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Culture Documents
Tracy J. Benson1
Rafael Hernandez1
Research Article
Mark G. White1
W. Todd French1 Heterogeneous Cracking of an Unsaturated Fatty
Earl E. Alley2
William E. Holmes2
Acid and Reaction Intermediates on H+ZSM-5
Bethany Thompson3 Catalyst
1
Renewable Fuels and Chemicals
Laboratory, Chemical Engineering
Production of transportation fuels from renewable resources has been mostly ethanol
Department, Mississippi State University, and biodiesel. To alleviate some of the by-product generation and distribution issues
Mississippi State, MS, USA. associated with biodiesel, this paper describes the production of transportation fuel
2
Mississippi State Chemical Laboratory, using catalytic cracking. Oleic acid was used as a model compound. It was reacted at
Mississippi State University, Mississippi 4008C on H+ZSM-5 catalyst in an attempt to determine the reaction steps involved in
State, MS, USA. the catalytic transformation of an unsaturated fatty acid into green fuels. The reac-
3
Department of Chemistry, Rust College, tion products were identified using GC/MS and quantitated using GC thermal conduc-
Holy Springs, MS, USA. tivity detector analysis. Selected products of the oleic acid cracking were reacted sepa-
rately in an effort to elucidate the reaction pathway for producing green fuel related
compounds. The results showed that a wide range of products, including paraffins,
olefins, and aromatic compounds, were produced on the highly acidic, shape-selective
catalyst. These results contribute to the realization of using lipid feedstocks for trans-
portation fuels.
Keywords: Green gasoline; H+ZSM-5; Lipid cracking; Oleic acid; Shape selective; Catalysis; Fatty
acid;
Received: February 29, 2008; revised: April 11, 2008; accepted: April 26, 2008
DOI: 10.1002/clen.200800050
1 Introduction ard (ASTM D-6751) without these refining steps, which add to the
cost of the oil. Over 70% of biodiesel production costs are the cost of
Progress with renewable fuels is becoming increasingly essential in oil refining.
order to replace petroleum fuels as the dominant source of trans- Another challenge that biodiesel producers are experiencing is
portation energy. This can be readily seen with the exponential the reduction in market price of glycerine over the last 5 years.
growths of both the ethanol and biodiesel industries (www1.eere.e- Some producers are paying to dispose of the glycerine, selling the
nergy.gov/biomass/ethanol.html, www.biodiesel.org). Alternatives glycerine at less than $0.10/lb, or storing it for future disposal.
to fossil fuels have the potential to reduce the level of CO2 in the bio- Finally, there are concerns regarding the compatibility of biodiesel
sphere, eliminate U.S. dependence on foreign oil, and provide sus- and petroleum diesel. Biodiesel is an excellent solvent and would
tainable energy. wash the pipeline of deposits that are not desirable in the final prod-
Biodiesel is a mixture of fatty acid methyl esters currently pro- uct. Refineries, therefore, will not allow biodiesel to be transported
duced from vegetable oils and animal fats. It could also be produced via pipeline because it would cause havoc to the distribution pipe-
from other lipid feedstocks, such as algae, oleaginous yeasts, and line. For these reasons, biodiesel requires a separate distribution sys-
Chinese tallow. These other lipid feedstocks have the potential of tem apart from petroleum diesel, which adds to the overall cost of
displacing billions of gallons of petroleum without competing with biodiesel.
food-related applications. As these nonconventional lipid sources One option to using less refined oils to produce biofuels is the cat-
become available, challenges associated with the biodiesel produc- alytic cracking of lipids into green gasoline and green diesel. These
tion process will have to be overcome for biodiesel to remain cost are motor fuels comprised of equivalent types of compounds as tra-
competitive with other biofuels. For example, lipids used to produce ditional petroleum fuels. This process could use row-crop oils as raw
biodiesel using conventional base-catalyzed transesterification materials, as well as lipids from animal sources and microbial sour-
require removal of trace metals, free fatty acids, and unsaponifiable ces, such as oleaginous yeasts, oil-rich algae, and municipal waste
materials. It is difficult to conform with the biodiesel quality stand- sludges. Moreover, undesired by-products could be reduced, or elim-
inated, in the fuel from the catalytic cracking process. Another
Correspondence: Assistant Professor Rafael Hernandez, Dave C. Swalm advantage to this approach would be employment of current petro-
School of Chemical Engineering, Mississippi State University, Mississippi leum refining practices for renewable fuel production and distribu-
State, MS 39762, USA. tion.
E-mail: rhernandez@che.msstate.edu
Bakhshi and coworkers and Bhatia and coworkers have investi-
Abbreviations: CI, chemical ionization; TCD, thermal conductivity de- gated the cracking of canola and palm oils, respectively [1 6]. The
tector results from these works indicate that plant oils, which are mostly
Irvine, CA, USA) were used to determine the molecular size of oleic [2] S. Katikaneni, J. Adjaye, R. Idem, N. Bakhshi, Catalytic Conversion of
acid. These calculations provide evidence that cracking of fatty acids Canola Oil Over Potassium-Impregnated HZSM-5 Catalysts: C2 C4
begins at the acidic sites found along the outside surface of the cata- Olefin Production and Model Reaction Studies, Ind. Eng. Chem. Res.
1996, 35, 3332.
lyst (see Fig. 9).
[3] J. Adjaye, S. Katikaneni, N. Bakhshi, Catalytic Conversion of a Biofuel
Additions of monoaromatic compounds result in the formation
to Hydrocarbons: Effect of Mixtures of HZSM5 and Silica-Alumina
of naphthalene and methylnaphthalene. Both of these compounds Catalysts on Product Distribution, Fuel Process. Technol. 1996, 48, 115.
are precursors to coke, which is a rather ill-defined, inherent
[4] R. Idem, S. Katikaneni, N. Bakhshi, Catalytic Conversion of Canola
byproduct of heterogeneous catalytic cracking reactions [18, 23]. Oil to Fuels and Chemicals: Roles of Catalyst, Acidity, Basicity, and
Coke is a mixture of polynuclear aromatics that form inside the cat- Shape Selectivity on Product Distribution, Fuel Process. Technol. 1997,
alyst pores. When a coke molecule becomes too large to exit the cat- 51, 101.
alyst pore, it poisons the catalyst by preventing access to catalytic [5] Y. Ooi, R. Zakaria, A. Mohamed, S. Bhatia, Catalytic Conversion of
sites for future carbenium ion formations. In industrial applica- Fatty Acids Mixture to Liquid Fuel and Chemicals Over Composite
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5 Concluding Remarks [7] T. Benson, R. Hernandez, T. French, E. Alley, W. Holmes, Reactions of
Fatty Acids in Superacid Media: Identification of Equilibrium Prod-
While the reaction steps shown here are not the only pathway that ucts, J. Mol. Catal. A: Chem. 2007, 274, 173.
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temperature, heterogeneous reactions have a multitude of simulta- [9] H. Hussein, R. Mackie, N. Merchen, D. Baker, C. Parsons, Effects of
Oleaginous Yeast on Growth Performance, Fatty Acid Composition
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[11] S. Dufreche, R. Hernandez, T. French, D. Sparks, M. Zappi, E. Alley,
(ii) Additional cracking experiments using toluene and m-xylene Extraction of Lipids from Municipal Wastewater Plant Microorgan-
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phenylbutene were the secondary cracking products. Tertiary
Development of a Heterogeneous Catalytic Cracking Reactor Utiliz-
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Acknowledgements [19] J. Vedrine, P. Dejaifve, E. Garbowski, E. Derouane, Aromatics Forma-
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We gratefully acknowledge the financial support from the US DOE
lite: Mechanism and Intermediate Species, Catal. Zeolites 1980, 29.
Office of Energy Efficiency and Renewable Energy. We are also grate-
[20] V. Kissin, Chemical Mechanisms of Catalytic Cracking Over Solid
ful to the Mississippi State Chemical Laboratory for use of their
Acidic Catalysts: Alkanes and Alkenes, Catal. Rev. 2001, 43 (1), 85.
facilities and technical guidance.
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