Fuel 90 (2011) 25982608

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Fuel
journal homepage: www.elsevier.com/locate/fuel

New path in the thermal cracking of triacylglycerols (canola and soybean oil)
Alena Kubtov a,b, Yan Luo a,c, Jana tvov a,b, S.M. Sadrameli d, Ted Aulich e, a,b a,f, Evguenii Kozliak , Wayne Seames
a

The University of North Dakota SUNRISE Research Group, Grand Forks, USA Chemistry Department, University of North Dakota, Grand Forks, USA c Currently at Union Oil Products, Des Plaines, Illinois, USA d Chemical Engineering Department, Tarbiat Modares University, Tehran, Iran e Energy and Environmental Research Center, University of North Dakota, Grand Forks, USA f Chemical Engineering Department, University of North Dakota, Grand Forks, USA
b

a r t i c l e

i n f o

a b s t r a c t
Triacylglycerols (TGs) are naturally occurring oils abundant in many crops. A series of batch uncatalyzed thermal decomposition experiments were performed using canola and soybean oils to explore pathways of TG cracking. A detailed gas chromatographic protocol based on mass spectrometric identication and ame ionization quantication was applied to the organic liquid product generated upon cracking. Reaction conditions were identied that resulted in a novel organic liquid product (OLP) composition compared to previously reported work. Under these conditions (temperatures within a 420440 C range) a new route for TG thermolysis was discovered in which cracking reactions of original TG-bound fatty acids were nearly complete and led to the formation of 1525 wt.% C2C10 linear saturated monocarboxylic acids and ca. 30% linear alkanes. Less than 2 wt.% C16C18 fatty acids which were originally present in the feedstocks as glycerol triesters were found in the OLP. These reactions appear to be kinetically controlled due to abundant hydrogen formation. This route provides a signicant enrichment of low-MW compounds in the OLP (6570 wt.% being <C11) and thus may be considered as a new option for the production of replacement products for petroleum-based fuels and chemicals. 2011 Elsevier Ltd. All rights reserved.

Article history: Received 15 February 2010 Received in revised form 4 April 2011 Accepted 18 April 2011 Available online 1 May 2011 Keywords: Crop oils Thermal cracking Renewable fuels Canola oil Soybean oil

1. Introduction Triacylglycerols (TGs) are naturally occurring oils produced by a number of crops, microorganisms (bacteria, algae), and animals (fats). The diversity and prevalence of sources for these compounds suggests that they may serve as an attractive alternative to crude oil, i.e., as a feedstock for the production of chemicals utilized in transportation fuel formulations and industrial applications. In fact, TGs are currently used in the transesterication processes that produce most of the biodiesel products commercially available today. Literature on TG thermal cracking, primarily of the mixtures of TGs naturally occurring in various crops, has appeared sporadically in the last few decades whenever there is renewed interest in alternatives to petroleum-based transportation fuels (see [14] for reviews of early work in this area). Previous research (reviewed by Maher and Bressler [4]) suggests that thermal cracking resulting in the cleavage of carboncarbon bonds in TGs can produce lowerMW organic products that may be more attractive in fuel
Corresponding author at: The University of North Dakota SUNRISE Research Group, Grand Forks, USA. Tel.: +1 701 777 2958; fax: +1 701 777 3773. E-mail address: wayneseames@mail.und.edu (W. Seames).
0016-2361/$ - see front matter 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2011.04.022

formulations and/or chemicals than the simple transesterication reactions currently used to transform TGs into biodiesel [5]. Several principal organic reactions involved in the thermal cracking process, shown in Fig. 1, are typical for free-radical thermal decomposition reactions [2,4,68] (particular reactions will be referred to henceforth without mentioning Fig. 1). The reactions shown in Fig. 1 are representative yet not detailed. For example, cycles and aromatics may be formed by alternative intramolecular cyclizations [9]. Work in progress to address this and several other reactions and their details are beyond the scope of the present paper. Due to the lack of detailed knowledge on cracking reactions, the diverse distribution of chemical constituents generated under different conditions is only partially understood. The available information, organized with a focus on the pertinent chemistry of TG cracking, is discussed below. The quantitative cracking product distributions of known overall process routes are summarized in Table 1 (see the footnote for a list of routes) involving both catalytic and non-catalytic processes. As shown, signicantly different product distributions can be obtained under different conditions. It should be noted that the data reported in the literature and shown in Table 1 were based only on the species that were identied and quantied by GC. Mass balance closure is usually not attempted in

A. Kubtov et al. / Fuel 90 (2011) 25982608

2599

1. Thermolysis of the TG ester bond

O CH3 (CH2)6 CH2 CH=CH CH2 (CH2)6 C O CH3 (CH2)6 CH2 CH=CH CH2 (CH2)6 C O CH2 R CO2 CH R' CO2 CH2 O CH2 R CO2 CH R' CO2 CH2 CH2 R CO2 CH R' CO2 CH2 similar processing of RCOOH and R'COOH

1a 1b

O CH3 (CH2)6 CH2 CH=CH CH2 (CH2)6 C O

2. Deketenization (continuation of reaction 1a)

O CH3 (CH2)6 CH2 CH=CH CH2 (CH2)6 C CH3 (CH2)6 CH2 CH=CH CH2 (CH2)5 CH2=C=O (ketene) gases and high-MW products

3. Decarboxylation (continuation of reaction 1b)

O CH3 (CH2)6 CH2 CH=CH CH2 (CH2)6 C O CO2 + CH3 (CH2)6 CH2 CH=CH (CH2)5 CH2

4. Stabilization of radicals
-H CH3 (CH2)6 CH2 CH=CH (CH2)n CH2 CH2 4a +H 4b CH3 (CH2)6 CH2 CH=CH (CH2)n CH CH2 CH3 (CH2)6 CH2 CH=CH (CH2)n CH2 CH3

5. Cracking of unsaturated hydrocarbons (shown for the predominant allyl position)

5a CH3 (CH2)6 CH2 CH=CH CH2 5a (CH2)6 CH3 5b 5b CH3 (CH2)5 CH2

CH2 CH=CH CH2 (CH2)6 CH3

CH3 (CH2)6 CH2 CH=CH CH2

+ CH2 (CH2)n-1 CH3

6. Isomerization
6a. Moving the double bond CH3 (CH2)6 CH2 CH=CH CH2 CH2 (CH2)n CH CH2 6b. Forming more stable radicals CH3 (CH2)n CH2 CH2 CH3 (CH2)n CH CH3 CH3 (CH2)6 CH2 CH=CH CH CH (CH2)n CH2CH3

7. Formation of branched radicals

7a. Direct isomerization to form more stable radicals CH3 alkanes and alkenes according to reactions 4 R CH CH2 CH3 R C CH3 7b. Reactions of radicals with double bonds R CH2 + R1 CH=CH R2 CH2R alkanes and alkenes according to reactions 4

R1 CH CH R2

8. Diels-Alder reaction (one of the possible pathways toward the formation of cycles)
R CH CH CH CH R1 + R2 CH CH R3 R R3 R2 R1 cyclic alkenes

9. Hydrogen abstraction and dehydrogenation

R R3 R2 R1
- 2 H2 9a

R R3 R R3 R2 R2

R1

aromatic hydrocarbons

+ H2 9b

R1

cycloalkanes

10. Termination
R CH 2 + R 1 CH 2 R CH 2 CH 2 R 1

11. Fatty acid cracking (previously unknown or uncommon reaction)

CH3 (CH2)6 11a CH3 (CH2)5 CH2 + hydrocarbons by reaction 49 CH2 CH2=CH CH2 (CH2)6 CO2H 11b CH3 (CH2)6 CH2 CH=CH CH2 + CH2 (CH2)6 CO2H +H further cracking as in reaction 11b further cracking -H H2C CH (CH2)5 CO2H CH3 (CH2)6 CO2H

CH2 CH=CH CH2 (CH2)6 CO2H

Fig. 1. Primary reactions involved in the general mechanism of TG cracking.

When catalyzed by either Lewis/Bronsted acids (e.g., alumina, sulfated zirconia, transitional metals, zeolites, etc.) or sodium carbonate, thermal decomposition of canola oil [8,1014], and other TG sources [14,6,7,1522], is directed toward a specic reaction path (Table 1, Columns 1 and 2) in which the deoxygenation of the intermediately formed acyl and acyloxyl radicals (Reactions 12) becomes predominant. Depending on temperature, catalytic cracking leads either to Route 1 (Column 1; temperatures below 300360 C conducting the process in glassware [24], or using highly selective Pd-based catalysts [21,25]) or Route 2 (Column 2, observed at higher temperatures). The difference between them is that Route 2 involves additional cracking reactions [7,1113,18,22]. Olens and dienes can be formed by the abstraction of hydrogen at higher reaction temperatures (Reactions 4a and 9a). These olens and dienes are particularly important, due to their contribution to the synthesis of cycles, aromatics and high-MW polymer-like tars. The hydrogen released in these reactions is then available to participate in hydrogenation reactions that yield saturated products (Reactions 4b, 9b). Note that for some catalysts (particularly acids), the reactions in Fig. 1 are not mechanistically valid (because radical reactions are partially replaced by electrophilic/cationic processes [23]) although the correct ultimate products are identied. Only a few studies have been conducted on the non-catalyzed pyrolysis of TGs (or using catalysts for reactions other than decarboxylation) depicted as Route 3 in Table 1 (Column 3) [7,8,2732]. The most distinctive feature of Route 3 is that long-chain FAs persist as stable reaction products (thus ending longons by-(lo271.2r-1.cy4(us9e)-2298.6

TG cracking studies. Undetected unknown and non-GC-elutable organic liquid product (OLP) components are not typically accounted for in the reported results. In this manuscript, this problem is addressed for short-chain fatty acids by describing a protocol for their quantitation and its application. Similar work for other potentially missing cracking products, leading to a more complete mass balance closure, is in progress and will be reported separately. Given this limitation, Mailhe [1], Gusmao et al. [6], and Dupain et al. [7], demonstrated that TG pyrolysis starts from the formation of long chain (C16C18) fatty acids (FAs) as a result of ester bond thermolysis (Reaction 1). The glycerol backbone of TGs decomposes to gaseous low-MW chemicals, e.g., ethylene [1,6]. In addition, some of the unsaturated products and intermediates produce solid and viscous high-MW products, i.e., coke and tar, respectively [7,8]. The glycerol backbone appears to contribute to this by yielding reactive intermediates which initiate polymerization, e.g., acrolein [8]. For the purposes of the research presented herein, the focus is on the non-aqueous organic liquid product (OLP) fraction following the fate of the TG original high-MW FAs formed, as major process intermediates.

2. Experimental 2.1. Materials Rened soybean oil was obtained from Ag Processing Inc (AGP), a cooperative located in the state of Minnesota, USA. Canola oil was obtained from ADM processing in Velva, North Dakota, USA and was of rened quality. Composition data, reported as the percentages of the fatty acid chains incorporated into TGs, are shown in Table 2. Solvents [acetonitrile (ACN), HPLC grade, methylene chloride, GC grade] were purchased from Fischer (Waltham, MA, USA). N-methyl-N-trimethylsilyltriuoracetamide (MSTFA) was used as a derivatization agent (Supelco, Bellefonte, PA, USA). For preliminary quantication and identication, dened mixtures of alkanes (C720, 25, 28, 35) (Protocol Analytical, LLC Metuchen, NJ, USA), alkenes (C9, 11, 13, 14, 1619), aromatics [benzene, toluene, ethylbenzene, o-xylene, p-xylene (BTEX)] and FAs (C410, 12) were employed [Sigma & Aldrich (St. Louis, MO, USA, USA)]. For detailed identication, the following mixtures were purchased from Supelco (Bellefonte, PA, USA): isoparafn-, aromatic-, naphthene-, and olen-Alphagaz PIANO (ASTM D5134); naptha, reformate, and alkylate qualitative reference standards; crude oil qualitative and quantitative standards (ASTM D5307). For detailed quantication of the cracking products, individual chromatographic standards of analytical grade were used representing the complete series of unbranched alkanes (C5C18), selected alkenes (C6, 9, 14, 18), and additional (to BTEX) aromatics (1,2,4-trimethylbenzene, indane, naphthalene). Internal standard calibrations were performed in the range of

A9 4E5 FA10 BOctylcyclopentane Abundance GC-MS ful l 2E5

6 6 69JE 1.2E 1E6

8E5 6E5

4j34.28D61590lT 437.8951062(aj 8.7906l3TD512

scanA11

E125374

7E6

6E6

924.3Tj1860l5 79.-1jT3864l052 cm7-.f1)j308T4562A

canbdAneucnadnubA

using GCFID calibrated with a series of representative standards (the list is provided under Materials). The advantage of FID for accurate quantication (compared to MS) is that its response is proportional to the number of carbon atoms and thus different species of the same class of compounds can be quantied using only a few or even just one calibration standard. The nondiscriminative character of FID vs. MS is demonstrated in Fig. 4A and B, showing that, in contrast to GCFID, the MS response of alkanes declined signicantly with a decreasing number of carbon atoms. Samples were quantied using the internal standard calibration method (see Materials for the list of standards). The response factors (RFs) of non-calibrated compounds were calculated using the RFs of the corresponding analogs with the same number of carbon atoms (e.g., alkanes) with correction factors obtained upon calibration for species representing particular classes of compounds. Polar species with hydroxyl groups (e.g., acids, alcohols and glycerol) exhibit low sensitivity when analyzed directly (Fig. 4A). This leads to difculties in both the identication and quantication of carboxylic acids while using FID or full scan MS, respectively, as demonstrated in Fig. 4A and B (much broader, near-baseline, peaks of FAs compared to hydrocarbons). Note the difference in the scale of the y-axis of the gures. Thus, even though the acids shown in Fig. 4C could be quantied using the EIC (extracted ion chromatogram), the sensitivity of such a quantication method would be fairly low. To address the low sensitivity observed, sample derivatization with MSTFA was performed followed by a GCFID analysis. This derivatization signicantly improved the response of acids (compared to alkanes) even in the GCMS full scan (Fig. 4D). Samples (20

lized within the 420440 C range then gradually declined at higher temperatures [36]. Thus, further experimentation was conducted between 420 and 440 C with a focus on OLP yield and composition. Results from the ve most signicant of the twelve experimental runs as derived statistically following the PlackettBurman design of experiment methodology (Table 3) are summarized in Table 4 (complete results are available in Ref. [39]). These results show that reaction temperature was the most important and only statistically signicant variable with increasing temperature leading to increased OLP yield, whereas the variation of stirring/heating rates, reaction time and initial pressure (within the range used) were not statistically signicant. 3.2. The inuence of external hydrogen The results shown in Table 4 also conrm our previous work that the presence of externally added hydrogen does not positively impact thermal cracking at temperatures above 400 C [36]. However, at 380 C the positive impact of externally added hydrogen was signicant as shown in Table 5. Even though some overhead

product was produced at this temperature in the absence of hydrogen, it did not contain measurable quantities of C7C16 sized products that would signify cracking. By contrast, the overhead produced in the presence of hydrogen contained signicant amounts of cracked products. This observation is consistent with a reforming mechanism at temperatures below 400 C with no H2 added rather than a cracking mechanism. The main product under such conditions was a yellow solid, along with some viscous liquid. Apparently in the absence of cracking, competing polymerization reactions became dominant. The observed marked switch in the systems behavior upon a small temperature increase led us to suggest that ample hydrogen is generated in situ above the temperature threshold. To test this hypothesis, several experiments were conducted with soybean methyl esters (SME), i.e., soybean oil transesteried with methanol. The reason for using this modied feedstock was the removal of glycerol whose decomposition could generate hydrogen in situ. The results, also shown in Table 5, show that the effect observed was even more pronounced with SME cracking than with soybean oil. Both the OLP yield and the yield of products in the target size ra2i9-362.7(observed)]25.1(i9D[(was)-2842857.8(g9(the0TD[(,)-33813.9ho

added hydrogen, at temperatures between 350 and 380 C. By contrast, at higher temperatures external hydrogen did not inuence any of these values.

3.3. The effect of H2 formation upon TG cracking The composition of the non-condensable gases generated during the cracking reaction experiments provided evidence that internal hydrogen generation is sufcient to facilitate cracking under these conditions. Excess hydrogen was measured in the gas phase on the order of 5 vol.%. Furthermore, signicant CO amounts, 4050 vol.%, were observed compared to 1520 vol.% CO2. The prevalence of CO over CO2, despite the presumed abundant CO2 formation as a result of partial FA decarboxylation, is evidence of even more abundant hydrogen formation followed by its reactions with both alkenes and CO2. This evidence was supported by the formation of signicant amounts of water (23% of the TG mass) which could be formed as a by-product of CO2 reduction by hydrogen. Similar large amounts of hydrogen gas generated during TG cracking were reported earlier by Idem et al. [8]. Further evidence of in situ hydrogen generation was obtained while considering the OLP composition. A more detailed analytical protocol was utilized to more denitively quantify the cracking products. The observed distributions of the major classes of organic chemicals found in the reaction products are shown in Table 6 for both canola and soybean oil. As long as the temperature remained within a range of 420440 C, the product distribution became remarkably similar for these two different feedstocks (Tables 4 and 6

demonstrates that direct GC analyses revealed some of the lowerMW FAs only as relatively broad peaks of low intensity (Fig. 4A and B), which could be resolved only when using EIC (Fig. 4C). To enable sensitive quantication, acids had to be derivatized (Fig. 4D). Thus, even when present in fairly high concentrations, low-MW FAs may remain unnoticed in OLP unless specic identication and quantication methods are used. This is consistent with several reports in which carboxylic acids were converted to methyl esters prior to analysis; as a result, low-MW FAs were observed along with larger peaks of high-MW FAs [30,32,40,41]. Under the conditions present in the thermal cracking reactor, an abundant presence of lower-MW FAs among the products can only occur if these FAs are formed via the cracking of higher-MW FAs. Thus, the previously undocumented cracking of the original TGbound FAs to lower MW carboxylic acids and hydrocarbons, which is near-complete under the optimum conditions dened in this study, constitutes a new route (Route 4, cf. Table 1) for TG thermolysis, i.e., high temperature non-catalytic cracking.

The authors would like to acknowledge the contributions of the following personnel in this work: Ron Timpe and Jerry Petersburg of the UND Energy and Environmental Research Center, Michael Mann, Marko Jukic, Lu Zhang, Prasad Chavan, and Joe Miller of the UND Chemical Engineering Department, and Irina Smoliakova of the UND Chemistry Department.

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