Beruflich Dokumente
Kultur Dokumente
Abstract
The composition of VOC emissions from in-use passenger cars with di!erent engine types, i.e. cars with diesel engines,
cars with petrol engines equipped with three-way-catalysts, and cars with petrol engines without catalysts was
determined. Five cars of each engine type have been measured on a chassis dynamometer under conditions of the US
FTP 75 test procedure and the `Autobahna test developed by TUG V Rheinland. Measurements of C }C hydrocarbons
were made with a GC-FID system. In addition, samples on DNPH cartridges were taken and analysed by means of
a HPLC-system for the determination of aldehydes and ketones.The in#uence of cold/warm-conditions on the VOC
composition was determined. In the case of cars with diesel engines as well as for the petrol-driven cars without exhaust
treatment, the e!ect caused by the cold start only led to minor changes in the VOC composition. A similar behaviour was
observed for these car types at higher speeds. In contrast to the cars without catalysts, the cars with three-way-catalysts
showed a great variability of the VOC composition. During the cold start phase the aromatic compounds and the alkenes
yielded the main fraction of the VOC. During the warm phase the less reactive alkanes were predominant. With
increasing mean velocities the VOC composition changed in favour of the more reactive compounds. 2000 Published
by Elsevier Science Ltd.
Keywords: Passenger car emissions; C }C hydrocarbons; Aldehydes; Ketones; Ozone forming potential
1. Introduction
The volatile organic compounds (VOC) in the atmosphere comprise many di!erent species with various
properties. Some of these compounds directly in#uence
human health due to their toxicity. VOC are also important precursors of photochemically formed secondary
pollutants, such as ozone, which poses a serious air
pollution problem under speci"c summertime conditions. Since the individual VOC react with di!erent rates
and di!erent mechanisms, they also di!er in their contribution to photochemical ozone formation. For the development of e$cient abatement strategies to lower the
VOC emissions in order to improve air quality in urban
* Corresponding author.
E-mail address: th.schmitz@fz-juelich.de (T. Schmitz).
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In recent years new methods based on chassis dynamometer studies for determining emission data of motor
vehicles have been developed (Hassel et al., 1994). From
these data the dependence of the emissions of VOC, CO
and NO on the driving behaviour is known. In the
V
present work the dependence of the VOC-composition
on di!erent driving situations was investigated. Also the
in#uence of cold-/warm-conditions was quanti"ed.
2. Experimental
2.1. Vehicles, fuels and driving conditions
The measuring programme included 15 di!erent passenger cars. Three engine types were investigated: petrol
driven cars equipped with a fuel injection system and
a closed-looped controlled three-way-catalyst (TWC),
petrol-driven cars without any catalyst and cars with
diesel engines. Five cars of each engine type were measured. Three of the cars with diesel engines were equipped
with oxidative catalytic converters, one with a direct fuel
injection.
Because of the correlation between exhaust emissions
of individual hydrocarbons and fuel composition it was
necessary to use test fuels which are representative for the
average composition of German market fuels. The test
fuels, two unleaded fuels of di!erent quality for the catalyst cars and the cars without catalyst and diesel fuel,
were obtained from the ARAL research centre in
Bochum (Germany). The characteristics of the fuels used
in this programme are given in Table 1.
The emission measurements were performed on the
chassis dynamometer of TUG V Rheinland. A detailed description of the test facility is given in Hassel et al. (1994).
The measurements were carried out under the conditions
of the United States federal test procedure (US FTP 75)
and the `Autobahna test presented in Fig. 1.
The FTP test is divided into three phases. The test is
starting with a cold start. For this cold start procedure
the cars have been conditioned at a temperature of 203C
Table 1
Characteristics of the test fuels, analysis done by ARAL (Germany)
Fuel quality
Density (153C)
(g ml\)
ROZ/cetan
number
MOZ
Lead
(mg l\)
Sulphur
(mass %)
Super-Plus
Super
Diesel
0.7614
0.7574
0.8304
99.3/
96.4/
/51.8
88.1
85.1
1
1
0.0064
0.0124
0.0325
Super-Plus
Super
Benzene
(vol %)
0.8
1.9
Toluene
(vol %)
14.0
10.3
Methanol
(vol %)
0.0
0.0
Aromatics
(vol %)
46.0
45.8
MTBE
(vol %)
8.79
2.74
Para$ns
(vol %)
41.8
46.9
Ole"ns
(vol %)
3.2
4.3
4641
4642
Fig. 2. Chromatogram taken from vehicle with TWC: 1"ethene; 2"ethyne; 3"ethane; 4"propene; 5"propane; 6"i-butane;
7/8"i-/1-butene; 9"1,3-butadiene; 10"n-butane; 11"trans-2-butene; 12"cis-2-butene; 13"i-pentane (coelution with acetone);
14"1-pentene; 15"n-pentane; 16"isoprene; 17"trans-2-pentene; 18"cis-2-pentene; 19"2,2-dimethylbutane; 20/21"cyclopentane/2,3-dimethybutane; 22"2-methylpentane; 23"3-methylpentane; 24"1-hexene; 25"n-hexane; 26"2,4-dimethyl-pentane;
27"benzene; 28"cyclohexane; 29"2-methylhexane; 30"2,3}dimethylpentane; 31"3-methylhexan; 32"i-octane; 33"n-heptane; 34"methylcyclohexane; 35"toluene; 36"2}methylheptane; 37"3-methylheptane; 38"n-octane; 39"ethylbenzene;
40/41"m/p-xylene; 42"styrene; 43"o-xylene; 44"n-nonane; 45"n-propylbenzene; 46"1,3,5-trimethyl-benzene; 47"1,2,4trimethylbenzene; 48"n-decane.
3. Results
3.1. Regulated emissions
The mean emissions of CO, THC, and NO obtained
V
for the single test phases are presented in Fig. 3. As it is
expected, the highest emissions were measured for the
cars without catalysts (Hassel et al., 1994; Lies et al.,
1988). For CO and THC the di!erences between diesel
engines and catalyst cars in comparison to the cars without catalyst span a factor of 10}100. NO emissions from
V
cars with diesel engines and cars without catalysts di!er
by a factor of "ve in all test phases, in case of the catalyst
cars the di!erences are between a factor of 15}20.
Looking into detail two points have to be noted: the
e!ect of cold start conditions, which can be derived by
comparison of the results obtained in phase 1 and phase
3 of the US test, and the e!ect of high engine loads, which
is best represented in the third phase of the `Autobahna
cycle.
In general, the relative increase of emissions caused by
the cold start process is less pronounced for cars with
diesel engines and cars without catalysts than for catalyst
cars. For TWC cars the highest increase is observed for
the hydrocarbon emissions. For cold start conditions the
THC emissions are higher by about a factor of 10 compared to warm start conditions.
In the `Autobahna cycle for all engine types the increase of NO emissions is about 25% between the
V
4643
Table 2
Measured components and detection methods
Component
CO
CO
THC
NO
V
CH
L K
CH O
L K
Measuring method
Carbon monoxide
Carbon dioxide
Total hydrocarbons
Nitrogen oxides (NO,NO )
C }C hydrocarbons
Carbonyls; phenol and cresols
second and third phase. In case of CO and THC emissions the behaviour is comparable to that for cars without catalyst and cars with diesel engines. In contrast, for
the TWC cars the emissions of CO increase by a factor of
6 and for THC the emissions are higher by a factor of 4.
The observed emission behaviour of TWC vehicles
indicates that in case of CO and THC the conversion
e$ciency of the catalyst strongly depends on the operating conditions of the engine. During the cold phase the
catalytic converter does not reach its optimum work and
the emission reduction is diminished.
Under driving conditions with high mean speeds and
high engine loads the conversion e$ciency is low too,
although the catalyst is warmed up completely. For the
acceleration phases of the third phase of the `Autobahna
cycle rich air/fuel mixtures are injected. Under these
engine operating conditions the oxidation capacity of the
catalytic converter for CO and the hydrocarbons is diminished. For NO a decreasing e$ciency of the catalyst at
V
conditions with high engine loads does not occur due to
the fact that the reducing conditions in the catalyst promote the conversion of NO .
V
3.2. VOC-composition
The relative composition of the VOC measured for the
di!erent engine types is shown in Fig. 4. In order to get
a better overview the single compounds were grouped
into "ve substance classes. The alkynes ethyne and
1-butyne are listed together with the alkenes.
The relative VOC pattern which is obtained for the
TWC cars shows strong variations in dependence of
the di!erent test phases. Under cold start conditions the
VOC pattern is dominated by the fraction of the aromatic compounds followed by the alkanes and the
alkenes. The amount of carbonyls and phenols is less
than 5%. In the corresponding warm phase (US FTP 75
phase 3) the VOC pattern is changing completely. The
more reactive alkenes and aromatic compounds are reduced more e$ciently. Therefore, the main fraction of the
VOC is given by the alkanes, a fact which also is reported
in an Australian study (Du!y et al., 1999). Looking
Non-dispersive infrared
Non-dispersive infrared
Flame ionization detector
Chemiluminescence detector
Gas chromatography/#ame ionization
High-pressure liquid chromatography/diode
array detector; gas chromatography/mass
spectroscopy
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4645
Table 3
Emission rates of the VOC in mg km\ measured in the di!erent phases
Substance
US 75
phase 1
mean values
Con"dence
level (%)
US 75
phase 2
mean values
Con"dence
level (%)
US 75
phase 3
mean values
Con"dence
level (%)
(a) US FTP 75
Cars with TWC
Alkanes
Alkenes
Alkynes
Aromatics
Carbonyls
Phenol and cresols
130.20
62.63
21.00
250.81
12.26
1.66
74.25
90.11
105.45
81.76
*
*
5.47
0.38
0.04
2.92
3.59
1.54
92.99
110.02
93.38
82.40
*
*
18.79
1.89
0.08
10.23
2.96
1.66
52.09
95.47
108.33
87.68
*
*
661.87
344.27
139.12
1266.70
90.42
6.05
36.86
42.71
38.90
35.47
*
46.58
650.88
341.32
100.90
1138.44
113.58
15.80
65.32
48.21
43.75
45.07
*
65.02
567.60
291.71
77.32
975.62
95.08
11.52
63.24
50.97
30.41
43.71
*
43.12
Diesel cars
Alkanes
Alkenes
Alkynes
Aromatics
Carbonyls
Phenol and cresols
8.23
44.35
8.83
9.14
24.36
1.61
83.91
60.79
79.21
63.07
*
*
7.87
35.41
5.94
7.49
25.67
1.49
95.54
67.47
90.33
59.52
*
*
5.16
20.23
4.15
4.56
17.07
1.59
80.85
80.82
94.54
61.72
*
*
Substance
Autobahn
phase 1
mean values
Con"dence
level (%)
Autobahn
phase 2
mean values
Con"dence
level (%)
Authobahn
phase 3
mean values
Con"dence
level (%)
18.02
4.16
0.12
16.68
3.06
1.22
102.43
107.70
89.86
95.61
*
*
11.81
7.49
0.21
18.76
80.50
106.75
154.47
105.40
28.81
60.71
0.94
129.48
3.73
0.77
90.13
124.74
133.41
92.32
214.96
292.54
86.34
580.16
67.75
9.58
51.13
65.08
40.77
54.53
*
29.86
259.14
366.57
118.60
723.96
48.90
86.52
46.02
66.16
224.48
502.86
175.92
846.70
40.61
13.17
67.12
90.20
43.98
90.51
Diesel cars
Alkanes
Alkenes
Alkynes
Aromatics
Carbonyls
Phenol and cresols
1.57
6.48
1.66
1.86
8.23
1.11
99.67
132.72
141.41
94.16
*
*
1.46
8.11
2.32
2.16
1.22
9.35
4.34
3.02
7.55
0.71
133.94
135.08
141.79
150.48
106.19
120.51
136.09
102.35
25.96
The second and the third test phase of the `Autobahna cycle were measured as one sample in order to reach the detection limits of the
methods.
4646
Acknowledgements
This work is supported by BMBF as part of the `Forschungsschwerpunkt TroposphaK renforschunga (TFS),
principal subject 2: `Anthropogenic and biogenic emissions as well as deposition of trace gasesa in the course of
the joint project A.2: `Analysis, development and evaluation of emission models and data sets for road tra$c in
Germany and Europea. The authors thank the ARAL
research centre for providing and for the detailed analysis
of the test fuels. They acknowledge Dr. U. Metzner
for the analysis of the carbonyl compounds and
Dr. G. Kuropka for the measurements of phenol and
cresols. They also thank Dr. D. Klemp for the critical
review of the manuscript.
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