Fuel 83 (2004) 23012311 www.fuelrst.

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Inuence of fuel and air/fuel equivalence ratio on the emission of hydrocarbons from a SI engine. 1. Experimental ndings
E. Zervasa,*, X. Montagnea, J. Lahayeb
a b

trole, 1 et 4 avenue du Bois Pre au, F-92500 Rueil-Malmaison cedex, France Institut Franc ais du Pe Institut de Chimie des Surfaces et Interfaces, 15 rue Jean Starcky, F-68057 Mulhouse cedex, France Received 19 January 2004; revised 22 June 2004; accepted 24 June 2004 Available online 8 August 2004

Abstract A spark ignition engine was used to study the impact of fuel composition and of the air/fuel equivalence ratio on exhaust emissions of specic hydrocarbons. The fuel blends used contained eight main hydrocarbons and four oxygenated compounds. The fuel components that produce each exhaust pollutant are identied. The emissions of all HC generally decrease with the addition of oxygenated compounds, except sometimes in the case of methane, ethane and cyclohexane. Under rich conditions, the relative increase of exhaust methane and benzene is more important than the other saturated HC. Some HC are correlated with the physical properties of the fuel and other exhaust pollutants. q 2004 Elsevier Ltd. All rights reserved.
Keywords: Exhaust emissions; Internal combustion engines; Specic hydrocarbons

1. Introduction Correlations between fuel composition and exhaust emissions from spark ignition (SI) engines have been extensively researched for regulated pollutants ([14] and many others). However, exhaust hydrocarbons is a sum of several species, and the emissions of individual hydrocarbons have not been thoroughly investigated yet. Many authors look for the correlations between families of fuel components (parafns, olens, aromatics,.) and exhaust pollutants [5,6], and main attention is given to the two toxic hydrocarbons, benzene and 1,3 butadiene [2,6]. Even if in some cases the correlations between some fuel components and some pollutants are studied [1,7,8,9,10], the detailed correlations between each fuel component and each exhaust individual hydrocarbon are not presented yet. Moreover, modern SI engines are not working only under stoichiometry but also under lean
e * Corresponding author. Address: Renault-CTLL26 0 60, 1, Alle Cornuel, Fr-91510 Lardy, France. Tel.: C331-6927-8477; fax: C3316927-8292. E-mail address: efthimios.zervas@renault.com (E. Zervas). 0016-2361/$ - see front matter q 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2004.06.029

and rich conditions, as for example in the case of cold start or full load. Exhaust hydrocarbons increase at rich conditions due to oxygen lack, but the detailed inuence of air/fuel equivalence ratio (l) on the emission of each individual hydrocarbon is not very well established. In three previous works, we presented the inuence of fuel and of l on the emission of organic acids [11], alcohols and carbonyl compounds [12], and regulated pollutants (CO, total HC and NOx, 13) of a SI engine. Continuing this work, this paper is the rst of two ones presenting the inuence of fuel on the emission of individual hydrocarbons from a SI engine, focusing on the experimental ndings. The second article [14] presents the formation pathways of these pollutants and the modelling of combustion processes. Specic fuel blends, containing hydrocarbons and oxygenated compounds, and a commercial fuel, are used for this study. As lean and rich conditions are currently in use in commercial SI engines (full load, cold start,.), the inuence of the air/ fuel equivalence ratio (l) is also studied. The correlations between the exhaust individual hydrocarbons and the physical parameters of the fuel used, and also with the other exhaust compounds are researched.

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2. Experimental section
5.6 5.6 5.6 5.6 5.6 5.6 5.6 5.6 0 0 0 20 3.60 35.2 93.1

A Cooperative Fuel Research Committee (CFR) spark ignition engine (displacement: 6.11 !10K4 m3, bore: 0.08255 m and stroke: 0.1143 m) was used for these tests. This engine is a small monocylinder engine used for octane number determination. The l used was from 0.83 to 1.25 (calculated from the exhaust gas analysis), while all the other engine parameters were kept constant [11,15]. Modern engines emit lower concentrations of pollutants than the CFR engine, but this last one allows the determination of the most important correlations between fuel composition and emitted pollutants It is known that a catalytic converter has not the same oxidation efciency for each HC [16], and as the subject of this work was to nd out the above correlations, no catalytic converter was used. Two fuel matrixes were adopted in this study (Table 1): the rst one (synthetic fuels matrix) contains eight representative hydrocarbons (n-hexane, 1-hexene, cyclohexane, n-octane, isooctane (2,2,4-trimethylpentane), toluene, o-xylene, and ethylbenzene (ETB)), while the second one (oxygenated fuels matrix) contains also four oxygenated compounds (methanol, ethanol, 2-propanol, and MTBE). An experimental design, specially adapted for mixtures, was used to determine each component quantity in the blend of synthetic fuels [15]. To avoid a high dispersion in physical properties of the fuels used, an alkylate (containing basically isooctane, but also 1.5% of benzene) was used as the base fuel for these blends. The reference fuel (R) contained an equal content of each of the eight compounds, while the other fuels contain 42% of a major component. These matrixes allow the direct comparison of each fuel with the reference one; if the exhaust concentration of a pollutant is greater than that of the reference fuel, the major component of this fuel enhances the formation of this pollutant. The oxygenated matrix was obtained by the addition of 5 or 20% of one of the four oxygenated compounds to the fuel R. Two simple fuels were also used: iC8, which is pure isooctane and iC8T, which is a mixture of 80% of isooctane and 20% of toluene. These fuels allow the study of the addition of an aromatic component to an alkylate basis. Finally, a commercial gasoline was also tested. The name of each fuel was chosen to recall its major component. More details about these fuels may be found elsewhere [15]. Exhaust individual HC were analyzed on line by GC/FID. A standard solution containing 25 hydrocarbons (methane, ethane, ethylene, propane, propylene, acetylene, isobutane, 1-butene, cis-2-butene, isobutene, trans-2butene, butane, isopentane, pentane, 1,3 butadiene, cyclohexane, hexane, 1-hexene, benzene, isooctane, octane, toluene, ethylbenzene, o-xylene, isopropylbenzene) was used for the chromatograph calibration and for the identication of each hydrocarbon. This method allows a good separation of the C 1C 9 compounds with no

5.6 5.6 5.6 5.6 5.6 5.6 5.6 5.6 0 0 20 0 5.72 5.6 5.6 5.6 5.6 5.6 5.6 5.6 5.6 0 20 0 0 7.75 5.6 5.6 5.6 5.6 5.6 5.6 5.6 5.6 20 0 0 0 11.89 6.65 6.65 6.65 6.65 6.65 6.65 6.65 6.65 0 0 0 5 0.90 6.65 6.65 6.65 6.65 6.65 6.65 6.65 6.65 0 0 5 0 1.45 6.65 6.65 6.65 6.65 6.65 6.65 6.65 6.65 0 5 0 0 1.98 6.65 6.65 6.65 6.65 6.65 6.65 6.65 6.65 5 0 0 0 3.08 2 2 2 2 2 2 2 42 2 2 2 2 2 2 42 2 2 2 2 2 2 42 2 2 2 2 2 2 42 2 2 2 2 2 2 42 2 2 2 2 2 2 42 2 2 2 2 2 2 42 2 2 2 2 2 2 42 2 2 2 2 2 2 2 7 7 7 7 7 7 7 7

P20

M20

MTBE5

Oxygenated fuels

P5

E5

M5

ETB

Xylene

Toluene

Table 1 Chemical analysis and octane number of the synthetic fuels used (% vol. contents)

Isooctane

Octane

Cyclohexane

Hexene

Synthetic fuels

Hexane

Hexane 1-Hexene Cyclohexane n-Octane Isooctane Toluene o-Xylene ETB Methanol Ethanol 2-Propanol MTBE Oxygen (% weight) Alkylate RON

50

44 63.7

44 83.7

44 88.7

44 43.6

44 93.8

44 101.3

44 96.6

44 100

44 85.2

41.8 89.4

41.8 90.4

41.8 87.5

41.8 86.8

35.2 98.6

35.2 97.4

E20

35.2 96.6

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interference. The detailed conditions are presented elsewhere [15]. At each l, ve identical points of the fuel R were used to evaluate the repeatability of the engine and the analytical method. The relative standard deviation (RSD) of most HC is under 12% for every fuel/equivalence ratio (the RSD exceeds 20% only in one case). All tests were doubled and average values were used.

3. Results and discussion 3.1. Precursors of each pollutant at stoichiometry Methane is clearly enhanced by o-xylene, isooctane and n-hexane (Fig. 1), while all other fuel components decrease it. iC8T emits less methane than iC8, indicating that toluene produces less methane than isooctane. The addition of

Fig. 1. Exhaust concentration of methane, ethane, ethylene, acetylene and propylene for the different fuels used at stoichiometry. Mean, mean concentrations; min., max.; minimum and maximum concentrations for a 95% condence region.

the four oxygenated compounds generally increases the emission of this pollutant (as already presented in the case of MTBE [17,18], while only a small difference is observed in the case of ethanol [19]). Two explanations can be given: oxygenated compounds produce more methane than the fuel components they replace, or, as they enhance the oxidation of heavier hydrocarbons, they facilitate the production of methane, which is near the end of the combustion process, just before the CO formation. No clear tendency can be observed between the high and low oxygenated content fuels. The commercial fuel emits about the same concentration as fuel R. Ethane is clearly enhanced by the three straight chain hydrocarbons used (hexane, 1-hexene, octane), but also by cyclohexane (Fig. 1). This pollutant is not detected in the exhaust gas of pure isooctane or isooctane/toluene. The low content oxygenated fuels generally increase its exhaust concentration, while the high-oxygenated content ones generally decrease it. This increase must be explained by the statement that ethane is near the end of the combustion process; as oxygenated compounds facilitate the oxidation of higher HC, the formation of ethane is enhanced. At high contents, oxygenated compounds must facilitate the oxidation to methane or CO, decreasing the ethane concentration. Ethanol blended fuels do not increase exhaust ethane, indicating that ethanol is rather oxidized to other products than to ethane. Commercial fuel emits less ethane than fuel R due to the lower content of straight chain hydrocarbons. Straight chain hydrocarbons (octane, hexane and 1-hexene) are the fuel compounds enhancing the most the formation of ethylene (Fig. 1, [1,9]), due to the C2 radicals formed from b-scissions. Cyclohexane and isooctane also enhance its formation [20]. The addition of toluene to pure isooctane decreases the concentration of ethylene, but less than 20%, indicating that it enhances slightly the formation of this pollutant [20]. It must be noticed that aromatics enhance more the formation or ethylene than this of ethane. The addition of methanol, ethanol and MTBE decreases the concentration of ethylene [17,19], but this of 2-propanol increases it. Ethanol does not enhance the exhaust concentration of this pollutant: E5 fuel decreases ethylene concentration [18] by 3%, while the E20 one by 32% with regard to fuel R. Commercial fuel produces more ethylene than fuel R, due to a balance between straight chain and aromatic hydrocarbons between the two fuels. Exhaust acetylene comes from almost all fuel components or from a component of the alkylate (like benzene), as all fuels emit comparable concentrations (4060 ppmv, Fig. 1). Toluene produces less acetylene than alkanes or alkenes, and its addition to pure isooctane decreases its exhaust concentration. Literature presents that this pollutant is produced from fuel aromatics [20]. Straight chain hydrocarbons produce more acetylene than other fuel compounds due to b-scissions. The addition of oxygenated compounds decreases the exhaust concentration of this

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pollutant [17]: from 5.5 to 12.5% in the case of low oxygenated fuels and from 8 to 45% in the case of the high content ones. These decreases are generally more important than the content of the oxygenated compound, indicating that the addition of an oxygenated compound produces less acetylene, not only because of the fuel dilution, but also because of its contribution to the HC oxidation. The commercial fuel produces slightly more acetylene than fuel R. Propane and butane exhaust concentration is very low. These results are very scattered and not presented here. Propylene is mainly enhanced by fuel isooctane [1,20], 1-hexene, octane and hexane ([9], Fig. 1). Aromatics produce less propylene than alkanes or alkenes [1,9], and the addition of toluene to isooctane decreases propylene exhaust concentration. The addition of 2-propanol increases the exhaust concentration of propylene: P5 fuel increases it by 13% while the P20 one by 20%. For every l used, exhaust propylene is linear with the 2-propanol content in the fuel. The other three oxygenated compounds decrease exhaust propylene by 19% for the low oxygenated content fuels, and 142% for the high content ones [17]. Commercial fuel produces about the same concentration as fuel R. Exhaust isobutane is clearly enhanced by fuel isooctane (Fig. 2). The addition of 20% of toluene to pure isooctane decreases the emissions of this pollutant by about 20%, indicating that toluene does not produce it at all. All other synthetic fuels produce about the same quantity of this pollutant due to the same content of isooctane. The addition of oxygenated compounds generally decreases its exhaust concentration: the four low oxygenated content fuels produce 63115% of the quantity emitted from fuel R (an increase is observed in the case of E5 and P5 fuels), while the four high content ones produce from 41 to 130%. Except this last value corresponding to the MTBE20 fuel, these last fuels emit less isobutane than the rst four ones. It is not clear if MTBE enhances this pollutant; the MTBE5 fuel decreases exhaust isobutane by 37%, while the MTBE20 one increases it by 30%. Commercial fuel produces less isobutane than fuel R because of its lower content of isooctane. 1-Butene is mainly enhanced by fuel straight chain HC (n-hexane [9], n-octane and 1-hexene) and isooctane (Fig. 2). The addition of 20% of toluene to pure isooctane decreases its exhaust emissions by about 20%. The addition of oxygenated compounds decreases exhaust 1-butene [17]; high oxygenated content fuels decrease it more than the low content ones (MTBE excepted). Commercial fuel produces less 1-butene than fuel R because it contains less of its precursors. As isobutane, exhaust isobutene is clearly enhanced by fuel isooctane [1,21], while all other synthetic fuels emit the same concentrations (Fig. 2). The addition of 20% of toluene to pure isooctane decreases the emissions of this pollutant by about 20%. The addition of methanol

Fig. 2. Exhaust concentration of isobutene, 1-butene, isobutene, cis-2butene and trans-2-butene for the different fuels used at stoichiometry. Mean: mean concentrations, min., max.: minimum and maximum concentrations for a 95% condence region.

and ethanol decreases its emissions: the rst decreases it by about 20% while the second one by 143%. 2-Propanol blended fuels produce about the same quantity as fuel R, while these of MTBE increase the emission of isobutene [17,22], indicating that this fuel component participates to its formation. Commercial fuel produces less isobutene than fuel R because of its lower content of isooctane. Cis and trans-2-butene are found in less than 1 ppmv in stoichiometry; no clear inuence can be established between fuel composition and their exhaust concentration (Fig. 2). The only fuel component that seems to clearly enhance both pollutants is o-xylene; they are not formed from pure isooctane and toluene/isooctane. The addition of methanol, ethanol and MTBE [17] decreases their exhaust concentration by 143%, while this of 2-propanol does not signicantly change them. Commercial fuel produces about the same quantity of cis-2-butene as fuel R, but almost the double of the trans isomer.

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2305

Fig. 3. Exhaust concentration of 1,3 butadiene, pentane, isopentane, hexane and 1-hexene for the different fuels used at stoichiometry. Mean, mean concentrations; min., max., minimum and maximum concentrations for a 95% condence region.

Butadiene is mainly enhanced by fuel cyclohexane [1,9] and 1-hexene (Fig. 3). Other fuel compounds must also participate to its formation: pure isooctane [1] and toluene/ isooctane produce low concentrations of this pollutant and o-xylene slightly enhances it. Literature presents that 1,3 butadiene is also formed from n-heptane [23] and n-octane [1]. Generally, the addition of 5% of an oxygenated compound decreases its concentration by 125%, this of 20% by 543% [19], while this of MTBE increases it [17]. Commercial fuel produces about the same exhaust concentration as fuel R. All synthetic fuels tested produce about the same quantity of n-pentane (Fig. 3). As alkylate contains 0.2% of pentane, it seems that this is the only source of this pollutant. Leppard [24] presents that exhaust parafns are linear with their fuel content. Pure isooctane does not produce this pollutant, indicating that the extraction of the three methyls must be very difcult in this case. iC8T fuel also does not produce this pollutant, indicating that

toluene cannot give C5 products after a ring opening. The addition of oxygenated compounds decreases the exhaust emission of n-pentane by 2040% in the case of the low content oxygenated fuels, and more, 2960%, in the case of the high content xygenated ones. Commercial fuel produces less pentane than fuel R due to its lower pentane content. Isopentane is mainly enhanced by isooctane (Fig. 3). Fuel iC8T produces about the 80% of the fuel iC8, indicating that toluene does not produce this pollutant. All other synthetic fuels produce less isopentane than fuel R because of their lower content of isooctane. All these fuels produce about the same quantity of this pollutant due to the same content of isooctane and isopentane in the alkylate. The addition of oxygenated compounds decreases the exhaust emission of this pollutant by 1937% in the case of the low content oxygenated fuels, and more, 2045% in the case of the high content ones. The exhaust concentration of isopentane is comparable in both cases of commercial and R fuels, due to their comparable content of isopentane. Exhaust hexane is enhanced only by fuel hexane ([24], Fig. 3). Octane does not enhance the production of this pollutant, meaning that this latter is not produced by this fuel component after a b-scission. Pure isooctane or isooctane/toluene do not produce this pollutant at all. All other fuels produce lower quantity of this pollutant than fuel R due to lower hexane content. At stoichiometry, the addition of oxygenated compounds decreases the exhaust concentration of this pollutant (as presented in the case of the MTBE or ethanol addition, [18,19]) by 2344% for the low oxygenated content fuels and 4680% for the high content ones. Exhaust 1-hexene is enhanced by fuel 1-hexene and cyclohexane and slightly by n-octane (Fig. 3). As fuel hexane does not enhance its production, this pollutant is not produced from n-hexane after an H extraction. Pure isooctane or isooctane/toluene do not produce this pollutant at all. All other fuels, including the commercial one, produce less hexane than fuel R due to lower contents of its precursors. The addition of 5% of oxygenated compounds decreases its exhaust concentration from 11 to 65%, while the addition of 20% decreases it more: from 43 to 80%. Fig. 4 shows that exhaust cyclohexane is principally a product of unburned fuel, but aromatics also enhance its formation. iC8T fuel produces some cyclohexane comparing to pure isooctane that does not produce it at all, conrming the previous remark. As cyclohexane slightly enhances the formation of benzene [7,15], the inverse reaction must also be possible. All other fuels produce less cyclohexane than fuel R. Commercial fuel produces slightly less exhaust cyclohexane than fuel R; the cyclohexane content of the rst fuel is lower than this of the latter one, but its higher content of aromatics equilibrates partially this difference. The addition of the rst three oxygenated compounds enhances the formation of cyclohexane (except for E20 fuel), especially in low contents. This addition enhances the oxidation of fuel aromatics increasing

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oxygenated content fuels and 3766% in the case of the high content ones. Exhaust benzene is clearly produced from fuel aromatics (Fig. 4, [1,6,7,15,22]). Pure isooctane does not produce detectable concentrations of benzene, while it produces low amounts of benzeldehyde [7,12], meaning that this pollutant is produced from isooctane [7] in very low, but not detectable with our experimental facilities, concentration. The addition of toluene to isooctane produces signicant amounts of benzene. Cyclohexane enhances also the formation of this pollutant [1,8,15], but less than aromatics do. Commercial fuel produces more benzene than fuel R due to its higher content of aromatics. The addition of oxygenated compounds decreases the concentration of benzene ([18,19] in the case of ethanol and [17,18,19,25] in this of MTBE) by 529% in the case of the low content oxygenated fuels and 1360% in the case of the high content ones. Exhaust toluene is enhanced by fuel aromatics (Fig. 4, [15,21]), while the non-aromatic fuel components do not produce it. The addition of toluene to isooctane produces signicant exhaust concentrations of this pollutant

Fig. 4. Exhaust concentration of cyclohexane, octane, isooctane, benzene and toluene for the different fuels used at stoichiometry. Mean, mean concentrations; min., max., minimum and maximum concentrations for a 95% condence region.

consecutively the exhaust concentration of cyclohexane. Contrary to the other three oxygenated compounds, MTBE decreases the exhaust concentration of cyclohexane. Fig. 4 presents that exhaust octane is enhanced only by fuel octane [24]. Pure isooctane or isooctane/toluene do not produce this pollutant at all, and all other fuels produce less exhaust octane than fuel R due to lower octane content. The addition of oxygenated compounds decreases its exhaust concentration by 1045% in the case of low oxygenated content fuels and 4055% in the case of the high content ones. Exhaust isooctane is enhanced only by fuel isooctane ([24], Fig. 4). The addition of 20% of toluene to pure isooctane decreases the exhaust concentration of this pollutant by about 20%. All other fuels produce less isooctane than fuel R due to lower isooctane content. The addition of oxygenated compounds decreases exhaust concentration of isooctane by 1925% in the case of the low

Fig. 5. Exhaust concentration of o-xylene, ethylbenzene and isopropylbenzene for the different fuels used at stoichiometry. Mean, mean concentrations; min., max., minimum and maximum concentrations for a 95% condence region.

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comparing to pure isooctane that does not produce it at all. Fuel ETB enhances exhaust toluene even if its exhaust concentration is lower than the Rone. The explanation is that fuel R contains 7% of toluene that gives more exhaust concentration of ETB than the 42% of ETB of the corresponding fuel. The models presented in a following chapter conrm this statement. The addition of oxygenated compounds decreases exhaust toluene ([19] in the case of ethanol and [17,18] in this of MTBE), by 1139% in the case of the low oxygenated content fuels and more, 2462%, in the case of the high content ones. Commercial fuel produces more toluene than fuel R due to its higher aromatic content. Exhaust ETB is mainly produced from fuel ETB (Fig. 5, [15]). The addition of toluene to isooctane produces low quantities of this pollutant comparing to pure isooctane that produces no ETB at all, indicating that toluene enhances the formation of this pollutant [26]. The addition of oxygenated compounds to fuel R decreases exhaust ETB ([17] for the addition of MTBE) by 1335% in the case of low oxygenated content fuels, and more, 2171% in the case of the high content ones. Commercial fuel produces more ETB than fuel R due to its higher content of ETB. Exhaust o-xylene is only a product of the unburned fuel (Fig. 5 and [15]). No other compounds enhance the formation of this pollutant, even not toluene (toluene and iC8T fuels). All other synthetic fuels produce less than fuel R, while commercial fuel produces more, due to its higher
Table 2 Com, leana Com, richa

o-xylene content. The addition of oxygenated compounds to fuel R decreases exhaust o-xylene ([17] in the case of MTBE) by 1936% in the case of low oxygenated content fuels, and more, by 2071% in the case of the high content ones. Isopropylbenzene (iPB) comes mainly from fuel ETB (Fig. 5 and [15]), but other aromatics must produce minor quantities of this pollutant: fuel o-xylene produces about the same quantities than fuel R, while iC8T fuel produces detectable concentrations of this pollutant comparing to pure isooctane, where no exhaust isopropylbenzene is found. All other synthetic fuels produce less iPB than fuel R. Commercial fuel produces more isopropylbenzene than this latter fuel due to higher content of ETB. The addition of oxygenates compounds decreases exhaust iPB by 1835% in the case of low oxygenated content fuels and 2570% in the case of the high content ones.

4. Lambda inuence Exhaust hydrocarbons increase at rich conditions due to the lack of oxygen, but this change is not the same for all exhaust HC. Table 2 presents the relative increase or decrease of the exhaust concentration of each pollutant under rich or lean conditions comparing to stoichiometry. For each pollutant, these changes are not the same for all fuels tested (Fig. 6).
Fuelb Fuelb

Max decrease under lean conditionsb 18.0 37.8 4.6 34.3 4.4 18.0 16.0 4.0 4.4 6.3 7.5 5.7 9.3 7.8 6.1 12.0 10.0 2.2 9.5 14.4 11.9 9.3 4.1 7.0

Max increase under rich conditionsb 5.8 6.7 2.8 2.6 3.0 2.4 1.5 2.4 4.4 2.3 1.5 3.1 1.7c 3.5 3.0 3.0 3.7 4.9 7.0 4.7 3.3 3.3 1.8 3.2

Methane Ethane Ethylene Acetylene Propylene Isobutane 1-Butene Isobutene Cis-2-butene Trans-2-butene 1,3-butadiene Pentane Isopentane Hexane 1-Hexene Cyclohexane Octane Isooctane Benzene Toluene ETB o-Xylene IPB Total HC
a b c

9.612.4 2.019.3 2.32.9 2.94.4 2.62.8 9.815.3 2.72.9 2.43.1 2.36.3 4.06.3 2.93.2 2.83.3 3.76.5 3.36.6 1.52.6 5.010.2 2.22.4 2.73.0 3.94.8 2.52.9 2.94.6 2.67.0 2.84.0 2.94.0

4.55.8 1.31.5 2.12.3 1.52.3 1.92.1 0.70.8 1.11.4c 1.41.5 1.51.7 1.31.4 1.11.4c 2.73.1 1.3c 1.72.0 2.12.3 1.92.4 2.83.2 2.52.8 3.14.5 2.12.6 1.41.6 1.61.7 1.01.1 2.12.5

o-xylene MTBE5 IC8T Toluene MTBE5 IP20 M5 M5 o-Xylene COM M5 Cyclohexane Isooctane E5 R IP5 IP5 M20 o-Xylene o-Xylene MTBE5 MTBE5 COM o-Xylene

COM ETB M5 M5 M5 IP5 iC8 MTBE5 Cyclohexane M5 C6 COM M5 M5 MTBE5 E20 E5 MTBE20 ETB ETB M5 Toluene ETB M5

Increase under rich conditions and decrease under lean ones of the HC exhaust concentrations for the commercial fuel (times, relative to stoichiometry). Maximum decrease (at lZ1.25) and maximum increase (at lZ0.83) under rich and lean conditions (times) and the corresponding fuel. lZ0.91.

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E. Zervas et al. / Fuel 83 (2004) 23012311

a maximum concentration at stoichiometry or lZ0.91, depending on the fuel. The increase of benzene concentration under rich conditions is higher than this of the total HC and of the other aromatics, because under these conditions all other aromatics are cracking to it. At lean conditions, benzene concentration corresponds only to 20% of this of stoichiometry and less than this of other aromatics, because it is oxidized more easily than other aromatics and is less produced from them. The increase of toluene is lower than this of benzene but higher than this of other aromatics, because, under rich conditions, a part of toluene is dealkylated to benzene and a part of heavier aromatics is dealkylated to toluene. The increase of heavier aromatics is less important than this of benzene and toluene and also of total HC, because under rich conditions, these compounds give lighter aromatics. Their decrease under lean conditions is as much, or a little more than this of total HC. For each pollutant, the maximum decrease or increase is observed in the case of a specic fuel, which mainly contains an important precursor only in the case of isopentane. It is quite strange that the above fuels are not directly linked with the formation of each pollutant. These increases or decreases can be many times more important than those observed in the case of the commercial fuel.

5. Percentage over all exhaust HC The percentage of each specic HC over total exhaust HC is presented in Table 3. Literature presents some percentages [17,22,24]; the results are not always the same because the fuels used do not have the same composition, but the differences are generally not very important. At stoichiometry, exhaust methane corresponds to 5% (in ppmC) of the total exhaust HC of the commercial fuel, but this value can reach 17% in the case of the iC8 one. This percentage increases at rich conditions to reach 11% at lZ0.83, while it falls to less than 2.0% at lean ones. These values indicate that methane is favourably formed at rich conditions [7] because of the heavier HC cracking. The same trends are observed in the case of a compression ignition engine operating under lean conditions [27]. At stoichiometry, the more important unsaturated exhaust HC of the commercial fuel is ethylene (19%, Table 3) followed by acetylene (11.4%), propylene (5.4%) and 1,3 butadiene (1.6%), while the others represent less than 1%. The maximum value of ethylene, acetylene and 1-butene exhaust concentration is observed in the case of Octane fuel, due to b-scissions for the two rst pollutants and to breaking of octane into two parts for the last one. This maximum value can reach 23.1, 16.6, and 1.6% respectively. Under lean conditions, the percentage of ethylene, propylene, 1-butene, isobutene, and 1,3 butadiene increases, indicating that these pollutants are favourably formed under

Fig. 6. Exhaust concentration of ethane, isobutane, 1,3 butadiene and toluene, as a function of lambda for some representative fuels.

Under rich conditions, the relative increase of exhaust methane is more important than that of the other saturated HC, indicating that its formation is enhanced more than that of the other HC. Its decrease under lean conditions is also more important, indicating that this pollutant is favourably not formed or that its precursors are favourably oxidized under these conditions. In the case of methane, all fuels tested present almost the same results with l. Ethylenes increase is more important under rich conditions than this of the other C2 HC, because it can be easier formed by b-scissions than ethane or acetylene. The relative increase of ethane, C4 unsaturated hydrocarbons, isopentane, hexane, cyclohexane, octane and isooctane is less important than this of the total HC. Five HC present a specic correlation with l: propylene, 1-butene and butadiene isobutane and isopentane show

E. Zervas et al. / Fuel 83 (2004) 23012311 Table 3 Percentage of each exhaust HC over all exhaust HC (in %ppmC) Pollutant Methane Ethane Ethylene Acetylene Propylene Isobutane 1-Butene Isobutene Cis-2-Butene trans-2-Butene 1,3 Butadiene Pentane Isopentane Hexane 1-Hexene Cyclohexane Octane Isooctane Benzene Toluene ETB o-Xylene IPB
a b

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COM, lZ1.0 (%) 5 0.5 19.2 11.4 5.4 0.12 0.4 0.28 0.15 0.31 1.6 0.18 0.92 0.48 0.62 0.36 0.37 0.74 5.8 14.6 8.1 8.6 2.8

lZ1.0, max (%) 17 13.6 23.1 16.6 11.7 3.4 1.6 16.8a 0.25 0.321 5.9 0.49 3.2 8.7 6.5 8.5 8.7 22.9 9.4 33.5 19.2 28.2 10.7

Fuel iC8 Octane Octane Octane iC8 iC8 Octane iC8 Cyclohexane Cyclohexane Cyclohexane R iC8 Hexane Hexene Cyclohexane Octane iC8 Toluene Toluene ETB o-Xylene ETB

Com, lZ1.25 (%) 1.9 0.10.7 26.8 10.4 7.6 0.03 0.54 0.37 0.10 0.19 2.0 0.22 0.56 0.40 0.94 0.14 0.61 1.0 4.8 20.8 6.9 4.9 2.7

Com, lZ0.83 (%) 11.1 0.4 18.5 10.6 4.7 0.04 0.18 0.18 0.23 0.19 1.1 0.22 0.38 0.29 4 0.35 0.49 0.87 10.8 15.9 5.4 5.9 1.3

Other refs. [22,17,24] [22,17] [22,17,24] [22,17,24] [22,17,24] [22,17] [17] [17,24] [17] [17] [22,17,24] [17,24] [17,24] [17,24] [17] [22] [17,24] [24]b [22,17,24] [22,17,24] [17] [17]

% 34, 3.59, 1011 11.3 812, 78, 10 5.58 3.84.5, 3.33. 5, 5.4 0.51.0, 0.30.5 0.40.5 1.42.6, 1.8 0.150.40 0.270.36 0.5, 0.35, 1.11.3 2.5, 2.12.4 2.5,78 1, 1.21.3 0.10.16 1.0 1, 0.120.16 1.2 7.5, 3, 5.25.6 1517, 12, 7.28.8 1.11.4 1.72.4

In the case of pure isooctane Shore [10] and Kaiser [28] present 2446%. This percentage is 6.8% in the case of the MTBE20 fuel; Leppard [24] presents 5.3% in the case of a MTBE15 one.

these conditions, or that they are oxidized with more difculty than the other HC. Some similar trends are observed in the case of a compression ignition engine operating under lean conditions [27], where the percentage of ethylene, propylene and 1,3 butadiene also increases when l decreases. Ethylene remains the most important exhaust HC in this case [27]. Benzene represents 5.8% in the case of the commercial fuel, but this value reaches 9.4% in the case of the Toluene one. This percentage increases at rich conditions, due to the dealkylation of the other aromatics and can reach more than 10%. This percentage increases with lambda also in the case of the exhaust gas of a compression ignition engine [27]. Toluene is one of the major exhaust HC as it represents 14.6% of the total HC of the commercial fuel exhaust gas, while this percentage reaches 33.5% in the case of Toluene fuel. Contrary to benzene, this percentage decreases in the case of rich conditions, probably due to the dealkylation of toluene to benzene. ETB and o-xylene represent about 8% each and their maximum value corresponds to the respective fuels (19.2 and 28.2% respectively). The maximum values are observed in stoichiometric conditions. The other pollutants are minor exhaust pollutants, but they increase in the case of the fuel containing their major precursors, as in the case of ethane (0.5% in the case of

commercial fuel at stoichiometry, but 13.6% in the case of the octane one), isobutane, isobutene and isopentane (0.12, 0.28 and 0.92% respectively in the case of the commercial fuel, while they reach 3.4, 16.8 and 3.2% respectively in the case of the iC8 one). Hexane, 1-hexene, cyclohexane, octane and isooctane become important in the case of the respective fuels due to the unburned fuel (8.7, 6.5, 8.5, 8.7 and 22.9% respectively). Three C4 unsaturated HC: cis and trans-2-butene and 1,3 butadiene, reach their maximum percentage in the case of cyclohexane fuel (0.25, 0.3 and 5.9% respectively).

6. Inuence of physical properties For every l used, the correlations of the exhaust concentration of these pollutants with the physical properties of the fuel (H/C and O/C fuel ratio, RON and T90) are searched. Two good correlations (R2O0.8) are observed between the exhaust concentration of ethylene and acetylene and RON: these two concentrations decrease with octane number. Some other hydrocarbons present some correlations, but the R2 is always lower than 0.8. Methane increases with all these four parameters and pentane decreases with the rst three ones. The most of

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E. Zervas et al. / Fuel 83 (2004) 23012311

the unsaturated HC decrease with RON (except isobutene which increases) and O/C fuel ratio (except ethylene which is not correlated), and have no correlation with T90 (except ethylene, acetylene and propylene which decrease). The relation of the unsaturated HC with H/C ratio is more complex; some decrease (cis and trans-2-butene), while others increase (propylene, 1-butene, isobutene). Exhaust benzene increases with RON and T90 [6], and decreases with H/C and O/C fuel ratio. Exhaust ETB, o-xylene and iPB also increase with T90. The other specic hydrocarbons do not present correlations with the above fuel properties. Literature presents that total HC decrease with RON, H/C and O/C fuel ratio [1,3,13].

7. Correlation with other exhaust pollutants A correlation exists between the exhaust concentration of formic acid and this of all saturated HC (Fig. 7 presents the case of methane) and also ethylene, acetylene, propylene and benzene. This correlation indicates that the formation of methane and formic acid is competitive, following two parallel paths from a CH3 radical: the addition of an H in the case of methane or its further oxidation to formic acid. Methane does not have a good correlation with exhaust methanol, even if these two compounds are normally formed from a CH3 radical after the addition of an H or an OH, or formaldehyde, indicating that the formation paths of these compounds are more complex. Exhaust ethylene, acetylene and propylene are linear between them, indicating that these three pollutants are formed in parallel. Ye [30]

presents that exhaust 1,3 butadiene is linear with exhaust alkenes (especially propylene and isobutene), but using the same fuel on different vehicles. In our case, this last pollutant is not correlated with any other exhaust HC. Acroleine decreases linearly with propylene and benzene; methacroleine decreases linearly with cis-2-butene and trans-2-butene and not linearly with butadiene, 1-hexene, octane (Fig. 7) and aromatic HC. The above correlations indicate that the formation of these pollutants is competitive. McDonald [29] presents that the ratios between exhaust aromatics remain almost constant for different fuels, but we could not conrm this correlation. Other authors present some other correlations, but using the same fuel: a linear one between benzene and total exhaust HC during the different phases of the US FTP driving cycle [31], one between exhaust benzene and toluene, one between benzene and C2-benzenes, and one between toluene and C2-benzenes, during the European cycle [32]. No other correlation is found between the exhaust concentration of the above HC and other HC, oxygenated compounds (aldehydes, organic acids and alcohols), CO, NOx and total HC.

8. Conclusions This work allowed the determination of the main precursors of each exhaust specic hydrocarbon. At stoichiometry, exhaust methane is enhanced by o-xylene, isooctane and n-hexane, ethane is enhanced by the three straight chain hydrocarbons used (hexane, 1-hexene, octane) but also from cyclohexane. Ethylene comes from fuel octane, hexane, 1-hexene, cyclohexane and isooctane, while acetylene comes from all fuels, indicating that it is mainly produced from a common component, as fuel benzene. Propylene mainly comes from fuel isooctane, 2-propanol, 1-hexene and octane. 1-Butene is formed from fuel octane, hexane, 1-hexene and isooctane. Exhaust isobutene comes from fuel MTBE and isooctane. 1,3 Butadiene comes mainly from fuel cyclohexane, 1-hexene and o-xylene. Exhaust 1-hexene comes from fuel 1-hexene, but also from fuel cyclohexane and 1-octane. Exhaust benzene comes from fuel benzene, but also from ETB, toluene, o-xylene and cyclohexane, while toluene comes from fuel toluene, o-xylene and ETB. Exhaust isobutane, cyclohexane and isopropylbenzene come mainly respectively from fuel isooctane, cyclohexane and ETB. n-Pentane, isopentane, hexane, octane, isooctane, o-xylene and ETB come only or mainly from the respective fuel components. The addition of oxygenated compounds generally decreases the exhaust concentration of specic hydrocarbons, but with some exceptions: the emission of methane, ethane and cyclohexane increases in the case of the addition of the four oxygenated compounds studied here, the emission of ethylene and propylene from the addition of

Fig. 7. Correlation between the exhaust concentration of examined HC and this of the other exhaust pollutants, for all fuel and l used. Lower curve, methane versus formic acid; Upper curve, methacroleine versus octane.

E. Zervas et al. / Fuel 83 (2004) 23012311

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2-propanol, and this of isobutene, 1,3 butadiene and probably isobutane from the addition of MTBE. Under rich conditions, the percentage of exhaust methane, ethylene, propylene, 1-butene, isobutene, 1,3 butadiene, benzene and toluene increases, indicating that their formation is enhanced more under these conditions. Ethylene and acetylene decrease with RON. Other specic HC present some correlations with the physical properties of the fuel, but not very good ones (r2!0.8). At stoichiometry, exhaust methane corresponds to 5% (in ppmC) of the total exhaust HC of the commercial fuel. The more important unsaturated exhaust HC of the commercial fuel is ethylene (19%) followed by acetylene (11.4%), propylene (5.4%) and 1,3 butadiene (1.6%). Benzene represents 5.8%, but this percentage increases at rich conditions and can reach more than 10%, due to the dealkylation of the other aromatics. Toluene is one of the major exhaust HC as it represents 14.6%. ETB and o-xylene represent about 8% each. All these percentages increase in the case of fuels containing higher amount of precursors. Three oxygenated compounds are related with the exhaust concentration of some specic HC. Formic acid is correlated with the concentration of all parafns, ethylene, acetylene, propylene and benzene; methacroleine with the concentration of cis and trans-2-butene, 1,3 butadiene, 1hexene, cyclohexane, n-octane and aromatics; acroleine with propylene, and benzene. These correlations indicate that the formation of these compounds is competitive. Exhaust ethylene, acetylene and propylene are linear between them, indicating that these three pollutants are formed in parallel.

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