UNIVERSITY OF CINCINNATI

September 18
_____________ 03
, 20 _____

Phirun Saiyasitpanich
I,______________________________________________,
hereby submit this as part of the requirements for the
degree of:

Master of Science
________________________________________________
in:
Environmental Engineering
________________________________________________
It is entitled:
Influence of Different Applied Loads and Various Sulfur
________________________________________________
Levels in Diesel Fuels on Diesel Particulate Emissions
________________________________________________
________________________________________________
________________________________________________

Approved by:
________________________
Dr. Tim C. Keener
________________________
Dr. Mingming Lu
________________________
Dr. Soon-Jai Khang
________________________
________________________
 Influence of Different Applied Loads and Various Sulfur Levels in
Diesel Fuels on Diesel Particulate Emissions

A thesis submitted to the

Division of Research and Advanced Studies
Of the University of Cincinnati

in partial fulfillment of the

requirements for the degree of

MASTER OF SCIENCE

in the Department of Civil and Environmental Engineering

of the College of Engineering

2003

by

Phirun Saiyasitpanich

B.E. Envi, Chulalongkorn University, Thailand, 1998

Committee Chair: Dr.Tim C. Keener

 ABSTRACT

A Generac Model SD080 diesel generator rated at 80 KW, 60 Hz, is used as a DPM

emission source. This unit is powered by a Generac Model 5.0 DT diesel engine, which is

a 5 liter (304 in3) engine rated at 100 hp at 1800 rpm. A load bank (load simulator),

model Merlin 100 manufactured by Simplex is used to simulate loads by applying banks

of heaters from 0, 25, 50, 75 KW, respectively. Two types of diesel fuel containing

0.37% and 0.21% sulfur are selected as fuels supplied to this generator. The EPA

sampling method 1A - Sample and Velocity Traverses for Stationary Sources with Small

Stacks or Ducts – is selected as a reference method for measurement of the stack gas

velocity and DPM mass concentration. The results show DPM mass concentrations vary

from 10 mg/m3 to 38 mg/m3 as higher loads are applied to the generator and the sulfur

content in diesel fuels increases.

 ACKNOWLEDGEMENTS

I would like to deeply thank my advisor, Dr. Tim C. Keener, for his guidance,

instructions and encouragement through out my research. I would also like to thank my

other committee members, Dr. Mingming Lu and Dr. Soon-Jai Khang for their valuable

suggestions in this project.

I would like to acknowledge Achariya Suriyawong for her great assistance in the stack

sampling and data analyses for the entire two months.

Finally, I would like to send my special thank and gratefulness to my family and my

girlfriend for their forever love and support throughout my study.

 1

TABLE OF CONTENTS

TABLE OF CONTENTS 1

LIST OF TABLES 3

LIST OF FIGURES 4

LIST OF SYMBOLS 5

1. INTRODUCTION 7

1.1. Backgrounds and Significance 7

1.2 Research Objectives 9

2. LITERATURE REVIEW 11

2.1 DPM Compositions 11

2.2 DPM Measurement Methods 12

2.2.1 Size Selective Sampling with Gravimetric or EC analysis 14

2.2.2 Respirable Dust Sampling with RCD Analysis 17

2.2.3 Respirable Dust sampling with EC Analysis 18

2.2.4 Elemental Carbon (Diesel Particulate): NIOSH Method 5040 18

2.3 Overviews of DPM Concentrations 20

2.4 Overviews of DPM Control Technology 23

2.4.1 MSHA-Approved Engines with Low Emissions 24

2.4.2 Derated Engines 25

2.4.3 Fuels 25

2.4.4 Fuel Additives 27

 2

2.4.5 Diesel Oxidation Catalytic Converters (DOCCs) 29

2.4.6 Diesel Particulate Filters (DPFs) 30

2.4.7 Disposable Diesel Exhaust Filter (DDEF) 32

3. EXPERIMENTAL SETUP 33

4. DATA ANALYSIS 36

5. RESULTS AND DISCUSSION 41

6. CONCLUSION 50

7. FUTURE WORK 51

8. REFERENCES 52

9. APPENDIX 55
 3

LIST OF TABLES

Table 2.2.1 Exposure limits for DPM 15

Table 2.3.1 Summary of contributions to 24-hr average PM mass 21

or PM carbon concentrations from diesel exhaust or

a combination of diesel/gasoline exhaust

Table 2.3.2 Example of mass balance and chemical composition 22

from medium-duty diesel truck emissions

Table 2.3.3 Typical occupational DPM exposure levels 23

Table 2.4.3 Summary of diesel fuel regulations and incentive 28

programs for selected countries

Table 5.1 Summary of experimental results for 1st diesel fuel 42

(S=0.37%)

Table 5.2 Summary of experimental results for 2nd diesel fuel 45

(S=0.21%)

Table 5.3 %Excess O2 and %Excess air in stack flue gas 48

 4

LIST OF FIGURES

Figure 2.1 Schematic of Diesel Particulate Matter 11

and Vapor Phase Compounds

Figure 3.1 Schematic Diagram of DPM Sampling Systems 34

Figure 3.2 Picture of a DPM Sampling site 35

Figure 5.1 Variation of Fuel Utilization on Different Applied Loads 41

Figure 5.2 Variations of Stack Gas Flow Rates on 43

Different Applied Loads (0.37% S)

Figure 5.3 Variations of DPM Mass Concentrations on 43

Different Applied Loads (0.37% S)

Figure 5.4 Variations of Pollutant Mass Rates on 44

Different Applied Loads (0.37% S)

Figure 5.5 Variations of Stack Gas Flow Rates on 45

Different Applied Loads (0.21% S)

Figure 5.6 Variations of DPM Mass Concentrations on 46

Different Applied Loads (0.21% S)

Figure 5.7 Variations of Pollutant Mass Rates on 47

Different Applied Loads (0.21% S)

Figure 5.8 Variations of Pollutant Mass Rates on 47

Different Applied Loads for both type of diesel

Figure 5.9 SEM picture of DPM (75 kW, 0.21%S) 48

 5

LIST OF SYMBOLS

An = cross-sectional area of nozzle, ft2

As = cross-sectional area of stack, ft2

Bws = fraction of water vapor in gas stream (dimensionless)

Cp = pitot tube calibration coefficient (dimensionless)

Kp = pitot tube constant, 85.49 ft/sec

K1 = 0.04707 ft3/mL

K3 = 0.002669 in. Hg-ft3/mL-°R

mpar = mass of particulate matter collected, mg

Md = dry basis, molecular weight of stack gas, lb/lb-mole

Ms = wet basis, molecular weight of stack gas, lb/lb-mole

%I = the percent isokinetic, vn/vs * 100

pmr = pollutant mass rate, mass per time, lb/hr (kg/hr or g/min)

Pb = barometric pressure at measurement site, in. Hg (mmHg)

Ps = static pressure in stack, in.Hg

Ps = absolute static pressure in stack, Pb + (ps/13.6), in. Hg (mmHg)

Pstd = standard absolute pressure, 29.92 in. Hg (760 mmHg)

Qs = volumetric flow rate of dry stack gas, corrected to standard conditions, dscf/hr

Tm(avg) = absolute temperature at the meter, °R

Ts(avg) = average absolute temperature of stack gas over test period, °R

Tstd = standard absolute temperature, 528 °R

Vf = final volume of liquid in impingers, mL

Vi = initial volume of liquid in impingers, mL

V1c = volume of liquid collected in impingers, mL

 6

Vm = dry gas volume measured by dry gas meter, at actual conditions, dcf
Vm(std) = dry gas volume measured by dry gas meter, corrected to standard conditions, dscf

Vwe(std) = volume of water vapor condensed, corrected to standard conditions, scf

vs = stack gas velocity, ft/sec

Y = correction factor for dry gas meter (dimensionless)

∆H = average pressure differential across the orifice meter, in. H2O

∆pavg = average pressure drop across the pitot tube manometer during the test, in H2O

C = Carbon

H2 = Hydrogen

N2 = Nitrogen

S = Sulfur

O2 = Oxygen

EA = Excess Air
 7

1-Introduction

1.1 Backgrounds and Significance

Particulate Matter (PM) is one of the six criteria pollutants listed by U.S.EPA

whose emissions are limited and monitored in order to prevent its harmful impact on

human health and public welfare. PM mainly consists of a mixture of solid particles and

liquid droplets found in the air. Primary PM is emitted directly from a variety of sources

such as cars, factories, construction sites, unpaved roads, stone crushing, and burning of

woods. Secondary PM is commonly formed when emissions of Sulfur Dioxide (SOx),

Nitrogen Oxides (NOx), ammonia, organic compounds and other gases react in the

atmosphere.

PM is generally classified into two distinct size modes, which are PM10 and PM2.5

principally associated with its impact on human health. The former refers to particles less

than or equal to 10 µm in diameter while the latter describes the “fine” particles that are

less than or equal to 2.5 µm in diameter. “Coarse fraction” particles refer to the particles

that fall between these two size ranges. In general, coarse PM can comprise of both

primary and secondary particles and fine PM contains mainly secondary particles.

Between 1992 and 2001 EPA reported summary data obtained from 770

nationwide monitoring sites stating that average PM10 concentration decreased by 14%

[1]. Direct PM10 and PM2.5 emissions also decreased by 13% and 10%, respectively [1].

Even though we have achieved significant decrease in DPM after the enactment of clean
 8

air act amendment in 1990, there are still over 20 millions of people dwelling in areas

with PM concentration above the national standard [1].

As situation of PM in ambient air seems to be attenuated at a certain level,

recently, effect of the particulate matter generated from nonroad diesel engines used in

most kinds of mining, agricultural, construction, and industrial equipment, particularly in

underground mining, have gained substantial attention of researchers and various

regulatory agencies.

Diesel Particulate Matter (DPM) has become a major issue due to its physical

characteristics and chemical complexity. DPM has typical size ranges mainly between 5

nm to 1.0 µm with 90% of the particles being < 1.0 µm in diameter, and has a mass

median diameter of 0.2 µm [2], [3], [4]. DPM is composed of the highly respirable

particulate matter. It is consequently significant in terms of potential health impacts due

to its ability to penetrate more deeply into the bronchial passages and alveoli of human

lungs. DPM is also found to bind with Polycyclic Aromatic Hydrocarbons (PAHs),

alkylated benzenes, nitro-PAHs, and a variety of polar, oxygenated and nitrated

derivatives for which these compounds are associated with carcinogenicity and

mutagenicity in human health.

The effect of DPM on human health due to specific components of DPM is still

open to question. Several previous laboratory studies have reported a wide variety of

DPM potential effects. Most of attention has focused on the carcinogenic potential of

inhaled DPM owing to its characteristic as stated in the former paragraph. At least two

components are now considered to have potential to provoke the carcinogenic effect: the

inorganic “carbon core” portion (SOL) and the adsorbed organics or soluble organic
 9

fraction (SOF) portion. According to several laboratory studies with rats performed by

Mauderly et al. 1991, Heinrich 1993, and Nikula et al. 1993, the SOL was indicated to be

essential for initiation of tumor formation. The SOF particularly associated with PAHs

and Nitro-PAHs could have a contribution to the overall carcinogenic effect.

In 1988, the National Institute of Occupational Safety and Health (NIOSH) first

recommended that DPM be considered as a potential carcinogenic substance. In 1989, the

International Agency for Research on Cancer (IARC) deduced that DPM was possibly

carcinogenic to humans. The World Health Organization (WHO), the U.S. Department

of Health and Human Services (DHHS), and the Environmental Protection Agency

(EPA) also identified DPM as a probable human carcinogen [2], [5], [6].

The studies done by the Health Effect Institute (HEI) showed that long-term

occupational exposure to diesel particulate exhaust is associated with a 20%-50%

increase in the relative risk of lung cancer [7].

NIOSH used several quantitative risk models to predict lung cancer in miners

subject to diesel exhaust. All the models suggest high relative risks (i.e., 1/1000) for

miners with long-term exposures greater than 1000 µg/m3 of DPM [8].

1.2 Research Objectives

The overall goal of this project is to determine correlation between DPM mass

concentration and generator operating loads. Influence of sulfur contents in diesel fuels

on DPM mass concentrations will also be measured and presented in association with the

generator operating loads. In addition, data obtained from this project will be used as
 10

criteria parameters for design of a new DPM control device for the underground mine

application.
 11

2-Literature Review

2.1 DPM Compositions [9]

DPM is a complex mixture of organic and inorganic compounds in liquid and

solid phases. The organic species are generated primarily from unburned fuels and

lubricating oil, even though some may be formed during the combustion process and/or

reaction with catalysts. These species include groups of compounds such as aldehydes,

alkanes, alkenes, (both straight and branched chains), and aromatic compounds (single

rings, substituted, and polynuclear). Species like carbonyl (C=O), hydroxyl (OH), and

nitro (NO2) may also be present in DPM. The inorganic fractions comprise of sulfur,

oxygen, and carbon components such as sulfate (SO4 – basically H2SO4 and some metal

ion sulfates), and solid carbon particles (SOL) or soot. Schematic of DPM and Vapor

phase Compounds are shown in Figure 2.1.

Figure 2.1: Schematic of Diesel Particulate Matter and Vapor Phase Compounds
(from Ref. 9)
 12

As shown in Fig 2.1, DPM primarily consists of an agglomerate of SOL; adsorbed

to the SOL are SO4 that can be removed by water and hydrocarbons (named the soluble

organic fraction or SOF) that can be removed by an organic solvent. In addition, DPM

may be associated with droplets of liquid, condensed hydrocarbons, and SO4 particles.

Condensed hydrocarbons or particle phase hydrocarbons deposited on DPM surfaces are

not volatile enough to exist in the vapor phase and may not be adsorbed onto the SOL

due to low SOL levels but will also be removed by an organic solvent as SOF.

The structure and chemical composition and the diameter of DPM is however a

function of copious parameters including fuel compositions, engine design, engine

operating conditions, and the exhaust aftertreatment processes. In general, DPM can be

characterized into two lucid size modes: the agglomeration mode and the nucleation

mode. The former mode accounts for the particles with the diameters ranging from 50 nm

to 1.0 µm and contributes to the majority of the DPM mass [9], while the latter contains a

great number of the particle numbers, but does not contribute significantly to the total

DPM mass. It has been found that volatile or semivolatile organic compounds, sulfur

compounds, and trace elements are major compositions of the nucleation mode particles.

2.2 DPM Measurement Methods

The concerns about the health impacts of DPM exposure have lead to the issuing

of regulations by several government agencies. Mine Safety and Health Administration

(MSHA) has issued regulations at 30 CFR 7 to define DPM as “ any material collected on

a specified filter medium after diluting exhaust gases with clean, filtered air at a

temperature of <125 °F (52 °C), as measured at a point immediately upstream of the

 13

primary filter. This material is primarily carbon, condensed HC, sulfates, and associated

water.” In addition, Bagley et al. 1993 described DPM as any exhaust components other

than uncombined water that collects on a filter in a dilution tunnel at a temperature < 53

°C. These designated definitions provide the testing facilities to assess the DPM

emissions by measuring weight collected on the filter, i.e., by gravimetric method.

Nevertheless, using the gravimetric determination is not adequate to be used for

comparison of performance of some control technologies and equally insufficient in

providing an evaluation of health impact.

In 1995, the ACGIH proposed that DPM be considered as an A2 level carcinogen

(suspected to human carcinogen) and suggested the Threshold Limit Value-Time

Weighted Average (TLV-TWA) of 0.15 mg/m3 for particles with an aerodynamic

diameter of less than 1 µm [9]. In 1999 and 2001, the ACGIH has amended its proposal

and lowered the TLV-TWA from 0.15 mg/m3 to 0.05 mg/m3 and 0.02 mg/m3,

respectively. The 50 mg/m3-TLV proposed earlier, indeed, applied to total DPM, which

includes both organic and elemental carbon (OC/EC). Nevertheless, the majority of DPM

compositions are not organic carbon (there are many other sources of organic carbon);

thus, using it as a marker component for measurement of DPM could provoke misleading

results. Based on several studies, NIOSH has indicated that elemental carbon is a

substance fairly characteristic of DPM; in other words, there are just few other sources of

elemental carbon in most workplace where workers could be exposed. It has also been

suggested that elemental carbon constitutes about 40% of total carbon in DPM [9].

Studies by Perez and Williams, 1989, also indicated that in general, non-extractable

elemental carbon accounts for a greater fraction of DPM mass than organic carbon.
 14

In January 2001, MSHA promulgated two novel rules to regulate the exposure of

underground miners to DPM. The interim DPM concentrations measured as total carbon

by means of NIOSH Analytical Method 5040 (NIOSH 1999) is set at 0.4 mg/m3 and

requires underground metal and nonmetal mine operators to comply by July 19, 2002.

The compliance level DPM concentration limit will be lowered to 0.16 mg/m3 on January

19, 2006. Presented in the US CFR Part 70, the coal mining regulations require that

exposure of personnel to respirable coal mine particles be limited to an 8 hr-TWA that

does not exceed 2.0 mg/m3 in order to provide protection against coal worker’s

pneumoconiosis (CWP) [10]. In addition to ACGIH and NIOSH exposure limits for

DPM, table 2.2.1 shows the summary of DPM exposure limits designated by several

nationwide organizations.

In general, two sampling methods are commonly used in underground mines to

collect DPM samples for analysis; these are respirable dust sampling and size selective

sampling. Three analytical methods have been used to quantify DPM in collected

samples: submicrometer particulate mass analysis (gravimetric), respirable combustible

dust analysis (RCD; also gravimetric), and EC analysis. Integrating the sampling and

analysis methods produces three methods to measure DPM referred to as 1) size selective

sampling with gravimetric or EC analysis, 2) respirable dust sampling with RCD

analysis, and 3) respirable dust sampling with EC analysis (Watts, 1995; Cantrell and

Watts, 1996).

2.2.1 Size Selective Sampling with Gravimetric or EC analysis

This method makes use of the difference in the aerodynamic diameter size

between combustion and mechanically generated aerosols to separate diesel aerosol from
 15

noncombustion aerosols in the collecting process. Unlike respirable dust sampling, which

collects a fraction of particles up to 10 µm in size, this method separate respirable aerosol

Country or Organization Value, mg/m3 DPM Measured

Current Limits

U.S.: MSHA metal/nonmetal July 19, 2002: 0.4 EC+OC as determined

underground mines July 19, 2006: 0.16 by NIOSH Method 5040
[66 Fed. Reg. 5706 (2001)]

U.S.: MSHA Emissions rates set for Total DPM measured in

Underground coal mines [66 various classes of accordance with ISO 8178
Fed. Reg. 5526 (2001)] equipment, e.g., heavy procedures
duty equipment 2.5 g/hr [30 CFR7 (1996)]

Canada: Underground, metal 1.5 RCD

and nonmetal mining

Germany: Underground, 0.3 EC, coulometric

metal and nonmetal mining
and construction Sites

Germany: general 0.1 EC, coulometric

occupational environment
Switzerland 0.1 EC, coulometric
[Majewski 1999]
Proposed Limits:

ACGIH [1995] 0.15 Particles<1 µm in size

ACGIH [1998] 0.05 Total carbon in particles
< 1µm in size
ACGIH [2001] 0.02 (EC = 40% of EC particles < 1 µm in size
DPM)

Table 2.2.1 Exposure limits for DPM DieselNet (2001)

 16

particles from DPM by using inertial impaction on greased, aluminum foil substrate.

Inertial impaction removes almost all (>90%) nondiesel particles and small percentage

(<15%) of large DPM [4]. The submicron DPM is collected on the final filter

downstream of the impactor (i.e., a specialized impactor with a 0.8 µm cutpoint).

Gravimetric method allows determination of the mass fraction in each size range

and its advantage over the traditional respirable dust sampling is that it separates large

particles (predominately nondiesel in origin), but still enables the respirable fraction to be

calculated.

The size selective sampling was originally designed to be used in coal mines

where water scrubber is used to remove larger DPM (>0.8 µm) and thus minimize the

amount of DPM not captured on the filter. However, this method is also applicable to be

used in metal/nonmetal mines where scrubbers are rarely used. In this situation, studies

by Cantell et al., 1990b point out that approximately 10-15% of total DPM will be lost

seeing that it is larger than 0.8 µm and will not be collected on the aluminum foil

substrate.

The target of the gravimetric method is to capture submicrometer DPM aerosol

because diesel particulate is largely submicrometer and, therefore, interference of larger

dusts is minimized. Nevertheless, the drawback of this method is when other

submicrometer aerosols (e.g., cigarette smoke or other combustion aerosols, condensation

aerosols) are present; these particles will interfere in the gravimetric determination of

diesel particulate. This approach is also limited to relatively high concentration of

particles because of its poor sensitivity when adopted for personal monitoring.
 17

In addition, EC analysis can be used in conjunction with size selective sampler

when a pre-combusted glass fiber filter is used to collect the submicrometer material.

This method provides an advantage over other aerosol measurement techniques, which

either do not capture submicrometer particles or destruct samples during analysis.

2.2.2 Respirable Dust Sampling with RCD Analysis

RCD approach was originally developed in Canada for determination of DPM

concentrations in non-coal mines (Makery, 1978) and is widely used in the Canadian

mining industry. The RCD method focuses on the respirable fraction, not just

submicrometer particles; therefore, only portion of RCD is attributable to DPM aerosol.

In the RCD method, a 23 or 37 mm, 0.8 µm silver membrane (or quartz-fiber)

filter or pre-combusted, glass fiber filter are used to collect airborne respirable aerosols.

The cyclone with 50% cut point of 4.0 µm can also be used as a respirable dust

preclassifier. Gravimetric determination of respirable dust is achieved by weighing the

silver membrane or glass fiber filter before and after the sample is collected. RCD is

gravimetrically determined by the difference of particle weight on the filter after

combustion for 1 or 2 hours at 400 °C (500 °C for the glass fiber filter) [4]. This approach

is however subject to interferences from non-diesel, respirable combustible matter and

other potential problems (e.g., hygroscopic materials, negative bias with metal oxide

formation).
 18

2.2.3 Respirable Dust sampling with EC Analysis

The principle of this method is similar to those described in section 2.2.2 except

the EC analyzer is used to determine the amount of organic and elemental carbons in the

sample collected on the filter; thus, the EC analysis is restricted by filter loading.

2.2.4 Elemental Carbon (Diesel Particulate): NIOSH Method 5040 [10]

In addition to EC (accounting for 40-50% of total DPM [3], [4]) considered as a

specific marker of occupational exposure to DPM, this method makes use of the thermal-

optical analysis to determine carbonaceous aerosols, speciation of OC/EC under

controlled temperature and atmosphere by continuous monitoring of filter transmittance.

This method has an optical feature to correct the pyrolytically generated EC or “char”,

which is formed during the analysis of some materials (e.g., cigarette, wood smokes, and

pollen). Laser light is passed through the filter to allow continuous monitoring of filter

transmittance. At a very high analytical temperature (in excess of 850 °C), quartz-fiber

filters must be used. A punch (1.5 cm2) from the sample filter is taken for analysis, and

OC/EC are reported in terms of µg per cm2 of filter area. By assuming DPM

homogeneously distributed on the filter, the total OC/EC are calculated by multiplying

the reported values by the deposit area. The analyzer can be calibrated by injecting a

known amount of methane into the sample oven, prior to the end of the analysis (i.e.,

after EC is evolved).

The analytical procedures of this method are classified in two stages. In the first

stage, organic and carbonate (if present) carbon are catalytically oxidized to CO2 in a bed

of granular MnO2 under a controlled helium atmosphere as the temperature is stepped to

 19

about 850 °C (750 °C if EC loss is obvious). The CO2 is subsequently reduced to CH4 in

a Ni/firebrick methanator. A Flame Ionization Detector (FID) is used to quantify CH4. In

the second stage, the sample oven temperature is reduced. However, the temperature is

stepped to about 940 °C when an oxygen-helium mixture is introduced to the sample

oven. A synchronal increase in filter transmittance occurs as oxygen enters the oven, and

oxidization of pyrolytically generated carbon (PC) takes place. The point at which the

filter transmittance reaches its initial value is referred to as the "split" between OC and

EC. Carbon evolved before the split is considered as OC (including carbonate), and

carbon volatilized after the split is considered as EC

.
In order to measure carbonate carbon (if present in the sample), a second filter

punch is exposed to HCl vapor prior to analysis. A dessicator containing concentrated

HCl can be used to acidify the punches to a pH near 2 by exposing the punches to HCl

vapor for about 1 hr (large particles can require more time). After acidification, allow the

residual acid on the punch to volatilize in hood for at least one hour before analyzing.

During the analysis, a much-reduced (or absent) peak indicates carbonate in the original

sample and the difference between the TC results obtained for the two punches (i.e.,

before and after acidification) gives an estimate of carbonate-source carbon. Even though

acid treatment may change the appearance of the carbon profile, the EC result itself

should not be affected significantly.

 20

2.3 Overviews of DPM Concentrations

In 1997, R.A. Haney et al. reported that the generation rates of DPM for coal

mines operations not using exhaust aftertreatment devices could vary from 70 g/hr to 114

g/hr (numbers were not normalized for horsepower of vehicles operating). The DPM

generation rates measured from the primary sources of DPM emissions (two to three

diesel haulage vehicles without aftertreatment devices) were approximately 60 g/hr to 90

g/hr. Studies by MSHA reported that the DPM generation rates measured from

metal/nonmetal mines ranged from 72 g/hr to 474 g/hr; however, the use of exhaust

aftertreatment devices and the normalization of the generation rates for horsepower of

vehicles not mentioned in this report. In 1993, EPA reported the summary of particulate

emissions data for diesel engine. The emission factor of DPM less than 1.0 µm in

diameter is 0.152 g/hr-hp. The emission rate for total DPM in all size ranges is 0.197

g/hr-hp.

Table 2.3.1 shows the results obtained from several studies that estimate

contributions from diesel exhaust or a combination of diesel and gasoline exhaust to

24-hr average PM mass or PM carbon concentrations. DPM mass concentrations from

1 to 20 µg/m3 are found to contribute to ambient PM; however, these numbers are

dependent upon monitoring location, sampling period, and method of estimating diesel

source contribution.
 21

Table 2.3.1 Summary of contributions to 24-hr average PM mass or PM carbon

concentrations from diesel exhaust or a combination of diesel/gasoline exhaust

[from Ref. 11]

Table 2.3.2 shows examples of mass balance and chemical composition from

medium-duty diesel truck emission. Values are from a chassis dynamometer study on the

Federal Test Procedure urban driving circle with hot start [12]. The results show that EC

are found predominantly in fine particle mass.

 22

Table 2.3.2 Example of mass balance and chemical composition from medium-duty

diesel truck emissions [from Ref. 12]

Table 2.3.3 shows the summary of the occupational exposures to DPM of miners

and of those in other occupations. DPM exposure levels vary from 0.004 up to 2.1 mg/m3

dependent on a group of occupations and the aftertreatment control devices.

 23

Occupational Group Exposure Level, mg/m3

Underground miners, coal, no aftertreatment 0.9-2.1

[13]

Underground miners, coal, disposable diesel 0.1-0.2

exhaust filter [13]

Underground miners, coal, wire mesh filter 1.2

[13]

Underground miners, metal/nonmetal, no 0.3-1.6

aftertreatment [13]

Surface miners [13] <0.2

Urban fire station [14] 0.1-0.48

Forklift operators, dock workers, railroad 0.02-0.10

workers [14]

Truck drivers [14] 0.004-0.006

Table 2.3.3 Typical Occupational DPM Exposure Levels [3]

2.4 Overviews of DPM Control Technology

The six control technology categories are found to be appropriate for discussion;

1) MSHA-approved engines with low emissions, 2) Derated engines, 3) Fuels, 4) Fuel

Additives, 5) Diesel Oxidation Catalytic Converters (DOCCs), and 6) Diesel Particulate

Filter (DPFs)
 24

2.4.1 MSHA-Approved Engines with Low Emissions

The principle of this approach is to optimize the combustion and fuel injection

systems and minimize the lube oil consumption of the engine in order to reduce the DPM

emissions. This can be done by high compression, air intercooling of turbocharged

engines, center positioning of the injector nozzle, increased number of the nozzle

perforations, very high injection pressure, suppression of air swirl, and a shallow piston

bowl.

In November 1999, MSHA approved lists of diesel engines that can be used in

coal mines [30 CFR 75.1907 (1996)], [13]. In March 2001, MSHA and EPA approved

lists of all diesel engines, which could be introduced into metal and nonmetal mines. As a

result, one can examine the MSHA approval lists sorted by horsepower or select an

engine with lowest (MSHA) particulate index, PI (the amount of air needed to dilute the

engine-produced DPM to 1 mg/m3) that closely matches the engine power and rated

speed required for the application.

In 1997 Mayer reported that modern designed engines emit 10% of the total

particulate mass released by the engines designed 15 to 20 years ago. Bagley et al. 1993,

Baumgard and Johnson 1996, and Mayer 1997 found that the new lower-emission

engines emit more ultrafine particles at all load points than the older engine of the same

family; nevertheless, tests of DPFs using several different filter media confirm that filters

are effective in removal of the nonoparticles [14].

 25

2.4.2 Derated Engines

Derating engines is to limit the maximum fueling rate of a particular engine to

less than its rated maximum specifically to reduce emissions. There is no restriction by

MSHA on derating the engines; thus, it is not unheard of for some mines choose to derate

their engines to reduce DPM and CO. MSHA reported the effects of derating on gaseous

and DPM emissions from an Isuzu C240MA engine. The DPM emission rate can be

reduced by 55% with the only a 7% reduction in engine power.

2.4.3 Fuels

In parallel to the development of the cleaner diesel engine technologies, diesel

fuel quality has gained a lot of attention from researchers.

Low- sulfur diesel fuel: During the combustion, the sulfur mostly oxidizes to

produce SO2, while only a fraction (<5%) of which can be further oxidized to SO3 and

then combines with water to form a sulfuric acid aerosol [15]. Several studies found low-

sulfur diesel fuel has no influence on the number of relatively large particles (>0.04 µm),

while in contrast, it is found to reduce the concentration of nanaparticles (<0.04 µm) by

many orders of magnitude. However, if certain aftertreatment technologies such as DOCs

and DPFs are used, ultra low-sulfur diesel fuel should be selected to minimize sulfate

particulate formation and poisoning of the catalyst from the conversion of SO2 to SO3.

On October 25, 1996 MSHA published a final rule under 30 CFR Parts 7, 31, 32,

36, 70, and 75, Approval, Exhaust Gas Monitoring, and Safety Requirements for the Use

of Diesel-Powered Equipment in Underground Coal Mines, which requires underground

 26

diesel-powered equipment to use only a diesel fuel having a sulfur content no greater than

0.05% and a flash point of 100 oF or greater, effective April 25, 1997. Likewise, low-

sulfur diesel fuel (Federal LS No.2) currently used in the US. highway trucks is on

average of 340 ppm (maximum 500 ppm) by weight and, most likely, will be reduced

further in the future.

Alternative fuels

Fisher-Tropsch: this process converts gas to liquid for synthesis of HC from CO

and hydrogen. This process has received attention recently because of its ability to

produce very high quality fuel by converting natural gas resources to liquid fuels and

chemicals. The benefits of F-T fuel are most pronounced in reducing PM emissions due

partly to the almost complete absence of sulfur (<10 ppm) and its accompanying sulfate

emissions [16]. The high cetane number (>70) in F-T fuel is found to significantly lower

the soluble organic fraction (OC) of the integrated PM, but this benefit is offset by an

increase in the insoluble (EC) portion of the total particulate matter. In addition, absence

of sulfur also enables the use of catalytic oxidation technologies without the catalyst-

poisoning problem or PM emission penalties from the catalytic creation of sulfates.

Nevertheless, F-T fuel is not yet commercially available in the United States (available in

the Republic of South Africa from companies such as Salson and Mossgas) even though

companies including Shell, Chevron, Exxon, and ARCO are working to develop it.

Biodiesel is defined as the monoalkyl esters of long–chain fatty acids derived

from renewable lipid sources [3]. Pure biodiesel has substantially low sulfur content

(maximum 50 ppm) and no aromatic content with the cetane number comparable to that

of commercial No.2 diesel. Use of biodiesel in a conventional engine revealed a

 27

considerable reduction of unburned HC, CO, and PM. However, a slight increase in the

NOx emission contributed by a significant increase in NO2 was observed for pure

biodiesel or biodiesel blends compared with regular diesel fuel. Precautions are needed

when using high-percentage blends of biodiesel because over time biodiesel will soften

and degrade certain types of elastomers and natural rubber compounds.

Fuel-Water Emulsion: Adding water to diesel fuel has been extensively studied

recently. It is found that introducing water to the combustion chamber of diesel engine

facilitate to reduce combustion temperature and thus decrease the production of NOx,, and

PM, but increase CO and HC emissions. Langer and Daly 1999 reported that the use of

fuel-water emulsions reduces both NOx and PM by 40% to 50%. The disadvantage of this

fuel is that special blending technologies, usually involving additives, are required and

corrosion of engine parts, freezing, reduced lubricity can occur.

Table 2.4.3 shows summary of diesel fuel regulations and incentive programs for

several countries [from Ref. 11].

2.4.4 Fuel Additives

Metals such as platinum (Pt), copper (Cu), and iron (Fe) and the rare earths (e.g.

cerium (Ce)) added to diesel fuel in small concentrations are found to be efficient at

oxidizing the soot, thus reducing visible smoke [17]. Studies by Lepperhoff et al. 1995

showed that fuel additives might decrease the solid PM in raw exhaust by 15% to 25%.

Use of fuel additives, however, requires cautious consideration in possibilities of trace

metal emissions.
 28

Country Regulation or Max S Limit Conventional Fuel Introduced

Limit
Incentive

(and typical content)

United States 1) Highway diesel 1) 15 ppmw 1) 3300 ppmw 1) June 1, 2006

fuel sulfur control (Refinery production)

requirement July 15, 2006

(Highway diesel fuel sold as LS

fuel)

2) Nonroad diesel fuel 2) 500 ppmw 2) 3400 ppmw 2) In 2007

15 ppmw In 2010

3) Diesel fuel for 3) 500 ppmw - 3) April 25, 1997

underground coal mine diesel

equipments

EU 1) EURO2 - 1) 500 ppmw (450) 1) Jan 1, 1997

2) 98/70/EC EURO3 2) 350 ppmw 2) Jan 1, 2000

3) 98/70/EC EURO4 3) 50 ppmw 3) Jan 1, 2005

Belgium National incentive 50 ppmw 350 ppmw Oct 1, 2001

Germany 1) National incentive 1) 50 ppmw 1) 350 ppmw 1) Nov 1, 2001

2) National incentive 2) 10 ppmw - 2) Jan 2003

Netherlands National incentive 50 ppmw 350 ppmw Jan 2001

UK 1) National incentive 1) 50 ppmw 1) 500 ppmw 1) March 1999

2) National incentive 2) 50 ppmw 2) 350 ppm 2) March 7, 2001

Australia 1) National regulation 1) 50 ppmw 1) 1300 ppmw 1) Jan 2006

2) BP initiative 2) 50 ppmw 2) 500 ppmw 2) End 2000

Table 2.4.3 Summary of diesel fuel regulations and incentive programs for selected
countries (from Ref. 11)
 29

2.4.5 Diesel Oxidation Catalytic Converters (DOCCs)

The major function of a DOC is to oxidize CO and HC to CO2 and water in an

exhaust gas stream without itself being consumed in the process. DOCs reduce DPM

emissions by oxidizing some of the less volatile HCs that contribute to the SOF of DPM

or that could be adsorbed on to the soot particles. DOCCs, in general, appear as two

forms of cellular monoliths including ceramic and metallic monoliths. Both are designed

to provide a high substrate area-to-volume ratio. Catalyst substrates are designed to last

the entire lifetime of the engine and must be able to stand harsh operating conditions and

offer good thermal durability. The catalyst can be deactivated by high temperatures (>650

°C) and poisoned by the presence of lubricating oil additives and fuel sulfur. Therefore, it

is important in the purchase of DOCs to specify that it is for diesel use and the fuel sulfur

level.

Use of DOCs at high exhaust temperatures could result in the formation of sulfate

and NO2. The favorable gaseous phase reaction occurring in the DOCs are NO → NO2

and SO2 → SO3 and these reactions increase the toxicity of the exhaust. Many studies

have found that particulate mass and particle numbers increase extremely in the exhaust

treated with DOCs. The concentration of sulfur in diesel fuel and the exhaust temperature

are again found to play a very important role in the production of sulfate aerosols.

Consequently, the sulfur content of diesel fuel is critical in the design and application of

catalyst technology.
 30

Pataky et al 1994 studied the influence of a DOCC on regulated and unregulated

emissions from a 1991 prototype Cummins L10-310 diesel engine fueled with 100 ppm

by weight sulfur fuel. The DOCC with metallic substrate and Pt coating showed no

significant effect on NOx and NO at any test mode. It was found that HCs were reduced

by 60% to 70% and TPM were reduced by 27% to 54%, primarily owing to a 53% to

71% reduction of SOF.

2.4.6 Diesel Particulate Filters (DPFs)

DPFs are technically feasible, controllable in the field, and a cost-effective

technology for controlling DPM. The crucial parameters of DPFs are filtration efficiency

of the system and the ability of the system to regenerate and provide long-term operation

without dropping the filtration efficiency of the filter and the performance of the engine.

Designs of particulate filters are based on filter media such as porous cordierite and

silicon carbide (SiC) wall-flow monoliths and on deep-bed fiber filters fabricated from

matted, woven, or knitted glass or ceramic fibers. By comparison, SiC is found to have

lower shock resistance, but this disadvantage is compensated by its higher melting

temperature that makes it more durable over cordierite, which results in less back

pressure.

Filter media can also be coated with catalysts to enhance filtration efficiency and

removal of some gaseous compounds and to lower the regeneration temperature.

Nevertheless, the formulation and quantity of a catalyst are required to be designed and

optimized for a particular application, specific to the exhaust temperature of the engine

considered, the engine duty cycle, and the formulation of the fuel. An excess amount of
 31

the catalyst may increase emissions of sulfates or NO2. In contrast, inadequate amount of

the catalyst in the system may reduce efficiency of the filter and/or the inability of the

system to regenerate under the duty cycle.

Back pressure accumulating on the filter must be monitored by a gauge or a visual

and audio alarm located where the driver can easily observe it to assure that the back

pressure is in the range recommended by the engine manufacture (usually between 100

and 200 mbar). If the back pressure exceeds the recommended limits, cleaning

accumulated ash from the filter is needed. In general, the need for filter cleaning occurs at

2000 hr or more depending upon the fuel borne catalyst (FBC) dosing and amount of

lubricating oil ash.

A generation process for DPF systems are designed either on-board the vehicle

during the shift use or on-board and off-board while the vehicle is off-shift. However, the

concept of on-board, on-shift are found to be superior to off-shift regeneration owing to

significantly lower operating costs and unrestricted vehicle operation. Two types of

generation techniques are known for DPF system regeneration: active and passive on-

board regeneration. The active method provides more flexibility pertaining to engine

operation, but requires a source of energy for the heaters. The temperature-time profile of

the exhaust temperature must be considered for the vehicle to be equipped with the DPF.

The passive method requires that vehicles operate at high part-loads or at full loads for at

least 20% to 25% of the time with idling periods minimized; therefore, it is not

recommended for the engine operated at low to medium part load. Passive generation

flexibility of the filter, nevertheless, can be enhanced by use of catalytic coating and/or

FBCs. The catalysts have played important roles in reducing the ignition temperature
 32

necessary for oxidation of the PM. In addition, passive and active technologies can be

combined to enable filter regeneration to take place at low exhaust gas temperatures,

which reduces demand for external energy and lowers the cost for active components of

the system.

2.4.7 Disposable Diesel Exhaust Filter (DDEF)

DDEF systems are widely used by the underground coal mining industry [18].

DDEF systems normally comprise of a heat exchanger, filter element, filter housing,

flame arrester, complete water jacketing to keep surface temperatures below MSHA

requirements, exhaust temperature and exhaust back pressure monitor, and engine shutoff

system. By using heat exchangers to reduce the exhaust temperature to below 150 °C for

dry exchangers or 185 °C for water scrubber (requirement for diesel equipment used in

inby areas of underground coal mine [30 CFR 7 (1966]) disposable paper filters can be

used. However, the major drawbacks of these systems are short service life of the filter

(1-3 hr) and extraordinarily high costs of the filter elements ($35 to $143).
 33

3-Experimental Setup

A Generac Model SD080 diesel generator rated at 80 kW, 60 Hz, is used as a

DPM emission source. This unit is powered by a Generac diesel engine (5.0 direct

injection, turbocharged, 4 cylinders, multi-hole, nozzle type), which is a 5 liter (304 in3)

engine rated at 100 hp at 1800 rpm. The generator locates at the UC Center Hill Research

Facilities in Cincinnati, Ohio, where measurement of fuel consumption rates and DPM

mass concentrations are performed. A load bank (load simulator), model Merlin 100

manufactured by Simplex is used to simulate loads by applying banks of heaters in three,

25 kW sets, which can then be used to simulate loads of 25, 50, 75 kW, respectively.

Diesel fuels with 0.21% and 0.37% sulfur contents are used for the tests. The fuel system

of the generator is modified so that the fuel consumption rates can be measured. A 1-L

glass burette is installed on the outside case of the generator. Two three-way valves are

used to connect fuels hoses (fuel supplying and fuel returning hoses) from the fuel

storage tank to the burette. By switching the three-way valves to allow the flow of diesel

fuels from and to the burette, fuel consumption rates are measured by reading differences

of fuel levels on burette scales over time. An inner diameter of an existing exhaust stack

of this generator is 4.74 inches (0.395 ft). The length of the stack is prolonged to

approximately 7.9 ft to allow the flow profile, temporarily disturbed by the presence of a

sampling probe and a standard pitot tube, to redevelop and stabilize. The schematic of the

experiment is shown in Figure 3.1-3.2. The EPA sampling method 1A - Sample and

Velocity Traverses for Stationary Sources with Small Stacks or Ducts – is selected as a

reference method for measurement of the stack gas velocity and DPM mass
 34

concentrations. The sampling equipments used in this method are similar to those used in

EPA method 5 – Source Test Sampling for Particulate; as a result, the schematic diagram

of the sampling train is also shown in Figure 3.1. In this method, a dry gas meter pump

pulls slipstream of generator exhaust gases through a selected nozzle, and a sampling

probe heated at 250οF to prevent condensation. The filter holder is in a heated box

(250οF), where particulate matters are then trapped on an 8.2-mm glass micro fiber filter

(particle retention > 1.5 µm). Downstream of the filter holder, the stream is cooled to

remove water vapor. Dry gases then go to a pump, and to a dry gas meter, where the gas

volume is read.

Exhaust Gas

Pitot tube to Sample Exhaust Gas

measure probe coming from
pressure the Generac
velocity Generator

S ampling Train-E PA
Method 1A

Figure 3.1 Schematic Diagram of DPM Sampling Systems (from Ref. 23)
 35

Figure 3.2 Picture of a DPM Sampling site

After the test, the total DPM collected (DPM collected on the filter and DPM

collected from rinsing the nozzle, sampling probe, and front part of filter holder with

acetone) will be placed in a desiccator for at least 24 hours so as to remove the moisture.

Total mass of DPM will then be obtained by means of gravimetric analysis.

 36

4-Data Analysis

After each DPM sampling is performed, all data collected such as stack gas

temperature (Ts) and pressure (Ps), barometric pressure, stack velocity pressure (∆P),

pressure drop across the orifice (∆H), etc. were used for calculation of percent isokinetic.

Should percent isokinetic of the sampling run falls in the range of 90% to 110%, it will be

utilized to analyze for DPM mass concentrations. Otherwise, it will be discarded. Percent

isokinetic was calculated by using the following formula.

1. Standard Volume of Dry Gas

∆H
Pb +
Vm ( std ) = VmYTstd 13.6 (1)
Pstd Tm ( avg )

2. Moisture Content in Stack Gas

Vwe ( std ) = K1 (V f − Vi )
(2)
Vwe ( std )
Bws =
Vwe ( std ) + Vm ( std )
 37

3. Molecular Weight of Stack Gas

3.1 Dry molecular weight

M d = .44% × CO2 + .32 × O2 + .28 × ( N 2 + CO2 ) (3)

3.2 Wet molecular weight

M s = M d (1 − Bws ) + 18 Bws (4)

4. Average Stack Gas Velocity

vs =
[
K pC p Ts ( avg ) ] [∆p ]
.5
( avg )
.5

(5)
[Ps M s ].5

5. Percent isokinetic

 ∆H 
 K 3V1c + (VmY )( Pbar + 13.6 ) 
% I = 100Ts   (6)
 60θv s Ps An 
 

DPM mass rates and DPM mass concentrations can be reckoned by using the following

equations.
 38

1. Average Stack Gas Volume Metric Flow Rate

sec
3600 v s As (1 − Bws )Tstd Ps
Qs = hr (7)
Ts ( avg ) Pstd

2. Total DPM weight, m part

3. Pollutant Mass Rates

 m par 
pmr =  Qs (8)
Vm ( std ) 

4. DPM Mass Concentration

m part
Cs = (9)
Qs

The percentages of excess air and excess O2 in stack flue gas are also calculated by using
the following equation.

 %O2 − 0.5%CO 
% EA =   × 100 (10)
 0.264% N 2 − (%O2 − 0.5%CO ) 

% ExcessO2 = % EA × 0.21 (11)

 39

Where: EA = percent excessive air

%O2 = percent O2 by volume (dry basis)

%CO = percent CO by volume (dry basis)

%N2 = percent N2 by volume (dry basis)

0.264 = ratio of O2 to N2 in air, Volume/Volume

The percentages of excess air and excess O2 were also calculated by means of the
combustion balance analysis in order to compare results with those obtained from
Equation (10) and Equation (11).

lbm
1. Fuel consumption rates [F ],
hr

2. %Weight of each constituent in fuels [ Wi ]

i = C,H2, and S

lb − moles
3. Moles of constituents in fuel [ M i ],
hr

Wi × F
Mi = (12)
100 × MWi

4. Moles of O2 required for each mole of Mi M o , i ,

2
[ ] lb − hrmoles
M o2 , c = M c × 1 (13)

M o2 , H 2 = M H 2 × 0.5 (14)

M o2 , S = M S × 1 (15)

5. Total O2 for stoichiometric balance [∑ M ], lb − hrmoles

o2

∑M o2 = M o2 ,C + M o2 , H 2 + M o2 , S (16)
 40

[
6. Moles of O2 in flue gas no2 , F , ] lb − hrmoles
avg.Ps × avg.Qs
n o2 , F = (17)
R × avg.Ts

Where: avg.Ps = average stack absolute pressure for numbers of tests at the same

generator operating load

avg.Qs = average flow rate of stack gas for numbers of tests at the same

generator operating load

avg.Ts = average stack absolute temperature for numbers of tests at the

same generator operating load

R = universal gas constant, 0.7302 ft3-atm/lb-mole-°R

7. %Excess O2

 ∑ M o + no , F  
% ExcessO2 =  2 2  − 1 × 100 (18)

 ∑ M o2  
 

8. %EA

% ExcessO2
% EA = (19)
0.21
 41

5-Result and Discussion

Figure 5.1 shows the result of fuel consumption rates for two types of diesel fuels.

The rate of diesel utilization varies from 5 L/hr to 20 L/hr as the applied loads on the

generator increase. A fairly good relationship of data is found (R-squared = 0.993).

Fuel Consumption Rates versus Applied Loads

21.00
Fuel Consumption Rates (L/hr)

18.00
R2 = 0.993
15.00

12.00

9.00

6.00

3.00

0.00
0 25 50 75 100
Applied Loads (KW)

Figure 5.1 Variation of Fuel Utilization on Different Applied Loads

Table 5.1 shows the summary of the experimental results from the use of the

0.37% S diesel fuel. It obviously proves that increasing loads on the generator influences
 42

three main factors including stack gas flow rates, DPM mass concentrations, and PMR.

The flow rates range from 278 dscm/hr at a 0 kW applied load up to 380 dscm/hr at a 75

kW applied load. The DPM mass concentrations also follow the same trend. They

increase from 15 mg/m3 up to 39 mg/m3 as the applied loads rise from 0 kW to 75 kW.

The Relative Standard Deviation (RSD) of data obtained from each specific applied load

ranges from 0.01% to 7.69% indicating that the data measured have fairly high precision.

Table 5.1 Summary of experimental results for 1st diesel fuel (S=0.37%)

Relative
Applied Loads, Flow rate, Standard
kW dscm/hr Conc., mg/m3 PMR, g/hr-hp % Isokinetic Deviation
(RSD, %)
0 277.58 15.40 0.0428 99.98 0.01
0 287.49 15.74 0.0452 102.86
25 318.16 25.21 0.0802 98.78 4.24
25 326.61 25.00 0.0817 98.10
25 337.13 25.79 0.0869 102.92
50 349.78 31.88 0.1115 100.84 8.40
50 345.46 28.67 0.0990 98.59
75 379.09 38.65 0.1465 100.53 7.69
75 378.44 37.23 0.1409 98.57
75 365.61 34.46 0.1260 99.58

Nevertheless, It can be seen that the ratio of increase in the DPM mass

concentrations to increase in applied loads on the generator, decreases. The DPM masses

emitted per horsepower is also calculated and the results show that the DPM PMR varies

from 0.043 g/hr-hp to 0.147 g/hr-hp in accordance with the generator loads. It is believe

that at higher loads, the fuel combustion is more effective and therefore, results in lesser

increment of the DPM mass concentrations.

Figure 5.2 indicates the fairly good linear relationship of stack gas flow rates

versus the generator loads (R2=0.946). Figure 5.3 also shows increasing of DPM mass
 43

concentrations has a good linear relationship with the different applied loads (R2=0.969).

So does the Pollutant Mass Rate (PMR), the linear relationship gives R squared at 0.961

as presented in Figure 5.4.

Flow rate vs Applied Loads

425

400

375
Flow Rate, dscm/hr

R2 = 0.946
350

325

300

275

250
0 25 50 75 100

Applied Loads, kW

Figure 5.2 Variations of Stack Gas Flow Rates on Different Applied Loads (0.37%S)

Mass concentrations vs Applied loads

45
40
3
Mass concentrations, mg/m

35
2
30 R = 0.969
25
20
15

10
5
0
0 25 50 75 100

Applied loads, kW

Figure 5.3 Variations of DPM Mass Concentrations on Different Applied Loads (0.37%S)
 44

Pollutant m ass rates vs Applied loads

0.16

0.14
Pollutant mass rates, g/hr-hp

0.12

0.10 y = 0.0012x + 0.048

2
R = 0.961
0.08

0.06

0.04

0.02

0.00
0 25 50 75 100

Applied loads, kw

Figure 5.4 Variations of Pollutant Mass Rates on Different Applied Loads (0.37%S)

Table 5.2 shows the summary of the test results obtained by the use of the 0.21%

S diesel fuel. It can be deduced that changing the % S in the diesel fuels does not

significantly affect the stack gas flow rates. This can also be supported from the results of

the fuel consumption rates. Two types of diesel fuels give somewhat close amount of

diesel fuel utilization. The stack gas flow rates range from 271 dscm/hr at a 0 kW

applied load up to 398 dscm/hr at a 75 kW applied load. The DPM mass concentrations

slightly decrease compared with the numbers obtained from the 0.37% S diesel fuels.

They range from 9 mg/m3 up to 32 mg/m3 as the applied loads rise from 0 kW to 75 kW.

The DPM PMR varies from 0.0251 g/hr-hp to 0.1271 g/hr-hp. It can be seen that

%S in diesel fuel plays important roles on the amount of DPM emissions. The RSD

calculated from the measured data at each specific generator load varies from 0.03% to

5.43% indicating a good precision of data.

 45

Table 5.2 Summary of experimental results for 2nd diesel fuel (S=0.21%)

Relative
Applied Loads, Flow rate, Standard
kW dscm/hr Conc., mg/m3 PMR, g/hr-hp % Isokinetic Deviation
(RSD, %)
0 270.44 10.81 0.0292 95.26 0.03
0 260.28 9.64 0.0251 98.95
25 314.65 13.00 0.0409 108.90 5.43
25 317.67 14.34 0.0456 98.36
25 316.24 13.68 0.0433 106.16
50 352.54 20.70 0.0730 92.63 3.03
50 346.26 22.02 0.0762 97.67
75 397.63 31.96 0.1271 98.63 3.01
75 392.79 30.58 0.1201 100.55
75 382.40 32.39 0.1259 98.64

Figure 5.5 indicates the fairly good linear relationship of stack gas flow rates

versus the generator loads (R2=0.984).

Flow rate vs Applied Loads

425

400
R2 = 0.984
375
Flow Rate, dscm/hr

350

325

300

275

250
0 25 50 75 100

Applied Loads, kw

Figure 5.5 Variations of Stack Gas Flow Rates on Different Applied Loads (0.21%S)
 46

The results obtained from the tests trend to give a good linear relationship of the

DPM mass concentrations and the DPM PMR versus the generator loads. Figure 5.6

shows increasing of DPM mass concentrations has a fairly good linear relationship with

the different applied loads (R2=0.985). So does the Pollutant Mass Rate (PMR), the linear

relationship gives R squared at 0.950 as presented in Figure 5.7.

Mass concentrations vs Applied loads

35
30
)
3

2
R = 0.985
Mass concentrations ( mg/m

25
20
15
10
5
0
0 25 50 75 100
Applied loads, kw

Figure 5.6 Variations of DPM Mass Concentrations on Different Applied Loads (0.21%S)

Figure 5.8 shows correlation of between DPM emission rates and generator

operating loads for both types of diesel fuels. It is found that DPM emission rates and

generator operating loads could be linearized and give a relationship with R-squared

0.805. The general equation for DPM emission rates prediction is also reported.
 47

Pollutant m ass rates vs Applied loads

0.14

0.12
Pollutant mass rates, g/hr-hp

0.1
y = 0.0013x + 0.0168
R2 = 0.950
0.08

0.06

0.04

0.02

0
0 25 50 75 100

Applied loads, kw

Figure 5.7 Variations of Pollutant Mass Rates on Different Applied Loads (0.21%S)

PMR (norm alized for %S) vs Applied Load

0.7

0.6 y = 0.0048x + 0.1049

Normalized PMR, g/hr-hp-%S

R2 = 0.805
0.5

0.4

0.3

0.2

0.1

0.0
0 25 50 75 100
Applied Load, kW

Figure 5.8 Variations of Pollutant Mass Rates on Different Applied Loads for both type of diesel
 48

Table 5.3 %Excess O2 and %Excess Air in stack flue gas

0.37%S diesel fuel 0.21%S diesel fuel
Related Parameters Load, kW Load, kW
0 25 50 75 0 25 50 75
%Excess O2 calculated
from combustion
balance analysis 305.93 126.64 78.53 53.37 301.58 127.39 81.43 57.08
%Excess O2 calculated
from stack sampling
analysis 300.80 121.38 75.88 52.23 300.80 121.38 75.88 52.23
%Excess Air calculated
from combustion
balance analysis 1456.79 603.03 373.94 254.13 1436.09 606.62 387.76 271.81
%Excess Air calculated
from stack sampling
analysis 1432.40 578.02 361.31 248.70 1432.40 578.02 361.31 248.70

Table 5.3 shows that %excess O2 and %excess air reduced when higher loads
were applied to the diesel generator. It is believed that the combustion efficiency of diesel
fuels is higher at the higher applied loads. The detail of calculation is shown in Appendix
[Table A4 and A5].

Figure 5.9 SEM picture of DPM (75 kW, 0.21%S)

 49

Figure 5.9 shows a dense cloud of DPM collected on the glass micro fiber filter

taken by the scanning electron microscope (SEM). The generator was operated at 75 kW

by using 0.21% S diesel fuels. However, this picture does not give a salient view of the

DPM. The thick layer of the DPM collected on the filter is believed to be interference of

the SEM resolution; however, the size of the individual DPM can be roughly estimated to

be smaller than 1 µm.

 50

6-Conclusion

The use of diesel engines is expanding every year, particularly in underground

mining industries. The DPM emissions have recently become a major issue, which gains

substantial attention of researcher and various regulatory agencies. Long-term exposure

to DPM by workers, who spends most of times working in the underground mines is

believed to lead to the critical health diseases associated with cancer. Several stringent

regulations are issued to limit the emission rates for diesel equipment used in U.S.

underground mines. This is to prevent underground mines workers from being over

exposed to DPM emissions.

This research is performed to study the correlation of the DPM mass

concentration and the different levels of loads applied to the selected diesel generator.

The test results show that the generator loads, and %S in diesel fuels play an important

role on DPM mass concentration emissions. Estimate of DPM mass concentrations

emitted from the similar type of the diesel engine could be usefully predicted by using

these relationships
 51

7-Future Work

The results of DPM mass concentrations are already further used as CESP design

criteria. This unit is being constructed at the University of Cincinnati. The principle of

CESP design is to attain condensation of flue gas water vapor by means of heat exchange

and cooling of the flue gas stream below the dew point temperature. The prototype unit

will be evaluated as a function of engine load (0, 25, 50, 75 kW) and fuel type as well as

applied voltage and polarity. Results are given showing the particulate removal efficiency

as a function of uncontrolled versus controlled emissions for varying levels of the

operational parameters.
 52

References

1. Particulate Matter: http://www.epa.gov/ebtpages/airairpolparticulatematterpm.html

2. Diesel Fuel and Exhaust Emissions-Environmental Health Criteria 171: World Health

Organization, Geneva, Switzerland, 1996.

3. George H. Schnakenberg, Jr., and Aleksandar D. Bugarsk: Review of Technology

Available to the Underground Mining Industry for Control of Diesel Emissions,

Information Circular 9462.

4. Winthrop F. Watts, Jr., and Gurumurthy Ramachandran, School of Public Health,

Department of Environmental Health: Diesel Particulate Matter Sampling Methods

(Statistical Comparison), November 2000.

5. 9th Report on Carcinogens: U.S. Department of Health and Human Services, National

Toxicology Program, Research Triangle Park, NC, 2000.

6. Health Assessment Document for Diesel Exhaust-SAB Review Draft: EPA /600 /890

/057 E, U.S.EPA, Office of Research and Development, National Center for

Environmental Assessment, Washington, DC, 2000.

http://epa.gov/ncea/pdfs/diesel/frmatterfinal.pdf.

7. Diesel Exhaust: A Critical Analysis of Emissions, Exposure and Health Effects, A

special Report of the Institute’s Diesel Working Group, Health Effects Institute,

Cambridge, MA, 1995.

8. Stayner L, Dankovic D, Smith R, Steenland K: Predicted Lung Cancer Risk among

Miners Exposed to Diesel Exhaust Particles, Am. J. Indust. Med.1998, 34, 207-219.
 53

9. John H. Johnson, Susan T. Bagley, Linda D. Gratz, and David G.Leddy: A Review of

Diesel Particulate Control Technology and Emissions Effects-1992 Horning Award

Lecture, Diesel Particulate Emission, Landmark Research 1994-2001.

10. Title 30 1995 US Code of Federal Regulations Part 70.100 July, p 413, 1995.

11. Alan C., Lloy and Thomas A. Cackette: Diesel Engines: Environmental Impact and

Control, J.Air&Waste Manage. Assoc. 51, 809-847, June 2001.

12. Schauer J., Kleeman M., Cass G.: Characterization and Control of Organic

Compounds Emitted from Air Pollution Sources, 93-329, California Air Resource Board,

Sacramento, CA, 1998.

13. MSHA: MSHA-approved diesel engines, powerpackages, and equipment.

[http://www.msha.gov/S&HINFO/DESLREG/APPENG.HTM], 2001.

14. Mayer A, Matter U, Czerwinski W, Heeb N: Effectiveness of particulate traps on

construction site engines: VERT final measurements. DieselNet technical report.

[http://www.DieselNet.com/papers/9903mayer/index.html], 1999.

15. Heywood JB: Internal combustion engine fundamentals, New York, NY: Mcgraw-

Hill, Inc., 2001.

16. Schaberg et al.: Diesel exhaust emissions using Sasol slurry phase distillate process

fuels, Warrendale, PA, Society of Automotive Engineers, SAE paper 972898, 1997.

17. Harward JB, Kausch WJ Jr.: Soot control by fuel additives, Prog Energy Combust

Sci 6:263, 1980.

 54

18. Ambs JL, Cantrell BK, Watts WF, Olson KS: Evaluation of a disposable diesel

exhaust filter for permissible mining machines, Minneapolis, MN: U.S. Department of

the Interior, Bureau of Mines, RI 9508, 1995.

19. NIOSH Manual of Analytical Methods (NMAM), Fourth Edition: Elemental Carbon

Diesel Particulate 5040.

20. DieselNet: Exposure to diesel exhaust. DieselNet technology guide.

[http://www.DieselNet.com/tg.html], 1999.

21. Haney RA, Saseen GP, Waytulonis RW: An overview of diesel particulate exposures

and control technology in the U.S. mining industry. Appl Env Hyg 12:1013-1018, 1997.

22. Federal Register, Part II, Environmental Protection Agency, 40 CFR Part 60, 61, and

63, Amendments for Testing and monitoring Provision; Final Rule, Tuesday, October 17,

2000.

23. Mayer A: VERT: Curtailing emissions of diesel engines in tunnel sites, Technical

report to VERT. TTM, 1997.

24. J.A. Jahnke: Student Workbook: Source Sampling for Particulate Pollutants, APTI

Course 450, Edition 3.0, Industrial Extension Service, College of Engineering, North

Carolina State University, 1995.

25. Acurex Environmental Corporation , Research Triangle Park, NC 27709: Emission

factor documentation for AP-42 section 3.4, “Large stationary diesel & all stationary dual

fuel engines”, p.4-16, 1993.

 55

APPENDICES-Measurement Data

Table A1- Measurement data obtained from the use of 0.37% Sulfur diesel fuels

Loads,kW 0 0 25 25 25 50 50 75 75 75
Avg Fuel Consumption
Rate, (L/hr) 4.93 10.83 14.73 19.41
Diesel Fuel
Compositions (%weight)
C 85.51 85.51 85.51 85.51 85.51 85.51 85.51 85.51 85.51 85.51
H2 13.08 13.08 13.08 13.08 13.08 13.08 13.08 13.08 13.08 13.08
N2 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01
S 0.37 0.37 0.37 0.37 0.37 0.37 0.37 0.37 0.37 0.37
O2 (assumed negligible) - - - - - - - - - -
Sampling Conditions
Vm(std), dscf 30.43 29.52 29.32 29.89 32.94 31.17 28.43 29.31 29.31 29.79
Bws, % 1.2 1.6 3.4 4.2 3.6 5.4 6.2 5.8 6.8 7.1
Md, lb/lb-mole 29.01 29.00 29.21 29.21 29.21 29.37 29.38 29.54 29.54 29.54
Ms, lb/lb-mole 28.87 28.83 28.83 28.73 28.81 28.76 28.67 28.88 28.76 28.73
∆p(avg), in.H2O 0.16 0.17 0.26 0.27 0.29 0.37 0.37 0.49 0.49 0.46
∆H, in.H2O 0.7 0.7 0.92 0.92 0.99 1.2 1.2 1.4 1.4 1.3
%CO2 1.4 1.4 3.1 3.1 3.1 4.5 4.5 5.9 5.9 5.9
%O2 19.53 19.53 17.82 17.82 17.82 16.39 16.39 14.95 14.95 14.95
%(CO+N2) 79.07 79.07 79.08 79.08 79.08 79.11 79.11 79.15 79.15 79.15
As, ft2 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12
2
An, ft 0.00034 0.00034 0.00034 0.00034 0.00034 0.00034 0.00034 0.00034 0.00034 0.00034
Ts(avg), R 710.8 711.4 827.6 816.4 841.75 956.6 964.75 1059.75 1060.75 1052.5
Tm(avg), R 535 535.5 551.2 543 540.5 539.7 559.5 543 551.4 542.5
Ps, in.Hg 29.05 29.01 29 28.98 29.32 29.17 29.09 29.28 29.26 29.17
vs, ft/s 31.17 32.47 42.61 45.54 45.5 54.98 55.37 65.99 66.68 64.33
9798 10148 11231 11529 11900 12347 12194 13381 13358 12906
Qs, dscf/hr (dscm/hr) (278) (287) (318) (327) (337) (350) (345) (379) (378) (366)
mpar, g 0.01328 0.01316 0.02094 0.02117 0.02406 0.02815 0.02309 0.0321 0.03091 0.02909
Sampling Time, min 67 61 57 57 58 54 51 47 48 50
%I 99.98 102.86 98.78 98.10 102.92 100.84 98.59 100.53 98.57 99.58
Cs, mg/m3 15.40 15.74 25.21 25.00 25.79 31.88 28.67 38.65 37.23 34.46
pmr, g/hr 4.28 4.52 8.02 8.17 8.69 11.15 9.90 14.65 14.09 12.60
 56

Table A2- Measurement data obtained from the use of 0.21% Sulfur diesel fuels

Loads,kW 0 0 25 25 25 50 50 75 75 75
Avg Fuel Consumption
Rate, (L/hr) 4.95 10.91 14.79 19.74
Diesel Fuel
Compositions
(%weight)
C 83.51 83.51 83.51 83.51 83.51 83.51 83.51 83.51 83.51 83.51
H2 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5
N2 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01
S 0.21 0.21 0.21 0.21 0.21 0.21 0.21 0.21 0.21 0.21
O2 (assumed negligible) - - - - - - - - - -
Sampling Conditions
Vm(std), dscf 31.62 31.61 32.86 31.26 29.67 32.07 38.74 32.73 32.96 36.55
Bws, % 1.2 1.2 3.6 4.0 4.0 45.0 4.6 4.4 4.1 4.9
Md, lb/lb-mole 29.00 29.00 29.21 29.21 29.21 29.38 29.38 29.54 29.54 29.54
Ms, lb/lb-mole 28.88 28.88 28.81 28.76 28.76 28.86 28.85 29.03 29.07 28.98
∆p(avg), in.H2O 0.15 0.14 0.35 0.36 0.26 0.37 0.36 0.52 0.51 0.69
∆H, in.H2O 0.56 0.52 1 1 1 1.2 1.2 1.5 1.5 1.3
%CO2 1.4 1.4 3.1 3.1 3.1 4.5 4.5 5.9 5.9 5.9
%O2 19.53 19.53 17.82 17.82 17.82 16.39 16.39 14.95 14.95 14.95
%(CO+O2) 79.07 79.07 79.08 79.08 79.08 79.11 79.11 79.15 79.15 79.15
2
As, ft 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12 0.12
An, ft2 0.00034 0.00034 0.00034 0.00034 0.00034 0.00034 0.00034 0.00034 0.00034 0.00034
Ts(avg), R 699.4 692.4 805.5 808.5 840 958.2 959.4 1052.6 1052.7 1036.8
Tm(avg), R 521.2 515.4 504.75 503.4 524.6 545.3 547.3 536.7 530.13 528.3
Ps, in.Hg 29.31 29.25 29.19 29.27 28.9 29.13 29.07 29.16 29.16 29.1
vs, ft/s 29.6 28.26 40.81 41.45 43.38 55.03 54.32 68.05 67.03 64.92
9546 9187 11106 11213 11163 12444 14036 13865 13498
Qs, dscf/hr (dscm/hr) (270) (260) (315) (318) (316) (353) 12223 (346) (398) (393) (382)
mpar, g 0.00968 0.00863 0.0121 0.0127 0.0115 0.0188 0.02417 0.0296 0.02856 0.0341
Sampling Time, min 75 75 60 60 54 60 70 51 51 58
%I 95.26 98.95 108.90 98.36 106.16 92.63 97.67 98.63 100.55 98.64
Cs, mg/m3 10.81 9.64 13.00 14.34 13.68 20.70 22.02 31.96 30.58 32.93
pmr, g/hr 2.92 2.51 4.09 4.56 4.33 7.30 7.62 12.71 12.01 12.59
 57

Table A3-DPM emission rates normalized for %S in diesel fuels

Loads, kW Normalized PMR (0.37%S), Normalized PMR (0.21%S),

g/hr-hp-%S g/hr-hp-%S
0 0.116 0.140
0 0.123 0.120
25 0.222 0.196
25 0.218 0.218
25 0.236 0.207
50 0.303 0.350
50 0.269 0.365
75 0.397 0.607
75 0.382 0.574
75 0.342 0.601

Table A4-Measurement data for the calculation of %Excess Oxygen and %Excess Air in

the stack flue gas

0.37% S diesel fuels 0.21% S diesel fuels

Related Parameters Load, kW Load, kW
0 25 50 75 0 25 50 75
Avg. Fuel Consumption
Rate, (L/hr) 4.93 10.83 14.73 19.41 4.95 10.91 14.79 19.74
Fuel Compositions
(%weight)
C 85.51 85.51 85.51 85.51 83.51 83.51 83.51 83.51
H2 13.08 13.08 13.08 13.08 12.5 12.5 12.5 12.5
N2 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01
S 0.37 0.37 0.37 0.37 0.21 0.21 0.21 0.21
O2(assumed negligible) - - - - - - - -
*Avg. Ts, R 711.10 828.58 960.68 1057.67 695.90 818.00 958.80 1047.37
*Avg. Ps, in.Hg 29.03 29.10 29.13 29.24 28.93 29.12 29.10 29.14
*Avg. Qs, dscf/hr 9973 11553.33 12270.5 13215 9366.5 11160.7 12333.5 13799.67
*%O2 in stack flue gas 19.53 17.82 16.39 14.95 19.53 17.82 16.39 14.95
* Average values for numbers of tests at the particular applied load
 58

Table A5-Calculation of %Excess Oxygen and %Excess Air in the stack flue gas by

means of stack sampling analysis and combustion balance analysis

0.37%S diesel fuel 0.21%S diesel fuel

Related Parameters Load, kW Load, kW
0 25 50 75 0 25 50 75
Fuel (lbm/hr) 8.69 19.10 25.98 34.23 8.73 19.24 26.08 34.81
*Flue gas compositions from stack sampling, %
CO2 1.40 3.10 4.50 5.90 1.40 3.10 4.50 5.90
O2 19.53 17.82 16.39 14.95 19.53 17.82 16.39 14.95
CO 0.07 0.08 0.11 0.15 0.07 0.08 0.11 0.15
N2 79.00 79.00 79.00 79.00 79.00 79.00 79.00 79.00
Theoretical O2 requirement, moles/hr, from fuel combustion
C 0.62 1.36 1.85 2.44 0.61 1.34 1.82 2.42
H2 0.57 1.25 1.70 2.24 0.55 1.20 1.63 2.18
N2 0.00043 0.00096 0.00130 0.00171 0.00044 0.00096 0.00130 0.00174
S 0.00101 0.00221 0.00300 0.00396 0.00057 0.00126 0.00171 0.00228
Total O2 for stoichiometric balance, moles/hr 1.19 2.61 3.55 4.68 1.15 2.54 3.45 4.60
O2 in stack flue gas, moles/hr 3.64 3.31 2.79 2.50 3.48 3.24 2.81 2.63
%Excess O2 calculated from combustion balance analysis 305.93 126.64 78.53 53.37 301.58 127.39 81.43 57.08
%Excess O2 calculated from stack sampling analysis 300.80 121.38 75.88 52.23 300.80 121.38 75.88 52.23
%Excess Air calculated from combustion balance analysis 1456.80 603.00 373.90 254.13 1436.00 606.60 387.76 271.80
%Excess Air calculated from stack sampling analysis 1432.40 578.00 361.30 248.70 1432.00 578.00 361.31 248.70