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Proceedings of the Combustion Institute 31 (2007) 10151022

Combustion Institute
www.elsevier.com/locate/proci

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S.M. Sarathy a, S. Ga l a, S.A. Syed a, M.J. Thomson

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a,*

A comparison of saturated and unsaturated C4 fatty acid methyl esters in an opposed ow diusion ame and a jet stirred reactor
, P. Dagaut
b
Department of Mechanical and Industrial Engineering, University of Toronto, Toronto, Ont., Canada b ` mes Re actifs, 1C, Ave de la recherche scientique, CNRS, Laboratoire de Combustion et Syste ans cedex 2, France 45071 Orle

Abstract

Biodiesel fuels, made up primarily of fatty acid methyl esters (FAME), are advantageous because they are renewable and generally have lower pollutant emissions. In order to study in detail the eect of the FAME molecular structure on the combustion chemistry, a saturated (i.e., methyl butanoate) and an unsaturated (i.e., methyl crotonate) C4 FAME were oxidized in an opposed ow diusion ame and a jet stirred reactor. Some consistent trends were seen in both experiments. Both fuels have similar reactivity. The experimental results show that methyl crotonate combustion produces much higher levels of C2H2, 1-C3H4, 1-C4H8, and 1,3-C4H6 than methyl butanoate. The methyl butanoate combustion had higher levels of C2H4. In the opposed ow diusion ames, the methyl crotonate also produced benzene while for methyl butanoate it was not detected. These species are relevant to soot formation. In addition, the experiments measured higher levels of 2-propenal, methanol, and acetaldehyde for methyl crotonate than for methyl butanoate. The reactions controlling these dierences are discussed. 2006 The Combustion Institute. Published by Elsevier Inc. All rights reserved.
Keywords: Biodiesel; Methyl butanoate; Methyl crotonate; Opposed ow diusion ame; Jet stirred reactor

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1. Introduction

Corresponding author. Fax: +416 978 7753. E-mail address: thomson@mie.utoronto.ca (M.J. Thomson).

1540-7489/$ - see front matter 2006 The Combustion Institute. Published by Elsevier Inc. All rights reserved. doi:10.1016/j.proci.2006.07.019

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Biodiesel fuels, made up primarily of fatty acid methyl esters (FAME), are advantageous because they are renewable and generally have lower pollutant emissions. Engine combustion studies [1] have shown that the biodiesel feedstock has a signicant eect on emissions. The results suggest that animal fat-based biodiesel fuels emit lower quantities of NOx, particulate

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matter (PM), and CO compared to soybean based fuels. No signicant dierence was noted in hydrocarbon emissions from the three source categories. Vegetable oils and animal fats tend to be mixtures of saturated and unsaturated FAME. However, soybean oil predominantly contains unsaturated fats (88%) while beef tallow contains more saturated fats (54%) than unsaturated fats (46%) [2]. McCormick et al. [3] tested 21 bio-diesel fuels derived from feed stocks as well as pure fatty acids in a heavy-duty truck engine using the U.S. heavyduty federal test procedure to understand the eect of biodiesel chemical structure, i.e., fatty acid chain length and number of double bonds,

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2. Experimental methodology 2.1. Opposed experiments ow diusion ame burner

Experimental measurements were conducted at atmospheric pressure using an opposed ow diusion ame burner. The experimental setup is similar to that described earlier by Sinha et al. [6]. The burner consists of two opposing identical stainless steel inlets that direct the fuel stream and oxidizer stream into a stagnation point ow. Each inlet port consists of two co-axial cylinders of diameters 25 and 38 mm, respectively, forming an inner tube for the main ow (fuel or oxidizer), and an annulus for the nitrogen co-ow. The two cylinders are spaced 20 mm apart. Fuel and oxidizer streams have inlet velocities of 13 and 14 cm/s, respectively. The oxidizer stream containing 42% O2 and 58% N2 was sent through the top burner port; 4.7% fuel (methyl butanoate or methyl crotonate) and 95.3% N2 was sent through the bottom. The purities of the methyl butanoate and methyl crotonate were 99% and 98%, respectively. The temperatures of the gases exiting the top and bottom inlets are 140 and 82 C, respectively. The inlet oxidizer and fuel stream concentration were selected based on the following criteria: (i) a low sooting ame is desired to prevent clogging of the sampling probe; (ii) a very hot ame that will damage the probe is unwanted; (iii) a balanced momentum of the two streams is required to create a stagnation plane at their intersection; (iv) excessive unburned fuel is not desired; (v) at the ame plane, an N2/O2

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2.2. Jet stirred rector experiments The JSR experiments were conducted at atmospheric pressure using an experimental setup similar to that described earlier [8]. The reactor consisted of a sphere of 40 mm diameter made of fused-silica (to minimize wall catalytic reactions), equipped with four nozzles of 1 mm i.d. for the admission of the gases which achieve the

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on the emissions of NOx and PM. It was found that increasing the number of double bonds (quantied as iodine number) correlated with increasing NOx emissions while PM emissions remained unchanged. In addition, for fully saturated fatty acid chains, the NOx emissions increased with decreasing chain length for tests using 18, 16 and 12 carbon chain molecules while PM emissions did not show signicant change. The aim of this study was to provide insights into the eect of the FAMEs chemical structure on the formation of intermediates, unburned hydrocarbons, and pollutants. For this purpose, a saturated and an unsaturated C4 FAME were oxidized in an opposed ow diusion ame and a jet stirred reactor (JSR). The selected fuels are methyl butanoate (CH3CH2CH2C(@O)OCH3) and methyl crotonate (CH3CH@CHC(@O)OCH3). The chemical kinetic mechanism for the oxidation of methyl butanoate was proposed earlier [4] and updated recently [5]. A detailed chemical kinetic mechanism for methyl crotonate oxidation is currently under development and not presented here.

ratio near that of air is desired to make the study relevant to actual ames. The fuel ow rate was controlled using a peristaltic pump. In order to vaporize the fuel, an ultrasonic atomiser was used to spray the fuel into a stream of nitrogen heated to about 80 C. Sampling was accomplished by continuously withdrawing gases from within the ame using a quartz microprobe with an orice diameter of 120150 lm; low visible disturbance to the ame was observed. The probe was kept stationary, and the burner was moved to measure the axial concentration prole of the ame. An oil-free dual-stage heated-head vacuum pump drew the samples from the microprobe along heated Teon tubing through a lter and pushed the sample through the sample loop of a Varian 3800 series GC/FID (ame ionization detector). A vacuum pressure of 710730 mm Hg, measured just downstream of the microprobe, promoted rapid cooling in the probe tip. Simultaneous reduction of pressure and the destruction of free radicals on the probe walls were sucient to stop the reactions and ensure accurate data on ame composition. Microprobes of various diameters were tested to determine the appropriate size. All the runs were conducted in low or no sooting conditions to avoid any clogging of the microprobe. The GC system measured C1C5 alkanes, alkenes and alkynes and benzene using an HP-AL/S PLOT Column. A DB-624 column was used to measure methyl butanoate, methyl crotonate, methanol, and acetone in the ame. The GC system was calibrated for hydrocarbons using commercial standards, and for oxygenated compounds using laboratory prepared standards. The CO/CO2 concentrations were measured using a separate NDIR analyzer. Measurement of formaldehyde, acetaldehyde and 2-propenal was performed using the HPLC technique. The gas samples were allowed to pass through an LpDNPH cartridge where the carbonyls were trapped. The samples were then elutriated using acetonitrile, and the liquid sample was analyzed with HPLC using a variable wavelength UV detector and LC-18 column. Temperature measurements were taken using a 250-lm diameter R-type thermocouple. The measured temperatures were corrected to account for radiation losses from the thermocouple [7]. The accuracy of measurements is estimated to be 15%.

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Table 1 A comparison of the measured peak species mole fractions in methyl butanoate (MB) and methyl crotonate (MC) in the opposed ow diusion ame and jet stirred reactor Measured species Name Carbon Dioxide Carbon Monoxide Methane Formaldehyde Ethane Ethylene Acetylene Propene Propyne Acetaldehyde 1-Butene 1,3-Butadiene 2-Propenal Propane n-Pentane 2-Butyne Butane Acetone Benzene Methanol 1,2-Propadiene Propanal Formula CO2 CO CH4 CH2O C2H6 C2H4 C2H2 C3H6 1-C3H4 CH3CHO 1-C4H8 1,3-C4H6 CH2@CHCHO C3H8 C5H12 2-C4H6 C4H10 CH3OCH3 C6H6 CH3OH 1,2-C3H4 C2H5CHO Opp. ow di. ame (ppm) Results (MC) 1.00E+05 3.00E+04 2185 280 1802 2567 4781 1394 434 40 353 568 50 31 13 34 61 21 16 617 Results (MB) 1.01E+05 3.00E+04 1957 222 1405 4842 1951 790 62 43 58 48 <3 62 2 6 12 <3 <5 <5 Ratio (MC/MB) 1.0 1.0 1.1 1.3 1.3 0.5 2.5 1.8 7.0 0.9 6.1 11.8 0.5 6.5 5.7 5.1 232 30 <1 148 <2 27 1.6 Jet stirred reactor (ppm) Results (MC) 2622 1196 135 168 146 252 270 43 112 25 15 27 25 Results (MB) 3071 2136 154 176 139 480 76 55 <2 8 5 2 7 Ratio (MC/MB) 0.9 0.6 0.9 1.0 1.1 0.5 3.6 0.8 3.1 3.0 13.5 3.6

Note: Species with peak concentrations less than 1 ppm are not included in the table.

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stirring. A nitrogen ow of 100 L/h was used to dilute the fuel and to avoid its pyrolysis before admission in the reactor. All the gases were preheated before injection in order to minimize temperature gradients inside the JSR (61 K/cm). The reactants were diluted by nitrogen and mixed at the entrance of the injectors. High-purity reactants were used; the fuels were sonically degassed before use. A piston pump was used to deliver the fuel to an atomizervaporizer assembly maintained at 145 C. The reacting mixtures were sampled at steady temperature and residence time via a low-pressure fused-silica sonic probe. They were analyzed o-line after collection and storage in 1 L Pyrex bulbs. All the products were analyzed by an identied chromatographic peak. The experiments were performed at steady state, at a constant mean residence time of 0.07 s, the reactants owing continually in the reactor, varying stepwise the JSR temperature. A high degree of dilution (0.075% vol. of fuel) was used, reducing temperature gradients in the JSR and heat release (no ame occurred in the JSR). Several GC, equipped with capillary columns (Poraplot-U, Molecular Sieve-5A, DB-5ms, DB624, Plot-Al2O3/KCl, Carboplot-P7), thermal conductivity detector (TCD), and FID, were used. Compound identications were made through GC/MS analyses. CH2O and CO2 were measured

by FID after hydrogenation on a methanizer (Ni/H2 catalyst) connected to the exit of the Poraplot-U, GC column. A good repeatability of the measurements and a reasonably good carbon balance (100 15%) were obtained. The accuracy of measurements is estimated to be 15%. 3. Results and discussion

Experiments in an opposed ow diusion ame allow us to compare the fuels in a non-premixed ame. The ow rates of the fuels were set to have the same molar ow rates. Table 1 summarizes the measurements showing the peak mole fractions of measured species. Methyl butanoate and methyl crotonate ames produced similar peak mole fractions of CO2, CO, CH4, CH2O, CH3CHO and C2H6. The methyl crotonate ame has approx. twice the mole fraction of C2H2 and C3H6 and half that of C2H4 and C3H8. Note, a similar trend was observed in previous studies on propane [9] and propene [10] in a JSR at 1 atm, wherein C2H4 decreases (0.5 times) and C2H2 increases (3 times) when going from propane to propene. The methyl crotonate ame has ve to seven times more 1C3H4, 1-C4H8, 2-C4H6, C4H10 and C5H12 and 12

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3.1. Opposed experiments

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Fig. 1. Measured mole fractions in the methyl butanoate and methyl crotonate opposed ow diusion ames.

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times more 1,3-C4H6. In addition, CH3OH, CH2@CHCHO, CH3OCH3, and C6H6 were detected in methyl crotonate ames but were below the detection limit for methyl butanoate. Selected species proles across the ame are shown in Fig.1. Little dierence is seen in the fuel, CO, and CO2 proles. The methyl crotonate ame has consistently higher C2H2 levels and consistently lower C2H4 and C3H8 levels. The methyl crotonate ame also has much higher levels of 1-C3H4, 1-C4H8, 2-C4H6 and 1,3-C4H6 across the ame. To analyze these dierences, the major reaction pathways were examined based on existing detailed chemical kinetic studies [4,5]. Many of the dierences can be explained by analogous reaction pathways for the two fuels with the unsaturated methyl crotonate creating more unsaturated species (refer to Fig. 4). For example, hydrogen abstraction and decomposition reactions produce C3H7 (i.e., CH3CH2CH2) and C3H5 (i.e., CH3CH@CH) for methyl butanoate and methyl crotonate, respectively. In the case of methyl butanoate, these reactions are: (The num-

bers in the following discussion correspond to the reactions shown in Fig. 4.) CH3 CH2 CH2 C(@O)OCH3 $ CH3 CH2 CH2 C(@O)O + CH3 #1

CH3 CH2 CH2 C(@O)O $ CH3 CH2 C H2 + CO2 #2

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CH3 CH2 CH2 C(@O)OCH3 + X $ CH3 CH2 CH2 C(@O)OC H2 + XH CH3 CH2 CH2 C(@O)OC H2 $

#3

CH3 CH2 CH2 C (@O) $ CH3 CH2 C H2 + CO #4b where X = CH3, H, O, OH, HO2 or O2. Whereas in the case of methyl crotonate, these reactions are:

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CH3 CH2 CH2 C (@O) + CH2 O

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CH3 CH@CHC(@O)OCH3 $ CH3 CH@CHC(@O)O + CH3

#5

CH3 CH@CHC(@O)O $ CH3 CH@C H + CO2 #6 CH3 CH@CHC(@O)OCH3 + X $ CH3 CH@CHC(@O)OC H2 + XH CH3 CH@CHC(@O)OC H2 $ CH3 CH@CHC (@O) + CH2 O

Fig. 2. These radicals produced by H-abstraction can react to produce 1-propenyl radical (CH3CH@CH) and methoxycarbonyl radical (CH3OCO). The methyl crotonate can also react by decomposition to produce the following radicals: CH3 CH@CHC(@O)OCH3 $ CH3 CH@C H + CH3 OCO #14

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#8a

CH3 OCO $ CO + CH3 O

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The methoxycarbonyl radical (CH3OCO) can react via decomposition: #15 As discussed previously, the CH3CH@CH fur-

CH3 CH@CHC (@O) $ CH3 CH@C H + CO #8b In the case of methyl butanoate, the C3H7 further reacts to form C3H8 by H addition (#9) and C2H4 by b-scission (#10). In the case of methyl crotonate, the C3H5 further reacts to form C3H6 by H addition (#11) and 1-C3H4 and C2H2 by b-scission (#12a, c). The C2H2 pyrolyzes in the presence of other small hydrocarbons to form 1-C4H8, 2C4H6 and 1,3-C4H6 and C6H6 (#13). This explains why higher levels of C2H2, 1-C3H4, 1-C4H8, 2C4H6, 1,3-C4H6, and C6H6 were observed in the methyl crotonate ame, while higher levels of C2H4 and C3H8 were observed in the methyl butanoate ame. The presence of the double bond in the methyl crotonate leads to the production of three equivalent radicals (A, B, and C), which are in equilibrium due to internal isomerization, as shown in

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Fig. 2. Radicals produced from methyl crotonate by H-abstraction.

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ther reacts to form C3H6, 1-C3H4 and C2H2 (#11, #12a, c). The radical CH3O forms CH3OH by H-atom abstraction (#16) from hydrocarbons and other easily abstractable sites. This explains why methanol levels were higher in the methyl crotonate ame. 2-Propenal (CH2@CHCHO) was greater in the methyl crotonate ame than the methyl butanoate ame. 2-Propenal can be derived from methyl crotonate by a series of decomposition and H addition reactions (#21#24), as shown in Fig. 4. In the case of methyl butanoate, it is evident that the analogous pathways (#17#20) would lead to propanal (C2H5CHO). Propanal was not detected in the opposed ow diusion ame for either species. 3.2. Jet stirred reactor experiments Experiments in a jet stirred reactor allow us to compare the reactivity of the fuels in premixed

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Fig. 3. Measured mole fractions in the methyl butanoate and methyl crotonate jet stirred reactor experiments (U = 1, s = 0.07 s).

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conditions. In these experiments, 750 ppm methyl butanoate or methyl crotonate react for a mean residence time of 0.1 s at an equivalence ratio of one and a pressure of one atmosphere. Table 1 summarizes the measurements showing the peak mole fractions of measured species. Methyl butanoate and methyl crotonate have similar peak mole fractions of CO2, CH2O, CH4, CH3OH, C3H6 and C2H6. The methyl crotonate combustion has over three times the mole fraction of C2H2 and approx. half the mole fraction of CO and C2H4. The methyl crotonate forms approx. thirteen times more 1,3-C4H6 and three times more CH3CHO and CH2@CHCHO. In addition, 1-C3H4 and 1,2-C3H4 were detected in methyl crotonate experiments but were below the detection limit for methyl butanoate. However, propanal (C2H5CHO) was detected for methyl butanoate but was below the detection limit for methyl crotonate. These results show good overall agreement with the opposed ow diusion ames data. Species mole fractions versus reactor temperature are plotted for selected species in Fig. 3. The

methyl butanoate and methyl crotonate have similar reactivity, as similar fuel, CO, and CO2 levels are measured for the two fuels. In Fig. 3, it is also interesting to note the modest cool ame behaviour of both esters (800950 K). The methyl crotonate results in consistently higher C2H2 levels and consistently lower C2H4 levels. The methyl crotonate combustion also has much higher levels of 1-C3H4, 1-C4H8, and 1,3-C4H6 at most reactor temperatures. Many of the dierences concerning products formation from the two esters can be explained by the analysis presented above in Section 3.1. However, in the opposed ow diusion ame H radicals are important while in a jet stirred reactor OH and O radicals are predominate. As shown in reactions (#1#8), hydrogen abstraction and decomposition reactions produce C3H7 (i.e., CH3CH2CH2) and C3H5 (i.e., CH3CH@CH) for methyl butanoate and methyl crotonate, respectively. In the case of methyl butanoate, the C3H7 further reacts to form C2H4 by b-scission (#9). In the case of methyl crotonate, the C3H5 further reacts to form 1-C3H4, 1,2-C3H4 and

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Fig. 4. Analogous reaction pathways for methyl butanoate and methyl crotonate.

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C2H2 by b-scission (#12a, b, c). The C2H2 pyrolyzes (#13) in the presence of other small hydrocarbons to form 1-C4H8, 2-C4H6 and 1,3-C4H6. Thus, higher levels of C2H2, 1-C3H4, 1,2-C3H4, 1-C4H8 and 1,3-C4H6 are observed for the methyl crotonate case, while higher C2H4 levels are observed for methyl butanoate. In addition, the methyl crotonate reacts via the following reactions (#28#30) to form acetaldehyde (CH3CHO): CH3 CH@CHC(@O)OCH3 + X $ CH2 @CHC HC(@O)OCH3 + XH

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CH2 @CHC HC(@O)OCH3 $ CH2 @CHCH@C(@O) + CH3 O CH2 @CHCH@C(@O) + OH $ HCCO + CH3 CHO

#29

#30

4. Conclusions

Comment

Ken Brezinsky University of Illinois at Chicago, USA. The methyl crotonate/2-butenoate has more C4 unsaturated intermediates than does the methyl butanoate, yet are oxidized at the same rate, and nal products CO, CO2 appear at the same rate. How do you explain that result?

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Premixed and non-premixed combustion experiments were used to investigate the eect of the chemical structure of C4 FAME on the combustion species. The unsaturated fuel, methyl crotonate, was compared to the saturated methyl butanoate. Some consistent trends were observed for both experiments. Both fuels have similar reactivity. The experiments measured higher levels of 2-propenal, methanol, and acetaldehyde for methyl crotonate than for methyl butanoate. The methyl butanoate combustion had higher levels of C2H4. In addition, the experimental results

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The radical species displayed in reaction #28 is a resonant structure of CH2CH@CH(@O)OCH3. In the case of methyl butanoate, the analogous reactions (#25#27) form C2H5OH rather than CH3CHO. This explains the higher levels of CH3CHO observed for the methyl crotonate case. Note, it was previously mentioned that OH and O radicals are predominate in the jet stirred reactor. This explains the more apparent dierence in CH3CHO concentrations for the two fuels in the JSR experiments. Higher levels of methanol and 2-propenal (CH2@CHCHO) were observed for methyl crotonate, while higher levels of propanal (C2H5CHO) were observed for methyl butanoate. As previously mentioned, the double bond in methyl crotonate leads to the formation of methanol by a series of decomposition reactions (#14, #15) followed by H addition (#16). Again, 2-propenal is formed from methyl crotonate by a series of decomposition and H addition reactions (#21 #24), while the analogous reactions (#17#20) form propanal in the case of methyl butanoate. This explains the observed dierences in concentrations of the before mentioned species.

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References

[1] U.S.E.P.A. Draft Technical Report EPA420-P-02001 (2002). [2] M. S Graboski, R.L. McCormick, Prog. Energy Combust. Sci. 24 (2) (1998) 125164. [3] R.L. McCormick, M.S. Graboski, T.L. Alleman, A.M. Herring, K.S. Tyson, Environ. Sci. Technol. 35 (9) (2001) 17421747. [4] E.M. Fisher, W.J. Pitz, H.J. Curran, C.K. Westbrook, Proc. Combust. Inst. 28 (2) (2000) 1579 1586. [5] S. Ga l, M. Thomson, S.M. Sarathy, S.A. Syed, P. vart, A.J. Marchese, F.L. Dryer, Dagaut, P. Die Proc. Combust. Inst. 31 (2007) 305311. [6] A. Sinha, M.J. Thomson, Combust. Flame 136 (4) (2004) 548556. [7] R.M. Fristrom, A.A. Westenberg, Flame Structure, McGraw Hill, New York, 1963. [8] S. Ga l, P. Dagaut, Combust. Flame 141 (3) (2005) 281297. [9] P. Dagaut, M. Cathonnet, J.C. Boettner, F. Gaillard, Combust. Sci. Technol. 56 (13) (1987) 2363. [10] P. Dagaut, M. Cathonnet, J.C. Boettner, J. Phys. Chem. 92 (3) (1988) 661671.

Reply. The peak concentrations of nal products are shown in Table 1. The concentrations of C4 unsaturated species are not large enough to signicantly aect the fuels oxidation rate and production of CO and CO2. In addition, higher molecular weight unsaturated hydrocarbons are only found in trace concentrations.

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vart for his help with The authors thank P. Die the JSR experiments and Auto21, NRCan, BIOCAP, NSERC and the Ontario Graduate Scholarship Program for funding the research.

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indicate that methyl crotonate combustion produces much higher levels of C2H2, 1-C3H4, 1-C4H8, and 1,3-C4H6 than methyl butanoate. In the opposed ow diusion ames, the methyl crotonate also produced benzene while for methyl butanoate it was not detected. These species are soot precursors. This suggests that an unsaturated FAME would have a greater tendency to soot than a saturated FAME. This is consistent with the EPA engine data [1] which saw the more unsaturated soybean methyl esters forming more soot than the more saturated beef tallow methyl esters. However, some engine data did not observe this [3].