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652 Clean 2008, 36 (8), 652 656

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

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Clean 2008, 36 (8), 652 656 Catalytic Cracking of a Fatty Acid 653

triglycerides, can be converted to gasoline range organics (GRO) and


diesel range organics (DRO). While these findings are significant in
the development of renewable fuels, little is known about the crack-
ing chemistry of specific oxygenated compounds. Information from
the catalytic cracking of lipids (fatty acids, acylglycerides, phospho-
lipids, etc.) will be necessary as catalysts and reaction conditions are
sought for industrial production of green fuels.
Previous studies [4 6] have shown that initial cracking of canola
oil over various catalysts is independent of catalyst characteristics
(i. e., amorphous vs. crystalline, Bronsted vs. Lewis acid sites, etc.).
Furthermore, secondary cracking was high in amorphous catalysts,
yielding higher hydrocarbon gas quantities with lower amounts of
liquid products. In contrast, highly crystalline catalysts, such as Figure 1. Diagram of the Quatra C illustrating the use of dual chromato-
H+ZSM-5, yielded less secondary cracking and a higher yield of graphic columns along with TCD and MS detectors.
organic liquid products (OLP). The OLP contains compounds that
are within the boiling ranges for gasoline and diesel fuels and are of
C can be found elsewhere [17]. This reaction/analysis device uses
the most economic value [4].
small amounts of catalyst, usually 5 25 mg, and approximately
The present work seeks to establish the reaction pathway for the
1 mg reactant for each experimental run. A typical reaction
heterogeneous catalytic cracking of oleic acid. Oleic acid, or cis-9-
sequence began with the loading of catalyst into a glass tube using
octadecenoic acid, is an 18 carbon fatty acid with a symmetrically
silanized glass wool to hold catalyst in place. The catalyst tube was
placed double bond. Selection of oleic acid for this study stems from
then placed into the reaction zone of the Quatra C and the temper-
previous work on the homogeneous cracking of oleic acid [7] and
ature was raised to 4008C. Air and water were monitored using the
also from its abundance in potential lipid feedstocks. For example,
mass spectrometer (MS), and reactions were not initialized until the
the oleic acid content of olive oil is 83% [8], canola oil is 60% [8], ole-
air was within 5 amu and water less than 5% of H2O+/H2O. When air
aginous yeasts 52% [9], soybean oil 23% [10], and sewage sludge oils
and water levels were sufficiently low, reactions were run by injec-
30% [11].
tion of reactant into the gas stream via an injection port.
The catalyst used in this study was H+ZSM-5, which is a highly crys-
Products were identified using GC/MS and quantitated using GC
talline, highly acidic, and well studied zeolite [12 14]. H+ZSM-5 has
thermal conductivity detector (TCD). Both electron impact ioniza-
an intrinsically high acidity, mostly Bronsted, and was first synthe-
tion (EI) and chemical ionization (CI) were used for product charac-
sized by Mobil Research Laboratories (Princeton, NJ, USA) in the mid-
terization. Acetonitrile was used as the CI reagent gas. The chroma-
1970s. The sample used in these studies showed a pore diameter of
tographic column used for the MS was an Rxi-1ms (30 m60.52 mm,
5.4 , surface area of 425 m2/g, and Si/Al = 23. Although H+ZSM-5 is
1.50 lm film thickness) and the column used for the TCD was an RT-
not a commercially used catalyst due to its instability at high temper-
QPlot (30 m60.53 mm). The thick film, megabore column to the MS
atures, it works well for reaction mechanistic studies [15, 16].
was selected to promote retention of compounds from C1 to C30
The objective of this work was to develop the specific reaction
hydrocarbons. The plot column to the TCD was selected for its abil-
steps as oleic acid was cracked into green fuel related compounds in
ity to separate fixed gases, as well as GRO and naphthenic com-
the absence of hydrogen. To our knowledge, the use of model fatty
pounds that are precursors to coke. The temperature profile for the
acid compounds has not been studied to determine specific reaction
GC oven started at 408C, held for 5 min, ramped at 58C/min to
steps during catalytic cracking of these compounds.
608C, then ramped at 88C/min to 3008C, and finally held for 12 min.
The segmentation parameters on the MS were set to scan 10 to 80 m/
2 Materials and Methods z for the first 10 min and then scan 50 to 200 m/z for the remainder
of the GC run. Scanning of lower mass ranges during the initial
2.1 Chemicals and Catalysts phase of the chromatographic run enabled maximum sensitivity
for early eluting, lower molecular weight compounds.
Oleic acid, toluene, m-xylene, propenylbenzene (trans-b-methylstyr- The reactions were performed in duplicate and error bars have
ene), and phenylbutene (4-phenyl-1-butene) were obtained from been provided. Calculation of error bars was from l one standard
Sigma Aldrich. All reactants were received at their highest purity deviation. Data were normalized to reflect the product yield per unit
available and were used without further purification. Helium car- mass of reactant (mg/g).
rier gas for the reaction/analysis system was ultra high purity grade.
The H+ZSM-5 was obtained from Zeolyst International in the
sodium form having an elemental SiO2/Al2O3 ratio of 23/1. The sam-
ple was converted to the ammonium form by ion exchange, then
3 Results and Discussion
calcined to develop the proton form: H+ZSM-5. The framework SiO2/
Al2O3 was determined to be 35/1 using the Hoffman Elimination 3.1 Identification and Quantitation of Reaction
technique for the titration with n-propylamine. Products
Figures 2 and 3 show typical total ion chromatograms of reaction
2.2 Reactions products from oleic acid. Once a peak had been identified using MS
methods, matching of retention times using compound standards
For this study, the Quatra C (see Fig. 1) was used for quick, online were used as further verification of a peak's identity. Figure 4 shows
analysis of reaction products. A complete description of the Quatra the product yields for the cracking of oleic acid, which was reacted

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654 T. J. Benson et al. Clean 2008, 36 (8), 652 656

Figure 2. GC/MS total ion chromatogram for cracking reaction of oleic


acid on H-ZSM-5 at 4008C. Note the scanning segmentation change at
10 min (m/z 10 80 for first 10 min and then m/z 50 200 for remainder of Figure 4. Product yield for oleic acid cracking (reaction T = 4008C).
chromatographic run).

Figure 3. GC/MS total ion chromatogram illustrating the aromatic com-


pounds formed from oleic acid cracking. Compounds were identified Figure 5. Product yield for toluene cracking (reaction T = 4008C).
using electron impact and CI methods, and by retention times from stand-
ard compounds.
dimethylnaphthalene, which are precursors to coke, implied that
at three levels of catalyst to oleic acid ratios (5, 10, and 20). While multiple aromatics fused together to form coke products.
this did not provide kinetic information, it demonstrated the
change in product yields with increasing residence times. As reactor
3.2 Development of a Reaction Pathway
residence times increased, so did the production of propylene, pro-
pane, and C4 olefins in the light hydrocarbon region and benzene, To develop a reaction pathway, a series of experiments were con-
toluene, trimethylbenzenes, naphthalene, and methylnaphtha- ducted using products from oleic acid cracking as reactants on the
lenes in the aromatic region. Also, the yield of propenylbenzene H+ZSM-5 catalyst. Toluene, m-xylene, propenylbenzene, and phenyl-
and phenylbutene decreased with increased residence times. butene were reacted separately to evaluate secondary product for-
Empty bed reaction runs indicated that little to no reaction was mation. Propenylbenzene and phenylbutene were selected for fur-
due to thermal effects. However, reactions using H-ZSM-5 showed a ther investigation due to their behavior, with respect to yield, as res-
small amount of methane in the product (see Fig. 4). As methane idence time increased. Toluene and m-xylene were examined to
production is due to a-cracking [18], which is purely a pyrolytic pro- determine whether or not ring-opening and subsequent cracking
cess, some thermal cracking occurred within this system. However, were occurring to produce lower molecular weight paraffins and
the production of the various olefins, paraffins, and aromatics is olefins.
largely due to the catalytic effects of the catalyst on the oleic acid. As can be seen from Figs. 5 and 6, toluene cracking on H+ZSM-5
These results suggested that the protonation of unsaturated fatty produced chiefly benzene, and m-xylene produced mostly toluene.
acids initiates at the double bond, followed by cyclization. It is It is believed that methyl rearrangements and subsequent aromatic
thought that propenylbenzene and phenylbutene are reaction substitution reactions resulted in the formations of trimethylben-
intermediates formed after b-scission with respect to the unsatu- zenes and methylnaphthalenes for both toluene and m-xylene reac-
rated bond. From these results, it appeared that propenylbenzene tions, and also for the formation of ethylbenzene and xylenes from
and phenylbutene were secondary cracking products, which then toluene. Due to the absence of lower molecular weight hydrocar-
underwent additional reactions to form other aromatic com- bons within these products, opening of ring structures did not
pounds. The production of naphthalene, methylnaphthalene, and appear to be occurring.

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Clean 2008, 36 (8), 652 656 Catalytic Cracking of a Fatty Acid 655

Figure 6. Product yield for m-xylene cracking (reaction T = 4008C).

Figure 8. Proposed cracking chemistry for the transformation of oleic


acid to green gasoline.

Figure 7. Product yield for propenylbenzene and phenylbutene cracking


(reaction T = 4008C).
Figure 9. Equilibrium geometry obtained using AM-1 calculations.

Figure 7 shows the cracking results for propenylbenzene and phe-


nylbutene. Reactions on 20 mg H+ZSM-5 gave conversions of 81% for sequences were assumed to follow previously described carbenium
propenylbenzene and 95% for phenylbutene. These results indi- ion chemistry pathways [19 22]. The authors assume that typical
cated significant breakdown of the parent compound to produce a cyclization and aromatization steps result in the formation of aro-
variety of paraffinic, olefinic, monoaromatic, and diaromatic com- matic compounds (chiefly propenylbenzene and phenylbutene),
pounds. Interestingly, in terms of identified products, propenylben- which are reaction intermediates. The cyclization and aromatiza-
zene had a mass balance of 58%, and only 34% for phenylbutene. tion steps are believed to occur in like fashion as reported by
These data (i. e., higher conversion but lower mass balance) may Vedrine et al. [19] in which olefins were reacted with carbenium ion
imply that phenylbutene cracking resulted in the formation of intermediates to form benzene, toluene, and xylenes. Decarboxyla-
more coke products. tion and decarbonylation steps are believed to be responsible for
the formation of CO2 and CO, respectively. Once decarboxylation
and decarbonylation occur, the resulting reaction intermediates
are believed to follow similar reactions as seen from reactions of lin-
4 Proposed Reaction Pathway
ear alkanes and alkenes on H+ZSM-5 [18, 20].
The reaction pathway from oleic acid to green fuels believed to be H+ZSM-5 catalyst is a shape-selective catalyst, and its pores with
occurring on H+ZSM-5 begins with the protonation of the unsatu- intersecting channels are ideal for producing aromatic compounds
rated bond of the fatty acid (see Fig. 8). The protonated charge may [12]. Light olefins, C2 C4, readily oligomerize, cyclize, and aroma-
then migrate along the fatty acid carbon chain. b-Scission, occur- tize inside the catalyst pores and form the aromatic compounds.
ring after hydride shifts, results in cracking of the fatty acid. Pre- The newly formed aromatic compounds can then either diffuse
vious work in which a homogeneous Bronsted super acid was from the catalyst or remain inside the pores forming coke.
reacted with oleic acid demonstrated this reaction chemistry [7]. Due to molecular size restrictions, protonation is believed to
The resulting species are small enough to readily enter the catalyst occur on the outside surface of the catalyst and not within the
pores where additional reactions occur. These secondary reaction pores. AM-1 calculations using Spartan software (Wavefunction,

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656 T. J. Benson et al. Clean 2008, 36 (8), 652 656

Irvine, CA, USA) were used to determine the molecular size of oleic [2] S. Katikaneni, J. Adjaye, R. Idem, N. Bakhshi, Catalytic Conversion of
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