation", paper 467d, 2010 Annual Meeting, AIChE, Nov. 7-12, Salt Lake City, UT (2010).
  • Hassan, A. M.; Zalokar, J; Miller, D.J.; Lira, C.T. "VLE of potential biofuel compounds using SPEAD simulations" 2010 Midwest Thermodynamics and Statistical Mechanics Conference, June 2-3, University of Notre Dame, South Bend, IN, (2010).
  • Orjuela, A;, Yanez, A.; Lira, C.T.; Miller, D.J. "Recovery of succinic acid from fermentative broth through esterification with ethanol", World Congress on Industrial Biotechnology and Bioprocessing, June 27-30, Washington, DC, (2010).
  • "Reactive Distillation for the Biorefinery : Pilot Plant Synthesis of Succinic Acid Esters", Kolah, A.K., Orjuela, A; Hannah, N.; Lira, C.T.; Miller, D.J. Spring National Meeting, AIChE, March 21-25, San Antonio, TX, (2010).
  • 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). DOI: 10.1016/j.fluid.2009.11.014
  • 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). DOI: 10.1016/j.fluid.2009.11.013


Progress 01/01/09 to 12/31/09

Outputs
OUTPUTS: During this reporting period, we have: (1) Improved the capabilities of the SPEAD method for simulation of vapor pressures and densities. A publication is in preparation.; (2) Measured phase equilibria for systems related to the recovery of succinic acid; (3) Constructed a small ebulliometer for measuring vapor pressure of small samples; (4) Developed a process for recovery of succinic acid from fermentation solutions. An invention disclosure has been filed with the Michigan State University intellectual property office.; (5) Presented research results at the Seventeenth Symposium on Thermophysical Properties. PARTICIPANTS: Carl T. Lira, Principal Investigator; Alvaro Orjeula, PhD student. TARGET AUDIENCES: Academic and engineering professionals interested in biofuels. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
The SPEAD method is capable of accurate vapor pressure estimation in homologous series where only one type of functional group exists. We achieve accuracies of approximately +-7% for vapor pressure and +-2% for density. We have eliminated the systematic errors present in previous versions of the method. We have encountered difficulties in predicting vapor pressures when multiple functional groups exist (30-70% error). We continue to work to understand the deficiencies. In the work with systems for recovery of succinic acid, we have correlated the measurements so that they can be utilized for process development. The publication listings below do not include two peer-reviewed journal publications that are in press.

Publications

  • Orjuela, A; Yanez-McKay, A; Lira, C.T; Miller, D.J. "A Novel Route for Carboxylic Acid Recovery from Fermentation Solutions", Feb 2009, TEC2009-0062 (SLW 3000.009PRV) Amended Oct 7. 2009.
  • Asthana, N. S.; Miller, D. J.; Lira, C. T.; Bittner, E. "Process for producing mixed esters of fatty acids as biofuels", US Patent Application A1, 20090126262, May 21, 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).
  • 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).
  • Hong, X.; Kolah, A.K.; Lira, C.T.; Miller D.J.; "A Novel Process for Improved Biodiesel Production", Genes to Products: Agricultural Plant, Microbe, & Biobased Product Research Project Director's Meeting, May 4-6, Bethesda, MD, 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, Montreal, 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).
  • Orjuela, A: Yanez, A.J.; Rossman, P.K; Vu, D.T; Lira, C.T; Miller, D.J. "Phase equilibria for mixtures containing diethyl succinate", presented at the 2009 Midwest Thermodynamics and Statistical Mechanics Conference, May 19-20, Detroit, MI, (2009).
  • Hassan, A.M.; Vu, D.T.; Bernard-Brunel, D.; Elliott, J.R.; Miller, D.J.; Lira, C.T. "Vapor pressures of oxygenated compounds: SPEAD Parameters and applications", presented at the 2009 Midwest Thermodynamics and Statistical Mechanics Conference, May 19-20, Detroit, MI, (2009).