An undiluted exhaust hydrocarbon (HC) speciation method, using flame ionization detector gas chromatographs, is developed to investigate HC species from conventional and low-temperature premixed charge compression ignition (PCI) combustion pre- and postdiesel oxidation catalyst (DOC) exhaust. This paper expands on previously reported work by describing in detail the method and effectiveness of undiluted diesel exhaust speciation and providing a more detailed analysis of individual HC species for conventional and PCI diesel combustion processes. The details provided regarding the effectiveness of the undiluted diesel exhaust speciation method include the use of a fuel response factor for HC species quantification and demonstration of its linearity, detection limit, accuracy, and precision. The listing of individual HC species provides not only the information needed to design surrogate exhaust mixtures used in reactor tests and modeling studies but also sheds light on PCI combustion and DOC characteristics. Significantly increased engine-out concentrations of acetylene, benzene, and toluene support the theory that net soot reduction associated with PCI combustion occurs due to the reduction of soot formation (as opposed to increased soot oxidation). DOC oxidation behavior differs depending on the combustion characteristics, which change exhaust species and temperature.

1.
Kimura
,
S.
,
Aoki
,
O.
,
Ogawa
,
H.
,
Muranaka
,
S.
, and
Enomoto
,
Y.
, 1999, “
New Combustion Concept for Ultra-Clean and High-Efficiency Small DI Diesel Engines
,” SAE Paper No. 1999-01-3681.
2.
Kimura
,
S.
,
Aoki
,
O.
,
Kitahara
,
K.
, and
Aiyoshizawa
,
E.
, 2001, “
Ultra-Clean Combustion Technology Combining a Low-Temperature and Premixed Combustion Concept for Meeting Future Emission Standards
,” SAE Paper No. 2001-01-0200.
3.
Akihama
,
K.
,
Takatori
,
Y.
,
Inagaki
,
K.
,
Sasaki
,
S.
, and
Dean
,
A.
, 2001, “
Mechanism of the Smokeless Rich Diesel Combustion by Reducing Temperature
,” SAE Paper No. 2001-01-0655.
4.
Shimazaki
,
N.
,
Tsurushima
,
T.
, and
Nishimura
,
T.
, 2003, “
Dual Mode Combustion Concept with Premixed Diesel Combustion by Direct Injection Near Top Dead Center
,” SAE Paper No. 2003-01-0742.
5.
Jacobs
,
T.
,
Bohac
,
S.
,
Assanis
,
D.
, and
Szymkowicz
,
P.
, 2005, “
Lean and Rich Premixed Compression Ignition Combustion in a Light-Duty Diesel Engine
,” SAE Paper No. 2005-01-0166.
6.
Sluder
,
C.
,
Wagner
,
R.
,
Lewis
,
S.
, and
Storey
,
J.
, 2004, “
Exhaust Chemistry of Low-NOx, Low-PM Diesel Combustion
,” SAE Paper No. 2004-01-0114.
7.
Mogi
,
H.
,
Tajima
,
K.
,
Hosoya
,
M.
, and
Shimoda
,
M.
, 1999, “
The Reduction of Diesel Engine Emissions by Using the Oxidation Catalysts of Japan Diesel 13 Mode Cycle
,” SAE Paper No. 1999-01-0471.
8.
Jackson
,
M.
, 1978, “
Effect of Catalytic Emission Control on Exhaust Hydrocarbon Composition and Reactivity
,” SAE Paper No. 780624.
9.
Siegl
,
W.
,
McCabe
,
R.
,
Chun
,
W.
,
Kaiser
,
E.
,
Perry
,
J.
,
Henig
,
Y.
,
Trinker
,
F.
, and
Anderson
,
R.
, 1992, “
Speciated Hydrocarbon Emissions From the Combustion of Single Component Fuels. I. Effect of Fuel Structure
,”
J. Air Waste Manage. Assoc.
1047-3289,
42
, pp.
912
920
.
10.
McCabe
,
R.
,
Siegl
,
W.
,
Chun
,
W.
, and
Perry
,
J.
, 1992, “
Speciated Hydrocarbon Emissions from the Combustion of Single Component Fuels. II. Catalyst Effects
,”
J. Air Waste Manage. Assoc.
1047-3289,
42
, pp.
1071
1077
.
11.
Hoekman
,
S.
, 1992, “
Speciated Measurements and Calculated Reactivities of Vehicle Exhaust Emissions From Conventional and Reformulated Gasolines
,”
Environ. Sci. Technol.
0013-936X,
26
, pp.
1206
1216
.
12.
Olson
,
K.
,
Sinkevitch
,
R.
, and
Sloane
,
T.
, 1992, “
Speciation and Quantization of Hydrocarbons in Gasoline Engine Exhaust
,”
J. Chromatogr. Sci.
0021-9665,
30
, pp.
500
508
.
13.
Nine
,
R.
,
Clark
,
N.
,
Mace
,
B.
, and
ElGazzar
,
L.
, 1997, “
Hydrocarbon Speciation for a Lean Burn Spark Ignited Engine
,” SAE Paper No. 972971.
14.
Siegl
,
W.
,
Kaiser
,
E.
,
Adamczyk
,
A.
,
Guenther
,
M.
,
DiCicco
,
D.
, and
Lewis
,
D.
, 1998, “
A Comparison of Conversion Efficiencies of Individual Hydrocarbon Species Across Pd- and Pt-Based Catalysts as a Function of Fuel-Air Ratio
,” SAE Paper No. 982549.
15.
Kaiser
,
E.
, and
Siegl
,
W.
, 1994, “
High Resolution Gas Chromatographic Determination of the Atmospheric Reactivity of Engine-Out Hydrocarbon Emissions From a Spark-Ignited Engine
,”
J. High Resolut. Chromatogr.
0935-6304,
17
, pp.
264
270
.
16.
Bohac
,
S.
, 2003, “
Reduction of Spark-Ignition Engine Hydrocarbon Emissions and the Associated Local Ozone Production Through Variable Exhaust Valve Timing
,” Ph.D. thesis, University of Michigan, Ann Arbor, MI.
17.
Bohac
,
S.
,
Assanis
,
D.
, and
Holmes
,
H.
, 2004, “
Speciated Hydrocarbon Emissions and the Associated Local Ozone Production From an Automotive Gasoline Engine
,”
Int. J. Engine Res.
1468-0874,
5
(
1
), pp.
53
70
.
18.
Jensen
,
T.
,
Siegl
,
W.
,
Richert
,
J.
,
Lipari
,
F.
,
Loo
,
J.
,
Prostak
,
A.
, and
Sigsby
,
J.
, 1992, “
Advanced Emission Speciation Methodologies for the Auto/Oil Air Quality Improvement Research Program—I. Hydrocarbons and Ethers
,” SAE Paper No. 920320.
19.
Siegl
,
W.
,
Richert
,
J.
,
Swarin
,
S.
,
Loo
,
J.
,
Prostak
,
A.
,
Nagy
,
D.
, and
Schlenker
,
A.
, 1993, “
Improved Emissions Speciation Methodology for Phase II of the Auto/Oil Air Quality Improvement Research Program—Hydrocarbons and Oxygenates
,” SAE Paper No. 930142.
20.
Jemma
,
C.
,
Lance
,
D.
, and
Shore
,
P.
, 1992, “
Speciation of Hydrocarbon Emissions from European Vehicles
,” SAE Paper No. 922376.
21.
Hammerle
,
R.
,
Ketcher
,
D.
,
Horrocks
,
R.
,
Lepperhoff
,
G.
,
Huthwohl
,
G.
, and
Luers
,
B.
, 1994, “
Emissions From Current Diesel Vehicles
,” SAE Paper No. 942043.
22.
Lepperhoff
,
G.
,
Huthwohl
,
G.
,
Luers-Jongen
,
B.
, and
Hammerle
,
R.
, 1994, “
Methods to Analyze Non-Regulated Emissions from Diesel Engines
,” SAE Paper No. 941952.
23.
Hammerle
,
R.
,
Siegl
,
W.
,
Herrmann
,
H.
, and
Wenclawiak
,
B.
, 1995, “
A Method for the Speciation of Diesel Fuel and the Semi-Volatile Hydrocarbon Fraction of Diesel-Fueled Vehicle Exhaust Emissions
,” SAE Paper No. 952353.
24.
Clark
,
N.
,
Atkinson
,
C.
,
McKain
,
D.
,
Nine
,
R.
, and
El-Gazzar
,
L.
, 1996, “
Speciation of Hydrocarbon Emissions From a Medium Duty Diesel Engines
,” SAE Paper No. 960322.
25.
Gautam
,
M.
,
Gupat
,
D.
,
El-Gazzar
,
L.
,
Lyons
,
D.
, and
Popuri
,
S.
, 1996, “
Speciation of Heavy Duty Diesel Exhaust Emissions under Steady State Operating Conditions
,” SAE Paper No. 962159.
26.
Durbin
,
T.
,
Zhu
,
X.
, and
Norbeck
,
J.
, 2003, “
The Effects of Diesel Particulate Filters and a Low-Aromatic, Low-Sulfur Diesel Fuel on Emissions for Medium-Duty Diesel Trucks
,”
Atmos. Environ.
1352-2310,
37
, pp.
2105
2116
.
27.
Westerholm
,
R.
,
Almén
,
J.
, and
Li
,
H.
, 1991, “
Chemical and Biological Characterization of Particulate-, Semivolatile-, and Gas-Phase-Associated Compounds in Diluted Heavy-Duty Diesel Exhausts: A Comparison of Three Different Semivolatile-Phase Samplers
,”
Environ. Sci. Technol.
0013-936X,
25
, pp.
332
338
.
28.
Siegl
,
W.
,
Hammerle
,
R.
,
Herrmann
,
H.
,
Wenclawiak
,
B.
, and
Luers-Jongen
,
B.
, 1999, “
Organic Emissions Profile for a Light-Duty Diesel Vehicle
,”
Atmos. Environ.
1352-2310,
33
, pp.
797
805
.
29.
Habibi
,
K.
, 1970, “
Characterization of Particulate Lead in Vehicle Exhaust-Experimental Techniques
,”
Environ. Sci. Technol.
0013-936X,
4
, pp.
239
248
.
30.
Bidleman
,
T.
, 1988, “
Atmospheric Processes
,”
Environ. Sci. Technol.
0013-936X,
22
, pp.
361
367
.
31.
Bohac
,
S.
,
Han
,
M.
,
Jacobs
,
T.
,
López
,
A.
,
Assanis
,
D.
, and
Szymkowicz
,
P.
, 2006, “
Speciated Hydrocarbon Emissions From an Automotive Diesel Engine and DOC Utilizing Conventional and PCI Combustion
,” SAE Paper No. 2006-01-0201.
32.
Tao
,
F.
,
Liu
,
Y.
,
RempelEwert
,
B. H.
,
Foster
,
D. E.
,
Reitz
,
R. D.
,
Choi
,
D.
, and
Miles
,
P. C.
, 2005, “
Modeling the Effects of EGR and Injection Pressure on Soot Formation in a High-Speed Direct-Injection (HSDI) Diesel Engine Using a Multi-Step Phenomenological Soot Model
,” SAE Paper No. 2005-01-0121.
33.
Jacobs
,
T.
, 2005, “
Simultaneous Reduction of Nitric Oxide and Particulate Matter Emissions From a Light-Duty Diesel Engine Using Combustion Development and Diesel Oxidation Catalyst
,” Ph.D. thesis, University of Michigan, Ann Arbor, MI.
34.
Lipari
,
F.
, 1990, “
Determination of Individual Hydrocarbons in Automobile Exhaust from Gasoline-Methanol-, and Variable-Fueled Vehicles
,”
J. Chromatogr.
0021-9673,
503
, pp.
51
68
.
35.
Huber
,
L.
, 2001, “
Validation of Analytical Methods: Review and Strategy
,” http://www.labcompliance.com.http://www.labcompliance.com.
36.
Peng
,
C.
, and
Batterman
,
S.
, 2000, “
Performance Evaluation of a Sorbent Tube Sampling Method Using Short Path Thermal Desorption for Volatile Organic Compounds
,”
J. Environ. Monit.
1464-0325,
2
, pp.
313
324
.
37.
Knafl
,
A.
,
Busch
,
S. B.
,
Han
,
M.
,
Bohac
,
S. V.
,
Assanis
,
D. N.
,
Szymkowicz
,
P. G.
, and
Blint
,
R. D.
, 2006, “
Characterizing Light-Off Behavior and Species-Resolved Conversion Efficiencies During In-Situ Diesel Oxidation Catalyst Degreening
,” SAE Paper No. 2006-01-0209.
38.
Wagner
,
T.
, and
Wyszyński
,
M. L.
, 1996, “
Aldehyde and Ketones in Engine Exhaust Emissions- A Review
,”
Proc. Inst. Mech. Eng., Part D (J. Automob. Eng.)
0954-4070,
210
, pp.
109
122
.
39.
McCabe
,
R. W.
,
King
,
E. T.
,
Watkins
,
W. L. H.
, and
Gandhi
,
H. S.
, 1990, “
Laboratory and Vehicle Studies of Aldehyde Emissions From Alcohol Fuels
,” SAE Paper No. 900708.
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