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A Study of Composition and Size Distribution of Particulate Matter From DI Diesel Engine
A Study of Composition and Size Distribution of Particulate Matter From DI Diesel Engine
A Study of Composition and Size Distribution of Particulate Matter from DI Diesel Engine
Shigeyuki Tanaka and Toshio Shimizu
COSMO Research Institute
Copyright 1999 Society of Automotive Engineers, Inc.
ABSTRACT
The objective of this study is to clarify the particulate composition at each particle size and the influence of engine operating conditions and fuel properties on diesel particulate size distribution. Size distribution of particulate matter emitted from the latest Japanese DI diesel engine was measured using a Cascade Impactor. Most of the particles were smaller than 10-micron aerodynamic diameter and a significant percentage of the particles were shown in the aerodynamic diameter range less than 50nm. The chemical analysis of particles collected at each stage of Cascade Impactor showed that the aerodynamic diameter of the sulfate particle was less than 50nm. A large amount of SOF and SOOT was found in small particle size range, but the percentage of SOF in the large aerodynamic diameter particles was higher than that in the small particles. Moreover, when the percentage of SOF in the total particulate matter became higher by lowering the engine torque, the particles with the small aerodynamic diameter decreased. On the other hand, the influence of the fuel properties, such as distillation characteristics, cetane number, and fuel compositions was small within the limit of usual diesel fuel properties. However, the particles of small aerodynamic diameter increased compared with usual diesel gas oil delivered from mineral oil when the n-paraffin fuel was used.
matter exhausted from diesel vehicles has been strictly regulated in JAPAN. However, an accomplishment rate of the air environmental standards of SPM10 is still at a low level. Therefore, more strict regulations are needed and more engine modification, development of aftertreatment, and fuel reformulation are desired. Recently, much work about effects of fuel properties and engine modifications on the total mass of particulate matter from diesel engines has been carried out in research laboratories around the world (1)-(11). In our previous researches, we investigated the effects of fuel properties on the regulated emissions from diesel engines and clarified which properties affected those emissions (1, 2). Actually, reformulated fuel, which has focused on the reduction of sulfur and aromatics as well as on the increase in cetane number, is sold in European countries and the USA. Furthermore, the effect of synthetic fuel produced by Fischer-Tropsch synthesis on diesel emissions was described in the literature (12). However, there is little information about the influences of fuel reformulation and engine modification on size distribution and composition of particles in these studies. The goal of this study is to clarify the particulate composition at each size and influence of engine operating conditions and fuel properties on diesel particulate size distribution.
Table 1 Engine Specifications Cylinder Number 6 Injection System DI Displacement L 7.961 Valve System OHC4Valve Intake System NA Rated Power kW/rpm 147/2900 Max Torque Nm/rpm 530/1700 EGR NO Aftertreatment NO Common Rail YES
PARTICLE SIZE MEASUREMENTS A Low Pressure Cascade Impactor was used to measure particulate size distribution in this study. This instrument was able to collect the particles whose diameter is less than 0.5m that is lower limit in a usual cascade impactor by impact under low pressure. Characteristics of this instrument are described in Table 2. Stages 0 through L4 were used to collect particulate mass in aerodynamic diameter cut-off ranges from 0.05m to greater than 12m. The particles were collected on stainless steel plates. The last stage was followed by back up filter of Teflon coated glass fiber to collect particles below 0.05m.
0 1 2 3 4 5 6 7 L1 L2 L3 L4
Back Up Filter
12.0 8.4 5.7 3.6 2.0 1.1 0.76 0.50 0.29 0.19 0.12 0.05
Below 0.05
2.52 2.00 1.17 0.86 0.59 0.40 0.32 0.25 0.25 0.25 0.25 0.25 -
Table 3. Properties of NO.2 Diesel Fuels S2000 S500 Density 15C g/cm3 0.8296 0.8274 Viscosity 30 3.690 3.760 C mm2/s Cetane Number 55.4 55.6 Distillation IBP C 161.0 161.5 10% C 205.5 206.0 50% C 290.0 289.5 90% C 334.5 333.5 FBP C 353.0 351.5 Sulfur mass% 0.20 0.05 HPLC Aromatics Totalvol.% 22.7 21.8 1Rvol.% 19.6 20.4 2Rvol.% 2.5 1.2 3Rvol.% 0.6 0.2
TEST FUELS The properties of the test fuels are described in Tables 3 and 4. Test fuels presented in Table 3 were used to measure compositions at each size of particles exhausted from the diesel engine. The fuel named as S500 is a Japanese NO.2 grade Diesel Fuel, which is available now, with the sulfur contents of 500ppm. The sample S500 is a deeply desulfurized fuel. Sample S2000 is a former Japanese NO.2 grade fuel with the sulfur contents of 2000ppm. The poly aromatic contents and sulfur contents of the S500 are low compared with those of the S2000 because of the treatment through deeply desulfurization. Sample S500 was also used to investigate the influence of the engine operating conditions on the diesel particulate size distributions. The test fuels shown in Table 4 were specially prepared to investigate the effects of the fuel properties on size distributions of diesel particulates. Sample HT90 was a base fuel in the special fuels, which was a paraffin fuel (mixtures of n-paraffin and iso-paraffin) with cetane number of 57 and 90% boiling point of 310C. Sample LT90 was lowered in 90% boiling point to 264C. Samples CN47, CN57, and CN87 were changed in cetane number by adjusting the ratio of n-paraffin in the fuel. Sample CN87 was a 100% n-paraffin fuel. Sample PA is the same as HT90 and 100% paraffin fuel. NA, 1RA, 2RA, and 3RA were blended with naphthene of 10%, 1R-aromatics of 10%, 2R-aromatics of 10% and 3R-aromatics of 2%, respectively. In these special fuels, only a target property was changed while keeping the rest of the properties constant as shown in Table 4. In this way, we could independently investigate the effects of fuel properties on the size distribution of diesel particles. EMISSION MEASUREMENT The emission measurement system is shown in Figure 1. PM (particulate matter) was measured through a mini-dilution tunnel according to the Japanese 13 mode test cycle. The Japanese 13 mode test cycle and dilution conditions are presented in Table 5. In this work, the torque points in the 13 mode test cycle for each test fuel were adjusted to the same level to eliminate the volumetric fueling effect. Namely, torque was adjusted while fuel flow remained constant to the base fuel (S500). In some test, engine was operated at 80% rpm and 80% load conditions (mode 12) or 60% rpm and 5% load condition (mode13). The tunnel was preconditioned by running engine at 80% rpm and 80% load condition for 20 minutes before each testing. The total particulate emissions were determined from particulate samples collected on a Teflon coated glass fiber filter of 70mm in diameter through a mini-dilution tunnel using the CVS system. The soluble organic fraction (SOF) was removed from the sampling filter by Soxhlet extraction with dichloromethane. The amount of SOF was determined from the filter weight difference before and after extraction. The sulfate was analyzed by ion chromatography. The remaining amount of the sample was determined as SOOT. 3
Engine Exhaust
D-13 MODE
Test Fuel
NOx,CO2,CO,HC
CVS
PM
Cascade Impactor
50 40
30 20 10 0 0.01
S500 BG
SIZE DISTRIBUTION OF SULFATE, SOF AND SOOT To investigate the size distribution of each component in particulate matter, particles collected on each stage were analyzed chemically. In this study, two fuels with different sulfur contents were used to clarify the size distribution of each component and the effects of deeply desulfurized fuel on the size distribution of particulate matter. Figure 4 shows the effects of deeply desulfurized fuel on the total weight of particulate matter and the compositions. The deeply desulfurized fuel has effects on reducing the SOF and sulfate emissions. The size distribution of particulate matter from S2000 and S500 was compared in Figure 5. The Wp in the figure shows the weight of each particle and the Wt presents the total weight of particulate matter collected as S2000 sample was used. When S500 fuel was used, the particles less than 3m were reduced compared with S2000 fuels. The ratio of SPM2.5 and SPM10 out of the total particulate matter emitted from diesel engine fueled with S500 sample was lower than the S2000 samples as shown in Figure 6. Compositions of each particle and size distribution of each component are presented in Figure 7. A significant percentage of sulfate particles was observed in the aerodynamic diameter less than 50nm. Moreover, the ultra fine PM less than 50nm were reduced by desulfurization of fuel. On the other hand, it was found that the larger amounts of SOOT particles were emitted in smaller aerodynamic diameter but the desulfurization of fuel had no influences on the emission level and the size distribution. Furthermore, the larger amounts of SOF were emitted in smaller aerodynamic diameter and its distribution had two peaks at 200nm and 2000nm. These peaks of SOF were reduced by desulfurization of fuel. The ratio of SOF and SOOT in each particle was compared in Figure 8. It was found that the SOF ratio was larger in the case of large particles. As mentioned above, the particulate compositions differed in the size, and the sulfate particles were mainly present in ultra fine particles less than 50nm. And SOF ratio in large particles was high. It might be explained that hydrocarbon species like SOF promote the agglomeration of particles. To confirm these assumption, the diesel engine was operated in several conditions. Generally, SOF was emitted significantly in the condition of low load. Therefore, the size distribution of particulate was measured at two different load conditions. The particulate emission is shown in Figure 9 and size distribution of particles was presented in Figures 10 and 11. In the low load condition, the SOF ratio was very high. It was confirmed that the particles with a large aerodynamic diameter were more numerous in the high SOF ratio conditions. Namely, it was able to enlarge the particle size appeared to be enlarge by an increase in the SOF emissions.
Wp/Wt (%)
0.03
0.1
0.3
10
Dp (m)
Figure 2 Size Distribution of Diesel Particulate
100 S500 80
SPM10
SPM2.5
60
%
40 20 0 0.01 0.03
0.1
0.3
10
Dp (m)
Figure 3 SPM10 and SPM2.5 out of Diesel Particulate
In which, the vertical axis is weight percentage of particles of each size out of total particulate emissions. Size distribution of back ground particles in the dilution air was also shown in Figure 2. The weight of back ground particles was less than 2% of total diesel exhaust particles weight and had no influences on size distribution of diesel particulate. Most of the particles from the test engine were smaller than 10m aerodynamic diameter and a significant percentage occurred in the aerodynamic diameter range less than 50nm. As shown in figure 3, greater than 95% of diesel particulate matter from the test engine are SPM10 and about 90 % of diesel particles are SPM2.5.
35
35
35
30
30
30
25
25
25
Wp/Wt (%)
20
20
Wp/Wt (%)
20
15
15
15
10
10
10
0 0.01 0.03
0.1
0.3
10
0 0.01 0.03
0.1
0.3
10
0 0.01 0.03
0.1
0.3
10
Dp (m)
Dp (m)
Dp (m)
S2000
S500
120
100
Wp/Wt (%)
Wp/Wt (%)
40
80
80
60
60
Wp/Wt (%)
30
S2000 S500
40
40
20
20
20
S2000
>0.05 -0.12 -0.19 -0.29 -0.5 -0.76 -1.1 -2.0 -3.6 -5.7 -8.4 -12.0 12.0<
S500
>0.05 -0.12 -0.19 -0.29 -0.5 -0.76 -1.1 -2.0 -3.6 -5.7 -8.4 -12.0 12.0< 0
10
Dp (m)
Dp (m)
0 0.01
0.03
0.1
0.3
10
Dp (m)
Figure 5 Comparison of Size Distribution between S2000 and S500 sample 100 80 60 2%
S2000 S500
40 20 0 0.01 0.03
EFFECTS OF FUEL PROPERTIES ON SIZE DISTRIBUTION OF PM As mentioned above, particulate compositions were able to change the size distribution because particulate composition was different at each size range. In previous papers (1 and 2), we have shown that fuel properties affected particulate composition. Therefore, the effects of fuel properties, such as distillation characteristics, cetane number, and fuel composition on size distribution of particulate matter were investigated. In this study, the tests were performed by using special fuels, which target property change only while holding of the other fuel properties. Furthermore, there was no sulfur in the special fuel and the level of sulfate in the particulate matter was below the detection limit.
0.1
0.3
10
Dp (m)
Figure 6 Reduction of SPM2.5 and SPM10 by Deeply Desulfurization 5
Effect of distillation characteristics The 90% boiling points of the test fuel were changed from 310C to 264C. The test results are presented in Figures 12 and 13. The Wp in Figure 13 shows the weight of each particle and the Wt presents the total weight of particulate matter collected as heavier fuel (HT90) was used. When the light fuel (LT90) was used, both SOOT and SOF in the particulate matter decreased as shown in figure 12. However, the ratio of SOOT and SOF in the particulate did not change. Therefore, the size distribution of particulate matter from light fuel was similar with that of heavier fuel. However, it was found that decrement of smaller particles was larger than the large particles in the use of lower 90% boiling points fuel. Effect of cetane number The cetane number of the test fuels was changed from 87 to 47 by adjusting the ratio of n-paraffin and iso-paraffin in the test fuel. Especially, CN87 fuel contained only n-paraffin with 12 to 20 of carbon number. Test results are shown in Figures 14 and 15. The Wp in Figure 15 shows weight of each particle and the Wt presents the total weight of particulate matter collected as the lowest cetane fuel (CN47) was used. When cetane number increased, the SOOT emission in particulate matter increased. SOF emissions did not change in this study. Size distributions of particles were changed as cetane number increased and ultra fine particles from high cetane fuels were emitted significantly compared with lower cetane fuels as shown in Figure 15. These phenomena showed that the aerodynamic diameter of particles became smaller by using fuel of high cetane number, which produced particles with low SOF ratio.
50 40
Wp/Wt (%)
30
60%rpm/5%load 80%rpm/80%load
20 10 0 0.01 0.03
0.1
0.3
10
Dp (m)
Figure 10 Effect of Engine Conditions on PM Size Distribution
100 10% 80
0.4
SOF SOOT
PM Emission g/kWh
60
60%rpm/5%load 80%rpm/80%load
0.3
40 20 0 0.01 0.03
0.2
0.1
0.1
0.3
10
Dp (m)
Figure 11 Effect of Engine Conditions on SPM2.5 and SPM10
HT90
LT90
50
50 40 CN47
HT90 LT90
40
Wp/Wt (%)
30
Wp/Wt (%)
20
10
0 0.01
0.03
0.1
0.3
10
Dp (m)
Figure 13 Effect of Distillation Characteristics on Size Distribution
0.03
0.1
0.3
10
Dp (m)
Figure 15 Effect of Cetane Number on Size Distribution
Effect of fuel compositions To investigate the effect of fuel compositions, naphthene, mono-aromatics, di-aromatics, and tri-aromatics were blended in the paraffin fuel. Test results were presented in Figure 16 and 17. It was found that poly-aromatics affected the particulate emissions. Especially, SOF emission in the particulate was increased when poly-aromatics were blended in the fuel. In this case, not only small particles but also relatively large particles were increased as show in Figure 17. Increase of SOF emissions by blending poly aromatics in the fuel tends to enlarge the size of particles, but the degree was not so large.
0.4
SOF SOOT
PM Emission g/kWh
0.3
0.2
0.1
0.4
SOF SOOT
PA
NA
PM Emission g/kWh
0.3
0.2
Wp/Wt (%)
40
PA
0.1
30
2RA
20
3RA
CN47
CN57
CN87
10 0 0.01
0.03
0.1
0.3
10
Dp (m)
Figure 17 Effect of Fuel Compositions on Size Distribution
Wp/Wt (%)
As mentioned above, fuel properties changes are able to decrease (or increase) the emission level of total particulate matter by weight. Moreover, there was a little influence on particle size. It was confirmed that the high SOF ratio tends to enlarge the aerodynamic diameter of particles. However, it is difficult to significantly change the size distribution of particles because SOF ratio did not change greatly by the fuel modification in this study. Comparison of diesel gas oil and n-paraffin fuel In this section, we compared the emissions from diesel gas oil (DGO) which is available in Japan (S500) and n-paraffin fuel prepared to imitate the FT fuel (CN87). The test results are presented in Figures 18 and 19. Gaseous emissions, such as NOx, CO, and HC decreased when the n-paraffin fuel was used. It was considered that high cetane number and no aromatics contributed to the low level of gaseous emissions. On the other hand, SOOT emissions in particulate matter increased when n-paraffin fuel was used. SOF emissions from n-paraffin were less than usual diesel gas oil. As the results, total particulate emissions of DGO and n-paraffin showed the almost same level. Furthermore, when n-paraffin was used, ultra fine particles less than 50nm were increased compared with DGO in this study.
Gaseous Emissions
DGO(S500) n-Paraffin(CN87)
0.1
0.3 1 Dp (m)
10
The n-paraffin fuel had desirable effects on reducing gaseous emissions, such as NOx. However, the SOOT emission in particulate matter increased as n-paraffin fuel was used in spite of the fact that the fuel was light as well as there were no aromatics. It was considered that extremely high cetane number might contribute to the increase of SOOT emissions.
0.5
PM Emission
SOOT SOF Sulfate
Emission g/kWh
The particulate composition at each particle size and the influence of engine operating conditions and fuel properties on diesel particulate size distribution were investigated in this study. The following conclusions can be stated. Most of the particles were smaller than 10m aerodynamic diameter and a significant percentage occurred in the aerodynamic diameter range less than 50nm. It was found that the aerodynamic diameter of the sulfate particle was less than 50nm. The large amount of SOF and SOOT was found in the small particle size range, but the SOF ratio in the large aerodynamic diameter particles was higher than that of the small particles. When the ratio of SOF in the total particulate matter was increased by lowering the engine torque, the particles of a small aerodynamic diameter decreased.
0.3
0.2
0.1
CO
THC
NOx
DGO(S500) n-Paraffin(CN87)
Fuel properties affected the emission level of total particulate matter by weight. Moreover, there was a little influence on particle size. It was confirmed that the high SOF ratio tends to enlarge the aerodynamic diameter of the particles. However, since SOF was not changed greatly in this study, a large change in size distribution was also not seen. When the n-paraffin fuel was used, the particles with the small aerodynamic diameter were increased compared with usual diesel gas oil delivered from mineral oil.
REFERENCES
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