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BTEX emissions from flex fuel motorcycles
Atmospheric Pollution Research xxx (2017) 1e10
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BTEX emissions from flex fuel motorcycles ria C. Macedo a, Luiz C. Daemme a, Renato Penteado a, Heloísa N. da Motta a, Vale ^a b, * Sergio M. Corre a b
LACTEC e Technology Institute for Development, 80210-170 Curitiba, PR, Brazil Faculty of Technology, Rio de Janeiro State University, 27537-000 Resende, RJ, Brazil
a r t i c l e i n f o
a b s t r a c t
Article history: Received 1 March 2017 Received in revised form 23 May 2017 Accepted 25 May 2017 Available online xxx
Comparative studies were developed with regard to the criteria emissions of THC - total hydrocarbons, CO - carbon monoxide and NOx - nitrogen oxides, and BTEX (benzene, toluene, ethyl benzene and xylenes). Three four-stroke motorcycles were fuelled with E22 fuel (gasoline with 22% of ethanol). One flex fuel motorcycle was also fuelled with E100, 100% Hydrated Reference Ethanol, and with E61 (61% of ethanol). Criteria emissions were quantified using traditional measurement techniques based on the European Directive 97/24/EC (EURO protocol). To determine the BTEX emissions, gas chromatography coupled with mass spectrometry was employed. All motorcycles were equipped with a catalyst (TWC) used to reduce the amount of toxic emissions in the exhaust gases. To evaluate the performance of the catalyst, one motorcycle was tested with and without the device. One motorcycle was tested according to two different test protocols, namely, the ECE/TRANS/180 WMTC, also known as the Worldwide Motorcycle Test Cycle, and the EURO protocol. The main results were that toluene emissions were more prevalent than other aromatics. The tests with and without the catalyst showed that after the catalyst was employed the conversion efficiencies for benzene, toluene, ethyl benzene and xylene were 52.3%, 84.0%, 85.0%, and 86.0%, respectively. The results regarding the flex fuel motorcycle show that BTEX emissions decrease with an increase of ethanol in the mixture. Comparing the EURO and WMTC protocols, it was observed that the WMTC protocol generates lower emissions compared to the EURO protocol; however, NOx showed the opposite trend of BTEX. © 2017 Turkish National Committee for Air Pollution Research and Control. Production and hosting by Elsevier B.V. All rights reserved.
Keywords: BTEX Emission Ethanol Motorcycles Hydrocarbons
1. Introduction In big cities, vehicular emissions reduce air quality, as they contain volatile organic compounds (VOCs), carbon monoxide (CO), nitrogen oxides (NOx), sulfur oxides (SOx), and particulate matter (MP), among others (CETESB, 2013). Among the VOCs, the BTEX, formed by benzene, toluene, ethyl benzene, o-xylene, m-xylene and p-xylene compounds, stands out. Automotive gasoline consists of a mixture of hydrocarbons derived from petroleum, and Brazilian type C gasoline is allowed a maximum of 1% (v/v) benzene and 35% (v/v) BTEX (Silva et al., 2009; ANP, 2013). From an environmental perspective, BTEX plays a prominent
* Corresponding author. ^a). E-mail address: [email protected] (S.M. Corre Peer review under responsibility of Turkish National Committee for Air Pollution Research and Control.
role as a primary pollutant, with fossil fuels serving as the main source of emissions from light, gasoline-powered vehicles. They are considered as some of the main ozone precursors, in addition to causing serious damage to health (Marc et al., 2015). Motorcycles are a rising form of transportation in large cities across the world, especially in emerging countries such as China, India and Brazil. The intensive use of motorcycles is explained by their high mobility in increasingly congested cities that lack affordable public transport, as a motorcycle with a less powerful engine (150 cc) usually costs 20e25% that of a small car and is also associated with low fuel consumption, ease of parking and low maintenance cost. These advantages outweigh the inherent dangers of this form of transportation and other disadvantages such as interfering rain and the high cost of insurance (Garcia et al., 2013). Brazil recorded 428,970 traffic accidents in 2008; the number of vehicles involved was 597,786, of which 246,712 were cars and 200,449 were motorcycles. The use of ethanol has many advantages such as a renewable
http://dx.doi.org/10.1016/j.apr.2017.05.006 1309-1042/© 2017 Turkish National Committee for Air Pollution Research and Control. Production and hosting by Elsevier B.V. All rights reserved.
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fuel, lower production of carbon monoxide, hydrocarbons and particulates, and higher octane numbers compared to gasoline, which leads to an increase in the engine compression ratio, promoting greater efficiency and engine power. Disadvantages stand out because of its lower caloric value and the increased emissions of carbonyl compounds, especially aldehydes (Daemme et al., 2016a,b; Anderson, 2015; Bayraktar, 2005). Another topic discussed in the literature deals with the criteria and non-criteria emissions according to the ethanol content and, more recently, the concern about the cold phase emissions (Clairotte et al., 2013; Suarez-Bertoa et al., 2015). In the initial minutes, the emissions of most pollutants are greater because the beginning of engine operation is associated with less efficient burning (Iodice and Senatore, 2014; Yao et al., 2017) and the catalyst is cold and therefore less effective. In this period, it is also common to observe significant emissions of ethanol and unconverted hydrocarbons, in addition to criteria pollutants (Hsieh et al., 2002). Overall, this scenario commonly occurs in short paths and becomes worrisome in the context of the medium and large cities. Brazil has a unique scenario for the intensive use of ethanol by automobiles, and flex fuel motorcycles have recently been launched on the national market, but their emissions require further study. In this work, the BTEX emissions of three 4-stroke motorcycles fuelled with blends of gasoline and ethanol were evaluated, as no 2stroke motorcycles are used in Brazil for transportation. The emissions of one of the motorcycles were compared with the EURO and WMTC test protocols, and those of another motorcycle were compared with and without a catalytic converter. The criteria pollutants were also monitored for data comparison.
2. Materials and methods The tests were performed in a laboratory of vehicular emissions that performs motorcycle homologation according to directive 97/ 24/EC. The three motorcycles were supplied with a standard fuel mixture called E22 (22% anhydrous ethanol in gasoline), and one of the motorcycles used different blends of ethanol in the gasoline. Details of the fuels used here are described in Table 1. Emission measurements were always performed in triplicate, and BTEX, THC, CO and NOx were also measured. The BTEX chemical analyses of the liquid fuel were performed by gas chromatography on a Varian CP 3800, using a Rtx-1 PONA
column (100 m, 0.25 mm, 0.50 mm). The fuel volume was 0.5 mL and was injected without dilution at 250 C and split at 1:200. The column temperature programming began at 35 C for 15 min, with a heating rate of 1 C/min up to 60 C, where the temperature remained for 20 min, followed by heating at 2 C/min to 200 C, where it remained for 10 min. A flame ionization detector was used at 300 C, and Helium 5.0 used as carrier gas at a constant flow of 22.4 cm s1. Quantification was performed by external standardization using a Supelco BTEX mix standard (47993) with a 5-point calibration curve and dilutions of 0.710e4.259 mg L1, with a coefficient of determination (R2) better than 0.99. Details of the three motorcycle configurations used are described in Table 2. These motorcycles had the highest percentages of sales of the Brazilian fleet in the period of 2009e2014. They will be designated as M1G (used with the original catalyst) and the same motorcycle without the catalyst (M1Gwc), M2G (used with the EURO and WMTC protocol) and M3F (flex fuel engine with different ethanol blends) (see Table 3). The tests were conducted using the two standard protocols for motorcycles in Brazil, the European Directive 97/24/EC and ECE/ TRANS/180. The European Directive 97/24/EC was used for the three motorcycles, and ECE/TRANS/180 was only employed to test €llner of the M2G motorcycle to compare the emissions. An AVL Zo AN 40770 dynamometer was used (648 mm and 100 kW). The temperature of the test room was between 20 and 30 C, with an average of 24 C. The temperature of the lubricating oil was maintained at room temperature ±2 C before beginning the test. The EURO protocol (European Directive 97/24/EC) simulates runway loads for THC, CO and NOx emissions measurements. A preestablished route, divided into one or two phases, was followed. Motorcycles up to 150 cm3 had only one phase (urban protocol), and those more than 150 cm3 had a second phase referred to as extra urban, with speeds reaching 120 km h1. The distance travelled in each phase was approximately 6.0 km as shown in Figs. 1 and 2 (Daemme et al., 2014). Following changes in European legislation, a new protocol for testing motorcycles in Brazil, considered more representative of actual use conditions (CONAMA Resolution 432/11), was defined in 2014, a transient driving protocol named WMTC - “Worldwide Motorcycle Test Cycle”. The main differences between the methodologies are the transient mode and the number of phases, which that can be one, two or even three phases, depending on the maximum speed of the motorcycle combined with the engine
Table 1 Fuels details. Parameter Total Sulfur Ethanol Specific gravity at 20 C Total aromatics Total C14 þ Total Iso e Paraffins Total Naphthenics Total Olefins Total Oxygenates Total Paraffinics Totals Unknowns Benzene Toluene p e Xylene m e Xylene o e Xylene Ethyl benzene Other aromatics
(mg kg1) (% vol.) (kg m3) % vol.
E22
E61
E100
10 23 742.7 19.338 0.003 29.488 4.076 5.301 22.774 15.280 3.741 0.154 13.661 0.304 0.595 0.389 0.200 4.035
9.6 62 776.1 10.412 0.003 13.778 2.561 2.721 60.912 7.248 2.367 0.075 7.051 0.009 0.296 0.181 0.104 2.696
1.1 N.D. 809.9 N.D. N.D. N.D. N.D. N.D. 100 N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D.
N.D.: not detected.
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Table 2 Details of the motorcycles used. Identification Emission regulation Engine displacement (cm3) Year
Injection fuel system Fuel
Engine cycle Power (cv) Inertia class (kg) Catalyst (TWC)
M1Gwc M1G M2G M3F
EFI EFI EFI EFI
4-stroke 4-stroke 4-stroke 4-stroke
Euro Euro Euro Euro
III III III III
124.9 124.9 291.6 149.2
2009 2009 2010 2011
Gasoline Gasoline Gasoline Flex fuel
9.1 9.1 26.5 14.3
180 180 230 200
No Yes Yes Yes
Table 3 Kinematic characteristics of the two driving cycles (Barlow et al., 2009). Parameters
Euro
WMTC
Phase 1
Phase 2
Phase 1
Phase 2
Phase 3
Total distance (km) Total time (s) Driving time (s) Average speed (km h1) Maximum speed (km h1) Average positive acceleration (m s2) Positive kinetic energy (m s2)
5.968 1170 900 18.4 50.00 0.348 3.812
6.955 400 365 62.6 120.00 0.266 2.427
4.065 600 506 24.4 59.99 0.447 0.398
9.111 600 558 54.7 94.91 0.429 0.380
15.736 600 586 94.4 125.31 0.236 0.224
Fig. 1. Speeds reached by the motorcycle for the WMTC protocol.
displacement. Each phase lasts 600 s, as show in Figs. 1 and 2 for WMTC and EURO protocols, respectively (Favre et al., 2009; Steven, 2002). The tests were performed according to the methodology defined by the EURO or WMTC protocol test standards. The resistive power applied to the motorcycle by the dynamometer during the developed course was determined by adding 75 kg to its mass, accounting for the standard weight of the pilot. The cooling of the motorcycle engine was executed by a fan positioned frontally to the vehicle with power proportional to the motorcycle speed, thus simulating the real conditions of operation. Throughout the test, exhaust emissions were directed to the constant volume sampler (CVS Horiba 7200S), where they were diluted with ambient air to avoid condensation and compound losses. Measurements of the criteria emissions were performed on-line on the diluted gas stored in 90 L bags, as well as for the dilution air of the test room. As shown in Fig. 3, the collection of non-criteria emissions was performed using an aldehyde sampler bench (tubes, pump and flow meter) that directs the samples to coconut shell cartridges
(CSC) using a line for collection of ambient air and another for the exhaust gases. The THC was determined by a flame ionization detector (FID) analyser (model FIA-720, 0e50 ppmC), CO and CO2 by nondispersive infrared (NDIR) analysers (model AIA-721A e 0e200 ppm and AIA-722 e 0-20% vol, respectively) and NOx by a chemiluminescence analyser (model CLA-720A, 0e50 ppm), all from the Horiba MEXA 7200 bench. All measurements were performed within the calibration range as all analyzers have a multi rage calibration. An active charcoal cartridge (Supelco ORBO 32 400/200 mg) was used at a flow rate of 1.0 L min1 throughout the protocol. One cartridge was used for each phase of the driving protocol, and another cartridge for collection of dilution air. To evaluate the sample recovery, 1.0 mL of a 100 ng mL1 solution of deuterated toluene was added to each cartridge after sample collection. Then, the contents of each cartridge were transferred to a 2 mL vial and added to this 1000 mL of dichloromethane at 20 C to prevent the volatilization of the lighter BTEX, since the extraction process is exothermic. The flasks were capped with septum caps,
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Fig. 2. Speeds reached by the motorcycle for the EURO protocol.
Fig. 3. Diagram of the tests for emission measurements from the motorcycle.
placed in an ultrasonic bath for 20 min, and then allowed to rest for ^a et al., 2012; Corre ^a and Arbilla, 2006, 2007; Garcia et al., 1 h (Corre 2013; Martins et al., 2007, 2016; Daemme et al., 2016a,b). The BTEX chemical analyses were performed by gas chromatography with mass spectrometry (GC-MS) on a Varian 450GC 220MS chromatograph using a VF-5MS column (30 m, 0.25 mm and 0.25 mm). Injections of 1.0 mL of sample were conducted at 200 C, with a split ratio of 1:4, using Helium 5.0 as carrier gas at 2.0 mL min1. The initial column temperature was 40 C, which was maintained for 3 min, followed by a heating rate of 15 C min1 up to 200 C, where it was held for 6 min. The temperatures of the ion trap, manifold and transfer line were 150 C, 40 C and 180 C, respectively. The MS detector monitored ions from 72 to 79, 89 to ^a et al., 2012; Corre ^a and 93, 101 to 107, and 119 to 121 (m/z) (Corre
Arbilla, 2006, 2007; Garcia et al., 2013; Martins et al., 2007, 2016; Daemme et al., 2016a,b). The calibration was performed with a standard BTEX solution (Supelco EPA TO-1 Mix 1A) by external standardization with concentrations between 0.1 and 4.0 ng mL1, as an acceptance criterion of the analytical curve determination coefficients better than 0.99. The calculated quantification limit for each BTEX compound was 5.6 pg mL1, corresponding to a concentration of 1.0 mg m3 in the ^a et al., 2012). All measurements were within the gas phase (Corre analytical curves for all samples and no dilution was necessary. The details of the tests are described in Table 4. The results of the non-criteria measurements were calculated in ppm per phase, defined according to the test protocol. For the conversion to g km1, the calculation was adapted from ECE/
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Table 4 Tests details. Identification
M1Gwc M1G M2G M3F
E22
E100
E61
EURO
WMTC
EURO
EURO
4 4 4 4
X X 4 X
X X X 4
X X X 4
TRANS/180, which defines the calculation method for THC, CO and NOx in the exhaust gas according to Equation (1):
BTEX g ¼ km
! 1 V ed dHC BTEX e1 BTEX d1 1 RD 106 D1 Fp (1)
where: BTEX g ¼ compound mass - BTEX per phase in g km1 km Ved ¼ sampling gas volume at the CVS entrance, corrected to standard pressure and temperature conditions (293.15 K and 101.325 kPa) dHC ¼ specific BTEX mass at 20 C in kg m3 BTEXe1 ¼ BTEX concentration in the gas, in ppmC (106 C) BTEXd1 ¼ BTEX concentration in the dilution gas, in ppmC (106 C) RD ¼ dilution ratio D1 ¼ distance travelled Fp ¼ weighting factor The values of the weighting factors, used for the final result by assigning different weights to each phase of the protocol, were used according to the methodology used in the protocol (97/24/EC 2006 or ECE/TRANS/180). Motorcycles that performed one phase tests (M1G and M3F) used a factor of 1.0 and for the M2G motorcycle the factor used was 0.50 for each phase of the EURO cycle and 0.25, 0.50 and 0.25 for phases 1, 2 and 3 of the WMTC cycle, respectively.
3. Results and discussion Fig. 4 shows the mean results of all THC and BTEX emission tests. The presence of the catalyst has a positive influence on the reduction of BTEX emissions when analysing the behaviour of the M1G motorcycle. For the M3F motorcycle, when fuelled with E22, E61 and E100, the BTEX values are lower than the THC values; however, this does not occur when it is fuelled with E22. The unexpected results for M3F motorcycle using 22% of ethanol has no comparison with similar works done by our group and other authors. Wallner (2011) and Poulopoulos and Philippopoulos (2002) discussed about the differences between the FID measurements by gas chromatography and THC measurements by on-line analyzers. But we cannot follow this line of reasoning for E22 because this did not occur for E61 and E100. Although the tests have been performed in triplicate, systematic experimental errors may have occurred. Fig. 3 shows a BTEX reduction with increasing ethanol content in the mixture due to the lower concentration of these compounds in this fuel. Li et al. (2015a) studied the evaporative and exhaust emissions in three motorcycles with different characteristics that were fuelled with E10 and gasoline using a dynamometer and observed that THC reduces with ethanol content and that toluene has higher emissions than the other compounds. Fig. 5 shows the results of BTEX emissions individually. The higher emissions of toluene can be observed, which can be explained by the BTEX content in the liquid gasoline, according to Table 1, where toluene presents the highest concentration. The emissions of the flex fuel motorcycle can be also observed in Fig. 5. It is verified that the increase in ethanol content in the fuel
Fig. 4. BTEX and THC results.
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Fig. 5. BTEX emissions from the three motorcycles tested.
results in decreased BTEX emissions, as expected. Fig. 5 shows an emission comparison of motorcycle M1G with and without catalyst (M1Gwc) and fuelled with E22 gasoline. It can be concluded that the after-treatment system (catalytic converter) has an emission conversion efficiency of 52.3% for benzene, 84% for toluene, 85% for ethyl benzene and 86% for xylenes. The lower conversion for benzene may indicate that the other compounds, which contain a benzene ring and a radical in their chemical structure, can lose this radical through action of the catalyst, thus generating benzene. The M2G motorcycle was tested using two protocols, namely, EURO and WMTC, with E22 gasoline. Fig. 6 shows the results for criteria emissions and non-methane hydrocarbon (NMHC) emissions in both protocols. It can be seen that in the WMTC protocol, the THC, CO and NMHC emissions are reduced compared to in the EURO protocol. The inverse situation is observed for NOx. This is possibly due to the protocol characteristics, such as time, acceleration and speed to which the vehicle is subjected. Fig. 7 shows the BTEX emissions for the two driving protocols. A situation similar to Fig. 6 is observed, where the emissions in the WMTC protocol are also smaller than in the EURO. This tendency can be justified by the fact that the BTEX compounds are part of the
THC, which presents a reduction in emissions with application of the WMTC protocol. Regarding CO emissions, the M2G motorcycle presents values above the limits foreseen in the legislation for both tested protocols. For NOx emissions, only the M1G motorcycle, when tested without a catalytic converter, exceeds the limits of legislation (Euro III). The M2G motorcycle in both protocols (Fig. 6) also exceeds the CO limits. Clairotte et al. (2012) studied two-stroke mopeds, not used in Brazil. They found that after-treatment devices used to comply EURO-2 emission standard may be responsible for the production of more potentially harmful particles compared to the EURO-1 moped emissions. Also studying two-stroke mopeds, Adam et al. (2010) measurements for non-criteria pollutants indicated that regulation on THC alone might not be sufficient to regulate PM. They also analyzed the ozone forming potential and toxicity equivalents for the moped emissions. Fig. 8 shows the criteria emissions of THC, CO and NOx from the 3 motorcycles. Comparing the emissions with the limits of current Brazilian legislation, the equivalent of Euro III, it is observed that all motorcycles meet the emission limits for THC, regardless of fuel, protocol or presence of catalyst (case M1Gwc). Regarding CO
Fig. 6. Criteria emissions from the motorcycle M2G using the EURO and WMTC protocols.
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Fig. 7. BTEX emissions for the EURO and WMTC protocols using E22.
Fig. 8. Criteria emissions for THC, CO and NOX for the three motorcycles.
emissions, the M2G motorcycle presents values above the limits foreseen in the legislation in both protocols in which it was tested. For NOx emissions, only the M1G motorcycle, when tested without a catalytic converter, exceeds the limits of the legislation. The literature has scarce results involving motorcycle powered with ethanol-gasoline blends. A recent publication (Yao et al., 2017) indicated that CO, THC, total VOCs, alkanes, alkenes, and aromatic groups reduced when the ethanol-gasoline blends were used to fuel the motorcycles. E30 demonstrated approximately 1.2-fold increases in carbonyl group emissions compared with gasoline. Emissions of the target air toxics demonstrated a reduction potential on benzene, toluene, ethyl benzene, and xylene (BTEX), but increased the emissions of formaldehyde and acetaldehyde by 65% and 330%, respectively. Other publications presented results only for gasoline-methanol blends, as the results reported by Li et al. (2015a and 2015b).
Costagliola et al. (2016) investigated the effect of bioethanolegasoline blends (3e30 5 v/v) on the exhaust emissions and engine combustion of a four-stroke motorcycle over the execution of chassis-dynamometer tests. They found a significant reduction in CO and particle number associated with the ethanol content of the fuel. VOCs, mainly alkanes and aromatics, are not substantially influenced by the bioethanol content of the fuel. Jia et al. (2005) measured the emission from a four-stroke motorcycle engine using E10 on the chassis dynamometers. The results using E10 indicate that CO and THC emissions are lower as compared to the use of gasoline, whereas the effect of ethanol on NOx emission is not significant. Benzene, toluene, xylene isomers, ethyl toluene isomers, trimethyl benzene isomers, ethylene, methane, acetaldehyde, ethanol, butene, pentane and hexane are major compounds in motorcycle engine exhaust. The no significant reduction of aromatics is using E10.
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Tsai et al. (2014) presented results similar of our work indicating that volatile organic compounds (VOCs) emission factors were in the range of several decades mg km1 during on-road driving. Toluene, isopentane, 1,2,4-trimethylbenzene, m þ p-xylenes, and oxylene were the most abundant VOCs in motorcycle exhaust. Leong et al. (2001) investigated the exhaust emission from motorcycles in Bangkok Metropolitan Region (BMR). The test result revealed that average pollutant concentrations of the test motorcycles in terms of THC, CO and NO2 were 8.38, 16.69 and 0.04 g km1, respectively. These values are higher than obtained in this work for CO and THC, but lower for NO2. To provide an evaluation of BTEX emissions, the mass balance was calculated for each BTEX, as shown in Figs. 9 and 10. The balance was considered as a system whose input is the mass (g) of each BTEX present in the fuel. The processes include the combustion and catalysis, and the output is the BTEX present in the exhaust. For the input, values of benzene, toluene, ethyl benzene and the sum of the xylenes were defined according to Table 1. The input values were expressed in volume (%), the exit values were calculated in ppm and then converted into g km1, and for mass balance, they were converted to mass (g). The specific mass of the fuel, the consumption of the vehicle and the distance travelled during the driving protocol were used for the input compounds. The consumption was calculated according to the ABNT NBR 7024/2010 standard, which determines the method for the measurement of the fuel consumption of automotive vehicles through calculation by carbon balance, where the exhaust gas is collected and analyzed during the operation of the motorcycle following the EURO or WMTC driving protocol. Consumption (in km L1) is calculated from the masses of THC, CO and CO2 in g km1 emitted by the motorcycle engine. The input value was used in Equation (2) and the output value was used in Equation (3).
Mfuel ¼
dfuel
D 1000 C
(2)
where: Mfuel ¼ fuel mass in kg dfuel ¼ specific mass of fuel at 20 C in kg m3 D ¼ travelled distance in km C ¼ consumption in km L1
BTEXmass ¼ Ved dHC
BTEXe1 BTEXd1
1
1 RD
106 where:
(3)
BTEXmass ¼ BTEX mass in g Ved ¼ sampled gas volume at the inlet of CVS, corrected to 293.15 K and 101,325 kPa
dHC ¼ specific mass of BTEX at 20 C in kg m3 BTEXe1 ¼ BTEX concentration measured in the exhaust diluted gas in ppmC (106 C) BTEXd1 ¼ BTEX concentration measured in ambient air in ppmC (106 C) RD ¼ dilution ratio Fig. 10 shows the percentage variation between the input and output masses during the process. It should be noted that the emissions with E100 are not present in view of the lack of BTEX in ethanol fuel, although traces of BTEX in the exhaust have been identified. From the tests in which gasoline and its mixtures were used, the following observations were made: a) In all tests, there was a TEX reduction in the exhaust gas compared to those present in the fuel. b) This statement applies to all tested motorcycles - (Euro III, with or without catalyser in the different protocols). c) It was also verified that a TEX reduction occurs in the fuels containing mixtures of gasoline and ethanol. d) For benzene, there was an increase noted for three conditions: the motorcycle without catalyst fuelled with E22, the flex fuel motorcycle fuelled with E22 and the motorcycle in the EURO protocol using E22. e) In cases where there was an increase in benzene, a marked reduction of the other compounds was observed, indicating the possible conversion of these compounds into benzene by the loss of an alkyl radical. f) Concerning the catalytic converter performance, using the same fuel (M1G), an improvement in BTEX destruction was observed when compared to that without the catalyst. g) The flex fuel M3F motorcycle requires a specific catalyst configuration to meet criteria emissions that allow the use of gasoline, ethanol or mixtures thereof. In this motorcycle, a considerable increase of benzene was observed with gasoline use, while with the other compounds there was a significant reduction. This fact may be correlated with the catalyst configuration. h) In the same motorcycle fuelled with E61, with a 50% reduction in the input of BTEX due to the greater ethanol content, the catalyst possibly operates in a condition more favourable to the conversion of all compounds in the group, perhaps due to the presence of oxygen from ethanol. (i) For the M2G motorcycle, tested with two different protocols, a higher BTEX conversion was observed under the WMTC protocol. As previously mentioned, the same was observed for the THC, which includes BTEX. This fact can be explained by the different characteristics of the protocols, where the WMTC protocol has higher accelerations, velocities and duration, allowing the catalyst to heat up rapidly and maintain the catalytic conversion conditions (temperature) during the execution of the test.
Fig. 9. Mass balance details for BTEX.
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Fig. 10. Results summarized only with % changes. Positive values indicate a reduction of the pollutant in the combustion process.
4. Conclusions
References
The comparison of the results of the tests conducted with the flex fuel motorcycle indicates that the use of ethanol is an option for reducing BTEX emissions. The results allow us to infer that BTEX emissions are directly linked to the concentration of ethanol in the fuel due to not only the reduction of BTEX content in the fuel but also the catalyst efficiency. When the results of the EURO and WMTC protocols were compared, it was observed that the THC and CO emissions were lower with the WMTC protocol than with EURO. This can be explained by the difference between the different vehicle engine requirements. The NOx emission results are directly linked to the combustion chamber process and temperature. This factor may have impacted the NOx increase and the reduction in other compounds. Considering that the BTEX compounds are part of the THC group, the emission values were also lower. BTEX, which belongs to the THC group, did not exceed the legislated limit in any test. The results obtained for the BTEX group provide an understanding of the vehicle emissions under normal use conditions. The mass balance showed that there was a reduction in the mass of toluene, ethyl benzene and xylenes present in the fuel when compared to the exhaust gases. It can be concluded that this reduction was due to the combustion process in the engine, associated with catalyst conversion. In some motorcycles, an increase in benzene emissions could be observed, indicating the transformation of TEX into benzene (in the combustion chamber and/or the catalyst), since all the TEX compounds have a benzene ring linked to an alkyl radical.
ABNT, 2010. NBR 7024. Light Road Vehicles - Fuel Consumption Measurement - Test Method. Brasil. Adam, T., Farfaletti, A., Montero, L., Martini, G., Manfredi, U., Larsen, B., Santi, G.D., Krasenbrink, A., Astorga, C., 2010. Chemical characterization of emissions from modern two-stroke mopeds complying with legislative regulation in Europe (EURO-2). Environ. Sci. Technol. 44 (1), 505e512. Anderson, Larry G., 2015. Effects of using renewable fuels on vehicle emissions. Renew. Sustain. Energy Rev. 47, 162e172. ANP, 2013. Resolution No 40. Specification of Automotive Gasoline. http://nxt.anp. gov.br/NXT/gateway.dll/leg/resolucoes_anp/2013/outubro/ranp%2040%20-% 202013.xml?f¼templates$fn¼document-frame.htm$3.0$q¼$x¼$nc¼2230. Barlow, T.J., Latham, S., McCrae, I.S., Boulter, P.G., 2009. A Reference Book of Driving Cycles for Use in the Measurement of Road Vehicle Emissions. IHS. ISBN 0968e4093. Bayraktar, Hakan, 2005. Experimental and theoretical investigation of using gasolineeethanol blends in spark-ignition engines. Renew. Energy 30 (11), 1733e1747. CETESB, 2013. Vehicular Control Pollution Plan of S~ ao Paulo State. http://www. cetesb.sp.gov.br/ar/documentos/Plano_de_Controle_de_Poluicao_Veicular_do_ Estado_de_Sao_Paulo2011-2013.pdf. Clairotte, M., Adam, T.W., Chirico, R., Giechaskiel, B., Manfredi, U., Elsasser, M., Sklorz, M., DeCarlo, P.F., Heringa, M.F., Zimmermann, R., Martini, G., , E., Pre vo ^t, A.S.H., Astorga, C., 2012. Online Krasenbrink, A., Vicet, A., Tournie characterization of regulated and unregulated gaseous and particulate exhaust emissions from two-stroke mopeds: a chemometric approach. Anal. Chim. Acta 717, 28e38. Clairotte, M., Adam, T.W., Zardini, A.A., Manfredi, U., Martini, G., Krasenbrink, A., , E., Astorga, C., 2013. Effects of low temperature on the cold Vicet, A., Tournie start gaseous emissions from light duty vehicles fuelled by ethanol-blended gasoline. Appl. Energy 102, 44e54. CONAMA, 2002. Resolution No 297. Establish the Emission Limits for Gaseous Pollutants by Motorcycles and Similar. http://www.mma.gov.br/estruturas/ a3p/_arquivos/36_09102008030453.pdf. ^a, Se rgio Machado, Arbilla, Graciela, 2006. Aromatic hydrocarbons emissions Corre in diesel and biodiesel exhaust. Atmos. Environ. 40 (35), 6821e6826. ^a, Se rgio M., Arbilla, Graciela, 2007. A two-year monitoring program of aroCorre matic hydrocarbons in Rio de Janeiro downtown area. J. Braz. Chem. Soc. 18 (3), 539e543. Correa, Sergio M., Arbilla, Graciela, Marques, Monica R.C., Oliveira, Katia M.P.G., 2012. The impact of BTEX emissions from gas stations into the atmosphere. Atmos. Pollut. Res. 3 (2), 163e169. Costagliola, Maria Antonietta, Prati, Maria Vittoria, Florio, Salvatore, Scorletti, Pietro, Terna, Daniele, Iodice, Paolo, Buono, Dario, Senatore, Adolfo, 2016. Performances and emissions of a 4-stroke motorcycle fuelled with ethanol/gasoline blends. Fuel 183, 470e477. Daemme, L.C., Neto, R.A.P., Errera, M.R., Zotin, F.M.Z., 2014. Preliminary Study of the Influence of Fuel Sulfur Content on the Ammonia Emission from Motorcycles and Light Vehicles of Otto and Diesel Cycles. XXI SIMEA, pages 627-636. S~ ao Paulo, Brazil. http://dx.doi.org/10.5151/engpro-simea-PAP88. ^ Daemme, L.C., Errera, M.R., Zotin, M.F.Z., Correa, S.M., Penteado, R.A., Forcetto, A.L.S., 2016a. The Effect of Fuel Sulfur Content on Ammonia, Aldehyde and Regulated Emissions Emitted from a Euro III Motorcycle. SAE Technical Paper Series 2016-
Acknowledgements This work was partially supported by FAPERJ (E-26/111.159/ 2011), FINEP (01.14.0081.00) and CNPq (473607/2013-1). The authors acknowledge the Brazilian Ministry of Science and Technology (MCT), the Brazilian National Council for Technological and Scientific Development (CNPq), law 8010, and the staff members of the LACTEC Automotive Laboratory (LEME) for providing support for this work.
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36-0158, S~ ao Paulo, Brazil. ^a, S.M., Zotin, F., Errera, M.R., 2016b. Emissions of Daemme, L.C., Penteado, R., Corre criteria and non-criteria pollutants by a flex-fuel motorcycle. J. Braz. Chem. Soc. 27, 2192e2202. European Union. The European Parliament, on Certain Components and Characteristics of Two or Three-wheel Motor Vehicles e 97/24/EC, 17/07/1997. Official Journal of the European Communities, 18/0897. Favre, C., Bosteels, D., May, J., De Souza, I., Beale, L., Andersson, J., 2009. An Emissions Performance Evaluation of State-of-the-art Motorcycles over EURO 3 and WMTC Drive Cycles. SAE Technical Paper Series 2009-01-1841, S~ ao Paulo, Brazil. ^a, S.M., Penteado, R., Daemme, L.C., Gatti, L.V., Garcia, L.F.A., Gatti, L.V., Corre Alvim, D.S., 2013. Measurements of emissions from motorcycles and modeling its impact on air quality. J. Braz. Chem. Soc. 24, 375e384. Hsieh, W.D., Chen, R.H., Wu, T.L., Lin, T., 2002. H. Engine performance and pollutant emission of an SI engine using ethanolegasoline blended fuels. Atmos. Environ. 36, 403e410. Iodice, Paolo, Senatore, Adolfo, 2014. Cold start emissions of a motorcycle using ethanol-gasoline blended fuels. Energy Proced. 45, 809e818. Jia, L.W., Shen, M.Q., Wang, J., Lin, M.Q., 2005. Influence of ethanolegasoline blended fuel on emission characteristics from a four-stroke motorcycle engine. J. Hazard. Mater. 123, 29e34. Leong, S., Muttamara, S., Laortanakul, P., 2001. Evaluation of air pollution burden from contribution of motorcycle emission in Bangkok. Water Air Soil Pollut. 131, 41e60. Li, L., Ge, Y., Wang, M., Peng, Z., Song, Y., Zhang, L., Yuan, W., 2015. Exhaust and evaporative emissions from motorcycles fueled with ethanol gasoline blends. Sci. Total Environ. 502, 627e631. Li, Lan, Ge, Yunshan, Wang, Mingda, Li, Jiaqiang, Peng, Zihang, Song, Yanan, Zhang, Liwei, 2015. Effect of gasoline/methanol blends on motorcycle emissions: exhaust and evaporative emissions. Atmos. Environ. 102, 79e85. Marc, M., Bielawska, M., Wardencki, W., Namiesnik, J., Zabiegala, B., 2015. The influence of meteorological conditions and anthropogenic activities on the seasonal fluctuations of BTEX in the urban air of the Hanseatic city of Gdansk,
Poland. Environ. Sci. Poll. Res. 22, 11940e11954. Martins, E.M., Arbilla, G., Bauerfeldt, G.F., de Paula, M., 2007. Atmospheric levels of aldehydes and BTEX and their relationship with vehicular fleet changes in Rio de Janeiro urban area. Chemosphere 67 (10), 2096e2103. ^a, S.M., 2016. Martins, E.M., Borba, P.F.S., Santos, N.E., Reis, P.T.B., Silveira, R.S., Corre The relationship between solvent use and BTEX concentrations in occupational environments. Environ. Monit. Assess. 188, 608e614. Poulopoulos, S.G., Philippopoulos, C.J., 2002. The effect od adding oxygenated compounds to gasoline on automotive exhaust emissions. J. Eng. Gas. Turbines Power 125, 344e350. Silva, F.L.N., Santos, J.R., Neto, J.M.M., Silva, R.L.G.N.P., Flumignan, D.N., Oliveira, J.E., 2009. Determination of benzene, toluene, ethyl benzene and xylenes in commercial gasoline from Piaui state. Quím. Nova 32, 56e60. Steven, H., 2002. Worldwide Harmonised Motorcycle Emissions Certification Procedure. Institute for Vehicle Technology. Draft Technical Report, UN/ECE-WP 29-GRPE WMTC Working Group. Suarez-Bertoa, R., Zardini, A.A., Keuken, H., Astorga, C., 2015. Impact of ethanol containing gasoline blends on emissions from a flex-fuel vehicle tested over the Worldwide Harmonized Light duty Test Cycle (WLTC). Fuel 143, 173e182. Tsai, J.H., Huang, P.H., Chiang, H.L., 2014. Characteristics of volatile organic compounds from motorcycle exhaust emission during real-world driving. Atmos. Environ. 99, 215e226. UN, 2005. Global Technical Regulation No.2, Measurement Procedure for Two Wheeled Motorcycles Equipped with a Positive or Compression Ignition Engine with Regard to the Emissions of Gaseous Pollutants, CO2 Emissions and Fuel Consumption: ECE/TRANS/180/Add2. Wallner, T., 2011. Correlation between speciated hydrocarbons emissions and flame ionization detector response for gasoline/alcohol blends. J. Eng. Gas. Turbines Power 133, 0828011e0828018. Yao, Y.C., Tsai, J.H., Wang, I.T., Tsai, H.R., 2017. Investigating criteria and organic air pollutant emissions from motorcycles by using various ethanol-gasoline blends. Aeros. Air Qual. Res. 17, 167e175.
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H O S T E D BY
Contents lists available at ScienceDirect
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BTEX emissions from flex fuel motorcycles ria C. Macedo a, Luiz C. Daemme a, Renato Penteado a, Heloísa N. da Motta a, Vale ^a b, * Sergio M. Corre a b
LACTEC e Technology Institute for Development, 80210-170 Curitiba, PR, Brazil Faculty of Technology, Rio de Janeiro State University, 27537-000 Resende, RJ, Brazil
a r t i c l e i n f o
a b s t r a c t
Article history: Received 1 March 2017 Received in revised form 23 May 2017 Accepted 25 May 2017 Available online xxx
Comparative studies were developed with regard to the criteria emissions of THC - total hydrocarbons, CO - carbon monoxide and NOx - nitrogen oxides, and BTEX (benzene, toluene, ethyl benzene and xylenes). Three four-stroke motorcycles were fuelled with E22 fuel (gasoline with 22% of ethanol). One flex fuel motorcycle was also fuelled with E100, 100% Hydrated Reference Ethanol, and with E61 (61% of ethanol). Criteria emissions were quantified using traditional measurement techniques based on the European Directive 97/24/EC (EURO protocol). To determine the BTEX emissions, gas chromatography coupled with mass spectrometry was employed. All motorcycles were equipped with a catalyst (TWC) used to reduce the amount of toxic emissions in the exhaust gases. To evaluate the performance of the catalyst, one motorcycle was tested with and without the device. One motorcycle was tested according to two different test protocols, namely, the ECE/TRANS/180 WMTC, also known as the Worldwide Motorcycle Test Cycle, and the EURO protocol. The main results were that toluene emissions were more prevalent than other aromatics. The tests with and without the catalyst showed that after the catalyst was employed the conversion efficiencies for benzene, toluene, ethyl benzene and xylene were 52.3%, 84.0%, 85.0%, and 86.0%, respectively. The results regarding the flex fuel motorcycle show that BTEX emissions decrease with an increase of ethanol in the mixture. Comparing the EURO and WMTC protocols, it was observed that the WMTC protocol generates lower emissions compared to the EURO protocol; however, NOx showed the opposite trend of BTEX. © 2017 Turkish National Committee for Air Pollution Research and Control. Production and hosting by Elsevier B.V. All rights reserved.
Keywords: BTEX Emission Ethanol Motorcycles Hydrocarbons
1. Introduction In big cities, vehicular emissions reduce air quality, as they contain volatile organic compounds (VOCs), carbon monoxide (CO), nitrogen oxides (NOx), sulfur oxides (SOx), and particulate matter (MP), among others (CETESB, 2013). Among the VOCs, the BTEX, formed by benzene, toluene, ethyl benzene, o-xylene, m-xylene and p-xylene compounds, stands out. Automotive gasoline consists of a mixture of hydrocarbons derived from petroleum, and Brazilian type C gasoline is allowed a maximum of 1% (v/v) benzene and 35% (v/v) BTEX (Silva et al., 2009; ANP, 2013). From an environmental perspective, BTEX plays a prominent
* Corresponding author. ^a). E-mail address: [email protected] (S.M. Corre Peer review under responsibility of Turkish National Committee for Air Pollution Research and Control.
role as a primary pollutant, with fossil fuels serving as the main source of emissions from light, gasoline-powered vehicles. They are considered as some of the main ozone precursors, in addition to causing serious damage to health (Marc et al., 2015). Motorcycles are a rising form of transportation in large cities across the world, especially in emerging countries such as China, India and Brazil. The intensive use of motorcycles is explained by their high mobility in increasingly congested cities that lack affordable public transport, as a motorcycle with a less powerful engine (150 cc) usually costs 20e25% that of a small car and is also associated with low fuel consumption, ease of parking and low maintenance cost. These advantages outweigh the inherent dangers of this form of transportation and other disadvantages such as interfering rain and the high cost of insurance (Garcia et al., 2013). Brazil recorded 428,970 traffic accidents in 2008; the number of vehicles involved was 597,786, of which 246,712 were cars and 200,449 were motorcycles. The use of ethanol has many advantages such as a renewable
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fuel, lower production of carbon monoxide, hydrocarbons and particulates, and higher octane numbers compared to gasoline, which leads to an increase in the engine compression ratio, promoting greater efficiency and engine power. Disadvantages stand out because of its lower caloric value and the increased emissions of carbonyl compounds, especially aldehydes (Daemme et al., 2016a,b; Anderson, 2015; Bayraktar, 2005). Another topic discussed in the literature deals with the criteria and non-criteria emissions according to the ethanol content and, more recently, the concern about the cold phase emissions (Clairotte et al., 2013; Suarez-Bertoa et al., 2015). In the initial minutes, the emissions of most pollutants are greater because the beginning of engine operation is associated with less efficient burning (Iodice and Senatore, 2014; Yao et al., 2017) and the catalyst is cold and therefore less effective. In this period, it is also common to observe significant emissions of ethanol and unconverted hydrocarbons, in addition to criteria pollutants (Hsieh et al., 2002). Overall, this scenario commonly occurs in short paths and becomes worrisome in the context of the medium and large cities. Brazil has a unique scenario for the intensive use of ethanol by automobiles, and flex fuel motorcycles have recently been launched on the national market, but their emissions require further study. In this work, the BTEX emissions of three 4-stroke motorcycles fuelled with blends of gasoline and ethanol were evaluated, as no 2stroke motorcycles are used in Brazil for transportation. The emissions of one of the motorcycles were compared with the EURO and WMTC test protocols, and those of another motorcycle were compared with and without a catalytic converter. The criteria pollutants were also monitored for data comparison.
2. Materials and methods The tests were performed in a laboratory of vehicular emissions that performs motorcycle homologation according to directive 97/ 24/EC. The three motorcycles were supplied with a standard fuel mixture called E22 (22% anhydrous ethanol in gasoline), and one of the motorcycles used different blends of ethanol in the gasoline. Details of the fuels used here are described in Table 1. Emission measurements were always performed in triplicate, and BTEX, THC, CO and NOx were also measured. The BTEX chemical analyses of the liquid fuel were performed by gas chromatography on a Varian CP 3800, using a Rtx-1 PONA
column (100 m, 0.25 mm, 0.50 mm). The fuel volume was 0.5 mL and was injected without dilution at 250 C and split at 1:200. The column temperature programming began at 35 C for 15 min, with a heating rate of 1 C/min up to 60 C, where the temperature remained for 20 min, followed by heating at 2 C/min to 200 C, where it remained for 10 min. A flame ionization detector was used at 300 C, and Helium 5.0 used as carrier gas at a constant flow of 22.4 cm s1. Quantification was performed by external standardization using a Supelco BTEX mix standard (47993) with a 5-point calibration curve and dilutions of 0.710e4.259 mg L1, with a coefficient of determination (R2) better than 0.99. Details of the three motorcycle configurations used are described in Table 2. These motorcycles had the highest percentages of sales of the Brazilian fleet in the period of 2009e2014. They will be designated as M1G (used with the original catalyst) and the same motorcycle without the catalyst (M1Gwc), M2G (used with the EURO and WMTC protocol) and M3F (flex fuel engine with different ethanol blends) (see Table 3). The tests were conducted using the two standard protocols for motorcycles in Brazil, the European Directive 97/24/EC and ECE/ TRANS/180. The European Directive 97/24/EC was used for the three motorcycles, and ECE/TRANS/180 was only employed to test €llner of the M2G motorcycle to compare the emissions. An AVL Zo AN 40770 dynamometer was used (648 mm and 100 kW). The temperature of the test room was between 20 and 30 C, with an average of 24 C. The temperature of the lubricating oil was maintained at room temperature ±2 C before beginning the test. The EURO protocol (European Directive 97/24/EC) simulates runway loads for THC, CO and NOx emissions measurements. A preestablished route, divided into one or two phases, was followed. Motorcycles up to 150 cm3 had only one phase (urban protocol), and those more than 150 cm3 had a second phase referred to as extra urban, with speeds reaching 120 km h1. The distance travelled in each phase was approximately 6.0 km as shown in Figs. 1 and 2 (Daemme et al., 2014). Following changes in European legislation, a new protocol for testing motorcycles in Brazil, considered more representative of actual use conditions (CONAMA Resolution 432/11), was defined in 2014, a transient driving protocol named WMTC - “Worldwide Motorcycle Test Cycle”. The main differences between the methodologies are the transient mode and the number of phases, which that can be one, two or even three phases, depending on the maximum speed of the motorcycle combined with the engine
Table 1 Fuels details. Parameter Total Sulfur Ethanol Specific gravity at 20 C Total aromatics Total C14 þ Total Iso e Paraffins Total Naphthenics Total Olefins Total Oxygenates Total Paraffinics Totals Unknowns Benzene Toluene p e Xylene m e Xylene o e Xylene Ethyl benzene Other aromatics
(mg kg1) (% vol.) (kg m3) % vol.
E22
E61
E100
10 23 742.7 19.338 0.003 29.488 4.076 5.301 22.774 15.280 3.741 0.154 13.661 0.304 0.595 0.389 0.200 4.035
9.6 62 776.1 10.412 0.003 13.778 2.561 2.721 60.912 7.248 2.367 0.075 7.051 0.009 0.296 0.181 0.104 2.696
1.1 N.D. 809.9 N.D. N.D. N.D. N.D. N.D. 100 N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D.
N.D.: not detected.
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Table 2 Details of the motorcycles used. Identification Emission regulation Engine displacement (cm3) Year
Injection fuel system Fuel
Engine cycle Power (cv) Inertia class (kg) Catalyst (TWC)
M1Gwc M1G M2G M3F
EFI EFI EFI EFI
4-stroke 4-stroke 4-stroke 4-stroke
Euro Euro Euro Euro
III III III III
124.9 124.9 291.6 149.2
2009 2009 2010 2011
Gasoline Gasoline Gasoline Flex fuel
9.1 9.1 26.5 14.3
180 180 230 200
No Yes Yes Yes
Table 3 Kinematic characteristics of the two driving cycles (Barlow et al., 2009). Parameters
Euro
WMTC
Phase 1
Phase 2
Phase 1
Phase 2
Phase 3
Total distance (km) Total time (s) Driving time (s) Average speed (km h1) Maximum speed (km h1) Average positive acceleration (m s2) Positive kinetic energy (m s2)
5.968 1170 900 18.4 50.00 0.348 3.812
6.955 400 365 62.6 120.00 0.266 2.427
4.065 600 506 24.4 59.99 0.447 0.398
9.111 600 558 54.7 94.91 0.429 0.380
15.736 600 586 94.4 125.31 0.236 0.224
Fig. 1. Speeds reached by the motorcycle for the WMTC protocol.
displacement. Each phase lasts 600 s, as show in Figs. 1 and 2 for WMTC and EURO protocols, respectively (Favre et al., 2009; Steven, 2002). The tests were performed according to the methodology defined by the EURO or WMTC protocol test standards. The resistive power applied to the motorcycle by the dynamometer during the developed course was determined by adding 75 kg to its mass, accounting for the standard weight of the pilot. The cooling of the motorcycle engine was executed by a fan positioned frontally to the vehicle with power proportional to the motorcycle speed, thus simulating the real conditions of operation. Throughout the test, exhaust emissions were directed to the constant volume sampler (CVS Horiba 7200S), where they were diluted with ambient air to avoid condensation and compound losses. Measurements of the criteria emissions were performed on-line on the diluted gas stored in 90 L bags, as well as for the dilution air of the test room. As shown in Fig. 3, the collection of non-criteria emissions was performed using an aldehyde sampler bench (tubes, pump and flow meter) that directs the samples to coconut shell cartridges
(CSC) using a line for collection of ambient air and another for the exhaust gases. The THC was determined by a flame ionization detector (FID) analyser (model FIA-720, 0e50 ppmC), CO and CO2 by nondispersive infrared (NDIR) analysers (model AIA-721A e 0e200 ppm and AIA-722 e 0-20% vol, respectively) and NOx by a chemiluminescence analyser (model CLA-720A, 0e50 ppm), all from the Horiba MEXA 7200 bench. All measurements were performed within the calibration range as all analyzers have a multi rage calibration. An active charcoal cartridge (Supelco ORBO 32 400/200 mg) was used at a flow rate of 1.0 L min1 throughout the protocol. One cartridge was used for each phase of the driving protocol, and another cartridge for collection of dilution air. To evaluate the sample recovery, 1.0 mL of a 100 ng mL1 solution of deuterated toluene was added to each cartridge after sample collection. Then, the contents of each cartridge were transferred to a 2 mL vial and added to this 1000 mL of dichloromethane at 20 C to prevent the volatilization of the lighter BTEX, since the extraction process is exothermic. The flasks were capped with septum caps,
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Fig. 2. Speeds reached by the motorcycle for the EURO protocol.
Fig. 3. Diagram of the tests for emission measurements from the motorcycle.
placed in an ultrasonic bath for 20 min, and then allowed to rest for ^a et al., 2012; Corre ^a and Arbilla, 2006, 2007; Garcia et al., 1 h (Corre 2013; Martins et al., 2007, 2016; Daemme et al., 2016a,b). The BTEX chemical analyses were performed by gas chromatography with mass spectrometry (GC-MS) on a Varian 450GC 220MS chromatograph using a VF-5MS column (30 m, 0.25 mm and 0.25 mm). Injections of 1.0 mL of sample were conducted at 200 C, with a split ratio of 1:4, using Helium 5.0 as carrier gas at 2.0 mL min1. The initial column temperature was 40 C, which was maintained for 3 min, followed by a heating rate of 15 C min1 up to 200 C, where it was held for 6 min. The temperatures of the ion trap, manifold and transfer line were 150 C, 40 C and 180 C, respectively. The MS detector monitored ions from 72 to 79, 89 to ^a et al., 2012; Corre ^a and 93, 101 to 107, and 119 to 121 (m/z) (Corre
Arbilla, 2006, 2007; Garcia et al., 2013; Martins et al., 2007, 2016; Daemme et al., 2016a,b). The calibration was performed with a standard BTEX solution (Supelco EPA TO-1 Mix 1A) by external standardization with concentrations between 0.1 and 4.0 ng mL1, as an acceptance criterion of the analytical curve determination coefficients better than 0.99. The calculated quantification limit for each BTEX compound was 5.6 pg mL1, corresponding to a concentration of 1.0 mg m3 in the ^a et al., 2012). All measurements were within the gas phase (Corre analytical curves for all samples and no dilution was necessary. The details of the tests are described in Table 4. The results of the non-criteria measurements were calculated in ppm per phase, defined according to the test protocol. For the conversion to g km1, the calculation was adapted from ECE/
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Table 4 Tests details. Identification
M1Gwc M1G M2G M3F
E22
E100
E61
EURO
WMTC
EURO
EURO
4 4 4 4
X X 4 X
X X X 4
X X X 4
TRANS/180, which defines the calculation method for THC, CO and NOx in the exhaust gas according to Equation (1):
BTEX g ¼ km
! 1 V ed dHC BTEX e1 BTEX d1 1 RD 106 D1 Fp (1)
where: BTEX g ¼ compound mass - BTEX per phase in g km1 km Ved ¼ sampling gas volume at the CVS entrance, corrected to standard pressure and temperature conditions (293.15 K and 101.325 kPa) dHC ¼ specific BTEX mass at 20 C in kg m3 BTEXe1 ¼ BTEX concentration in the gas, in ppmC (106 C) BTEXd1 ¼ BTEX concentration in the dilution gas, in ppmC (106 C) RD ¼ dilution ratio D1 ¼ distance travelled Fp ¼ weighting factor The values of the weighting factors, used for the final result by assigning different weights to each phase of the protocol, were used according to the methodology used in the protocol (97/24/EC 2006 or ECE/TRANS/180). Motorcycles that performed one phase tests (M1G and M3F) used a factor of 1.0 and for the M2G motorcycle the factor used was 0.50 for each phase of the EURO cycle and 0.25, 0.50 and 0.25 for phases 1, 2 and 3 of the WMTC cycle, respectively.
3. Results and discussion Fig. 4 shows the mean results of all THC and BTEX emission tests. The presence of the catalyst has a positive influence on the reduction of BTEX emissions when analysing the behaviour of the M1G motorcycle. For the M3F motorcycle, when fuelled with E22, E61 and E100, the BTEX values are lower than the THC values; however, this does not occur when it is fuelled with E22. The unexpected results for M3F motorcycle using 22% of ethanol has no comparison with similar works done by our group and other authors. Wallner (2011) and Poulopoulos and Philippopoulos (2002) discussed about the differences between the FID measurements by gas chromatography and THC measurements by on-line analyzers. But we cannot follow this line of reasoning for E22 because this did not occur for E61 and E100. Although the tests have been performed in triplicate, systematic experimental errors may have occurred. Fig. 3 shows a BTEX reduction with increasing ethanol content in the mixture due to the lower concentration of these compounds in this fuel. Li et al. (2015a) studied the evaporative and exhaust emissions in three motorcycles with different characteristics that were fuelled with E10 and gasoline using a dynamometer and observed that THC reduces with ethanol content and that toluene has higher emissions than the other compounds. Fig. 5 shows the results of BTEX emissions individually. The higher emissions of toluene can be observed, which can be explained by the BTEX content in the liquid gasoline, according to Table 1, where toluene presents the highest concentration. The emissions of the flex fuel motorcycle can be also observed in Fig. 5. It is verified that the increase in ethanol content in the fuel
Fig. 4. BTEX and THC results.
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Fig. 5. BTEX emissions from the three motorcycles tested.
results in decreased BTEX emissions, as expected. Fig. 5 shows an emission comparison of motorcycle M1G with and without catalyst (M1Gwc) and fuelled with E22 gasoline. It can be concluded that the after-treatment system (catalytic converter) has an emission conversion efficiency of 52.3% for benzene, 84% for toluene, 85% for ethyl benzene and 86% for xylenes. The lower conversion for benzene may indicate that the other compounds, which contain a benzene ring and a radical in their chemical structure, can lose this radical through action of the catalyst, thus generating benzene. The M2G motorcycle was tested using two protocols, namely, EURO and WMTC, with E22 gasoline. Fig. 6 shows the results for criteria emissions and non-methane hydrocarbon (NMHC) emissions in both protocols. It can be seen that in the WMTC protocol, the THC, CO and NMHC emissions are reduced compared to in the EURO protocol. The inverse situation is observed for NOx. This is possibly due to the protocol characteristics, such as time, acceleration and speed to which the vehicle is subjected. Fig. 7 shows the BTEX emissions for the two driving protocols. A situation similar to Fig. 6 is observed, where the emissions in the WMTC protocol are also smaller than in the EURO. This tendency can be justified by the fact that the BTEX compounds are part of the
THC, which presents a reduction in emissions with application of the WMTC protocol. Regarding CO emissions, the M2G motorcycle presents values above the limits foreseen in the legislation for both tested protocols. For NOx emissions, only the M1G motorcycle, when tested without a catalytic converter, exceeds the limits of legislation (Euro III). The M2G motorcycle in both protocols (Fig. 6) also exceeds the CO limits. Clairotte et al. (2012) studied two-stroke mopeds, not used in Brazil. They found that after-treatment devices used to comply EURO-2 emission standard may be responsible for the production of more potentially harmful particles compared to the EURO-1 moped emissions. Also studying two-stroke mopeds, Adam et al. (2010) measurements for non-criteria pollutants indicated that regulation on THC alone might not be sufficient to regulate PM. They also analyzed the ozone forming potential and toxicity equivalents for the moped emissions. Fig. 8 shows the criteria emissions of THC, CO and NOx from the 3 motorcycles. Comparing the emissions with the limits of current Brazilian legislation, the equivalent of Euro III, it is observed that all motorcycles meet the emission limits for THC, regardless of fuel, protocol or presence of catalyst (case M1Gwc). Regarding CO
Fig. 6. Criteria emissions from the motorcycle M2G using the EURO and WMTC protocols.
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Fig. 7. BTEX emissions for the EURO and WMTC protocols using E22.
Fig. 8. Criteria emissions for THC, CO and NOX for the three motorcycles.
emissions, the M2G motorcycle presents values above the limits foreseen in the legislation in both protocols in which it was tested. For NOx emissions, only the M1G motorcycle, when tested without a catalytic converter, exceeds the limits of the legislation. The literature has scarce results involving motorcycle powered with ethanol-gasoline blends. A recent publication (Yao et al., 2017) indicated that CO, THC, total VOCs, alkanes, alkenes, and aromatic groups reduced when the ethanol-gasoline blends were used to fuel the motorcycles. E30 demonstrated approximately 1.2-fold increases in carbonyl group emissions compared with gasoline. Emissions of the target air toxics demonstrated a reduction potential on benzene, toluene, ethyl benzene, and xylene (BTEX), but increased the emissions of formaldehyde and acetaldehyde by 65% and 330%, respectively. Other publications presented results only for gasoline-methanol blends, as the results reported by Li et al. (2015a and 2015b).
Costagliola et al. (2016) investigated the effect of bioethanolegasoline blends (3e30 5 v/v) on the exhaust emissions and engine combustion of a four-stroke motorcycle over the execution of chassis-dynamometer tests. They found a significant reduction in CO and particle number associated with the ethanol content of the fuel. VOCs, mainly alkanes and aromatics, are not substantially influenced by the bioethanol content of the fuel. Jia et al. (2005) measured the emission from a four-stroke motorcycle engine using E10 on the chassis dynamometers. The results using E10 indicate that CO and THC emissions are lower as compared to the use of gasoline, whereas the effect of ethanol on NOx emission is not significant. Benzene, toluene, xylene isomers, ethyl toluene isomers, trimethyl benzene isomers, ethylene, methane, acetaldehyde, ethanol, butene, pentane and hexane are major compounds in motorcycle engine exhaust. The no significant reduction of aromatics is using E10.
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Tsai et al. (2014) presented results similar of our work indicating that volatile organic compounds (VOCs) emission factors were in the range of several decades mg km1 during on-road driving. Toluene, isopentane, 1,2,4-trimethylbenzene, m þ p-xylenes, and oxylene were the most abundant VOCs in motorcycle exhaust. Leong et al. (2001) investigated the exhaust emission from motorcycles in Bangkok Metropolitan Region (BMR). The test result revealed that average pollutant concentrations of the test motorcycles in terms of THC, CO and NO2 were 8.38, 16.69 and 0.04 g km1, respectively. These values are higher than obtained in this work for CO and THC, but lower for NO2. To provide an evaluation of BTEX emissions, the mass balance was calculated for each BTEX, as shown in Figs. 9 and 10. The balance was considered as a system whose input is the mass (g) of each BTEX present in the fuel. The processes include the combustion and catalysis, and the output is the BTEX present in the exhaust. For the input, values of benzene, toluene, ethyl benzene and the sum of the xylenes were defined according to Table 1. The input values were expressed in volume (%), the exit values were calculated in ppm and then converted into g km1, and for mass balance, they were converted to mass (g). The specific mass of the fuel, the consumption of the vehicle and the distance travelled during the driving protocol were used for the input compounds. The consumption was calculated according to the ABNT NBR 7024/2010 standard, which determines the method for the measurement of the fuel consumption of automotive vehicles through calculation by carbon balance, where the exhaust gas is collected and analyzed during the operation of the motorcycle following the EURO or WMTC driving protocol. Consumption (in km L1) is calculated from the masses of THC, CO and CO2 in g km1 emitted by the motorcycle engine. The input value was used in Equation (2) and the output value was used in Equation (3).
Mfuel ¼
dfuel
D 1000 C
(2)
where: Mfuel ¼ fuel mass in kg dfuel ¼ specific mass of fuel at 20 C in kg m3 D ¼ travelled distance in km C ¼ consumption in km L1
BTEXmass ¼ Ved dHC
BTEXe1 BTEXd1
1
1 RD
106 where:
(3)
BTEXmass ¼ BTEX mass in g Ved ¼ sampled gas volume at the inlet of CVS, corrected to 293.15 K and 101,325 kPa
dHC ¼ specific mass of BTEX at 20 C in kg m3 BTEXe1 ¼ BTEX concentration measured in the exhaust diluted gas in ppmC (106 C) BTEXd1 ¼ BTEX concentration measured in ambient air in ppmC (106 C) RD ¼ dilution ratio Fig. 10 shows the percentage variation between the input and output masses during the process. It should be noted that the emissions with E100 are not present in view of the lack of BTEX in ethanol fuel, although traces of BTEX in the exhaust have been identified. From the tests in which gasoline and its mixtures were used, the following observations were made: a) In all tests, there was a TEX reduction in the exhaust gas compared to those present in the fuel. b) This statement applies to all tested motorcycles - (Euro III, with or without catalyser in the different protocols). c) It was also verified that a TEX reduction occurs in the fuels containing mixtures of gasoline and ethanol. d) For benzene, there was an increase noted for three conditions: the motorcycle without catalyst fuelled with E22, the flex fuel motorcycle fuelled with E22 and the motorcycle in the EURO protocol using E22. e) In cases where there was an increase in benzene, a marked reduction of the other compounds was observed, indicating the possible conversion of these compounds into benzene by the loss of an alkyl radical. f) Concerning the catalytic converter performance, using the same fuel (M1G), an improvement in BTEX destruction was observed when compared to that without the catalyst. g) The flex fuel M3F motorcycle requires a specific catalyst configuration to meet criteria emissions that allow the use of gasoline, ethanol or mixtures thereof. In this motorcycle, a considerable increase of benzene was observed with gasoline use, while with the other compounds there was a significant reduction. This fact may be correlated with the catalyst configuration. h) In the same motorcycle fuelled with E61, with a 50% reduction in the input of BTEX due to the greater ethanol content, the catalyst possibly operates in a condition more favourable to the conversion of all compounds in the group, perhaps due to the presence of oxygen from ethanol. (i) For the M2G motorcycle, tested with two different protocols, a higher BTEX conversion was observed under the WMTC protocol. As previously mentioned, the same was observed for the THC, which includes BTEX. This fact can be explained by the different characteristics of the protocols, where the WMTC protocol has higher accelerations, velocities and duration, allowing the catalyst to heat up rapidly and maintain the catalytic conversion conditions (temperature) during the execution of the test.
Fig. 9. Mass balance details for BTEX.
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Fig. 10. Results summarized only with % changes. Positive values indicate a reduction of the pollutant in the combustion process.
4. Conclusions
References
The comparison of the results of the tests conducted with the flex fuel motorcycle indicates that the use of ethanol is an option for reducing BTEX emissions. The results allow us to infer that BTEX emissions are directly linked to the concentration of ethanol in the fuel due to not only the reduction of BTEX content in the fuel but also the catalyst efficiency. When the results of the EURO and WMTC protocols were compared, it was observed that the THC and CO emissions were lower with the WMTC protocol than with EURO. This can be explained by the difference between the different vehicle engine requirements. The NOx emission results are directly linked to the combustion chamber process and temperature. This factor may have impacted the NOx increase and the reduction in other compounds. Considering that the BTEX compounds are part of the THC group, the emission values were also lower. BTEX, which belongs to the THC group, did not exceed the legislated limit in any test. The results obtained for the BTEX group provide an understanding of the vehicle emissions under normal use conditions. The mass balance showed that there was a reduction in the mass of toluene, ethyl benzene and xylenes present in the fuel when compared to the exhaust gases. It can be concluded that this reduction was due to the combustion process in the engine, associated with catalyst conversion. In some motorcycles, an increase in benzene emissions could be observed, indicating the transformation of TEX into benzene (in the combustion chamber and/or the catalyst), since all the TEX compounds have a benzene ring linked to an alkyl radical.
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Acknowledgements This work was partially supported by FAPERJ (E-26/111.159/ 2011), FINEP (01.14.0081.00) and CNPq (473607/2013-1). The authors acknowledge the Brazilian Ministry of Science and Technology (MCT), the Brazilian National Council for Technological and Scientific Development (CNPq), law 8010, and the staff members of the LACTEC Automotive Laboratory (LEME) for providing support for this work.
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