ガソリンエンジンシステムにおける未燃炭化水素の生成・排出挙動解析
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1 23 Formation and Emission Characteristics of Unburned Hydrocarbons During Cold Start of a Spark-Ignited Engine System Shuichi Kubo 60% C2 C4 C2 C4 SR C2 C4 THC SR The emission characteristics of hydrocarbons during the cold start and the warm-up have been investigated with a timed gas sampling technique. The experimental results show that the emission characteristics of hydrocarbons are influenced by both the engine operating conditions and the heating characteristics of catalytic converters. The formation routes of engine-out hydrocarbons are estimated on the basis of the experimental results. In the case of engine-out hydrocarbons, about 60% of them are unburned fuel components and the percentage contribution of C2-C4 olefins to the engine-out hydrocarbons increases as the warm-up proceeds. The adsorption and desorption processes of the engine-out alkylbenzenes on the catalyst occur before the catalyst light-off. The catalyst conversion efficiencies after the catalyst light-off observed for various classes of hydrocarbons are in the order of C2-C4 olefins, alkylbenzenes and paraffins. Before the catalyst light-off, the C2-C4 olefins and unburned fuel components are dominant for the specific reactivity ( SR ). After the catalyst light-off, on the other hand, the unburned fuel components are dominant for the SR. Based on these characteristics, it has been clarified that the total hydrocarbons and the SR are greatly affected by engine operating conditions, the fuel composition and the structure of a catalytic converter. LEV/ULEV Specific reactivity C2 C4 R&D Vol. 30 No. 2 ( )
2 24 ( ) 1 90 ( 4g/mile 0.4g/mile ) 1990 ( Clean Air Act ) ( NO x CO ) ( LEV / ULEV Program ) Reformulated Gasoline ( RFG ) Auto/Oil Air Quality Improvement Research Program RFG ( NO x CO ) Phase 2 RFG FTP ( Federal Test Procedure ) ( LA#4 ) liter ( 16valve ) Close-coupled ( 30cm ) 6500km 3 - ( K type ) ( ) 2 ( 100wt%92wt% 8wt% o- ) Schematic diagram of experimental configuration. R&D Vol. 30 No. 2 ( )
3 25 ECU ( Electronic Control Unit ) THC ( Total Hydrocarbon ) NO x CO CO 2 ( MEXA-8120 ) 10 45mm 65mm Regular gasoline properties. Characteristics Test gasoline Density 15 C (g/cm 3 ) Boiling range temperature T50 ( C) 88 T90 ( C) 153 Paraffines (wt%) 41.6 Naphthenes (wt%) 6.4 Olefins (wt%) 18.4 Aromatics (wt%) 33.6 Sulfar (ppm) 45 RVP (kg/cm 2 ) 0.74 RON 91 ( Fig. 1 ) 150 C Fig. 2 5 ( 5 ) ( HP 5890A ) 6 5 ( ) 6 ( ) ( GC-MS ) ppmc Analytical conditions. Engine operating procedures and levels of timed HC sampling. DB-1 (0.53mmφ, 0.25µm, 0.5m) Column + DB-1 (0.25mmφ, 1.0µm, 60m) 50 C (2min hold) 20 C/min Temperature 4 C/min program 20 C 100 C 8 C/min 250 C (5.75min hold) He Carrier gas (Input pressure: 195kPa) Split ratio 35 : 1 R&D Vol. 30 No. 2 ( )
4 26 Specific Reactivity ( SR ) SR = [Σ(NMOGi)(MIRi)] / Σ(NMOGi) NMOGi ; i (g/ml) MIR (Maximum Incremental Reactivity) i ; i (go 3 /gnmog) ( ) 5 (1) (2) (3)C2 C4 (4) (5) (1) (3) (4) (5) C2 C4 1-1, ,3-1,2-9 ( THC : Total Hydrocarbon ) THC ( 3000 ppmc ) THC Fig. 3 THC THC Knepper 60 C2 C4 ( ) Kaiser Variation in air/fuel ratio and total hydrocarbon concentration in engine-out emissions during warm-up. R&D Vol. 30 No. 2 ( )
5 27 ( Fig. 3 ) C2 C4 - Kaiser ( 110 C ) 150 ( SR ) C2 C4 SR THC THC ( Fig. 3 ) SR THC SR Fig. 4 SR Variation in engine-out hydrocarbon composition during warm-up. Variation in specific reactivity of engine-out hydrocarbons during warm-up. R&D Vol. 30 No. 2 ( )
6 28 C2 C4 ( 12.3wt% 28.0wt% ) SR SR ( ) C2 C4 C2 C4 SR ( Catalyst light-off ) 2 THC SR C2 C4 (a) (b) C2 C4 C2 C4 Variation in catalyst temperature and total catalyst conversion efficiency during warm-up. Catalyst Conversion efficiencies of hydrocarbons as a function of temperature before catalyst light-off. R&D Vol. 30 No. 2 ( )
7 29 50 C C2 C4 ( ) Relationship between boiling points and catalyst conversion efficiencies at catalyst temperature of 50 C. Catalyst conversion efficiencies for various hydrocarbons as a function of temperature after catalyst light-off. ( ) C2 C4 THCSR THC THC ( 9 ) ( 950 ) THC SR ( ) SR C2 C4 ( SR 52 ) C2 C4 SR SR 480 SR 80 R&D Vol. 30 No. 2 ( )
8 30 SR C2 C4 THC SR ( ) Variation in total hydrocarbon concentration in engine-out and catalyst-out during warm-up. ( ) ( ) ( ) 9 Variation in specific reactivity of catalyst-out hydrocarbons during warm-up. Relationship between non-aromatic hydrocarbon Contents in fuel and engine-out hydrocarbon (methane and acetylene) concentrations at 9 sec after cold start. R&D Vol. 30 No. 2 ( )
9 31 C2 C4 ( 4 ) Fig. 13 C2 C4 ( β-scission ) H atom donor Relationship between percentage of non-aromatics in fuel and percentage of C2-C4 olefins to engine-out THC during warm-up. - Relationship between percentage of aromatics in fuel - and percentage of aromatics to engine-out THC during warm-up. R&D Vol. 30 No. 2 ( )
10 32 C2 C4 - ( β-scission ) C2 C4 RH (+ OH or Pyrolysis ) R'-CH 2 -CH 2 R'-CH 2 -CH 2 R' + CH 2 =CH 2 (Ethylene) RH Fig. 14 OH C-CC-H ( ) ( ) ( C2 C4 ) (1) 60 ( ) (2) (3) (4) C2 C4 (5)C2 C4 - (6) SR THC SR C2 C4 (1) (2) (3) ( C2 C4 ) (4)SR(1) (2) R&D Vol. 30 No. 2 ( )
11 33 (3) THC SR ( ) 1) Sawyer, R. F. : "Reformulated Gasoline for Automotive Emissions Reduction", 24th Symp. (Int.) Combust., (1992) ) Kaiser, E. W., et al. : "Effect of Fuel Structure on Emissions from a Spark-Ignited Engine", Env. Sci. Technol., 25 (1991) ) Shore, P. R., et al. : "Speciated Hydrocarbon Emissions from Aromatic, Olefinic, and Paraffinic Model Fuels", SAE Tech Pap. Ser., No , (1993) 4) den Otter, G. J., et al. : "Effect of Gasoline Reformulation on Exhaust Emissions in Current European Vehicles", SAE Tech Pap. Ser., No , (1993) 5) Hochhauser, A. M., et al. : "The Effect of Aromatics, MTBE, Olefins, and T90 on Mass Exhaust Emissions from Current and Older Vehicles - The Auto/Oil Air Quality Improvement Research Program", SAE Tech Pap. Ser., No , (1991) 6) Benson, J. D., et al. : "Effects of Gasoline Sulfur Level on Mass Exhaust Emissions - The Auto/Oil Air Quality Improvement Research Program", SAE Tech Pap. Ser., No , (1991) 7) Yamazaki, S. et al. : "Effects of the Gasoline Composition and Emission Control Systems on Exhaust HC Emissions", SAE Tech Pap. Ser., No , (1992) 8) Kaiser, E. W., et al. : "Time-Resolved Measurement of Speciated Hydrocarbon Emissions During Cold Start of a Spark-Ignited Engine", SAE Tech Pap. Ser., No , (1994) 9) Nitschke, R. G. : "Reactivity of SI Engine Exhaust Under Steady-State and Simulated Cold-Start Operating Conditions", SAE Tech Pap. Ser., No , (1993) 10) Kubo, S. et al. : "Speciated Hydrocarbon Emissions of SI Engine During Cold Start and Warm-up", SAE Tech Pap. Ser., No , (1993) 11) CARB Mail-out # ) Lowi, A. and Carter, W. P. L. : "A Method for Evaluating the Atmospheric Ozone Impact of Actual Vehicle Emissions", SAE Tech Pap. Ser., No , (1990) 13) Knepper, J. C., et al. : "Fuel Effects in Auto/Oil High Emitting Vehicles", SAE Tech Pap. Ser., No , (1993) 14) Kaiser, E. W., et al. : "Effect of Fuel-Air Equivalence Ratio and Temperature on the Structure of Laminar Propane-Air Flames", Combust. Sci. Technol., 33(1983), ) Cheng, W. K., et al. : "An Overview of Hydrocarbon Emissions Mechanisms in Spark-Ignition Engines", SAE Tech Pap. Ser., No , (1993) 16) Kaiser, E. W., et al. : "The Effect of Oil Layers on the Hydrocarbon Emissions Generated During Closed Vessel Combustion", 18th Symp. (Int.) Combust., (1981), ) Gatellier, B., et al. : "Hydrocarbon Emissions of SI Engines as Influenced by Fuel Absorption-Desorption in Oil Films", SAE Tech Pap. Ser., No , (1992) 1963 R&D Vol. 30 No. 2 ( )
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