ディーゼル排出ガスに及ぼす軽油性状の影響第1報）軽油の分析・評価法の開発

Size: px

Start display at page:

Download "ディーゼル排出ガスに及ぼす軽油性状の影響第1報）軽油の分析・評価法の開発"

まいかわたぬき
5 years ago
Views:

1 Fuel Effects on Particulate Emisions from D.I. Engine Part 1. Chemical Analysis and Characterization of Diesel Fuel Tadao Ogawa ( PM ) PM ( PM ) PM PM PM 1 R&D Vol. 32 No. 2 ( )

2 PM PM PM Table 1 ( ) 3 ( TLC ) ( HPLC ) ( ) / ( GC/MS : ) ( FIMS ) 92 ( Merck Kieselgel 60 F 254 ) n- GC/MS Analysis of diesel fuel - Analytical item and method. Item Average Type Analysis DBE type Molecular Type analysis Compound composition I (PA) II (POA) analysis formula III (PIONA) (Stereo isomer*) Result H/C ratio Concentration Concentration Concentration by Concentration by Paraffins *: The number of P: Paraffines P: Paraffines DBE mol. formula Isoparaffins compounds is more Olefins A: Aromatics O: Olefins Naphthenes than 10,000 O: Olefins A: Aromatics ( Ring number ) Aromatics Method Elemental FIA HPLC HPLC & FIMS HPLC & FIMS (NMR ) No method analysis Conventional- SFC, TLC HR-EIMS NMR HPLC Qualitative Partially possible Analysis Quantitative Partially possible Analysis Note ) P: Paraffines, I: Isoparaffines, O: Olefines, N: Naphthenes, A: Aromatics FIA: Fluorecent Indicator Adsorption chromatography HPLC: High Pressure Liquid Chromatography FIMS: Field Ionization Mass Spectrometry GC/MS: Gas Chromtography / Mass Spectrometry HR-EIMS: High Resolution Mass Spectrometry R&D Vol. 32 No. 2 ( )

3 ( UV 254nm ) GC/MS FIMS GC Pump GC ( Polar column ) GC ( Nonpolar column ) Column Column HPLC b.p. Polarity GC/MS TLC Mol. Wt. Analytical methods for diesel fuel. Mass spectrometry ( MS ) TLC ( Rf ) ( F1 F11 ) GC/MS F6 F6 Fig ( 1 ) / ( C/H ) Fig. 4 ( DBE ) 0 TLC chromatogram & GC/MS results. R&D Vol. 32 No. 2 ( )

4 GC/MS results of TLC fraction F6. DBE 13 HPLCUV Fig. 65 ( F1 F5 ) GC/MS F1 ( DBE = 4 ) ( DBE = 5 ) ( DBE = 6 ) 24 DBE DBE ( ) HPLC ( ) TLC GC/MS HPLC GC/MS GC Fig. 4(c)Window Window 0 13 HPLC Fig. 4(d) Window ( ) ( ) R&D Vol. 32 No. 2 ( )

5 C 8 H 18 Compositional map of diesel fuel. (a) Contour line of B.P. and polarity and typical compounds (b) B.P. of typical compounds ( literature ) (c) B.P. window and typical compounds (d) Polarity window and typical compounds Compositional map of diesel fuel. Fractionation of Aromatics by HPLC. R&D Vol. 32 No. 2 ( )

6 Window8 24 Window 1 { Fig. 4(d) ( DBE = 5, H/C = 1.00 ) ( DBE = Peak intensity (a. u.) Sub-total of peak intensity (a. u.) Results of GC/MS of HPLC fractions. R&D Vol. 32 No. 2 ( )

7 13 H/C = 1.00 ) 8 } 1) TLC HPLC TLC HPLC ( 1% ) GC/MS 1% 2) GC/MS ( 1 ) 3) GC ( FID ) GC n- GC/FID GC TLC HPLCDBE TLC HPLC ( ) GC/MS ( ) ( FI ) 1) FI ( EI ) 2 S/N 2) FI FIMS ( ) (1) ( ) (2) HPLC ( 7 ) (1)1) (2) HPLC ( ) DBE 4 FIMS ( ) FIMS Fig. 8(a) m/z = n ( n : 0 16 ) ( DBE = 0 ) ( DBE = 7 ) Fig. 8(b) m/z = n ( n : 0 10 ) ( DBE = 7 ) ( GC/MS ) DBE 3 DBE 1 3 DBE 1 3 R&D Vol. 32 No. 2 ( )

$9 14 310 C 19 310 C GC/MS 310 C Fig. 4(a) 310 C Fig. 10 Relative intensity (%) Carbon number distribution of paraffin in diesel fuel, backend fraction.$

8 FIMS spectra of diesel fuels with different sulfur content. TLC HPLC ( H/C ) [ Fig. 4(d) ] GC [ Fig. 4(c) ] ( 310 C ) ( GC ) ( HPLC ) Fig C C GC/MS 310 C Fig. 4(a) 310 C Fig. 10 Relative intensity (%) Carbon number distribution of paraffin in diesel fuel, backend fraction. ( DBE = 4 ) 310 C ( ) ( ) R&D Vol. 32 No. 2 ( )

9 HPLC chromatograms of diesel fuel, R 310, and E 310. Detector : (a) RI, (b) UV. Fig. 4 : Fig. 4(b) DBE 4 : 4 DBE 3 [ ( DBE = 7 ) ( DBE = 8 ) ( DBE = 9 ) ] / RI Cause of shift of alkylbenzene peak in HPLC chromatograms from diesel fuel to R 310. R&D Vol. 32 No. 2 ( )

10 H/C : DBE H/C DBE 5 ( ) H/C DBE ( H/C=0 ) DBE ( ) ( ) [ DBE 4 ( MW = 106 ) ( MW = 330 ) ] Carbon number H/C : H/C ( H/C ) H/C H/C ( NMR ) H/C ratio DBE = 0 DBE = 0 Piling up DBE = 2 DBE = 3 Mono-arom. DBE = 4 DBE = 5 DBE = 1 DBE = 6 DBE = 7 DBE = 1 DBE = 2 DBE = 3 DBE = 4 DBE = 5 DBE = 6 Cs S <--> CL L Cs S CL C L CCL L <--> <--> CCs S Possibility of separation by No. of Aroma-ring. C S : Hydrocarbon of small carbon number, C L : Hydrocarbon of large carbon number R&D Vol. 32 No. 2 ( )

11 C/H H/C C 460 C PM 1 H/C ( ) PM PM 1) HPLC GC/MS 2) C/H2 3) HPLC GC 4) H/C ) 1) Khatri, N. J., Johnson, J. H. and Leddy, D. G. : "The Characterization of the Hydrocarbon and Sulfate Fractions of Diesel Particulate Matter", SAE Tech. Pap. Ser., No , 24p 2) Bouffard, R. A. and Beltzer, M. : "Light Duty Diesel Particulate Emissions -Fuel and Vehicle Effects", SAE Tech. Pap. Ser., No , 14p 3) Kageyama, K. and Kinehara, N. : "Characterization of Particulate Emission from Swirl Chamber Type Light-Duty Diesel Engine as a Function of Engine Parameters", SAE Tech. Pap. Ser., No , 12p 4) Wall, J. C. and Hoekman, S. K. : "Fuel Composition Effects on Heavy-Duty Diesel Particulate Emissions", SAE Tech. Pap. Ser., No , 42p 5) Barry, E. G., McCabe, L. J., Gerke, D. H. and Perez, J. M. : "Heavy-Duty Diesel Engine / Fuels Combustion Performance and Emissions -A Cooperative Research Program-", SAE Tech. Pap. Ser., No , 23p 6) Yoshida, E., Nomura, H., Sekimoto, M. : "Fuel and Engine Effects on Diesel Exhaust Emissions", SAE Tech. Pap. Ser., No , 9p 7) Weidmann, K., Menrad, H., Reders, K. and Hutcheson, R. C. : "Diesel Fuel Quality Effects on Exhaust Emissions", SAE Tech. Pap. Ser., No , 11p 8) Otani, T., Shigemori, M., Suzuki, T. and Shimoda, M. : "Effects of Fuel Injection Pressure and Fuel Properties on Particulate Emissions from H.D.D.I Diesel Engine", SAE Tech. Pap. Ser., No , 8p 9) Ulmann, T. L. : "Investigation of the Effect of Fuel Composition on Heavy-Duty Diesel Engine Emissions", SAE Tech. Pap. Ser., No , 19p 10) Fukuda, M., Tree, D. R., Foster, D. E. and Surhem, B. R. : "The Effect of Fuel Aromatic Structure and Content on Direct Iinjection Diesel Engine Particulate", SAE Tech. Pap. Ser., No , 12p 11) McCarthy, C. I., Slodoeske, W. J., Sieniki, E. J. and Jass, R. E. : "Diesel Fuel Property Effects on Exhaust Emissions from a Heavy Duty Diesel Engine that meets1994 Emissions Requirements", SAE Tech. Pap. Ser., No , 23p 12) Burley, H. A. and Rosebrock, T. L. : "Automotive Diesel Engines Fuel Composition vs. Particulates", SAE Tech. Pap. Ser., No , 12p 13) Bertoli, C., Del Giacomo, N., Iorio, B. and Prati, M.V. : "The Influence of Fuel Composition on Particulate Emissions of DI Diesel Engines", SAE Tech. Pap. Ser., No , 10p 14) Tsurutani, K., Takei, Y., Fujimoto, Y., Matsudaira, J. and Kumamoto, M. : "The Effects of Fuel Propeties and Oxygenates on Diesel Exhaust Emissions", SAE Tech. Pap. R&D Vol. 32 No. 2 ( )

12 Ser., No , 12p 15) Montagne, X., Boulet, R. and Guibet, J. C. : "Relation between Chemical Composition and Pollutant Emissions from Diesel Engines", 13th World Petroleum Congr. Forum, Topic.16 16),,, : " ", 70Vol.D, (1992), ) ASTM D1319, Standard Test Method for Hydrocarbon Types in Liquid Petroleum Products by Fluorecent Indicator Adsorption 18) Hayes, Jr, P. C. and Anderson, S. D. : "Hydrocarbon Group Type Analyzer System for the Rapid Determination of Saturates, Olefins, and Aromatics in Hydrocarbon Distillate Products", Analytical Chem., (1986), ) Hayes, Jr, P. C. and Anderson, S. D. : "The Analysis of Hydrocarbon Distillate for Group Types Using HPLC With Dielectric Constant Detection: A Review", J. Chromatographic Sci., (1988), ), : " ( 3 ) ",, -2(1985), ) Di Sanzo, F. P. and Yoder, R. E. : "Determination of Aromatics in Jet and Diesel Fuels by Supercritical Fluid Chromatography with Flame Ionization Detection ( SFC- FID ) : A quantitative Study", J. Chromatographic Sci., (1991), ) Wright, B. W., Udseth, H. R., Chess, E. K. and Smith, R. D. : "Supercritical Fluid Chromatography and Supercritical Fluid Chromatography/Mass Spectrometry for Analysis of Copmplex Hydrocarbon Mixtures", J. Chromatographic Sci., (1988), ) Galleges, E. J., Green, J. W., Lindeman, L. P., LeTourneau, R. L. and Teeter, R. M. : "Petroleum Group- Type Analysis by High Resolution Mass Spectrometry", Analytical Chem., -14(1967), ) Lee, S. W., Coulombe, S. and Glavincevski, B. : "Investigation of Methods for Determining Aromatics in Middle-Distillate Fuels", Energy & Fuels, 4(1990), ),, : " ( 1 ) 1H 13C-NMR ",, -4(1982), ) Ogawa, T., Araga, T., Okada, M. and Fujimoto, Y. : "Fuel Effects on Particulate Emissions from D.I. Engine - Chemical Analysis and Characterization of Diesel Fuel", SAE Tech. Pap. Ser., No , 21p 27) Wang, Z., Fingas, M. and Li, K. : "Fractionation of a Light Crude Oil and Identification and Quantitation of Aliphatic, Aromatic, and Biomarker Compounds by GC-FID and GC- MS, Part 1", J. Chromatographic Sci., 32(1994), ) Beckey, H. D. : "Principle of Field Ionization and Field Desorption Mass Spectrometry", Int. Ser. in Analytical Chem., (197 ), 244, Pergamon Press 29) Scheppele, S. E., Grizzle, P. L., Greenwood, G. J., Marriott, T. D. and Perrela, N. B. : "Detemination of Field- Ionization Relative Sensitivities for the Analysis of Coal- Derived Liquids and Their Correlation with Low-Voltage Elecron-Impact Relative Sensitivities", Analytical Chem., -14(1976), ) Mead, W. L. : "Field Ionization Mass Spectrometry of Heavy Petroleum Fractions - Wax", Analytical Chem., 4(1968), ) : " ",, -4(1991), ), : " ",, -5(1983), R&D Vol. 32 No. 2 ( )

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

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 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