EPA-600/3-75-010f
September 1975
Ecological Research Series
ANNUAL CATALYST RESEARCH PROGRAM REPORT
APPENDICES
Volume V
leaitn tttects Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, N.C. 27711
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development,
U.S. Environmental Protection Agency, have been grouped into
five series. These five broad categories were established to
facilitate further development and application of environmental
technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in
related fields. The five series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ECOLOGICAL RESEARCH series.
This series describes research on the effects of pollution on
humans, plant and animal species, and materials. Problems are
assessed for their long- and short-term influences. Investigations
include formation, transport, and pathway studies to determine the
fate of pollutants and their effects. This work provides the
technical basis for setting standards to minimize undesirable
changes in living organisms in the aquatic, terrestrial and
atmospheric environments.
This document is available to the public through the National
Technical Information Service, Springfield, Virginia 22161.
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EPA-600/3-75-010f
September 1975
ANNUAL CATALYST RESEARCH PROGRAM REPORT APPENDICES
Volume V
by
Criteria and Special Studies Office
Health Effects Research Laboratory
Research Triangle Park, North Carolina 27711
U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF RESEARCH AND DEVELOPMENT
HEALTH EFFECTS RESEARCH LABORATORY
RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711
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CONTENTS
Page
CATALYST RESEARCH PROGRAM ANNUAL REPORT
EXECUTIVE SUMMARY 1
INTRODUCTION 5
PROGRAM SUMMARY 7
TECHNICAL CONCLUSIONS 17
DISCUSSION 22
REFERENCES 45
APPENDICES TO CATALYST RESEARCH PROGRAM ANNUAL REPORT
VOLUME 1
A. OFFICE OF AIR AND WASTE MANAGEMENT
Al. AUTOMOTIVE SULFATE EMISSIONS 1
A2. GASOLINE DE-SULFURIZATION - SUMMARY 53
A2.1 Control of Automotive Sulfate Emissions
through Fuel Modifications 55
A2.2 Production of Low-sulfur Gasoline 90
VOLUME 2
B. OFFICE OF RESEARCH AND DEVELOPMENT
Bl. FUEL SURVEILLANCE
Bl.1 Fuel Surveillance and Analysis 1
B1.2 The EPA National Fuels Surveillance
Network. I. Trace Constituents in Gasoline
and Commercial Gasoline Fuel Additives ... 19
B2. EMISSIONS CHARACTERIZATION
B2.1 Emissions Characterization Summary 44
B2.2 Sulfate Emissions from Catalyst- and Non-
catalyst-equipped Automobiles 45
B2.3 Status Report. Characterize Particulate
Emissions - Prototype Catalyst Cars 68
B2.4 Status Report. Characterize Particulate
Emissions from Production Catalyst Cars. . . 132
B2.5 Status Report: Survey Gaseous and Particu-
late Emissions - California 1975 Model Year
Vehicles 133
B2.6 Status Report: Characterization and Meas-
urement of Regulated, Sulfate, and Particu-
late Emissions from In-use Catalyst Vehicles -
1975 National Standard 134
B2.7 Gaseous Emissions Associated with Gasoline
Additives - Reciprocating Engines. Progress
Reports and Draft Final Report - "Effect of
Gasoline Additives on Gaseous Emissions" . • 135
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Page
B2.8 Characterization of Gaseous Emissions from
Rotary Engines using Additive Fuel -
Progress Reports 220
B2.9 Status Report: Exploratory Investigation of
the Toxic and Carcinogenic Partial Combus-
tion Products from Oxygen- and Sulfur-
containing Additives 232
B2.10 Status Report: Exploratory Investigation of
the Toxic and Carcinogenic Partial Combus-
tion Products from Various Nitrogen-
containing Additives 233
B2.11 Status Report: Characterize Diesel Gaseous
and Paniculate Emissions with Paper "Light-
duty Diesel Exhaust Emissions" 234
B2.12 Status Report: Characterize Rotary Emissions
as a Function of Lubricant Composition and
Fuel/Lubricant Interaction 242
B2.13 Status Report: Characterize Paniculate
Emissions - Alternate Power Systems
(Rotary) 243
VOLUME 3
B.3 Emissions Measurement Methodology
B3.1 Emissions Measurement Methodology Summary 1
B3.2 Status Report: Develop Methods for Total
Sulfur. Sulfate. and other Sulfur Compounds
in Paniculate Emissions from Mobile Sources 2
B3.3 Status Report: Adapt Methods for SO2 and SO3
to Mobile Source Emissions Measurements 3
B3.4 Evaluation of the Adaption to Mobile Source
SO2 and Sulfate Emission Measurements of
Stationary Source Manual Methods 4
B3.5 Sulfate Method Comparison Study. CRC APRAC
Project CAPI-8-74 17
B3.6 Determination of Soluble Sulfates in CVS
Diluted Exhausts: An Automated Method 19
B3.7 Engine Room Dilution Tube Flow Characteristics. ... 41
B3.8 An EPA Automobile Emissions Laboratory 52
B3.9 Status Report: Protocol to Characterize Gaseous
Emissions as a Function of Fuel and Additive
Composition - Prototype Vehicles 89
B3.10 Status Report: Protocol to Characterize Panicu-
late Emissions as a Function of Fuel and Additive
Composition 90
B3.11 Interim Report and Subsequent Progress Reports:
Development of a Methodology for Determination
of the Effects of Diesel Fuel and Fuel Additives
on Paniculate Emissions 192
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Page
B3.12 Monthly Progress Report #7: Protocol to
Characterize Gaseous Emissions as a Function
of Fuel and Additive Composition 200
B3.13 Status Report. Validate Engine Dynomometer Test
Protocol for Control System Performance 218
B3.14 Fuel Additive Protocol Development 221
B3.15 Proposed EPA Protocol: Control System
Performance 231
VOLUME 4
B3.16 The Effect of Fuels and Fuel Additives on Mobile
Source Exhaust Paniculate Emissions 1
VOLUME 5
B3.17 Development of Methodology to Determine the
Effect of Fuels and Fuel Additives on the Perform-
ance of Emission Control Devices 1
B3.18 Status of Mobile Source and Quality Assurance
Programs 260
VOLUME 6
B4. Toxicology
B4.1 Toxicology: Overview and Summary 1
B4.2 Sulfuric Acid Effect on Deposition of Radioactive
Aerosol in the Respiratory Tract of Guinea Pigs,
October 1974 38
B4.3 Sulfuric Acid Aerosol Effects on Clearance of
Streptococci from the Respiratory Tract of Mice.
July 1974 63
B4.4 Ammonium and Sulfate Ion Release of Histamine
from Lung Fragments 89
B4.5 Toxicity of Palladium. Platinum and their
Compounds 105
84.6 Method Development and Subsequent Survey
Analysis of Experimental Rat Tissue for PT, Mn,
and Pb Content, March 1974 128
B4.7 Assessment of Fuel Additives Emissions Toxicity
via Selected Assays of Nucleic Acid and Protein
Synthesis 157
B4.8 Determination of No-effect Levels of Pt-group
Base Metal Compounds Using Mouse Infectivity
Model, August 1974 and November 1974 (2
quarterly reports) 220
B4.9 Status Report: "Exposure of Tissue Culture
Systems to Air Pollutants under Conditions
Simulating Physiologic States of Lung and
Conjunctiva" 239
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Page
B4.10 A Comparative Study of the Effect of Inhalation of
Platinum, Lead, and Other Base Metal Compounds
Utilizing the Pulmonarv Macrophage as an Indicator
of Toxicity 256
B4.11 Status Report: "Compare Pulmonary Carcinogenesis
of Platinum Croup Metal Compounds and Lead Com-
pounds in Association with Polynuclear Aromatics
Using [n vivo Hamster System 258
B4.12 Status Report: Methylation Chemistry of Platinum,
Palladium, Lead, and Manganese 263
VOLUME 7
B.5 Inhalation Toxicology
B5.1 Studies on Catalytic Components and Exhaust
Emissions 1
B.6 Meteorological Modelling
B6.1 Meteorological Modelling - Summary 149
B6.2 HIWAY: A Highway Air Pollution Model 151
B6.3 Line Source Modelling 209
B.7 Atmospheric Chemistry
B7.1 Status Report: A Development of Methodology to
Determine the Effects of Fuel and Additives on
Atmospheric Visibility 233
Monthly Progress Report. October 1974 255
B7.2 Status Report: Develop Laboratory Method for Collec-
tion and Analysis of Sulfuric Acid and Sulfates . . . 259
B7.3 Status Report: Develop Portable Device for Collection
of Sulfate and Sulfuric Acid 260
B7.4 Status Report: Personal Exposure Meters for
Suspended Sulfates 261
B7.5 Status Report: Smog Chamber Study of SO_
Photo-oxidation to SO. under Roadway
Condition 262
B7.6 Status Report: Study of Scavenging of SO2 and
Sulfates by Surfaces near Roadways 263
B7.7 Status Report: Characterization of Roadside
Aerosols: St. Louis Roadway Sulfate Study 264
B7.8 Status Report: Characterization of Roadside
Aerosols. Los Angeles Roadway Sulfate Study .... 269
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Page
VOLUME 8
B.8 Monitoring
B8.1 Los Angeles Catalyst Study. Background Pre-
liminary Report 1
B8.2 Los Angeles Catalyst Study; Summary of Back-
ground Period (June, July, August 1974) 13
B8.3 Los Angeles Catalyst Study Operations Manual
(June 1974, amended August 1974) 33
B8.4 Collection and Analysis of Airborne Suspended
Particulate Matter Respirable to Humans for
Sulfates and Polycyclic Organics (October 8, 1974). . .194
VOLUME 9
B.9 Human Studies
B9.1 Update of Health Effects of Sulfates, August 28, 1974. . 1
B9.2 Development of Analytic Techniques to Measure
Human Exposure to Fuel Additives, March 1974. .... 7
B9.3 Design of Procedures for Monitoring Platinum
and Palladium, April 1974 166
B9.4 Trace Metals in Occupational and Non-occupation-
ally Exposed Individuals, April 1974 178
B9.5 Evaluation of Analytic Methods for Platinum and
Palladium 199
B9.6 Literature Search on the Use of Platinum and
Palladium .209
B9.7 Work Plan for Obtaining Baseline Levels of Pt
and Pd in Human Tissue .254
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Appendix B3.17
Development of Methodology to Determine
the Effect of Fuels and Additives on the Performance
of Emission Control Devices
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I. INTRODUCTION
The advent of oxidation catalysts as control devices for the
removal of hydrocarbon and carbon monoxide emissions from
vehicle exhaust necessitates a completely new look at fuels
and fuel additives/ with respect to the effect these addi-
tives will have on the durability and efficiency of the
catalysts. While it is generally recognized that tetraethyl
lead (TEL) and the additives necessary for the proper func-
tioning of TEL have a long range detrimental effect on
catalyst efficiency, very little is known about the effect
of other additives on catalysts. Since fuel additives must
be registered with the Federal government and data pre-
sented as to the effects on emission that these fuel addi-
tives might have, a series of government contracts were
written directed toward the collection of fuel additive
emission data, and the subsequent development of methodology
for further data collection.
This report describes work directed at the development of
methodology for determining the effect of fuel additives
on the efficiency and durability of oxidation catalysts.
Other contracts in the EPA fuel additive study program
included contracts on the effect of fuel additives on the
composition of the total hydrocarbon exhaust portion
(Bureau of Mines), the effect of fuel additives on parti-
culate emissions (Dow Chemical Co.), the effect of fuel
additives on exhaust visibility (Cornell Aeronautics Lab),
and development of a model for fuel additive emissions
determinations (Battelle Institute).
In addition to evaluating the effect of fuel additives on
catalysts, and the subsequent effect on hydrocarbons and
carbon monoxide emissions, during this study analyses were
made of particulate matter emitted from the catalyst
equipped engines and vehicles.
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The study was divided into two basic approaches: 1) Engine
dynamometer durability runs were made/ measuring emissions
before and after both beaded and monolith type noble metal
catalysts. Three fuels were used. The baseline fuel was
Indolene 0, while the two test fuels consisted of Indolene
O plus the manufacturer's recommended level of a polybutene
amine additive (hereafter referred to as Additive A), and
Indolene 0 plus the manufacturer's recommended level (at
the time of the study) of methylcyclopentadienylmanganese
tricarbonyl (hereafter referred to as Additive B). 2) The
second part of the study was the evaluation of three vehicles
equipped with beaded type catalysts and run on the three
test fuels described above. These three vehicles were
driven by three different drivers under a variety of normal
highway and city driving conditions.
The gaseous emissions were measured using a Heath Inter-
national Constant Volume Sampler to sample over the 41
minute Federal Cycle. In the case of the particulate
studies, 60 mph steady state runs were used as well as
Federal Cycle.
The final result of the study described in this report
was the development of a method for determining the short
and long range effects of fuel additives on catalytic
devices. This methodology is described in Section II of
the report/ with the data used to support the method pre-
sented in detail in Section III.
A general conclusion of the study was that although an
engine stand test procedure is adequate for catalyst evalu-
ations as it relates to fuel additives/ such procedure
offers no great benefits over vehicle testing in regards to
ease of data generation or data reproducibility and, in fact,
is disadvantageous from a cost standpoint. The availability
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of catalyst equipped vehicles as of the 1975 model year
eliminates the need for any special technology which would
be necessary for equipping an engine with a catalyst.
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II. METHODOLOGY
A. GENERAL CONCLUSIONS
The basic purpose of this study was to gather data from
both engine and chassis dynamometer durability runs for
use in setting up a proposed methodology for determining
the effect of fuel additives on catalytic devices. It is
recognized that an inexpensive and reproducible test se-
quence is needed in order to evaluate the many materials
which will find use as functional fuel additives.
The studies which were made included 140 hour durability
runs on an engine dynamometer, using both monolith and
beaded catalysts. Three fuels were used/ consisting of an
indolene baseline, indolene fuel with 1.84 grams/gallon of
polybutene amine, designated Additive "A", and indolene
fuel with .26 grams/gallon of Mnf added as methycyclopenta-
dienylmanganese tricarbonyl, designated Additive "B". Both
additives were used at the manufacturer's recommended levels
Both catalyst types tested were noble metals on inert sub-
strates. A 350 CID Chevrolet engine, modified according to
the manufacturer's specification to accept the catalysts,
was used for these studies.
In addition to the engine dynamometer runs, three vehicles
were equipped with beaded catalysts and operated under
normal driving conditions, using the same three fuels
mentioned above. The three vehicles were Chevrolets, with
350 CID engines, modified to accept 1973 EGR controls,
and tuned to operate according to the manufacturer's recom-
mendations for catalyst equipped vehicles. The vehicles
were broken in for approximately 2000 miles before the
catalysts were installed, to eliminate any-aberations
due to normal engine breakin. During the first 2000 miles,
blowby measurements were made to ascertain proper ring and
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valve seating. (The procedure for blowby measurements is
described in Section II-B-1 and Table 1).
The vehicles were tested at 2000 mile intervals after
catalyst installation. Gaseous measurements were made
using a Heath International 5 Bag Constant Volume Sampling
System. In addition to gaseous measurements, particulates
were also collected and analyzed. (See Government Report
EPA-650/2-74-061 for complete details on particulate testing
techniques.)
Some of the pertinent major conclusions which can be drawn
from the various runs, both engine and vehicle, are as
follows:
1. There did not appear to be any greater reproducibility
or less scatter of data when testing on the engine stand
than was noted while testing using vehicles. This is signi-
ficant since the engine stand tests are generally more
expensive than the corresponding vehicle tests both in terms
of operating costs and capital equipment. In addition,
catalyst equipped vehicles are readily available with
supplemental equipment such as EGR, air pumps, etc., already
in place. The location of the catalyst itself in the down-
stream exhaust is thereby also specified.
2. Wherever conversion efficiency appeared to decrease as
a function of time or miles, the trend was more pronounced
in the vehicle tests than it was in the 140 hour engine
durability tests. This might be due in part to the fact
that the vehicles saw slightly more severe operating con-
ditions (70 mph expressway driving, for example) than did
the engine stand catalysts. In any event, a negative effect
due to an additive seems to be more pronounced in a vehicle
than on an engine stand.
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3. The use of a 41 minute Federal Cycle Modified (meaning
in this study that the test sequence was initiated with the
engine and exhaust systems fully warmed up, rather than at
the end of the 12 hour soak period) gave much more consistent
and repeatable data than did thp corresponding Cold Start
Federal Cycle, as measured by gaseous emissions. Recognizing
that a Modified Federal Cycle is of limited value as far as
gaseous emissions certification is concerned, it does seem
that starting the Federal Cycle with a fully warmed up
engine eliminates variables which might otherwise be present
in the Cold Start Federal Cycle, allowing a more true reading
of the actual state of the catalyst. In addition, Modified
Federal Cycles can be repeated with no undo time delay as
would be necessary for the Federal Cycle requirement specify-
ing a 12 hour soak period.
4. Although in several instances the two additives tested
appeared to have some negative effect on catalyst efficiency,
in no case was the negative effect dramatic enough to state
categorically that the additive under test was unsatis-
factory. Unfortunately, time limitations did not permit
longer mileage accumulations on the vehicles to determine
if the long range effects would continue in the same direction.
The engine durability studies were terminated after 140 hours
of operation. This test length appears to be inadequate
for determining any fuel additive effect on catalysts for
any additive other than those which would be extremely
harmful.
B. RECOMMENDATIONS FOR PROPOSED FUEL ADDITIVE/CATALYST
METHODOLOGY
In view of the conclusions stated above, a proposed methodology
for fuel additive testing as regards catalyst life and
efficiency has been developed containing the following key
points: 1. Vehicles are superior to engine dynamometer
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for these tests. 2. The Federal Cycle, with the 12 hour
cold soak, introduces variables which the Federal Cycle Modi-
fied would eliminate, such as low temperature spark plug misfire
and air/fuel difference due to the choke. 3. Artifical
means of inducing catalyst degradation, such as cold shock-
ing or high temperature aging are generally unreliable in
determining an additive effect on the catalyst. These
techniques may be valuable, however, for determining the
relative merits of different catalysts. A bibliography of
papers and articles on catalyst studies, including some on
artifical aging, is included in Appendix A. 4. In order
to determine the effect of fuel additives on catalysts and
the subsequent effect on particulate, more sophisticated
and expensive analytical and collection techniques are
needed than for only gaseous exhaust measurements. The
methodology for particulate emission studies, as relates to
fuel additives, is presented in Government Report #EPA-650/2-
74-061 titled "Determination of Effect on Particulate Exhaust
Emissions of Additives and Impurities in Gasoline". For par-
ticulate studies an engine dynamometer is a more appropriate
method of emission generation than is a vehicle, since the
variables of operation can be more easi]y controlled on an
engine stand. In addition, the dilution tube apparatus
necessary for particulate collection is more easily adopted
to engine stand studies than to a chassis dynamometer. The
details of particulate collection and measurement are also
described in Government Report EPA-650/2-74-061.
1. Vehicle Selection
In the study described in this report, 350 CID Chevrolet
engines were used. It is suggested that this engine be
specified as the test engine of choice, if for no other
reason than that much data already exists for comparative
purposes. It is recognized, however, that any standard
engine could be used, and that the engine choice itself
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should have little effect on catalyst durability as a
function of fuel additives.
The vehicles chosen for the test should be equipped with
catalysts, installed by the manufacturer, and containing
all supplemental control devices necessary for the proper
function of the catalysts. Since catalyst equipped cars
will be readily available as of the 1975 model year, it is
recommended that purchased or leased vehicles be used with
no additional modifications to the emission control system.
As of this writing, it appears that both beaded and monolith
type noble metal catalysts will be used to meet the Federal
emissions requirements. Our studies did not show any signi-
ficant differences between the two types which could be
attributed to a fuel additive effect. If base metal catalysts
find commercial application, however, it would be appro-
priate to test both catalyst types since the chemical effect
of a given additive on a base metal catalyst could be signi-
ficantly different than on a noble metal catalyst.
The vehicles used for the tests should be tested for blowby
every 1000 miles by the procedure outlined in Table 1.
Blowby is a measurement of the exhaust gas which is escaping
past the piston rings, and is measured via pressure on the
crankcase and valve train cover.
Blowby tests are necessary to determine when and if the
engine is properly broken in and stabilized. It is obvious
that poor ring seating or valve seating will result in
emission levels not representative of a nornal engine. The
need for ascertaining proper break-in is even more important
when testing fuel additives, since it is conceivable that
certain additives may lengthen or shorten the normally
expected break-in period.
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TABLE 1
BLOWBY TEST PROCEDURE
Clayton CT-200 Chassis Dynamometer Used
1. Thermocouples installed as follows to record accurate
temperatures:
a. Top radiator hose
b. Carburetor venturi
c. Oil pan
d. Ambient air
e. Blowby gas flow tube
2. Close oil dip stick tube
3. Close rocker cover vent to carburetor (right side on
350 CID Chevrolet)
4. Install tube from PCV (left side) to Sharp orifice
meter intake (1/4" port)
5. Install Venier band throttle
6. Place wind fan in front of car
7. Connect accurate tachometer
8. Connect blowby apparatus as follows (see diagram for
details):
a. Use cooling water to maintain 75-85°F blowby
b. Connect condensate trap to tube from PVC
c. Connect outlet from condensate trap to Sharp
orifice meter (use 1/4" orifice)
d. Connect incline water monometer across orifice
meter
e. Connect mercury monometer to engine vacuum
9. All tests run at 2000 rpm
10. Collect the following data at each load condition:
a. MPH
b. RPM (maintain at 2000)
c. Load
d. Intake manifold pressure
e. Ambient air
f. Carburetor air
g. Coolant temperature
h. Oil temperature
i. Barometer reading
j. Wet and dry bulb temperatures
k. Blowby temperature before orifice meter
1. Pressure drop observed across water monometer
m. Observed cfm blowby - read from Sharp orifice
meter chart relating pressure drop to cfm
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TABLE 1 (Cont'd)
CFM at standard conditions was calculated using a dfm
correction factor to compensate for barometric pressure
and a standard conversion factor to bring the final
result to cfm at standard conditions.
The initial reading was taken at the lowest horsepower
load measurable. Subsequent readings at multiples of
10 hp.
See attached data collection sheet for an example of
a typical blowby run.
10
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BLOW 13Y MEASUREMENTS
TABLE 1 (Cont'd)
SHEET NO. 34
OBSERVER
WT
DATE ' July 10, 1973
VEHICLE MAKE Chevrolet
YEAR 1972
NUMBER D2549
MILES ON VEHICLE 16.352
IGNITION TIMING 6°
DISPL. 350 NO. OF CYL. V8
AT 600 RPM CARB
C.R.8-5-1
TRANSMISSION 350 Th
VAC. IDLE
RP
BBL
HP
RPM
BAROMETER IN HE 29.40 at 82 WET BULB 66.0 °F DRY BULB 82.0
CORRECTED BAROMETER(DRY) 28.79 at 28.5°F ABS. HUMIDITY_
INERTIA WEIGHT 4500
.470
LBS
VALVE COVER PRESSURE +
SPARK PLUG TYPE R44T
0"
DWELL
REMARKS: Corr Wet Bar = 29.26
30'
HP
GR/L3
RPM
' SPEED
RPM
LOAD
ENGINE VACUUM
AMB. AIR
CARB. AIR
WATER
OIL
BLOW- BY AIR
OBS. PRESS DROP
OBS. CFM
CI--M CORR. FACTOR
CORR CFM
STD. COHV. FACTOR
CFM at STD COND.
57
2000
3,4
18,9
90
118
206
242
85
,65
,65 '
,9963
,647
1,078
.697
56
2000
10
17,5
94
120
208
246
85
,86
,81
,9963
,807
1.078
.869
55 -
2000
20
15,0
98
120
212
250
85
1,38
1,01
,9963
1.006
1.07S
i.nwi
53
2000
31
11,0 .
99
320
214
256
85
2,00
1,23
,9963
1,225
i.n/P
i.^9n
52
2000
/n
8,3
99
122
??2
265
85
2,42
1,5:
,9963
1 , 345
1 078
i .aziq
CO
w
OS
W
m EH
s M
O EH
^ z
CQ W
K
00
11
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Once the blowby has stabilized, indicating proper break-in
of the engine, the frequency of the tests can be lengthened
to every 4000 miles. It is important to continue periodic
blowby tests as a check for abnormal ring or valve wear.
B. Test Procedures
The basic test sequence for evaluating the effect of a fuel
additive on a catalyst is the Federal Cycle/ 41 Minute Cold
Start Test. As mentioned previously, this test does seem to
give more scatter of the data than does the same test sequence
after the engine and exhaust system has been warmed up
(Federal Cycle Modified). The recommended procedure, there-
fore, is to run a Federal Cycle test, followed by two or
more 41 Minute Federal Cycle Modified (Hot Start) tests. The
Federal Cycle data will be useful in determining the actual
emissions level as necessary for the Federal certification
procedures, while the modified tests will be more representa-
tive of the actual state o^ the catalyst.
A series of steady state tests at 20, 30, 40 mph, etc. mea-
sured along with catalyst temperature, would be valuable in
giving a profile of the catalyst after aging with an additive.
Steady state testing procedures, while valuable for collection
of particulate matter, are of little use for gaseous analyses.
The only area where steady state might be of value is in
determining if a given additive has changed the temperature
at which the catalyst begins to function. A change in the
light-off temperature would show up in the cold or hot start
tests, but would not be as easily quantified as it would be
in a series of steady state runs.
The equipment necessary for vehicle testing according to
the Federal Cycle procedure is readily available. A chassis
dynamometer such as the Clayton used in this study is
sufficient. If the tests are run manually, using a test
driver to follow the 41 minute cycle, it is suggested that
the same driver be used for all tests, if possible. It
12
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has been our experience that different drivers, due to
slightly different driving techniques, can introduce enough
variance into the cycle to result in some data scatter. An
automatic cycling procedure will obviously eliminate this
problem.
The mileage accumulation procedures will have an effect on
the longevity of a given catalyst even without the added
variable of a fuel additive. Recommended procedures for
mileage accumulation are as follows:
1. A test track procedure for accumulating mileage is the
optimum. This allows for reproducible and repetitive
operation of the vehicle. High speed driving will obviously
put the most miles on the catalyst in the shortest period
of time. However, low temperature, low speed driving is
necessary to simulate city driving conditions. Any catalyst
aging will be more a function of engine hours than miles.
It is important under all circumstances to monitor the
temperature of the catalyst to ascertain that any catalyst
degradation is not due to a high temperature burnout of the
catalyst. In addition, temperature monitoring will imme-
diately pinpoint any mechanical failures such as fouled
spark plug or choke sticking. The best mechanism for
temperature monitoring is a direct readout temperature
meter mounted on the dashboard of the vehicle, and a strip
chart recorder mounted elsewhere in the vehicle to record
the actual catalyst temperatures as a function of engine
hours. Any high temperature due to mechanical failure or
overload would be readily noted, and aberations in the data
would be explained. Our studies did not utilize a temperature
recorder, but in retrospect it would have been valuable to
have such data.
13
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2. If test track mileage accumulation is not possible,
normal highway and city driving can be used. The best way
to make sure that the mileage is accumulated in a repre-
sentative fashion is to set up a driving sequence which
includes an appropriate amount of urban, suburban and cross
country type operation. While recognizing that flexibility
is necessary in developing a driving sequence, a suggested
format would be for a minimum of 50% of the engine hours
to be accumulated in urban and suburban type driving, and
for no more than 50% of the hours to be accumulated at
expressway speeds.
Since ambient temperature and humidity conditions will have
some effect on gaseous emissions, and since the statistical
significance of a fleet test is already low unless several
vehicles are used for each of the additives and the base-
line, it is important that the vehicles start and finish
the test period at about the same time.
The testing interval of the vehicles should be no less
frequent than 2000 miles for the first 10,000 miles, and
4000 miles thereafter. Since normal catalyst life is
expected to be 50,000 miles, any negative effect showing
up dramatically within the first 10,000 miles would be
reason enough to terminate the test at 10,000 miles. If
no effect is noted during this period, the tests should
be extended to 25,000 miles. Since the data available
from other sources to date shows little consistency as
pertaining to catalyst performance past 25,000 miles, it
is felt that a test lasting longer than this would contri-
bute little in the way of data which could be attributed to
a fuel additive effect.
Although we recommend that vehicles be used as the primary
test source, it is recognized that some manufacturers of
-------
additives are well equipped to run multi-engine dynamometer
studies. This technique is satisfactory, but for the reasons
previously described cannot be recommended as the method of
choice. If engines are to be used, however, several criteria
are necessary.
It is extremely important that the engines be equipped with
catalysts in a way which very closely simulates the given
catalyst system as it would exist on a vehicle. Accessory
emission control devices are necessary, as well as verifying
that the placement of the catalyst downstream from the
exhaust header be the same as the placement on a vehicle.
If a given test catalyst is used on a vehicle to catalyze
the exhaust stream from eight cylinders, than it must also
be used on all eight cylinders of the test engine exhaust.
The engine dynamometer cycle is an extremely important part
of the data collection process. Previous work (Government
Report EPA 650/2-74-061) involving particulate studies, used
the 23 Minute Federal Cycle which was repeated over and over
until the required number of hours were accumulated on the
engine. For the catalyst studies described in this report, the
sequence of 23 minute runs was felt to be unsatisfactory.
Basically, the average speed of approximately 19 miles per
hour was not felt to be adequate for promoting any severe
additive effect on the catalyst. In addition, the accelera-
tions in the Federal Cycle (23 minutes) do not severely
enough load the engine. Higher loads will cause short duration
catalyst temperature increases which more closely simulate
severe driving conditions such as wide open accelerations or
trailer towing.
The durability cycle of choice for the fuel additive effect
engine runs is described in detail on page 2'4319, Volume 37,
Number 221, Wednesday, November 15, 1972 of the Federal
Register. This cycle is summarized in Table 2. The per-
tinent factors in this cycle include rapid acceleration
15
-------
TABLE 2. ENGINE DURABILITY TEST CYCLE
0 to 3.7
miles
.st.°P
then accelerate
to Lap Speed
Decelerate
to 20 mph
then accelerate
to Lap Speed
Decelerate
to 20 mph
then accelerate
to Lap Speed
Start-Finish
Sto
then accelerate
to Lap Speed
Decelerate
to 20 mph
then accelerate
to Lap Speed
Decelerate
to 20 mph
then accelerate
to Lap Speed
Sto
then accelerate
to Lap Speed
Decelerate
to 20 mph
then accelerate
to Lap Speed
Lap
1
2
3
4
5
6
7
8
9
10
11
Speed-
m.p.h.
40
30
40
40
35
30
35
45
35
55
70
2.2 Stop
then accelerate
to Lap Speed
All Stops are 15 sec.
16
-------
TABLE 3
ENGINE DYNAMOMETER DURABILITY TEST SCHEDULE
Federal Accumulated
Accumulated with Without Federal Cycle Particulate Test Hours
Davs Converter Converter Cvcle Modified 60 MPH 23 Min. on Test
IX X
X . X 6
X X ,
1 1
t
1 1
.
2 XX
X X 25
x : , x ,
i X ' X
1
'
1
1 1 !
3 X : X
I X X 48
4 X • X :
X ; • X ; 67
X ' X
5 XX' i
X x : 86
: x x . '
6 X : X j 109
' X X
i !
7 X X : :
X . X 128
X X - ;
8 X X ,
X i X 137
X X
9 ' X ' X ; 140
X X
X X
Sequence Test
of Test Pairs Remarks
1 164 , The engine was oper-
2 265 ' ated on the Federal
3 ' ' Durability Driving
Cycle for 19 hours and
then stopped for 4
hours to simulate a
cold start test.
4 ' The engine was oper-
5 ' ated on the Federal
6 Durability Driving
7 ' Cycle for 24 hours
; with no engine shut
down as no simulated
cold stare is called
for before emission
: test.
8 '869
9
10 ' 10613 ' Same as Day SI
11 11612 !
12 '
13 . i Same as Day tl
14 14615 |
15 '
16 16617 : Same as Day 82
17 :
18 ' 18621 . Same as Day #1
19 j 19620
20
21 . ' Engine shut down at
22 22623 i end of day when the
23 I accumulated hours
! total 137 hours.
24 ! i Particulate test on
25 ! ' this day.
26 i
|
-------
and deceleration/ with a top speed of 70 mph, and an overall
average speed of about 40 mph. It is basically a cycle
adapted from test track driving. A 3.7 mile test course
was used, with a total of 11 laps. During the first 9 laps,
there are 4 stops with 15 ser-ci.ds idle. Normal accelerations
and decelerations are used. In addition, there are 5 light
decelerations each lap from the base speed to 20 mph fol-
lowed by light accelerations to the base speed. The 10th
lap is run at a constant 55 mph. The llth lap is begun
with a wide open throttle acceleration from stop to 70 mph.
A normal deceleration to idle followed by a second wide open
throttle acceleration occurs at the midpoint of the lap.
The durability schedule was transcribed onto computer tape,
which was used on a mode monitor manufactured by Northern
Ampower Corporation to control the engine and the dynamo-
meter. There are probably many ways in which a cycle can
be transcribed to control an engine dynamometer, but since
all of the work on this contract was done using the Northern
Ampower Mode Monitor, no attempt will be made to discuss
other systems. It is important, however, to use a cycle and
not a series of long steady state runs, since the effect on
a catalyst of a steady state run will not be the same as
the fuel additive effect which will occur as a result of
frequent acceleration and deceleration.
C. Analyses of Data
The gaseous emission data collected during this study was
determined using the Heath International 5 bag CVS system.
The procedures followed in all cases were those outlined in
the Federal Register for gaseous determinations.
The single most important piece of data generated from each
specific test is the total grams/mile hydrocarbon and car-
bon monoxide figure for the weighted average of the segments
18
-------
of the Federal Cycle. This number will be directly com-
parable to the figures obtained during certification of a
given engine or control system. The change, over time, in
the total grams/mile number is an accurate assessment of
the effect of a given additive on the control system under
test.
The various segments of the Federal Cycle, however, as mea-
sured by the 5 bag system, can be used individually to give
more detailed information about the specific effects of any
fuel additive under test. The cold start portion is the
least reproducible of the three segments, but when compared
to the stabilized or hot start segment can not only give
information about the relative durability of catalysts, but
is also a good check point for determining very quickly if
any mechanical malfunctions are occurring.
For example, if the cold start portion shows an increase in
grams/mile hydrocarbon or carbon monoxide as a function
of time, while the stabilized and hot start portion remains
relatively constant, this could be an indication that the
light-off temperature of the catalyst is increasing, while
the efficiency, once light-off temperature is reached, is
not affected. On the other hand, if the cold start portion
remains relatively constant while the stabilized segment
goes up, either sharply or as a function of time, this could
be an indication of high speed spark plug misfiring due to
mechanical ignition problems or an additive effect on the
spark plugs themselves. An overall rise in the weighted
averages, per the Federal Cycle procedure, can be more
easily relied on as an indication of catalyst degradation
if the same general effect is noted in the various segments
of the cycle. In Section III, the data from both the
engine runs and the vehicle tests are presented, and in
each case the effect of the additive fuels is discussed
19
-------
for the weighted average and the individual segments.
As mentioned previously, the raw data from the CVS system
was converted into grams/mile using the Federal Register
procedure outlined in the Wednesday, November 15, 1972
edition, Volume 37, Number 221. A computer program, ob-
tained from EPA, was used to perform the calculations. For
gaseous emission testing it is imperative that computer
capacity and an appropriate program be available for these
calculations. It would be virtually impossible to do them
any other way.
In addition to the gaseous emission data, it is appropriate
to also determine a fuel additive effect on a catalyst rela-
tive to particulate emissions. No attempt was made in this
study to further refine particulate collection and analysis
methodology. The methods described in report EPA-650/2-74-
061 are sufficient for these studies relative to particulate
mass and composition (carbon, hydrogen, nitrogen, benzo(^)
pyrene, and trace metals). However, since oxidation catalysts
are suspected of increasing the ratio of SO3/SO2 compared
to non-catalyst systems, measurement of these particular
species is appropriate. Some preliminary work was done using
a modification of Method 8, described in Federal Register,
Volume 36, page 24893. Basically, this method involves
sampling a direct exhaust gas stream from before and after
the catalyst, and running the stream through a series of
impingers, collecting the SO- in a peroxide solution and the
SO3 in an isopropyl alcohol solution. From the initial
attempts at ascertaining any shift in SO_/SO2 ratio, it
appears that this method can be used. However, not enough
work was done to warrant a detailed explanation as part of
the methodology of this contract.
Filtration techniques described in report EPA-650/2-74-061 can
also be used to determine any shift in the SO_/SO2 ratio,
20
-------
since in diluted exhaust the SO, will exist in the hydrated
form as H2SO4. This can be collected on the millipore
filter media, and analyzed by one of several techniques
specific for the SO~ ion. Barium precipitation is one
such method, and is described in Method 8. A technique
used on occasion in other studies involved induced electron
emission spectroscopy, and is specific for a given valence
state of sulfur. Total sulfur in the particulate can be
measured using readily available pyrolitic techniques.
In analyzing the data generated both on the engine stand and
the vehicles, it is recognized that the statistical signi-
ficance is low. For each test, there are enough uncon-
trollable variables present, such as minor undetected
mechanical malfunctions or ambient weather conditions, so
that in each durability run there always seemed to be one
or two points unexplainably higher or lower than the observed
trend from the rest of the data points. Where possible, an
attempt has been made to rationalize what the cause might
have been. However, in many cases there does not appear to
be any plausible explanation. It is suggested that any test
on an additive system that is expected to see widespread
usage be run with at least two vehicles on the baseline fuel
and two or more on the given additive fuel. A statistically
significant multi-engine or vehicle test can be set up using
one of any number of mathematical models.
Table 4 is an example of how a statistical test can be set
up by making certain assumptions about the repeatability
and closeness with which the engines or vehicles match. The
horizontal axis of the table is the standard deviation, or
the difference, plus or minus, which one would expect between
engines or vehicles in a normal situation. The vertical
axis, p, is the difference in the average emission levels
which is expected to be significant. The numbers in the
21
-------
body of the table are the numbers of vehicles or engines
needed to show the difference p. For example, if it is
assumed that a set of matched engines will show a normal
25% variation from the average on hydrocarbon or carbon
monoxide emissions when equipped with a catalyst and run on
a baseline fuel, and that an increase in emissions of 50%
(p = 1.5), compared to a baseline, is expected, than 15
engines would be necessary for both baseline and test fuel
in order to be assured that the 50% increase is statisti-
cally significant at the 95% confidence level, and not a
result of the normal variations expected between engines.
If the engines are felt to be closely enough matched so that
a deviation of 15% is expected, and a 150% (p = 2.5) increase
in emissions due to an additive is significant, than 4 engines
or vehicles can be used.
The graph on Table 4 shows the importance of the duration of
the test. Obviously, if an additive causes catalyst de-
gradation with time, the longer the test runs, the greater
the difference will become between the baseline and the
test fuel, until at some point a plateau is reached. If a
test is terminated before the plateau is reached, then p
will be smaller than necessary, and the statistical signi-
ficance will be lower for a given number of engines or
vehicles than would be expected.
In setting up a statistically significant test sequence,
as much prior information on the expected behavior of the
engines as can be obtained is quite helpful. For example,
if it has already been established that a given engine on
a given test sequence (either engine stand or vehicle) would
show a normal variance of 15% from the average, then a fewer
number of vehicles or engines can be used fpr the tests than
if the assumption was erroneously made that the engines
would show a 25% variance.
22
-------
Table 5 is a summary of some of the gaseous data obtained
from engine dynamometer runs, measured before the catalyst
via CVS. The intent is to show the variability in hydro-
carbon and carbon monoxide emissions which is present in the
same engine during a single run and also the variability in
the same engine from run to run. Although a slight increase
in both hydrocarbons and carbon monoxide might be expected
to occur as a result of engine hours, the deviations from
the average which occur apparently in a random fashion indi-
cate that a range of 15% to 40% deviation from the average
is not unlikely. For example, with the baseline fuel,
tested 7 times on a Federal Cycle modified with no catalyst,
the average hydrocarbon emission was .43 grams/mile, with a
low of .2 grams/mile (perhaps spurious, but if so, no reason
was readily apparent) and a high of .56 grams/mile, or
-53% and +30%, respectively. Another example, using fuel
Additive A, with no converter, showed a range of +22% and
-10% for hydrocarbons and +6% and -9% for carbon monoxide.
It is apparent from this data that before a statistically
significant test can be set up, some assumptions on the
expected repeatability of the data must be made, and the
repeatability will most likely be in the 15-40% range.
D. Expected Results
In light of the statistical significane of the data which
was just discussed, it is apparent that using a relatively
small (less than 10 vehicles) fleet test will give statisti-
cally sound results only if the additive under test shows
differences in gaseous emissions of around 2 times the
emissions measured under baseline conditions.
Since there are numerous additives used in fuel which will
need to be tested, and since many of these additives are
all organic compounds used at low percentages, it is rea-
sonable to assume that different sized fleet tests will be
necessary to generate the data needed to make reliable
23
-------
conclusions as to the effect of a given additive on catalysts
For example, a low molecular weight organic material such as
methyl alcohol/ used as an anti-icer, would be expected to
have little or no effect on a catalyst. Therefore, a large
number of test vehicles would be necessary to statistically
verify the exact magnitude of any change in emission rates.
However, since methyl alcohol is expected to have little
effect on catalyst life, and since it is also readily
oxidized and should have little effect on regulated gaseous
emissions, and also since the value of this additive in fuel
is such that a large expenditure for data generation might
be felt unreasonable, the argument could be reversed so that
a small fleet test would be enough to validate a qualitative
conclusion.
In the case of an additive used for octane improvement,
such as Additive "B" in this study, which will have a wide-
spread usage and which can also be expected to have some
chemical or physical effect on a catalyst, the cost and time
necessary to generate statistically sound data would be
justified.
The point being made is that there should be some flexi-
bility in the proposed fleet tests (or engine stand runs)
to allow for expected differences in various additives with
respect to catalyst efficiency and longevity, and should
also take into account the value of the given additive to
the industry or consumer.
Another consideration which was not looked at in this study
but which could be significant is a cummulative effect
when more than one additive is present in a given fuel. A
fully formulated gasoline containing an octane improver,
a dye, an antioxidant and a detergent couM have a larger
or smaller cummulative effect on catalyst efficiency than
any of the additives by themselves. The use of a detergent
-------
by itself could conceivably show a decrease in hydrocarbon
emissions compared to a baseline fuel containing no addi-
tives just as a result of forming lower engine and intake
manifold deposits, whereas in combination with other addi-
tives this effect would be negated. It is suggested that
where feasible, tests be run on fully formulated fuels to
determine any effects on the catalysts. If negative effects
are noted/ then the individual additives can be tested via
the same procedure.
This study primarily involved testing for the regulated
gaseous emissions (carbon monoxide and unburned hydrocarbons)
which would be affected by oxidation catalysts. Analysis of
particulate emissions was also looked at/ but in general,
showed so much scatter that meaningful conclusions are dif-
ficult to draw. In analyzing the data collected from a test
on a given additive, there are several key points to consider.
First, an increase in carbon monoxide or hydrocarbons as a
function of miles is significant as an absolute measurement
only if the increase takes the emission level past the
Federal Standard in effect at the time. For example, if
carbon monoxide in a given test goes from 1 g/mile to 3
g/mile, the absolute numbers are not of much value in terms
of drawing conclusions about the additive since both the
start and finish numbers are below the. 3.4 g/m5le standard.
The second point, which logically follows from the example
just stated, is that catalyst efficiency is the most im-
portant measurement. Following the previous example, if the
baseline test showed an increase in carbon monoxide from
1.0 g/mile to 2.0 g/mile over the same time period that the
test fuel showed a 1.0 g/mile to 3.0 g/mile increase, then
the conclusion would have to be that although the additive
shows some negative effect on the catalyst, the effect is
not significant in terms of an overall reduction in air
quality.
25
-------
The third point to consider is that any additive which
causes an increase in emissions which takes the levels
above the regulated standard should be considered suspect.
This point has to be tempered somewhat, however, with the
recognition that a baseline fuel can also show an increase
to a point above the standard as a result of normal catalyst
attrition. The data presented in this study in Section III
shows that the baseline as well as the.two additives ended
up above 3.4 g/mile carbon monoxide at the conclusion of
the 17,000 mile vehicle tests.
F. Summary
To summarize, the methodology suggested for testing fuel
additives for the effect on catalyst operation with respect
to gaseous emissions is as follows:
1. Select a statistically significant fleet size (or
engine runs, if so desired) based on assumed parameters of
reproducibility and precision, and based on whether prior
data is available on the given additive system and engines
used for the tests.
2. Break in the vehicles, testing for blowby every 1,000
miles until stabilized, and every 4,000 miles after test.
3. Run the vehicles according to a prescribed test sequence
(test trade or road), testing for gaseous emissions every
2,000 miles for the first 10,000 test miles, and 4,000 miles
thereafter, using the Federal Test Cycle (both modified and
cold start).
4. Collect and tabulate the data in such a way that the
catalyst efficiency at the end of each test sequence is
the prime consideration. Apply statistical methods of
analysis to the results to verify statistical significance.
26
-------
TABLE 4. STATISTICAL TEST EXAMPLE
Standard Deviation
.15 .20 .25 .30 .40
1.5
2.0
2.5
3.0
7
4
<4
<4
10
5
<4
<4
15
6
4
<4
22
7
5
<4
37
11
6
4
Q)
iH
•H
41
On
(0
C
o
•H
in
in
••-I
e
0)
p. a
Operating Hours
27
-------
TABLE 5. VARIABILITY OF DATA
KJ
00
Engine Runs
Baseline Fuel
No Catalyst, g/mile
HC
.53
.56
.53
.44
.20
.38
.40
.43
+30%
-53%
CO
22.1
25.8
29.9
24.8
11.4
22.2
23.9
22.3
+33%
-49%
HC
.58
.56
.58
.61
.63
.59
+7%
-5%
CO
17.3
17.3
17.7
17.7
17.6
17.5
+1%
-1%
Additive A
No Catalyst, g/mile
HC
.59
.62
.57
.66
.88
.58
,74
.66
+33%
-14%
CO
17.3
17.4
17.6
17.6
17.2
17.4
17.2
17.4
+1%
-1%
HC
.37
.39
.38
.39
.50
.45
.41
+22%
-10%
CO
22.6
21.8
23.2
19.9
21.9
21.8
21.9
+6%
-9%
No
HC
1.03
.99
1.12
1.16
1.28
.94
1.02
1.08
+19%
-13%
Additive B
Catalyst, g/mile
CO
24.1
25.3
21.1
22.8
23.9
15.4
17.0
21.4
+18%
-28%
HC
1.37
1.44
1.43
1.83
1.52
+20%
-10%
CO
17.6
17.6
17.6
15.9
17.2
+2%
-8%
Average
Max. Deviation
from Average
Min. Deviation
from Average
-------
III. EXPERIMENTAL DATA, GASEOUS EMISSION
This section consists of the raw data from all of the
engine and vehicle tests which was used to verify con-
clusions regarding the methodology. The data is presented
in eight sections, with comments and conclusions for each
section. The eight sections are:
A. Raw Data, Engine Stand, Monolithic Catalyst,
Three Fuels.
B. Comparison of Three Fuels, Engine Stand,
Monolithic Catalyst.
C. Raw Data, Engine Stand, Beaded Catalyst,
Three Fuels
D. Comparison of Three Fuels, Engine Stand, Beaded
Catalyst.
E. Comparison of Beaded and Monolithic Catalysts,
Engine Stand, Three Fuels
F. Raw Data, Chassis Dynamometer, Beaded Catalyst,
Three Fuels
G. Comparison of Three Fuels, Chassis Dynamometer,
Beaded Catalyst
H. Comparison of Chassis Vs. Engine Dynamometer,
Beaded Catalyst, Three Fuels
The data is presented in tabular form, with graphs of
grams/mile or efficiency versus time or miles for comparative
purposes. The term "Federal Cycle" refers in all cases to
the 41 Minute Cycle as described in the Federal Register.
Modified Federal Cycle refers to the 41 Minute Cycle, starting
with a completely warmed up engine. Cold transient, stabilized
and hot transient refer to the respective segments of the
Federal Cycle. The weighted figure is the total grams/mi's
calculated via the Federal Cycle procedures.
29
-------
Physical data on the fuel used in each test is presented
in Tables 6, 1, 8. The same batch of Indolene fuel was used
for all three fuels, with the only difference being the test
additives in two of the fuels.
30
-------
TABLE 6
INDOLENE No.15214 91 OCTANE FUEL
BASE FUEL
API Gravity 58.7
IBP
5
10
20
30
40
50
60
70
80
90
95
EP
% Residue
RON
MON
RVP
% Saturates
Olefins
Aroma tics
Carbon
Hydrogen
Sulfur
Fe Ni Cu Al Ca
1. <1. 0.2 2 7
84
106
118
142
164
186
204
230
252
278
316
390
0.2
90.0
80.6
9.3
66.0
6.4
27.6
86.2%
13.3%
355 PPM
Mg Mn Fb Cr
<1. <0.5 12. <1
Trace Metals Fe Ni Cu Al Ca Mg Mn Fb Cr Sn Zn Ti
PPM
Lead by Atomic Absorption = 12.PPM
Phosphorus by Colormetric Data = <1.PPM
Bromine by X-ray Fluorescence = 4.PPM
31
-------
TABLE 7
INDOLENE No.15214 91 OCTANE FUEL
•f ADDITIVE "A"
API Gravity 59.7
Distillation:
IBP 96
5 114
10 126
20 148
30 166
40 188
50 208
60 226
70 244
80 270
90 304
95 378
EP
% Residue 0.2
RON 90.6
MON 80.4
RVP 8.0
Saturates 68.4
Olefins 3.8
Aromatics 27.8
Carbon 86.1%
Hydrogen 13.4%
Sulfur 460. PPM
Trace Metals Fe Ni Cu Al Ca Mg Mn Pb Cr Sn Zn Ti
PPM 3. <1. <0.2 1. 2 <1. <0.5 — <1. <1. <3. <1
Lead by Atomic Absorption = 66 ppm
Phosphorus = <2.PPM
Bromine by X-ray Fluorescence = 25 ppm
32
-------
TABLE 8
INDOLENE NO.15214 91 OCTANE FUEL
+ ADDITIVE "B"
API Gravity 59.5
Distillation:
Trace Metals
PPM
IBP
5
10
20
30
40
50
60
70
80
90
95
E.P.
% Residue
RON
MON
RVP
Saturates
Olefins
Aromatics
Carbon
Hydrogen
Sulfur
Fe Ni Cu Al
3. <1. <0.2 <1.
102
126
136
154
174
194
212
230
248
272
314
380
0.2
93.0
81.0
8.0
68.2
4.8
26.8
85.8%
13.4%
480. PPM
Ca Mg Mn Pb Cr Sn Zn Ti
2 <1. 82. — <1. <1. <3. <1
Lead by Atomic Absorption = 74 ppm
Phosphorus = <2.PPM
Bromine by X-ray Fluorescence = 25 ppm
33
-------
A. Raw Data, Engine Stand, Monolithic Catalyst, Three Fuels
The following set of data and graphs consists of the mea-
surements, via CVS, of carbon monoxide and hydrocarbon
emissions and the corresponding conversion efficiencies for
monolithic catalysts. For the "study, an engine was equipped
with a catalytic converter coupled to an engine dynamometer
and operated on a Federal Durability Cycle as described in
the November 15, 1972, Volume 37, Number 221, Federal
Register. Three different fuels were used: baseline,
Additive "A", and Additive "B".
The exhaust gases were collected using a Heath International
CVS 5 Bag System. They were analyzed using the following
analytical instruments:
1. Unburned hydrocarbons - Beckman Flame lonization.
2. Carbon monoxide - 0-280 ppm, 0-3000 ppm range, Beckman
Infrared Analyzer, Model 1R315.
The durability or conversion effieicney was measured by the
analysis of the exhaust gases at the start and periodically
during the test via the CVS method, using the Federal Cycle
and Modified Federal Cycle test sequence. Exhaust gas was
analyzed both before and after the catalytic converter.
The raw data is reported as well as shown graphically. The
cycle is broken down into the cold, hot, and stabilized
segments, and also the weighted average of each segment.
The catalysts were run for approximately 140 hours on each
fuel, using a fresh catalyst for each 140 hour run. In
addition to gaseous emission data, particulate measurements
were made at various points during the run. The particulate
data is reported in Section IV.
-------
COMMENTS - Baseline Fuel
1. All three portions of the cycle (cold, stabilized, and
hot) sampled before the converter, remained constant, as
measured by the Federal Cycle test procedure, for the
duration of each run.
2. With respect to carbon monoxide, all three portions as
above, sampled after the converter, showed some variation;
however, no significant reduction in conversion efficiency
was observed.
3. During the Modified Federal Cycle, before the converter,
the carbon monoxide emission levels were constant while the
emission levels after the converter showed a downward trend.
This is shown in the converter efficiency curves which show
an improvement with time.
4. With respect to hydrocarbon emissions, during the
Federal Cycle, except for the cold start portion, the grams/
mile for both before and after the converter remains rela-
tively constant, with a slight downward trend developing
after the converter. This is shown graphically in the
conversion efficiency curve.
5. With respect to hydrocarbons, data from the Modified
Federal Cycle show smaller differences and less scatter
between the before and after converter measurements than does
the data from the Federal Cycle. The after converter data
shows a downward trend, which indicates an improvement in
conversion efficiency, with time.
35
-------
TABLE 9. BASE FUEL. MONOLITHIC CATALYST, ENGINE STAND, RAW DATA, GRAMS/MILE *
Cold
hC CO
21.7
With Convertei
.94 13.6
.11 4.6
.23 4.5
.31 6.4
Without Convei
2.62 13.54
.74 20.61
.48 13.46
1.05 17.29
t Efficiency
64.1 0
85.1 77.6
52.0 «6.5
70.4 62.9
Hot
HC CO
22. 5
.88 7.6
.13 3.84
.24 4.16
.31 4.69
•ter
.85 13.6
.53 20.6
.46 13.46
.58 17.31
0 44.1
75.4 81.3
47.8 69.0
46.5 72.9
Cold
HC CO
64.1
1.25 13.56
.47 .84
.19 2.45
.55 3.82
1.51 13.8
.64 21.1
.53 13.8
.78 17.72
17.2 1.7
26.5 96.0
64.1 82.2
29. 5 76.7
Hot
HC CO
65.2
.35 5.68
.16 .81
.24 7.63
.22 3.60
.42 13.6
.63 20.6
.53 13.4
.56 17.32
16.6 58.2
74.6 96.0
54.7 43.0
60.7 79.2
Hot
HC CO
86.8
.54 5.95
.13 1.04
.16 3.11
.22 2.58
.57 13.8
.62 21.1
.50 13.8
.58 17.69
5.2 56.8
79.0 95.0
68.0 77.4
62.0 85.4
Hot
HC CO
108
.20 5.36
.17 .68
.17 4.61
.17 2.66
.58 13.88
.66 21.1
.53 13.8
.61 17.7
65.5 61.4
74.2 96.7
67.9 66.5
72.1 84.9
Cold
HC CO
131.8
4.2 13.5
.26 1.3
.19 2.8
1.04 4.16
1.85 13.7
.67 20.87
.53 13.76
.87 17.55
62.1 0
95.9 80.9
62.9 69.4
77.0 65.8
Hot
HC CO
131.8
.39 S.07
.19 1.43
.20 4.43
.23 2. 95
.80 13.74
.62 20.9
.52 13.76
.63 17.6
,
51.2 63.1
69.3 93.1
61.5 67.8
63.4 83.2
Durability Hours
Cold Transient
Stabilized
Hot Transient
Weighted
Cold Transient
Stabilized
Ho Transient
Weighted
Cold Transient
Stabilized
Hot Transient
Weighted
U)
en
•Corrected for ambient conditions.
-------
TABLE 10. AMBIENT CONDITIONS
BASE FUEL - MONOLITH CATALYST ENGINE DYNAMOMETER
Modified Federal Cycle X XXX X
Federal Cycle XX X
Durability Hours 0 22.5 64.1 65.2 86.8 108 131.8 131.8
ui
WITHOUT CONVERTER
Barometer
Corrected Barometer
Ambient Air °F
Wet Bulb °F
Dry Bulb °F
Humidity %
WITH CONVERTER
Barometer
Corrected Barometer
Ambient Air °F
Wet Bulb °F
Dry Bulb °F
Humidity %
29.32
29.19
77.
60.
77.
35.89
29.32
29.19
77.
60.
77.
35.89
29.18
29.08
62.
51.
62.
45.91
29.18
29.08
62.
51.
72.
45.91
29.60
29.48
74.
52.5
74.
19.05
29.63
29.48
82.
55.5
82.
13.74
29.33
29.19
81.
58.
80.
21.84
29.60
29.46
87.
59.
88.
13.83
29.18
29.05
78.
61.
78.
36.84
29.18
29.05
78.
61.
78.
36.84
29.60
29.48
"i.
52.5
74.
19.05
29.18
29.08
64.
52.
64.
43.34
29.60
29.48
74.
52.5
74.
19.05
29.63
29.48
82.
55.5
82.
13.74
29.62
29.49
77.
53.
76.5
16.03
29.60
29.46
87.
59.
88.
16.03
-------
w
00
20.
16,
12,
4.
itttd
44-144
10
20
30
Monolithic Catalyst
Base"Fuel
40 50 60 70 80 90
Durability Hours
CVS EMISSIONS FEDERAL CYCLE
FIGURE 1
100 110
120
130 140
Before Converter
After Converter
• Cold Transient
V Stabilized
D Hot Transient
O Weighted
-------
100
U)
a
90 -
80
40
0
10
20
30
Monolithic Catalyst
Base Fuel
40 50 60 70 80 90
Durability Hours
CVS EMISSIONS FEDERAL CYCLE
FIGURE 2
100 110 120 130 140
• Cold Transient
V stabilized
1 Hot Transient
O Weighted
-------
CJ
i
*
O (1)
20.
12.
8.
m
•HIT
H-T-H
o
10
20
40
50 60 70 80
Durability Hours
90
100
Monolithic Catalyst
Base Fuel
CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 3
110 120 130 140
Before Converter
After Converter
• Cold Transient
V Stabilized
D Hot Transient
O Weighted
-------
J.UU
90
80
. I. -i-j.
1-4-TL".
\. 1 jJ '.
i i j 11
rrH-r
10
20
30
40
50
60 70 80
Durability Hours
90
100
MonolitHc Catalyst
Base Fuel
CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 4
110 120 130 140
* Cold Transient
V Stabilized
D Hot Transient
O Weighted
-------
01
XT. LTD. irrn
0
10
20
30
40 50 60 70 80
Durability Hours
90
Monolithic Catalyst
Base Fuel
CVS EMISSIONS FEDERAL CYCLE
FIGURE 5
100 110 120 130 140
— After Converter
Before Converter
• Cold Transient
V stabilized
D Hot Transient
O Weighted
-------
100
L!_U- H i "\-
>\ [ '[
~T" * r~*~i - ir~r
40
Monolithic Catalyst
Base Fuel
50 60 • 70 80 90
Durability Hours
CVS EMISSIONS FEDERAL CYCLE
FIGURE 6
100 110 120 130
• Cold Transient
V Stabilized
D Hot Transient
- Weighted
140
-------
2.4 L:
.-
:
TEL
-H-HH
10
20
30
Monolithic Catalyst
Base Fuel
40 50 60 70 80 90 100
Durability Hours
CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 7
110 120 130 140
Before Converter
After Converter
• Cold Trar.sj.ent
V Stabilized
D Hot Transient
O Weighted
-------
100
4-1
o
3
H±HjH;H:H;
90
~t-t-
±H±t
i r
"J"jj±L
10
20
40
50 60 70 80
Durability Hours
90
100
Monolithic! Catalyst
Base Fuel
CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 8
110 120 130 140
« Cold Transient
V stabilized
D Hot Transient
O Weighted
-------
COMMENTS - Additive "A"
1. Due to a dead band in the range capability of the two
instruments used to measure carbon monoxide, the data points
which fell between 3000 ppm and 3500 ppm are estimates.
This does not appear to have a si-jnif icant effect on the
validity of the data as far as identifying trends.
2. The data obtained from the Federal Cycle shows a slight
drop in overall conversion efficiency with this same trend
a little more pronounced for the Modified Federal Cycle
test run.
3. With respect to hydrocarbons as measured by the Federal
Cycle test procedure, the differences between before and
after converter are quite small. When calculated to a per-
centage basis, this leads to an apparent significant drop
in conversion efficiency. However, the steep slope in the
efficiency curve is due to the relatively low hydrocarbon
levels seen before the converter, and as such the apparent
conversion efficiency drop takes on less significance.
4. The data for the Modified Federal Cycle hydrocarbon
emissions shows the same trends, however, they are less
pronounced.
-------
TABLE 11. "A' ADDITIVE, NOI.'OLITH CATALYST, ENGINE STAND, RAW DATA, GRAMS/MILE. *
Cold
HC CO
1
Hot
HC CO
17
With Converter
.35 13.59
.11 1.69
.11 3.64
.16 4.60
Without Conve
1.46 13.54
.63 20.51
.51 13.53
.77 17.25
t Efficiency
76.0 0
82.5 91.7
.78.4 73.0
79.2 73.3
.21 4.41
.12 1.67
.10 1.64
.13 2.21
rter
.64 13.53
.62 20.57
.50 13.51
.59 17.28
67.1 67.4
80.6 91. 6
80.0 B7.8
77.9 87.2
Hot
HC CO
38
.21 2.91
.20 1.37
.20 3.03
.20 2.12
.68 13.64
.65 20.74
.50 13.62
.62 17.42
69.1 78. 6
69.2 93.3
56.0 77.7
67.7 87.7
Hot
HC CO
60
.28 5.90
.21 3.69
.19 3.10
.22 3.98
.51 13.76
.65 20.95
.46 13.79
.57 17.61
45.0 57.2
67.7 82 i
58.7 77.5
61.4 77.4
Cold
HC CO
77
.44 7.34
.45 5.34
.21 8.74
.38 6.65
.67 13.44
.68 20.42
.52 13.48
.64 17.17
34.3 45.4
33. B 73.8
59.6 35.2
40.6 6^.3
Hot
HC CO
77
.26 5.90
.22 3.18
.21 5.41
.23 4.32
.73 13.45
1.05 20.49
.66 13.41
.88 17.20
64.4 56.1
79.0 84.5
68.2 59.5
73.8 74.8
Hot
HC CO
99
.23 5.05
.31 3.45
.25 5.05
.28 4.20
.51 13.82
.77 20.96
.56 13.77
.66 17.61
54.9 63.5
59.7 83.5
55.3 63.2
57.6 76.1
Hot
HC CO
116
.26 8.42
.24 2.49
.23 4.39
.24 4.19
.53 13.62
.65 20.71
.48 13.60
.58 17.40
50.9 38.2
63.1 87.9
52.1 67.7
58.6 75.9
Cold
HC CO
134
.91 12.2
.30 4.02
.30 5.79
.42 6.15
.95 13.71
.49 20.78
.46 13.67
.58 17.47
4.2 11.0
38.7 80.6
34.7 57.6
27.6 64.8
Hot
HC CO
134
.40 8.08
.28 1.90
.29 5.36
.30 4.06
.87 13.44
.76 20.43
.59 13.49
.74 17.18
54.0 39.8
63.1 90.7
50.8 60.2
59.5 76.3
Durability Hours
Cold Transient
Stabilized
Rot Transient
Weighted
Cold Tiansient
Stabilized
Hot Transient
Weighted
Cold Tiansient
Stabilized
Hot Transient
Weighted
•Corrected for ambient conditions.
-------
TABLE 12. AMBIENT CONDITIONS
"A" ADDITIVE - MONOLITH CATALYST ENGINE DYNAMOMETER
Modified Federal Cycle
Federal Cycle X
Durability Hours 1
17
X
38
X
60
X
77
X
77
X
99
X
116
X
134
X
134
WITHOUT CONVERTER
Barometer
Corrected Barometer
Ambient Air °F
Wet Bulb °F
Dry Bulb °F
Humidity %
WITH CONVERTER
Barometer
Corrected Barometer
Ambient Air °F
Wet Bulb °F
Dry Bulb CF
Humidity %
29.31
29.16
86.
61.
78.
36.77
29.31
29.16
86.
61.
78.
36.77
29.46
29.35
73.
55.
73.
29.23
29.66
29.53
78.
57.
79.
22.67
29.10
28.98
75.
61.
73.
50.12
29.10
28.98
75.
61.
73.
50.12
29.44
29.30
80.
56.
82.
20.17
29.20
29.08
74.
57.
75.
31.16
29.20
29.08
74.
57.
75.
31.16
28.96
28.84
73.
53.
74.
71.15
29.38
29.23
85.
63.
89.
21.47
29.38
29.23
85.
63.
89.
21.47
29.46
29.35
73.
55.
73.
29.23
29.66
29.53
78.
57.
79.
22.67
29.66
29.53
78.
57.
79.
22.67
29.10
28.98
75.
61.
73.
50.12
29.44
29.30
80.
58.
82.
20.17
29.20
29.08
74.
57.
75.
31.16
28.96
28.84
73.
53.
74.
21.15
28.96
28.84
73.
53.
74.
21.15
-------
24.
H
0)
•0
-H
X
0
c
0)
rH
•H
M
0)
a
X
Ifl
M
20.
16
12.
8.
Monolithic Catalyst
"A" Additive
60 70 80
Durability Hours
CVS EMISSIONS FEDERAL CYCLE
FIGURE 9
110 120 130 140
• Cold Transient
V Stabilized
D Hot Transient
O Weighted
Before Converter
• After Converter
-------
100
X
O
c
I
1
!M
0
u
u
c
O
•H
U
a
*
^
M
§
c
90
80
70
60
50
40
10
20
30
Monolithic Catalyst
"A" Additive
50 60 70 80 90
Durability Hours
CVS EMISSIONS FEDERAL CYCLE
FIGURE 10
100 110 120 130 140
• Cold Transient
V Stabilized
O Hot Transient
O Weighted
-------
24.
OJ
T3
•H
X
o
c
g
0
-2
M
Ifl
u
0)
^H
•H
as
M
CD
CO
M
O
20,
16.
12.
8.
4.
10
20
30
50 60 70 80
Durability Hours
90
100
Monolithic Catalyst
"A Additive
CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 11
110 120 130 140
• Cold Transient
V Stabilized
D Hot Transient
O Weighted
-Before Converter
After Converter
-------
u,
0)
•o
•H
id
CJ
c
Q]
-rH
U
-H
w
i4l
H
0)
^>
n
0)
o
U
90
70
60
40
1
1
— 1
1
1
1
1
1
i
_
-
-
-
;
_
:
;
V
3
.
•
-:
-
''
s
/
\
/
/
^
s
—
/
-1
\
^
f -
\
/
1
•^
h— *
L
/
•— •
\
-
/
r—-
s
/
*_
f
— 4
^7
*
J
s
N
\
\
\
S
•
V
s
V
\
s
• •
s
s
..
\
v
:
s
5
s
\
\
s
'
s
V
2
s
S
<
\
s
^
*"
1
V.
>
V
A
,
'
\
—
-».
S
•^
\
— -
•^
\,
N
^— ,
\
•—i
s
^-
V
s
v
k
c
7
)
r
rf^
c
-^
--
^*"
F^*
»"
-^
^
—
'-
^**
—
^"
>
*-«
^«
—
"^
X"
-
X
^
'
-
,
\
^
r-
\
\
-^
-
..
r--
[
\
**
.
'
\
V
s
-
\
\
s
•*
V
X
V
\
X
^
1
\
^
-
s
\
,
f^
I
T ,
^
^-«
•
s
^-
s
s»,
r-H
s
^-
-
fs
— -
•*
1
n
c
-i
r
:
10
20
30
Monolithic Catalyst
"A" Additive
40 50 60 70 80 90 100
Durability Hours
CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 12
110
120 130
140
• Cold Transient
V Stabilized
O Hot Transient
O Weighted
-------
L ^
5
-Q
~
fl
U
C
-
-
0
ft
[fl
E
ffl
-
10
20
40
Monolithic Catalyst
"A" Additive
50 60 70 80 90
Durability Hours
CVS EMISSIONS FEDERAL CYCLE
FIGURE 13
100 110 120 130
140
• Cold Transient
V Stabilized
O Hot Transient
O Weighte '.
— —- Before COP- erter
-After Converter
-------
100,
Ul
IT3
I
I
U
0)
•H
U
•H
w
<#>
2
(4
<
>
>
s,
*>
v
s
I
0
N
S
s
S
k.
S
k,
X,
,
s.
x.
s
S,
S
k,
,
"1
s
L
N
N
»s
s
^
s.
1
'•x
"<•,
V
;
s,
X;
s
?
s
s
-
s
;
•x
s.
]'
i
, i
•
" \
1
i
X
1
^i^
',
N
'
s
K
'
V
N
Is
s
.
S:
N
k,
^
*s
K
•s
x
^x
,
s
V,
k^
k
k
v,
X
•
-
S
x
-
V
^
3
^
-N,
s
s
Sx
V,
X
s
s,
s
X.
>,
x
l^
s
.
^
^x
'
'^
Si
>
V,
->
s^
1
•y"
,
K
M
<
'
s
.
V
.
s
s
^
i
V
*>
s
1
s
L
X
N,
1
10
20
30
Monolithic Catalyst
"A" Additive
40 50 60 70 80 90
Durability Hours
CVS EMISSIONS FEDERAL CYCLE
FIGURE 14
100
110 120 130 140
• Cold Transient
V Stabilized
D Hot Transient
O Weighted
-------
2.4|_
c
0
XI
M
"
0
v-
J
,
:
-
n
•:
10
20
30
Monolithic Catalyst
"A"' Additive
40 50 60 70 80 90 100
Durability Hours
CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 15
110 120 130
140
• Cold Transient
V Stabilized
D Hot Transient
O Weighted
Before C- averter
- —-After Converter
-------
100
01
C
o
£t
M
aj
u
o
u
C
cu
•H
U
-H
tW
•4-1
w
JJ
M
(U
>
B
0
U
10
20
30
40
50
60 70 80
Durability Hours
90
100
Monolithic Catalyst
"A" Additive
CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 16
110 120 130
• Cold Transient
V Stabilized
n Hot Transient
O Weighted
140
-------
COMMENTS - Additive "B"
1. With respect to carbon monoxide/ as measured by the
Federal Cycle, both the before and after converter data
points from a similarly shaped curve; however, the before
converter emission levels are 4-fold higher. The curves
show a slight increase in emission levels with time. This
effect is also seen on the conversion efficiency curve.
2. The emission levels of carbon monoxide as measured
during the Modified Federal Cycle again show a reduction of
converter efficiency with time.
3. The hydrocarbon levels measured during the Federal Cycle
test for both the before and after converter are consistant,
with approximately 3-fold higher values for the before con-
verter data points. The slope of the curve is upward with
time, indicating a reduction of converter efficiency with
time.
4. The hydrocarbon emission levels for the Modified Federal
Cycle gave similar curves as the Federal Cycle and also
showed a reduction in converter efficiency with time.
57
-------
TABLE 13. "B" ADDITIVE, MONOLITHIC CATALYST, ENGINE STAND, RAW DATA, GRAMS/MILE**
Cold
HC CO
0
Hot
HC CO
34
With Converter
.38 13.5
.22 2.43
.22 3.8
.25 5.0
Without Conv
1.82 13.5
1.30 20.4
.83 13.5
1.28 17.16
% Efficiency
79.2 0*
83.0 88.1
73.4 72
80.4 70.7
.32 2.92
.30 1.02
.34 5.25
.31 2.53
erter
1.24 13.8
1.53 20.8
1.14 13.8
1.37 17.6
74.1 78.8
80.9 95.1
70.17 61.9
77.3 85.6
Hot
HC CO
54
.41 4.94
.31 .67
.33 3.24
.33 2.21
1.18 13.8
1.64 20.9
1.21 13.7
1.44 17.6
65.2 64.2
81.1 96.8
72.7 76.4
77.1 87.3
Hot
HC CO
74
.51 6.0
.44 1.98
2.46* 13.8*
.99 4.95
1.42 13.8
1.80 21.0
1.30 13.8
1.43 17.6
64.8 56.0
75.5 90.6
0« 0*
30.7* 71.8*
Cold
HC CO
88
.98 13.5
.50 3.64
.56 9.74
.61 7.25
2.24 15.3
2.17 23.3
1.60 15.4
2.0 19.6
56.2 11.7
76.8 84.1
64.3 35.6
69.6 63.0
Cold
HC CO
136
.93 13.7
.68 5.05
.49 4.02
.68 6.50
2.88 12.4
1.93 18.8
2.04 12.4
2.15 15.8
67.7 0«
64.7 73.2
75.9 67.5
68.3 SB. 9
Hot
HC CO
136
.59 6.23
.56 2.16
.53 5.08
.56 3.75
1.38 12.5
2.13 18.8
1.59 12.4
1.83 15.9
57.2 50.1
73.7 88.5
66.6 59.1
69.6 76.4
Durability Hours
Cold Transient
Stabilized
Hot Transient
Weighted
Cold Transient
Stabilized
Hot Transient
Weighted
Cold Transient
Stabilized
Hot Transient
Weighted
00
•Instrumentation error.
••Corrected for ambient conditions.
-------
TABLE 14. AMBIENT CONDITIONS
'B" ADDITIVE - MONOLITH CATALYST ENGINE DYNAMOMETER
Modified Federal Cycle
Federal Cycle
Durability Hours
X
0
X
34
X
54
X
74
X
88
X
136
X
136
en
10
WITHOUT CONVERTER
Barometer
Corrected Barometer
Ambient Air °F
Wet Bulb °F
Dry Bulb °F
Humidity %
WITH CONVERTER
29.61
29.47
83.
61.5
79.0
22. 77
29.46
29.31
85.
60.
78.5
32.49
29.56
29.42
81.
62.
81.
36.25
29.73
29.59
80.
58.
80.
23.54
29.62
29.48
78.
68.
78.
59.97
29.57
29.41
87.
62.
88.
20.54
29.57
29.41
87.
62.
88.
20.54
Barometer
Corrected Barometer
Ambient Air °F
Wet Bulb °F
Dry Bulb °F
Humidity %
29.54
29.42
75.
56.
75.
27.85
29.46
29.31
85.
60.
78.5
32.49
29.56
29.42
81.
62.
81.
32.92
29.73
29.59
80.
58.
80.
23.54
29.57
29.42
83.
64.
84.
66.92
29.54
29.40
80.
59.
80.
27.86
29.54
29.40
80.
59.
80.
27.86
-------
10
20
30
40
Monolithic Catalyst
"B" Additive
50 60 70 80
Durability Hours
CVS EMISSIONS FEDERAL CYCLE
FIGURE 17
100
110
120
130
140
Before Catalyst
After Catalyst
• Cold Transient
V Stabilized
C] Hot Transient
O Weighted
-------
zoo
40
10
20
30
40
50
10
70
10.!'
Durability Hours
90
100
Monolithic Catalyst
"B" Additive
CVS EMISSIONS FFDFRAL CYCLE
FIGURE 18
110 120 130 140
• Cold Transient
V Stabilized
n Hot Transient
O Weighted
-------
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-------
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FIGURE 20 & Weighted
-------
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50 60 70 80
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CVS EMISSIONS FEDERAL CYCLE
FIGURE 21
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CVS EMISSIONS FEDERAL CYCLE
FIGURE 22
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Monolithic Catalyst
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- After Catalyst
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-------
B. Comparison of Three Fuels, Engine Stand, Monolithic
Catalyst
COMMENTS;
1. There was no appreciable catalyst degradation over the
durability test period.
2. With respect to carbon monoxide emissions/ the base
fuel started out on the durability test having the poorest
conversion efficiency of the three fuels/ but at the end of
the test the base fuel had the best conversion efficiency.
3. With respect to hydrocarbon emissions from the Federal
Cycle Modified, the converter efficiency was best for fuel
additive "B" and poorest for fuel additive "A".
4. With respect to hydrocarbon emissions from the Federal
Cycle conditions, the fuel additive "A" seemed to have
very poor conversion efficiencies compared to the base fuel/
while additive "B" was very similar to the base fuel.
5. Additive "B" fuel caused the engine to produce higher
quantities of hydrocarbons before the catalyst, in the
Federal Cycle.
68
-------
4-4-1 4-1.
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Engine Dynamometer
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Durability Hours
Monolithic Catalyst
CVS EMISSIONS FEDEPAL CYCLE
FIGURE 25
100
110 120 130 140
Before Catalyst
After Catalyst
• Base Fuel
D "A" Additive
O "B" Additive
-------
90
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CVS EMISSIONS FEDERAL CYCLE
FIGURE 26
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-------
24
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-------
90
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Durability Hours
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CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 28
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O "B" Additiye
-------
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-------
C. Raw Data, Engine Stand/ Beaded Catalyst, Three Fuels
This set of data and graphs shows the carbon monoxide emission
levels and the hydrocarbon emission levels on a grams/mile
basis, as well as the converter efficiency for the two
gases measured. The cycle is broken down into the cold
transient, hot transient, and stabilized segments of the
CVS measurement, as well as the weighted average of the
three.
77 .
-------
COMMENTS - Baseline
1. The conversion efficiency appears to be slightly better
for carbon monoxide than it is for hydrocarbon emissions in
both the Federal Cycle and the Modified Federal Cycle tests.
This observation is generally true for all three fuels and
for the monolithic catalyst as well.
2. Carbon monoxide conversion efficiency was reduced
during the durability test, as measured by the Federal
Cycle, but not for the Federal Cycle Modified.
3. Hydrocarbon conversion efficiency was reduced during
the durability test as measured by both the Federal Cycle
and the Modified Federal Cycle.
4. Measured grams/mile of hydrocarbon was lower at the end
of the durability test than at the beginning for both Federal
Cycle and Modified Federal Cycle.
5. Data point scatter for both grams/mile measurements,
and the corresponding conversion efficiencies appear to
be within normal experimental ranges.
78
-------
TABLE 15. B/SE FLEL, BEADED CATALYST. EtiGirE STAND, RAW DATA, GRAMS/MILE. •
Cold
HC CO
9
Without Conve
1.34 24.9
.73 27.4
.55 18.7
.81 24.6
With Converte
.80 24.6
' .14 .25
.11 1.28
.26 5.42
% Efficiency
40.2 0
80.8 99
80. 0 93.1
67.9 77.9
Hot
HC CO
9
rter
.48 17.7
.61 26.7
.41 16.2
.53 22.1
r
.14 2.7
.10 .28
.11 1.69
.11 1.14
70.8 84. 7
83.6 98.9
73.1 89. 5
79.2 94.8
Hot
HC CO
52
.47 19.0
.62 31.5
.50 19.5
.56 25.8
.11 1.4
.13 .34
.14 1.97
.13 .99
76.5 92.6
79.0 98.9
72.0 89.8
76.7 96.1
Cold
HC CO
70
.91 24.8
.54 27.4
.40 21.8
.58 25.4
1.03 24.9
.17 .61
.18 1.84
.35 5.82
0 0
68.5 97.7
55.0 91.5
39.6 77.0
Hot
HC CO
70
.37 20.3
.60 36.5
.52 24.0
.53 29.9
.33 9.12
.11 .39
.38 5.0
.23 3.39
10.8 55.1
81.6 98.9
26.9 79.2
56. 6 88.6
Hot
HC CO
88
.42 23.1
.47 26.7
.41 22.4
.44 24.8
.20 5.9
.47 .41
.14 2.58
.33 2.1
52.4 0
0 98.4
65.8 88.4
25.0 91. 5
Hot
HC CO
112
.40 21.84
.04 2.49
.35 21.3
.20 11.4
.15 3.8
.07 .34
.13 2.0
.11 1.48
62.5 82.6
0 86.3
62.8 90.6
45 87.0
Hot
HC CO
130
.39 24.1
.37 23.0
.37 19.1
.38 22.2
.21 6.76
.09 .41
.10 2.47
.12 2.23
46.1 71.9
75.6 98.2
72.9 88.4
68.4 89.9
Cold
HC CO
130
2.68 25.1
.46 23.8
.38 19.4
.89 22.9
.62 24.5
.12 .60
.17 4.13
.23 6.3
76.8 0
73.9 92.4
55. 2 78.7
74.1 72.4
Hot
HC CO
140
.34 22.8
.41 24.9
.41 22.7
.40 23.9
.17 3.51
.10 .56
.12 2.69
.12 1.71
50 84.6
75.6 97.5
70.7 88.1
70.7 92.8
Durability Hours
Cold Transient
Stabilized
Hot Transient
Weighted
Cold Transient
Stabilized
Hot Transient
Weighted
Cold Transient
Stabilized
Hot Transient
weighted
1C
•Corrected for ambient conditions.
-------
TABLE 16. AMBIENT CONDITIONS.
BASE FUEL - BEADED CATALYST ENGINE DYNAMOMETER
Modified Federal Cycle
Federal Cycle X
Durability Hours 9
X
9
X
52
X
70
X
70
X
88
X
112
X
130
X
130
X
140
oo WITHOUT CONVERTER
o
Barometer
Corrected Barometer
Ambient Air °F
Wet Bulb °F
Dry Bulb °F
Humidity %
WITH CONVERTER
Barometer
Corrected Barometer
Ambient Air °F
Wet Bulb 8F
Dry Bulb °F
Humidity %
29.61
29.47
80.
55.
81.
13.99
29.34
29.21
75.
50.5
76.0
10.27
29.47
29.33
82.
52.5
83.0
5.59
29.76
29.11
86.
60.5
84.
23.34
29.40
29.26
82.
57.
81.
19.27
29.26
29.11
86.
60.5
84.
23.34
29.63
29.51
75.
53.
72.
24.75
29.64
29.50
83.
58.
84.
16.87
29.64
29.50
83.
58.
84.
16.87
29.72
29.08
85.
63.
85.
22.11
29.22
29.11
68.
47.
70.
10.29
29.22
29.11
68.
47.
70.
10.29
29.47
29.33
82.
52.5
83.
5.59
29.46
29.31
76.5
54.
77.
17.98
29.46
29.31
76.5
54.
77.
17.98
29.26
29.11
86.
60.5
84.
23.34
29.63
29.51
75.
53.
72.
24.75
29.64
29.50
83.
58.
84.
16.87
29.01
28.89
74.0
52.
72.
22.11
29.01
28.89
74.
52.
72.
22.11
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EMISSIONS FEDERAL CYCLE
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-After Catalyst
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D Hot Transient
O Weighted
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CVS EMISSIONS FEDERAL CYCLE
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Durability Hours
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CVS EMISSIONS FEDERAL CYCLE
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10
20
Beaded Catalyst
Base Fu'el
30 40 50 60 70 80 90 100
Durability Hours
CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 39
110 120
130
140
-Before Catalyst
After Catalyst
• Cold Transient
V Stabilized
D Hot Transient
O Weighted
-------
40
10
20
Beaded Catalyst
Base Fuel
30 40 50 60 70 80 90 100
Durability Hours
CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 40
110 120 130 140
» Cold Transient
V Stabilized
D Hot Transient
O Weighted
-------
COMMENTS; Additive "A"
1. The conversion of carbon monoxide is much better than
the conversion of hydrocarbon emissions. This fact is generally
true for all three fuels and when using the monolithic
catalyst also.
2. Carbon monoxide conversion showed a drop in efficiency
over the durability test for the Federal Cycle, but no drop
in efficiency when tested under the Federal Cycle Modified.
3. Hydrocarbon conversion efficiency did not show any
converter degradation over the durability test period.
89
-------
TADI.I 17. "A" ADDIT1VI. U1.AUI I) CATALYST, FNCINF. STAND, PAH DATA, GRAfS/MIM. *
Cold
HC CO
17
Hot
HC CO
17
Without Converter
.72 24.7
.39 24.4
.34 17.4
.44 22.6
With Converte
.45 15.0
.12 1.92
.13 3.89
.19 5.08
.32 19.5
.39 24.5
.34 21.1
.37 22.6
r
.14 4.59
.11 2.27
.13 4.69
.12 3.38
t Efficiency
37.5 39.2
69.2 92.1
61.7 77.6
56.8 77.5
56.2 22.5
71.7 90.7
61'. 7 77.8
67. 5 85.0
Hot
hC CO
50
.42 20.4
.42 23.7
.33 19.1
.39 21.8
.22 9.0
.14 2.64
.16 4.94
.16 4.53
47.6 55.9
66.7 88.9
51.5 74.1
59.0 79.2
Cold
HC CO
69
.57 24.8
.41 25.8
.37 19.2
.43 23.8
.61* 20.3
.12 1.77
.14 4.69
.23 6.26
0 18.1
70.7 93.1
62.2 75.6
46.5 73.7
Hot
HC CO
69
.38 22.9
.40 25.0
.34 19.9
.38 23.2
.16 7.37
.11 2.13
.14 4.87
.13 3.91
57.9 67.8
72.5 91.5
58.8 75.5
65.8 83.1
Hot
HC CO
103
.40 20.9
.41 21.1
.33 17.1
.39 19.9
.21 9.41
.11 3.11
.16 5.92
.15 5.33
47.5 55. 0
73.2 85.3
51.5 65.4
61.5 73.2
Cold
HC CO
130
1.15 24.7
.49 24.5
.39 17.3
.60 22.7
.71 29.9*
.16 2.88
.19 6.91
.28 8.38
38.3 0
67.3 88.2
51.3 60.1
53.3 63.1
Hot
HC CO
130
.48 19.9
.54 24.4
.46 18.3
.SO 21.9
.12 2.63
.14 2.34
.17 4.72
.15 3.03
75.0 86.8
74.1 90.4
63.0 74.2
70.0 86.2
Hot
HC CO
140
.44 21.9
.48 23.1
.39 19.4
.45 21.8
.11 3.2
.13 2.2
.21 6. -.6
.15 3.61
Durability Hours
Cold Transient
Stabilized
Hot Transient
Weighted
Cold Transient
Stabilized
Hot Transient
Weighted
*
75.0 85.4
72.9 90.5
Cold Transient
Stabilized
46.2 65.2 Hot Transient
66.7 83.4 Weighted
to
o
•Corrected for ambient conditions.
-------
TABLE 18. AMBIENT CONDITIONS
"A" ADDITIVE - BEADED CATALYST ENGINE DYNAMOMETER
Modified Federal Cycle
Federal Cycle X
Durability Hours 17
X
17
X
50
X
69
X
69
X
103
X
130
X
130
X
140
X
140
WITHOUT CONVERTER
«> Barometer
Corrected Barometer
Ambient Air °F
Wet Bulb °F
Dry Bulb °F
Humidity %
WITH CONVERTER
Barometer
Corrected Barometer
Ambient Air *F
Wet Bulb °F
Dry Bulb °F
Humidity %
29.39
29.27
75.
53.
72.
24.96
29.39
29.27
75.
53.
72.
24.96
29.48
29.35
78.
55.
76.
22.7
29.33
29.19
80.
79.
52.
9.77
29.23
29.09
80.
57.
79.
22.91
29.62
29.49
78.
52.5
75.
17.27
29.56
29.43
75.
52.
73.
19.65
29.56
29.43
75.
52.
73.
19.65
29.81
29.67
78.
51.
75.
12.64
29.64
29.49
84.
59.
86.
16.34
29.64
29.49
84.
59.
86.
16.34
29.48
29.35
78.
55.
76.
22.7
29.23
29.09
80.
57.
79.
22.91
29.23
29.09
80.
57.
79.
22.91
29.62
29.49
78.
52.5
75.
17.27
29.65
29.53
74.
50.
72.
15.23
29.64
29.53
70.
49.
69.
18.24
29.81
29.67
78.
51.
75.
12.64
-------
NJ
•H
X
o
c
S
C
s
03
O
0)
I-l
-H
h
0)
25.
20.
15.
10.
5.
Beaded Catalyst
"A" Additive
60 70 80
Durability Hours
CVS EMISSIONS FEDERAL CYCLE
FIGURE 41
100
110
120
130
140
• Cold Transient
V Stabilized
O Hot Transient
O Weighted
• Before Converter
-After Converter
-------
QJ
-H
X
0
I
c
0
d
U
O
C
0)
•H
U
•H
U-l
M-l
C»P
M
O
C
o
U
50
40
20
30
40
50
60 70 80
Durability Hours
90
100
110 120
130
140
Beaded Caibalyst
"A" AdditiveJ
CVS EMISSIONS FEDERAL CYCLE
FIGURE 42
• Cold Transient
V Stabilized
n Hot Transient
O Weighted
-------
o
T!
•H
X
0
1
o
(0
u
o
-H
•H
£
Ifl
id
M
C
60 70 80
Durability Hours
90
100 110 120 130
140
Beaded Catalyst
"A" Additive
CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 43
• Cold Transient
V Stabilized
D Hot Transient
O Weighted
- —Before Converter
After Converter
-------
100 L;
-------
2.0
10
20
30
40
Beaded Catalyst
"A" Additive
50 60 70 80
Durability Hours
CVS EMISSIONS FEDERAL CYCLE
FIGURE 45
100
110
120 130
140
» Cold Transient
V Stabilized
O Hot Transient
O Weighted
Before Converter
After' Converter
-------
§
•2
-------
0
10
20
30
Beaded Catalyst
"A" Additive
40 50 60 70 80 90 100
Durability Hours
CVS EMISSIONS FEDERAL CYCLF .CODIFIED
FIGURE 47
110 120 130 140
* Cold Transient
V Stabilized
D Hot Transient
O Weighted
— Before Converter
After Converter
-------
100
66
20
30
40
50 60 70 80
Durability Hours
90
100
110 120
130
Beaded Catalyst
"A" Additive
CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 48
» Cold Transient
V Stabilized
D Hot Transient
O Weighted
-------
COMMENTS; Additive "B"
1. The carbon monoxide conversion efficiency appears to be
much better than the hydrocarbon conversion efficiency/ as
measured by both Federal Cycle and Modified Federal Cycle.
2. There is no significant degradation of catalyst
efficiency for carbon monoxide conversion during the
durability test period.
3. There is a somewhat significant drop in converter
efficiency over the durability test period for the con-
version of hydrocarbon emissions.
100
-------
TABLE 19. "B" ADDITIVE, BFRDFS CATALYST. ENGINE STAND, RAW DATA, GRAFS/KILE.*
Cold
HC CO
11
Without Conve
5.71 24.53
1.25 35.23
.83 24.53
2.03 30.24
-• With Converte
Hot
HC CO
11
rter
1.07 24.51
1.11 25.21
.83 21.51
1.03 24.09
r
O
~* .93 24.60
.20 1.93
.20 7.63
.34 8.00
t Efficiency
.83.7 x
84.0 94.5
75.9 69.3
83.2 73.5
.34 10.02
.22 2.92
.21 S.21
.24 4.9S
68.2 59.1
80.1 88.4
74.6 75.7
76.6 79.4
Hot
HC CO
49
.91 21.27
1.12 28.21
.79 22.48
.99 25.29
.24 1.58
.23 .93
.36 3.70
.27 1.80
73.6 92.5
79.4 95.6
54.4 83.5
72.7 92.8
Cold
HC CO
68
1.88 24.65
1.27 25.19
1.01 14.73
1.J2 22.3
.57 9.92
.26 .50
.40 3.76
.36 3.26
69.6 59.7
79.5 98.0
60.3 74.4
72.7 85.3
Hot
HC CO
68
1.01 19.09
1.23 22.73
.99 19.46
1.12 21.13
.66 8.41
.26 .87
.37 3.88
.37 3.18
34.6 55.9
78.8 96.1
62.6 80.0
66.9 84.9
Hot
HC CO
84
.99 20.19
1.30 24.36
.99 21.5
1.16 22.76
.90 15.07
.42 3.06
.51 7.08
.54 6.54
9.0 25.3
67.6 87.4
48.4 67.0
53.4 71.2
Hot
HC CO
104
1.19 22.51
1.40 26.56
1.11 19.46
1.28 23.87
.84 9.48
.38 .92
.49 3.74
.50 3.39
29.4 57.8
72.8 96.5
55.8 80.7
60.9 85.7
Cold
HC CO
130
1.17 25.06
.96 21.78
.75 18.81
.95 21.65
.74 22.27*
.30 1.62
.36 4.31
.41 6.48
36.7 11.1*
68.7 92.5
52.0 77.0
56.8 70.0
Hot
HC CO
130
.78* 18.78
1.04 13.95
.86 15.59
.94 15.36
.46 8.27
.31 1.40
.37 3.24
.36 3.27
41.0 56.9
70.1 89.9
56.9 79.2
61.7 78.7
Hot
HC CO
140
.85 15.96
1.14 17.56
.91 16.77
1.02 17. C3
.45 6.C4
.29 1.12
.49 5. f8
.38 3.14
47.0 62.1
74.5 91.3
46.1 66.1
62.7 79.2
Durability Hours
Cold Transient
Stabilized
Hot Transient
weighted
Cold Transient
Stabilized
Hot Transient
Weighted
Told Transient
Stabilized
Hot Transient
Weighted
•Corrected for ambient conditions.
-------
TABLE 20. AMBIENT CONDITIONS
"B" ADDITIVE - BEADED CATALYST ENGINE DYNAMOMETER
Modified Federal Cycle
Federal Cycle X
Durability Hours 11
X
11
X
49
X
68
X
68
X
84
X
104
X
130
X
130
X
140
o
NJ
WITHOUT CONVERTER
Barometer
Corrected Barometer
Ambient Air °F
Wet Bulb °F
Dry Bulb °F
Humidity %
WITH CONVERTER
Barometer
Corrected Barometer
Ambient Air °F
Wet Bulb °F
Dry Bulb °F
Humidity %
29.16
29.04
74.
52.5
74.
19.46
29.16
29.04
74.
52.5
74.
19.46
29.50
29.37
77.
53.
78.
13.54
29.16
29.03
77.
54.
78.
16.54
29.40
29.27
81.
55.
83.
11.37
29.16
29.03
77.
54.
78.
16.54
29.46
29.32
76.
51.
73.
16.58
29.54
29.46
77.
53.
78.
13.45
29.54
29.46
77.
53.
78.
13.45
29.78
29.65
76.
54.
78.
15.96
29.23
29.11
74.
54.
75.
21.92
29.23
29.11
74.
54.
75.
21.92
29.50
29.37
77.
53.
78.
13.54
29.42
29.30
75.
50.5
75.
11.63
29.40
29.27
81.
55.
83.
11.37
29.98
28.85
77.
55.
78.
19.42
29.56
29.42
80.
54.
79.
16.58
29.78
29.65
76.
54.
78.
15.96
29.54
29.46
77.
53.
78.
13.45
29.78
29.65
76.
54.
78.
15.96
-------
-H+i-
flffl
144-tX
-LU-S-L
-H
,rH±
!.±Ltl
10
20
30
40
50
60 70 80
Durability Hours
90
100
Beaded Catalyst
"B" Additive
CVS EMISSIONS FEDERAL CYCLE
FIGURE 49
110 120 130 140
Before Catalyst
After Catalyst
• Cold Transient
V Stabilized
D Hot Transient
O Weighted
-------
o
-c
111
H-ftrr
rrrri
rrn
40
20
30
40
50
60 70 80 90
Durability Hours
100
110 120
130
140
Beaded Catalyst
"B" Additive
CVS EMISSIONS FEDERAL CYCLE
FIGURE 50
• Cold Transient
V Stabilized
D Hot Transient
O Weighted
-------
25H-H-H
ffilb
4ffl4
ffl;
ffittB
40 50 60 70 80 90
Durability Hours
100
Beaded Catalyst
"B" Additive
CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 51
110 120 130 140
Before Catalyst
After Catalyst
• Cold Transient
V Stabilized
Q Hot Transient
O Weighted
-------
40
10
20
30
40
90
Beaded Catalyst
"B" Additive
50 60 70 80
Durability Hours
CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 52
100 110 120 130 140
» Cold Transient
V Stabilized
n Hot Transient
O Weighted
-------
2.0-
10
20
Beaded Catalyst
"B" Additive
30 40 50 60 70 80 90
Durability Hours
CVS EMISSIONS FEDERAL CYCLE
FIGURE 53
100 110 120 130 140
Before Catalyst
After Catalyst
• Cold Transient
V Stabilized
D Hot Transient
O Weighted
-------
40
10
20
Beaded Catalyst
"B" Additive
30 40 50 60 70 80 90
Durability Hours
CVS EMISSIONS FEDERAL CYCLE
FIGURE 54
100 110 120 fl.30
• Cold Transient
V Stabilized
d Hot Transient
O Weighted
140
-------
10
20
Beaded Catalyst
"B" Additive
30 40 50 60 70 80 90
Durability Hours
CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 55
100 110 120 130 140
Before Catalyst
After Catalyst
• Cold Transient
V Stabilized
D Hot Transient
O Weighted
-------
40
10
20
30
40
50
60 70 80 90
34.6 9.0
Durability Hours
100 110
29.4
120 130
140
Beaded Catalyst
"B" Additive
CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 56
« Cold Transient
V Stabilized
Q Hot Transient
O Weighted
-------
D. Comparison of Three Fuels, Engine Stand, Beaded Catalyst
COMMENTS!
1. With respect to carbon monoxide emissions for the Federal
Cycle Modified, the conversion efficiency for the base fuel
is slightly better than Additive "A" or Additive "B", at the
conclusion of 140 hours.
2. With respect to carbon monoxide emissions for the
Federal Cycle, the conversion efficiency for the three fuels
is similar with the base fuel being the best and Additive
"A" fuel somewhat poorer.
3. With respect to hydrocarbon emissions, when tested under
the Federal Cycle Modified, the conversion efficiency is
best for the base fuel, while Additives "A" and "B" are
slightly poorer.
4. With respect to hydrocarbon emissions from the Federal
Cycle, Additive "A" and "B" show somewhat poorer conversion
efficiency than the base fuel, as well as a decline in
efficiency over time.
5. The fuel containing Additive "B" produced higher hydro-
carbon emissions, as -measured before the catalyct, thus the
converter efficiency for Additive "B" appears to be the best,
This phenomena makes it difficult to make absolute compari-
sons of the relative efficiencies after the converter.
111
-------
0)
'd
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X
o
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id
u
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M
01
w
10.
10
20
30
Engine Dynamometer
40 50 60 70 80 90
Durability Hours
Beaded Catalyst
CVS E11ISSIONS FEDERAIr CYCLE
FIGURE 57
100 110 120 130 140
• Before Catalyst
----After Catalyst
» Base Fuel
D "A" Additive
O; "B" Additiye
-------
0)
03
•-H
X
0
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O
60
50
40
10
20
30
40
Engine Dynamometer
50 60 70 80 90
Durability Hours
Beaded Catalyst
CVS EMISSIONS FEDERAL CYCLE
FIGURE 58
100
110 120 130 140
• Base Fuel
D "A" Additive
O. "B" Additive
-------
o
X
c
I
G
C
ti
-- o
* o
•H
•H
2!
01
c
20
30
40
50
60
70
80
90
100
110
120 130 140
Engine Dynamometer
Durability Hours
Beaded Catalyst
CVS EMISSIONS FEDERAL PYCLE MODIFIED
FIGURE 59
• Before Catalyst
After Catalyst
• Base Fuel
D "A" Additive
O "B" Additive
-------
1UU
3
•H
X
o
c
o
c
s,
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<4-l
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w
o
-------
g
20
30
40
50
90
Engine Dynamometer
60 70 80
Durability Hours
Beaded Catalyst
CVS EMISSIONS FEDERAL CYCLE
FIGURE 61
100 110 120 130
140
—• Before Catalyst
•—'-After Catalyst
•I Base Fuel
D "A" Additive
O "B" Additive
-------
J.UU
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Engine Dynamometer
Durability Hours
Beaded Catalyst
CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 63
• Before Catalyst
•--J- After Catalyst
• Base Fuel
D "A" Additive
O "B" Additiye
-------
90
9
ti O A
a 80
IU
0
LI
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Beaded Catalyst
CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 64
• Base Fuel
D "A" Additive
O. "B" Additive
-------
E. Comparison of Beaded and Monolithic Catalysts, Engine
Stand/ Three Fuels
The following set of graphs are a comparison of the monolithic
type catalysts versus the beaded type catalysts/ using the
base fuel and the two additive fuels. This data compares
hydrocarbon and carbon monoxide emission levels under
Federal Cycle and the Federal Cvr?le Modified test condition,
measured on an engine dynamometer.
120
-------
COMMENTS: Base Line Fuel
1. Carbon monoxide emission levels were lower using the
beaded catalysts for both the Federal Cycle and the Federal
Cycle Modified.
2. Hydrocarbon emissions measured during the Federal Cycle
conditions showed little difference between the two catalysts
as far as efficiency. Under Federal Cycle Modified con-
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more efficient.
3. There was no significant degradation of either catalyst
over the durability hours study using base line fuel.
4. The beaded catalysts were slightly more efficient than
the monolithic catalysts at the end of the durability test.
5. Both the monolithic catalysts and beaded catalysts were
more effective in reducing the levels of carbon monoxide than
they were in reducing hydrocarbons. This is especially true
in the case of the Federal Cycle Modified.
121
-------
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-------
Engine Dynamometer
Base Fuel
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CVS EMISSIONS FEDERAL CYCLE
FIGURE 66
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-------
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Base Fuel
CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 68
D Monolithic Catalyst
O Beaded Catalyst
-------
±tr±t
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Engine Dynamometer
Base Fuel
70 80 90
Durability Hours
CVS EMISSIONS FEDERAL CYCLE
FIGURE 69
100 110 120 130 140
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• After Catalyst
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O Beaded Catalyst
-------
100
50
40
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Durability Hours
100 110 120 130
140
Engine Dynamometer
Base Fuel
CVS EMISSIONS FEDERAL CYCLE
FIGURE 70
P Monolithic Catalyst
O Beaded Catalyst
-------
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CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 71
Before Catalyst
After Catalyst
D Monolithic Catalys
O Beaded Catalyst
-------
COMMENTS; Additive "A" Fuel
1. Hydrocarbon emission levels measured during the Federal
Cycle were definitely oxidized more efficiently by the
beaded catalyst. The beaded catalyst was slightly more
efficient than the monolith at oxidizing hydrocarbons as
measured during the Federal Cycle Modified.
2. At the start of the test, the monolithic catalyst
efficiency is higher, for both carbon monoxide and hydro-
carbons, than the beaded catalysts; but the beaded catalyst
is more efficient at the conclusion of the durability test.
3. The conversion efficiency of carbon monoxide is greater
than that of hydrocarbons for both catalysts using Additive
"A" fuel.
4. There was not a significant degradation of conversion
efficiency using Additive "A" for both the duration of the
tests with respect to carbon monoxide.
5. Using the monolithic catalysts under Federal Cycle
conditions there appeared to be a large drop in conversion
efficiency for hydrocarbons. The same drop in conversion
efficiency for carbon monoxide did not materialize.
6. Fuel Additive "A" appears to have a more detrimental
effect on monolithic catalyst conversion efficiency than
the beaded catalysts.
129
-------
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Engine Dynamometer
Base Fuel
CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 72
O Monolithic Catalyst
O Beaded Catalyst
-------
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40 50 60 70 80 90
Durability Hours
CVS EMISSIONS FEDERAL CYCLE
FIGURE 73
100 110 120 130
140
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-------
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100 110 120 130
140
Engine Dynamometer
"A" Additive
CVS EMISSIONS FEDERAL CYCLE
FIGURE 74
D Monolithic Catalyst
O Beaded Catalyst
-------
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100 110 120 130
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Engine Dynamometer
"A"" Additive
CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 75
Before Catalyst
After Catalyst
D Monolithic Catalyst
O Beaded Catalyst
-------
00
fcffi ffl
10
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40
50
60 70 80 90
Durability Hours
100 110 120 130
140
Engine Dynamometer
"A" Additive
CVS EMISSIONS FEDERAL CYCLF MODIFIED
.FIGURE 76
D Monolithic Catalys
O Beaded Catalyst
-------
50
Engine Dynamometer
"A" Additive
60 70 80 90
Durability Hours
CVS EMISSIONS FEDERAL CYCLE
FIGURE 77
100 110 120 130
140
Before Catalyst
—— After Catalyst
D Monolithic Catalyst
O Beaded Catalyst
-------
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"A" Additive
40 50 60 70 80 90
Durability Hours
CVS EMISSIONS FEDERAL CYCLE
FIGURE 78
100 110 120 130
140
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-------
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130 140
Engine Dynamometer
"A" Additive
CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 79
Before Catalyst
- After Catalyst
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O Beaded Cats- 'st
-------
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_. U
w C
oo (U
•H
O
•H
(4-1
U-l
i-l
O
4-1
c
0
U
80
40
10
60 70 80 90
Durability Hours
100 110 120 130 140
Engine Dynamometer
"A" Additive
CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 80
D Monolithic Catalysl
O Beaded Catalyst
-------
COMMENTS; Additive "B" Fuel
1. Both types of catalyst show a deterioration in efficiency
over the time period studied using Additive "B".
2. Carbon monoxide emission levels were reduced more
efficiently using the beaded catalysts for the Federal
Cycle, compared to the monolith catalyst, but were not
significantly more efficient measured under the Federal
Cycle Modified conditions.
3. Hydrocarbon emission levels were significantly reduced
using the beaded catalysts compared to the monolithic
catalysts on cold start conditions, but the monolithic
catalysts were more efficient on the Federal Cycle Modified
tests.
4. The conversion efficiency of carbon monoxide versus
hydrocarbons was not different with Additive "B", but with
the base fuel and "A" additive we did observe a greater
conversion efficiency of the carbon monoxide than we did
for the hydrocarbons.
5. Carbon monoxide conversion efficiency with the beaded
catalysts was more efficient for both Federal Cycle and
Federal Cycle Modified using Additive "B", but the monolithic
catalyst was more efficient in the hydrocarbon conversion for
both Federal Cycle and Federal Cycle Modified.
139
-------
0
T)
-H
g
c
o
td
U
•H
r:
o
10
20
30
Engine Dynamometer
"B" Additive
70 80 90
Durability Hours
CVS EMISSIONS FEDERAL CYCLE
FIGURE 81
100 110 120 130
140
Before Catalyst
• After Catalyst
D Monolithic Catalys
O Beaded Catalyst
-------
100
40
60 70
Durability
80
Hours
100 110 120 130 140
Engine Dynamometer
"B" Additive
CVS EMISSIONS FEDERAL CYCLE
FIGURE 82
D Monolithic Catalyst
O Beaded Catalyst
-------
-t
KJ
10
20
30
50 70 80 90
Durability Hours
100 110 120 130
140
Engine Dynamometer
"B" Additive
CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 83
Before Catalyst
—— After Catalyst
D Monolithic Cataly
O Beaded Catalyst
-------
100
10
20
50
60 70 80 90
Durability Hours
100 110
120
130 140
Engine Dynamometer
"B" Additive
CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 84
D Monolithic Catalyst
O Beaded Catalyst
-------
10
20
30
Engine Dynamometer
"B" Additive
40 50 60 70 80 90
Durability Hours
CVS EMISSIONS FEDERAL CYCLE
FIGURE 85
100 110
120
130 140
Before Catalyst
* After Catalyst
D Monolithic Catalys
O Beaded Catalyst
-------
100
40
Engine Dynamometer
"B" Additive
80 90
Durability Hours
CVS EMISSIONS FEDERAL CYCLE
FIGURE 86
100 110 120 130
140
D Monolithic Catalyst
O Beaded Catalyst
-------
10
20
30
40 50 fO 70 80 90
Durability Hours
100 110 120 130
140
Engine Dynamometer
11B" Additive
CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 87
Before Catalyst
After Catalyst
Q Monolithic Cataly:
O Beaded Catalyst
-------
100
2
n
id
o
0
u
c
a
•H
U
I
0
O
60 70 80 90
Durability Hours
100 110 120 130
140
Engine Dynamometer
"B" Additive
CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 88
D Monolithic Catalyst
O Beaded Catalyst
-------
F. Raw Data, Chassis Dynamometer, beaded Catalyst, Three
Fuels
The data on the following set of graphs is the raw data
for the segments of the Federal Cycle, as determined from
tests on the three vehicles, each equipped with bead type
catalytic converters running on the three different fuels
previously described. Exhaust gases were collected using
a Heath International CVS (concLant volume sampler) System.
The gases were analyzed using the following analytical
instruments.
A. Unburned hydrocarbons by Beckman Flame lonization.
B. NO by Chemilumeuescence (EPA built instrument)
X
C. Argon «s
Hydrogen Fisher Gas Partitioner coupled
Oxygen > to a Hewlett Packard 3370A
Carbon Monoxide Integrator
Carbon Dioxide J
D. Carbon Monoxide 0-280 and 0-3000 ppm range, Beckman
Infrared Analyzer Model 1R315.
The results from the above analytical instruments were fed
into a computer, which returned all values as grams/mile.
148 .
-------
TABLE 21. DURABILITY MILES ON CATALYST. BEADED CATXLYST, CHASSIS DYNAMOMETER. GRAMS/MILE. *
Hot
HC CO VOX
Cold
IIC CO N0x
Zero Catalyst Miles
Base Fuel
.35 3.99 2.46
.OS .125 1.19
.10 .44 2.44
.14 -.98 1.78
.Cr "A" Additive
.07 .70 3.37
.06 .04 1.78
.06 .64 3.37
.06 .33 2.52
•B- Additive
.13 .97 2.53
.03 .04 1.63
.06 1.20 2.91
.06 .54 2.15
.66 6.16 2.29
.10 .15 1.25
.10 .41 2.31
.21 1.42 1.75
.72 6.05 2.85
.08 0 1.60
.17 1.53 3.16
.23 1.62 2.26
.55 6.64 2.53
.04 .11 1.63
.07 1.36 2.22
.15 1.75 1.97
Hot
HC CO N0y
Cold
HC CO N0x
2.000 Catalyst Miles
.09 .84 3.44
.11 .13 1.81
.12 .21 .49
.11 .29 1.79
.06 .23 .43
.04 .06 2.32
.08 .53 3.95
.06 .22 2.37
.16 5.06 2.29
.12 .40 1.61
.13 2.62 2.72
.13 1.93 1.91
.51 6.72 3.46
.12 .24 1.89
.17 3.98 3.51
.21 2.53 2.63
.46 8.20 4.24
.16 .08 2.32
.07 .53 4.34
.20 1.83 3.24
.47 6.69 1.92
.16 .47 1.66
.16 6.67 2.58
.22 3.37 1.95
Hot
HC CO N0x
Cold
HC CO N0x
4,000 Catalyst Miles
.16 2.41 5.23
.09 .15 2.69
.12 2.36 5.26
.11 1.19 3.89
.18 5.83 3.34
.07 .60 1.88
.11 3.96 6.29
.10 2.55 3.35
.21 3.82 2.31
.16 .77 1.39
.24 4.86 2.68
.19 2.47 1.92
.64 6.85 5.10
.10 .29 2.75
.14 2.34 4.56
.22 2.15 3.70
.12 6.72 2.76
.07 .55 1.77
.15 3.11 3.14
.10 2.47 2.33
.57 19.08 2.65
.16 .99 1.39
.21 4.08 2.14
.26 5.18 1.84
Hot
IIC CO N0x
Cold
HC CO NOX
6,000 Catalyst Miles
.15 2.38 3.24
.12 .22 1.59
.18 2.38 3.01
.14 1.23 2.30
.16 3.93 3.09
.11 1.06 2.05
.15 5.37 2.81
.13 2.78 2.46
.64 23.6* 2.87
.09 .38 1.74
.11 1.82 3.28
.21 5.43* 2.38
1.14 6.77 2.78
.07 1.15 1.89
.21 6.78 2.85
.32 3.78 2.32
Cold Transient
Stabilized
Hot Transient
Weighted
Cold Transient
Stabilised
not Transient
Weighted
Cold Transient
Stabiliied
Hot Transient
Weighted
-------
TABLE 21. DURABILITY PILES 0!>. CATALYST, BEADED CATALYST, CHASSIS DYNAVOIETER, GRAMS/I I
Hot
HC CO NOX
Cold
HC CO H0x
3,000 Catalyst Miles
Base Fuel
.14 1.59 2.44
.10 .24 2.09
.11 2.19 3.60
.11 1.03 2.56
ui "A" Additive
o
.17 4.38 3.28
.12 1.76 2.08
.17 5.10 3.24
.14 3.18 2.63
"B" Additive
.19 6.07 1.58
.16 .98 .86
.18 6.09 1.62
.17 3.36 1.21
.99 25.1 2.9
.09 .42 2.19
.18 3.58 4.28
.29 6.22 2.89
1.15* 24.8 3.49
.14 1.85 2.24
.17 4.13 4 09
.35 7.07 2.98
1.25 23.9 2.6
.29 1.81 1.29
.25 7.67 2.15
.47 7.81 1.78
Hot
HC CO NOX
Cold
HC CO N0x
9,500 Catalyst Miles
.16 1.57 3.92
.14 .23 2.09
.09 .20 3.17
.13 .49 2.75
.17 6.12 2.90
.08 1.71 1.76
.16 4.69 2.90
.12 2.29 2.29
.22 6.21 1.4
.14 1.09 .92
.16 3.97 1.36
.16 2.88 1.13
.33 15.0 3.06
.04 .28 1.92
.13 1.94 3.48
.13 3.69 2.57
.72 24.5 3.22
.12 .92 1.76
.12 4 92 2.80
.24 6.72 2.33
.69 24.8 1.59
.21 1.41 .86
Hot
HC CO NOx
-E (Cont'd)
Cold
HC CO NOX
9,500 Catalyst Miles
.12 5.17 3.43
.06 .72 1.27
.13 5.20 3.63
.09 2.81 2.37
.13 24.8 2.31
.12 1.75 1.93
.37 7.40 2.68
.19 7.88 2.21
.19 3.48 1.58 1
.31 6.66 1.20 U
.36 24.6 2.1
.06 .32 2.14
.05 4.03 2.33
.12 6.19 2.18
.56 24.71 1.68
.12 2.12 1.12
.10 4.95 1.91
.20 7.41 1.44
Hot
HC CO NOX
Cold
HC CO NOX
9,500 Catalyst Miles
.14 3.37 3.67
.10 .47 1.68
.11 2.7 3.4
.11 1.65 2.53
.15 15.5 2.6
.10 1.73 1.84
.26 6.0 2.79
.15 5.63 2.25
.20 6.14 1.5
.15 1.03 .89
.17 5.10 1.49
.165 3.12 1.2
.35 19.8 2.08
.05 .30 2.03
.09 2.98 2.90
.125 4.94 2.37
.64 24.6 2.45
.12 1.52 1.4
.11 4.93 2.35
.22 7.06 1.88
.97 24.4 2.09
.25 1.61 1.07
.22 5.57 1.86
.39 7.23 1.49
Cold Transient
Stabilized
Hot Transient
Weighted
Cold Transient
Stabilized
Hot Transient
Weighted
Cold Transient
Stabilized
Rot Transient
Weighted
•Corrected for airbient conditions.
-------
TABLE 22. AMBIENT CONDITIONS, VEHICLE TESTS.
Modified Federal Cycle
Federal Cycle
Catalyst Miles
ZERO
2000.
X
X
4000.
X
X
6000.
X
X
8000.
X
X
9500.
X
X
9500.*
BASE FUEL
Barometer
Corrected Barometer
Ambient Air °F
Wet Bulb °F
Dry Bulb CF
Humidity %
29.25
82.
58.44
29.48
29.33
84.
.
oc
OD.
47.84
29.61
29.46
84.
HA
34.
Q^
OJ .
8.99
29.53
29.40
77.
tit
3J.
*7Q
/y .
11.97
29.40
20.26
82.
CT
D / .
Ql
OJ. .
19.27
29.82
29.56
72.
HI
3 / .
"7 A
/4 .
33.04
29.26
29.00
72.
CO
39.
•JA
74.
40.14
"A" ADDITIVE
Barometer
Corrected Barometer
Ambient Air °F
Wet Bulb °F
Dry Bulb °F
Humidity %
29.22
29.08
82.
62.
79.
26.69
29.64
29.51
79.
63.5
79.
41.97
29.25
29.12
79.
61.5
79.
35.93
29.38
29.26
72.
54.
71.
28.35
29.45
29.31
80.
56.
79.
19.98
29.22
28.95
74.
61.
77.
39.14
29.15
29.00
74.
52.5
76.5
14.43
"B" ADDITIVE
Barometer
Corrected Barometer
.Wet Bulb °F
Dry Bulb °F
Humidity %
29.31
29.20
54.
61.
63.67
28.98
28.85
52.
78.
13.01
29.68
29.57
48.
68.
16.88
28.82
28.42
63.
75.
51.51
29.29**
29.04
58.
73.
39.34
*Repeat of 9500.
**Repeat of 6000.
-------
COMMENTS: Base Fuel
1. The CO, HC and NO emission levels, as analyzed from the
X
CVS, appeared in this order: Cold Start > Hot Start >
Weighted > Stabilized.
2. NO emission levels were higher during the Modified
Federal Cycle operation than during Federal Cycle testing.
3. Carbon monoxide emission levels were higher during the
Federal Cycle operation than during Modified Federal Cycle
testing.
4. Repeatability from run to run was better (less scatter
of data points) during the Modified Federal Cycle than
during the Federal Cycle tests for hydrocarbons.
5. The data shows that there was not significant deteriora-
tion of the catalyst for the duration of the test.
152
-------
-a
-H
g
C
o
c
o
-------
1.
2.
4. 5.
Durability Miles X
6.
1000
7.
8.
Chassis Dynamometer
Base Fuel Vehicle
CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 90
• Cold Trgmsien
V Stabilized
D Hot Transient
Q Weighted
-------
2.
Chassis Dynamometer
Base Fuel Vehicle
3. 4. 5. 6.
Durability Miles X 1000
CVS EMISSIONS FEDERAL CYCLE
FIGURE 91
• Cold Transient
V Stabilized
D Hot Transient
O Wcicjhtt I
-------
J.I I 1.44
i TTi rt
±J±:±
SI
Chassis Dynamometer
Base Fuel Vehicle
4. 5. 6.
Durability Miles X 1000
CVS EMISSIONS FFDFRAL CYCLE MODIFIED
FIGURE 92
• Cold Transien
V Stabilized
Q Hot Transient
O Weighted
-------
Ul
iffi
tri±i:rl±
.1. U j 1 U-
^T~ t'~r f' r"
.... . J I I I
•• 1":-i i j.ttf
4J.4-i--i-l-Uxb4.i-J-; J-l §
._.,_ _..
mrai
"H"""i ii'
*rq_LLj ' J..
- UX U -
ttrt-itl:
•H-H :T-H
±H±ttt:
rTrnxc
- 4 -H- -r—t-i
t • '' T •*• •* ~r* r
T i j | !
.T.l.i±t±EL
'Oxt'i'i .1'
±ttb±t:
4. 5. 6.
Durability Miles X 1000
T
Chassis Dynamometer
Base Fuel Vehicle
CVS EMISSIONS FEDEPAL CYCLF
FIGURE 93
• Cold Transien
V Stabilised
n Hot Transient
O Weighted
-------
o
S5
QJ
- s
00
M
0)
O
Chassis Dynamometer
Base Fuel Vehicle
5. 6.
Durability Miles X 1000
CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 94
• Cold Transier
V Stabilized
D Hot Transieni
O Weighted
-------
COMMENTS: Additive "A" Fuel
1. Carbon monoxide levels measured during Federal Cycle
tests are not significantly different from those measured
during the Modified Federal Cycle. The carbon monoxide
does increase, however, as mileage is accumulated, indicating
some catalyst degradation.
2. Hydrocarbon emission levels from the three CVS portions..
of the Modified Federal Cycle are consistent from test to
test, forming a nearly flat curve with a slight upward slope
with time.
3. Unlike the hydrocarbon emissions data mentioned above,
the data points from the Federal Cycle CVS are quite scattered
and it is difficult to form meaningful conclusions.
4. The NO emission level did not increase with durability
2C
miles for either the Federal Cycle or Modified Federal Cycle
tests.
5. NO emission data points, from the three CVS portions
JL
of the Federal Cycle, are quite close and form a nearly flat
curve; whereas, the Modified Federal Cycle data points showed
considerable scatter. This is not unexpected, since the
higher temperatures of the Federal Cycle Modified would tend
to generate higher NO levels.
X
6. The NO emissions, as analyzed from the CVS, appeared
3^
in the following order: Hot Start < Cold Start < Stabilized
< Weighted.
159
-------
3
O
-
'
• ,
-
M
•
-
•
U
.
(fl
:.
-
lU? H-j±±H
-.„-.-«- - - -1 _t__i_U_ __
LLJ-LJ . Li
:4±n±q u
Ml 111 !
Ml
r-1- , T :
liih-j iiith
•— —i 1 —, - ' - - — i -' - f i - ,—. - I - * A— .—*
Edffi Him
_.°:_
:"?•!-: •:; r;
U.4-1
_L_L. . , . /^l 1 4^_
/.
-: / --1 i -H-
, I LJ.__1_
! : _U.t .!
: MM 1 '
m±rn±:
I > !
! f j-;l i M-
; f -i-| ;-•-
-) I_L: u 1.4.!.! -
£. . M
v\-*n
^o—;vPr
IjffH
rttiii:ti
•i:b4^
T4-
PTTffff
R+ffffi
Chassis Dynamometer
"A" Additive Vehicle
3. 4. 5.
Durability Miles X 1000
CVS EMISSIONS FEDERAL CYCLE
FIGURE 95
• Cold Transient
V Stabilized
D Hot Transient
O Weighted
-------
15.5
H-i-M ••
r * :
I. ' U4-I-J.•
! I I I I 1
rTrrriT;
-±i±::±:
rtrrtfcx
a I I ' , ' ' I
—-f
i 4i)i:-ff
Tl-ph
wmr-
"•Hl-H-t-l
-±hL -I:1 ±ti±t
I I'M
r±
Chassis Dynamometer
"A" Additive Vehicle
3. 4. 5. 6.
Durability Miles X 1000
CVS EJ'ISPIONS FEDERAL CYCLE MODIFIED
FIGURE 96
• Cold Transient
V Stabilized
D Ho't Transient
O Weial
-------
Ol
t,
o
0
O
M
T3
&
0)
H
•H
a
M
QJ
3
M
O
EFHTE
!-H4fH4
:ifi
__ i _ |
c ±E±n±n '.
; i
±tn i-in"
rb±t±:
r±
PIT r VTTT ;••"! : r
Jfc1
i_' .4^, t—k-\—J- —--4—.- I ^-4-4-
:-\L.
•HfH-W
H H-rt-tH
xmttn
F±t±H
I... _i _ i—. _*..»_.i
iii; 11
I--1—I—t r—' -* - *
f 1 i i r i ! i
Stiff}
ffffffH
hitrtttiiB
3. 4.
Durability Miles X 1000
Chassis Dynamometer
"A" Additive Vehicle
CVS
FFDEPJU, CYCI-F
FIGURE 97
„ cold Transient
V Stabilized
D Hot Transient
O Weighted
-------
cr.
ui
-rnTr "'"
. i J — L,.L_._l -k. j._i_l_l— fc-.J
4. 5.
Durability Miles
10.
Chassis Dynamometer
"A" Additive Vehicle
CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 98
• Cold Transient
V Stabilized
D Hot Transient
O Weighted
-------
en
I
0)
.H
•H
E
o
o
~ i . I . ! i
• Tl TTT
4-U444. -!-
.
! 1.1 !
. _.
- -
t i i i i i '
... .—.—,„ .,. -i.~4 ..^
l i T T I IT
. i. . r i J—i- • -•
I • I
14044.44-.
Jill144
h-'-tr- t-r-r
rtnrrr
L' i : l ; i
O-HM'-rH
REffl
,_;. L.1_(_U4.J
it?
. _,_.(__._
rarr
1. rf4+44444
U i J ,
— ,' -I .!..'
n I r i i
ELVfTj-l
Lf.
"L! rt|-LTi
I i M
: I I i ! I
5. 6.
Durability Miles X 1000
Chassis Dynamometer
"A" Additive Vehicle
CVS EMISSIONS FEDERAL CYCLF
FIGURE 99
• Cold Transient
V Stabilized
n Hot Transient
O Weighted
-------
6
en
en
i
0)
o
03
M
U
• TTTT 1—'"
—^ i-4-,_!_!-1-
i— LlTo.
Chassis Dynamometer
"A" Additive Vehicle
4. 5. 6.
Durability Miles X 1000
CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 100
10
• Cold Transient
V Stabilized
D Hot Transient
O Weighted
-------
COMMENTS; Additive "B"
1. Carbon monoxide emission level data points from both
the Federal Cycle and the Modified Federal Cycle test pro-
cedures showed considerable scatter which had an overall
upward trend with time, indicative of a loss of converter
efficiency.
2. Hydrocarbon emissions from both the Federal Cycle and
the Modified Federal Cycle tests show much less scatter
than does carbon monoxide, however, both test cycles show
an upward trend with time for hydrocarbons as well as
carbon-monoxide.
3. NO emissions from both the Federal Cycle and the
Modified Federal Cycle tests show a downward trend with
test miles.
4. The NO emissions, as analyzed from the CVS, appeared
in the following order: Hot Start < Cold Start < Weighted
< Stabilized.
166
-------
S
X
o
c
2
0)
I
M
FTH4 PW
I H4-H
i iXQTL -
N±| 14-1-
. -i Mi
Trnjj
.
olU- ± i i
44414.^
LU-4-t.U
+itT±H
!
.U-ULLiO-l
I-L ' LLil
;rrr±i
TX41
rtl+M
2 I -J± -h-
,^.-.. I, i
i r :TTI ;
HI
i i i t
II14-LT7H
Ti Lfjxn
Ml11
Frffffff
Trri; i.!.. T
TGu i -....! ten
Chassis Dynamometer
"B" Additive Vehicle
3. 4. 5. 6.
Durability Miles X 1000
CVS EMISSIONS FEDERAL CYCLE
FIGURE 101
• Cold Transient
V Stabilized
[7J Hot Transient
O Weighted
-------
CC
•H
X
O
1
M
ifl
U
Q>
o
a
S
M
C
.2
i m miro.tt
>Ti
Chassis Dynamometer
"B" Additive Vehicle
5. 6.
Durability Miles X 1000
CVS EMISSIONS FFDFRAL CYCLE "ODIFIED
FIGURE 102
10
• Cold Transient
V Stabilized
D Hot Transient
O Weighted
-------
o
-Q
M
O
o
r; v
wi ^-
re
-------
B
O
JO
Ul
R)
u
o
01
8)
IX
Cfi
e
Ifl
M
U
HP-am 53
n.uii;d±E
II III
r;; rr
m
4. 5. 6.
Durability Miles X 1000
10.
Chassis Dynamometer
"B" Additive.Vehicle
CVS EMISSIONS FEDERAL CYCLE rODIFIED
FIGURE 104
• Cold Transient
V Stabilized
D Hot Transient
O Weighted
-------
o
SB-
0)
OJ
Oi
cn
Chassis Dynamometer
'B" Additive Vehicle
5. 6.
Durability Miles X 1000
CVS EMISSIONS FEDERAL CYCLE
FIGURE 105
10.
• Cold Transient
V Stabilized
D Hot Transient
O Weighted
-------
; -1 i .1.
U_;! 14. j-i.
±1!l±i 1
•|-H-H-?-ff
-fn-'-m-t-
" ''"~H
i: :..Li
+ly
ILL -L Lj_ii LLX
i ' i ii i i i i i
rr.l:LLJ±±iJ±r
; i -i i i • i r
u
1 ! i I MT
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"B" Additive Vehicle
4. 5. 6.
Durability Miles X 1000
CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 106
10
• Cold Transient
V Stabilized
D Hot Transient
O Weighted
-------
G. Comparison of Three Fuels, Chassis Dynamometer, Beaded
Catalyst
COMMENTS;
1. The NO values did not vary during the durability test
A .
for any of the fuels, whether tested via Federal Cycle or
Federal Cycle Modified.
2. The carbon monoxide emissions increased during the
durability test for all three fuels. This was true for
Federal Cycle and Federal Cycle Modified tests.
3. Carbon monoxide emissions, tested during the Federal
Cycle/ increased more rapidly during durability tests than
when measured during the Federal Cycle Modified. This
could be a result of a high light off temperature for the
converter.
4. Carbon monoxide emission levels during the durability
test increased the least with the base fuel car. The
Additive "A" car increased slightly more, while the Additive
"B" car had the greatest amount of carbon monoxide increase
during the durability test.
5. The carbon monoxide emission levels were lower during
the Federal Cycle than they were during the Federal Cycle
Modified.
6. Hydrocarbon emission levels were lower when tested under
the Federal Cycle Modified test than under the Federal Cycle,
7. Hydrocarbon emission levels did not increase during
durability testing for the base fuel car or for the Additive
"A" fuel car, but the Additive "B" car did show a slight
increase during the durability test.
173
-------
o
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2.
Chassis Dynamometer
3. 4. 5. 6.
Durability Miles X 1000
CVS EMISSIONS FEDERAL CYCLE
FIGURE 107
10
• Baseline
J7 "A" Additive
D "B" Additive
-------
0>
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3. 4. 5. 6.
Durability Miles X 1000
CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 108
10.
• Baseline
V"A" Additive
n"B" Additive
-------
Q
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Chassis Dynamometer
3. 4. 5. 6.
Durability Miles X 1000
CVS EMISSIONS FEDERAL CYCLE
FIGURE 109
• Baseline
v "A" Additive
n "B" Additive
-------
c
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Chassis Dynamometer
3. 4. 5. 6.
Durability Miles X 1000
CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 110
7.
8.
9.
10
* Baseline
^ "A" Additive
D"B" Additive
-------
6.
5.
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2.
1.
1.
2.
Chassis Dynamometer
3. 4. 5. 6.
Durability Miles X 1000
CVS FMIPSIONS FEDERAL CYCLE
FIGURE 111
9.
Baseline
"A" Additive
-'B" Additive
10
-------
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Chassis Dynamometer
2. 3. 4. 5. 6.
Durability Miles X 1000
CVS EMISSIONS FEDERAL CYCLE MODIFIED
FIGURE 112
8.
10
- Baseline
V"A" Additive
D"B" Additive
-------
H. Comparison of Chassis Vs. Engine Dynamometer, Beaded
Catalyst, Three Fuels
The following set of graphs is a comparison of the data
collected from the engine dynamometer and vehicle chassis
dynamometer studies running on the three different fuels.
Both engines and vehicles were equipped with identical beaded
type catalytic converters. The data obtained from the con-
stant volume sample (CVS) system was plotted as grams per
mile vs. durability miles. The following conclusions were
made from these graphs.
180
-------
COMMENTS: Baseline Fuel
1. Carbon monoxide levels during the cold start testing
were much higher for the engine dynamometer runs than those
made on the chassis dynamometer. Very little difference
was noted during the hot start test procedure.
2. Unburned hydrocarbons, as expected, were higher during
cold start testing than during hot start tests, with not
much difference between engine dynamometer and chassis
dynamometer runs.
181
-------
4tfftfH
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4. 5. 6.
Durability Miles X 1000
Beaded Catalyst Base Fuel
CVS EMISSIONS FEDERAL CYCLE
FIGURE 113
Hot Transient
Cold Transient
••. Chassis Dynamometer
Engine Dynanometer
-------
c
o
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2.
3. 4. 5. 6.
Durability Miles X 1000
Beaded Catalyst Base Fuel
CVS EMISSIONS FEDERAL CYCLE
FIGURE 114
7.
8.
9.
10.
Hot Transient
Cold Transient
• . Chassis Dynamometer
Engine Dynamometer
-------
COMMENTS; Additive "A"
1. Carbon monoxide emission levels were higher for the
engine dynamometer than for the chassis dynamometer runs
for both the cold and hot start tests.
2. Hydrocarbon emission levels are higher for the engine
dynamometer tests than for the chassis dynamometer tests for
both cold and hot start operations; however, the differences
were much smaller than in the case of carbon monoxide.
184
-------
8.3
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4 . 5. 6 .
Durability Miles X 1000
Beaded Catalyst "A" Additive
CVS EMISSIONS FEDERAL CYCLE
FIGURE 115
Rot Transient
-Cold Transient
• Chassis Dynamometer
Engine DYn mometer
-------
4. 5. 6.
Durability Miles X 1000
Beaded Catalyst "A" Additive
CVS EMISSIONS FEDERAL CYCLE
FIGURE 116
Hot Transient
Cold Transient
o Chassis Dynamometer
Fngine Dynamometer
-------
COMMENTS; Additive "B"
1. Carbon monoxide emission levels were higher initially
for the engine dynamometer runs, but stabilized to levels
not significantly different from the chassis dynamometer
tests. This appeared to be true for both hot and cold start
tests.
2. Carbon monoxide emissions increased as a function of
miles in the chassis dynamometer study, indicating some
catalyst deterioration. The data from the engine dynamometer
is somewhat inconclusive, although a slight decrease in
carbon monoxide as a function of time is noted.
3. Hydrocarbon engine dynamometer runs show higher levels
of unburned hydrocarbon in hot start studies, while the
final cold start measurements are quite close for both
engine and chassis.
4. Both engine dynamometer and chassis dynamometer studies
show an increase in hydrocarbons with time.
187
-------
•i rTT m
I I . - t- t • I • 1— i
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r •
Durability Miles X 1000
Beaded Catalyst "B" Additive
CVS EMISSIONS FEDERAL CYCLE
FIGURE 117
— Hot Transient
Cold Transient
• Chassis Dynamometer
Engine Dynar.oir.eter
-------
C
O
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4. 5. 6.
Durability Miles X 1000
Beaded Catalyst "B" Additive
CVS EMISSIONS FEDERAL CYCLE
FIGURE 118
_ Hot Transient
Cold Transient
• . Chassis Dynamorcetei
~) Engine Dynamometer
-------
IV. EXPERIMENTAL DATA, PARTICULATE EMISSIONS
The major emphasis of this contract was to evaluate the
effect of fuel additives on catalysts and the subsequent
effect on gaseous emissions. Since the facilities used for
the gaseous studies were the same as those used in prior
particulate studies (Reports APID-1567: "Characterization of
Particulates and Other Non-regulated Emissions from Mobile
Sources and the Effects of Exhaust Emissions Control Devices
on These Emissions"; EPA-R2-72-066: "Effect of Fuel Additives
on the Chemical and Physical Characteristics of Particulate
Emissions in Automotive Exhaust"; EHS70-101: "Development
of Particulate Emission Control Techniques for Spark-Ignition
Engines"; EPA-650/2-74-061: "Determination of Effect on
Particulate Exhaust Emissions of Additives and Impurities in
Gasoline"), several evaluations of the particulate emissions
were made. The details of the procedures and equipment for
particulate measurement is included in the reports mentioned
above. A summary of the particulate collection is as follovs:
The exhaust was diluted in a 26* x 18" dilution chamber, at
approximately 12 to 1 air/exhaust ratio, and 550 cfm diluted
exhaust was sampled at a constant 100°F, 1 cfm rate. The
particulate was collected in four locations. An Anderson
cascade impactor, backed up with a 142 mm fiberglass filter
was used for mass/size distribution studies. Two additional
142 mm fiberglass filters were used to collect particulate
for grams/mile determinations and for carbon, hydrogen,
nitrogen and benzo(a), pyrene analyses. A fourth 142 mm
millipore filter was used to collect particulate samples
for trace metal determinations.
A separate 47 mm filter with a millipore membrane was used
to collect samples for sulfate analysis. These filters were
sent to EPA for their analyses and the data is not included
190
-------
in this report. On several occasions/ after the vehicles
had accumulated several thousand miles, an attempt was made
to find platinum or palladium in the collected particulate.
These analyses were made using x-ray fluoresence, and in none
of the analyses could either of the noble metals be detected.
The sensitivity of the x-ray fluorescence was 1.0 u/g per
2
cm of filter area. This translates into a grams/mile sen-
sitivity of around .01 grams/mile, depending on the sample
size.
The particulate samples were collected from both the engine
runs and the vehicle runs. In the case of the engine runs,
the samples were collected only from the Federal Cycle Modi-
fied (starting with a fully warmed-up engine) and 60 mph
steady state. It was felt to be more appropriate to do the
gaseous analyses on the cold start and, because of the timing
of the runs, the only way to do the particulate was on a warm
engine. (See Table 3 for details on engine test sequence.)
Particulate samples were collected for both Federal Cycle
and Federal Cycle Modified, as well as 60 mph steady state,
for both vehicles.
In the case of the engine runs, the same engine was used for
all tests. At the conclusion of a run on a given additive
and catalyst, the engine was disassembled. Any deposits
were removed from the head, valves, and pistions. The valves
were reseated and a blowby and compression check was made.
The tests v/ere set up such that the baseline was bracketed
by the additive runs, with Additive A being run first and
Additive B being run after the baseline. The tests for
particulate were run at approximately 25 and 140 hours on
the engine stand, with the exception of the Additive B on
the monolith catalyst, which was run at 0 and 88 hours.
In the case of the vehicles the tests were run at about
3,000 and 9,000 miles.
191
-------
In general, it is felt that the duration of both engine and
vehicle tests was too short to allow any definitive prediction
as to particulate mass emission trends. Particulate tests
under contract 68-02-0332 (see report EPA-650/2-74-061) on
methodology for determining effects of fuel additives on
particulate emissions showed that some plateau seemed to be
reached at about 17,000 vehicle miles. It is also likely
that with a catalyst in the system, particulate buildup in
the catalyst would cause particulate stabilization to take
longer.
Since only two tests were run on each combination of additive
and catalyst, the statistical significance of any trend is
quite low. However, based on past experience with the
particulate collection techniques used in this study, it is
felt that large increases (2X or greater) in emitted parti-
culate are at least indicative of a reliable trend. With
this in mind, following are several general conclusions from
the particulate data. The data is plotted in Figures 119 and
120 for the engine runs and Figure 121 for the vehicle tests.
1. The engine stand data shows the monolithic catalyst
producing higher amounts of particulate than the beaded
catalyst. This is true for both the steady state and Modified
Federal Cycle at both the beginning and end of the durability
test. The base fuel and both Additives A and B show the same
trend. The analytical data does not account for the increase.
Since SO4~ was not specifically analyzed, the increase could
possibly be due to collection of the H^SO.. Another possible
explanation is that the beaded catalyst, with its longer
surface area and its different geometry, could be holding up
more of the particulate, although after 140 hours it is
expected that the particulate would have stabilized.
192
-------
2. In general, the engines equipped with monolith catalysts
showed lower particulate after the durability run, while
the beaded catalyst engines remained essentially constant.
3. The particulate emissions from the 60 mph steady state
runs are higher than the Federal Cycle Modified when measured
on the vehicles, while the engine stand data shows a reversal
in this tend with the Federal Cycle Modified being higher
than the steady state.
193
-------
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Durability Hours Engine Dynamometer
PARTICULATE EMISSION VS DURABILITY HOURS
120
140
Monolithic Catalyst
142 mm Glass Filter
FIGURE 119
60 MPH Steady State
Federal Cycle Hot
• Base Fuel
V "A" Additive
D "B" Additive
-------
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142 mm Glass Filter
40 60 80 100
Durability Hours Engine Dynamometer
PARTICULATE EMISSION VS DURABILITY HOURS
FIGURE 120
120
140
60 MPH Steady State
- Federal Cycle Hot
•^Base Fuel
^"A" Additive
D "B" Additive
-------
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2000. 3000. 4000. 5000.
Durability Miles Chassis Dynamometer
6000
7000.
Beaded Catalyst
142 mm Glass Filter
PARTICULATE EMISSION VS DURABILITY MILES
FIGURE 121
60 MPH Steady State
MFCCS
Federal Cycle Hot
* Base Fuel
V "A" Additive
D "n1 Additive
-------
Milligrams/Mile Particulate
M N) b) £» Ul a
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142 mm 142 mm Separator Filter 142 mm 142 mm
Federal Cycle Modified
60 mph Steady State
MONOLITH CATALYST
BASELINE FUEL
ENGINE DYNAMOMETER
FIGURE 122
16 Hours
139 Hours
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Federal Cycle Modified
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MONOLITH CATALYST
FUEL ADDITIVE "A"
ENGINE DYNAMOMETER
FIGURE 123
60 mph Steady State
18 Hours
138 Hours
-------
Milligrams/Mile Particulate
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-
—
—
—
-—
- —
I
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/
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X,
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X
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I
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2
%
s
'/
X
X
X
X
^
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Andersen Back-up Fiberglass Millipo
Separator Filter 142 mm 142 mm
60 mph Steady State
MONOLITH CATALYST
FUEL ADDITIVE "B"
ENGINE DYNAMOMETER
•pTrTTTDT? 1 *) A
re
—
-
—
—
i
1
1
\
i
i
1
1
0 Hours
88 Hours
-------
125
0)
100
^H
3
U
•H
4->
Is) iH
O -H
O ^
w
3
Cn
•H
:H
75
50
25
142 mm 142 mm
Federal Cycle Modified
f
1
i
1
i
s
j i
1
; j
1
1 1
! '
1
i
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mm
r"
•
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4-
-
Fiberglass
r
X
/;
x
X
x
xj
X
1
i
1
i
r
1 !
Millipore
I !
i
i
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i
i
I
i
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•
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1
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I
V
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X"
X
X
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I
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1
rj
X
X1
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>
H
MMH
1
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j
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£,
*J
X
MM
i
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i
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1
t j
i ' '
1
1
i
t
i
1
i
i
Andersen Back-up Fiberglass Millipore
Separator
Filter
142 mm
142 mm
60 mph Steady State
BEADED CATALYST
BASELINE FUEL
ENGINE DYNAMOMETER
FIGURE 125
n
D
56.3 Hours
146 Hours
-------
125
KJ
o
-P
u
•H
0)
i— l
•H
5-
\
0)
100
75
&
•H
H 50
25
j
i
:
j
1
1
1
i
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i
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i
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ft
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1
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Fiberglass Millipore
142 nun 142 mm
i
f^
^
4
^
<
,^^_
,
l
t.
^
^
£,
f
V?
//
y,
'/,
,
j
Andersen Back-up Fiberglass Millipore
Separator Filter 142 mm 142 mm
Federal Cycle Modified
60 mph Steady State
BEADED CATALYST
FUEL ADDITIVE "A"
ENGINE DYNAMOMETER
34 Hours
146 Hours
FIGURE 126
-------
ZQZ
Milligrams/Mile Particulate
H- M
fO tJ1 ~J O fO
in o en o en
!
•
I
— '
1
— ,
•
-—
1
_j —
— 1 —
1
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7
i
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p
/
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z
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—
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x
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MM*
X
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z
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-?n
2
/
x
^•^H
j
1
i
Fiberglass Millipore Andersen Back-up Fiberglass Millipore
142 mm 142 mm Separator Filter 142 mm 142 mm
Federal Cycle Modified
60 mph Steady State
BEADED CATALYST
FUEL ADDITIVE "B"
ENGINE DYNAMOMETER
FIGURE 127
8 Hours
p]132 Hours
-------
Engine Stand
VEHICLE TYPE: 1972 Chevrolet
FUEL: Baseline
CONVERTER: Monolith
DYNAMOMETER TEST
TABLE 23
Grams per 1.61 km (1 mile)
Vehicle Follow-up Glass Filter Millipore
lest Test Test Andersen glass Andersen + 142 mm 142 mm
No. Hours Miles Test Mode Sampler Filter Filter (Avq. of two)
2 76 A
276B
276C
276T
276U
276V
13.5
16.0
17.0
135.8
138.0
139.0
.GO ?*.PH SS
FCHS
FCHS
60 MPH
FCHS
FCKS
.0153
--
—
.0107
--
.1960
--
—
.1915
--
.2113
--
--
.2023
__
.2448
.2639
.1906
.2048
.1613
.2297
.2171
.2347
.2199
.1376
.1906
.2199
-------
TABLE 23 (Cont'd)
EXHAUST GAS ANALYSIS
Vehicle
Test
No.
276A
276B
276C
SJ
0
4?
276T
276U
276V
co2
10.45
10.50
10.50
10.70
10.50
9.35
10.20
10..40
% by V
°2
6.2
6.2
6.1
5.9
6.05
7.75
6.25
6.10
ol urne
82.45
81.40
82.5
82.55
82.55
82.0
82.65
82.7
Parts Per Million
CO
24.2
26.6
>250
>250
65.4
53.3
>250
>250
Cg II. C.
5.0
4.0
21.0
12.0
15.0
9.0
20.0
24.0
N02
NO
483
532
540
660
742
790
530
581
NV Nx
665
728
957
1121
983
975
895
968
Start
Final
Start
Final
-------
TABLF 23 (Cont'd)
ANALYSIS OF EXHAUST PARTICIPATE
o
in
Vehicle
Test
No.
276 A
276 B&C
276 T
276 U&V
Fe
.02
.5
.04
1.7
Ni
<.01
<.05
<.01
<.02
Cu
.02
..2'
.04
.29
Trace Metals on Milltpore Fil
Al Ca Mq Mn Cr Sn
<.0l
.1
.04
.17
.2
3.5
.3
2.8
.03
.6
.05
.55
.009
.16
<.005
.02
<.01
.06
.01
.06
<.01
<.05
<.01
<.02
ter (
Zn
<.03
.3
.07
.23
%)
T1
<.01
<.05
<.01
.03
Rb.
.07
:-2
.06
.04
%SO>!
. Glass Fiber Filters
0.1
<0.1
1.0
XK
1.42
<0.1
2.15
*N
. 2.77
<0.1
2.60
PPM
BAP
1
20
60
10
-------
99.99
99 98 95 90
80 70 60 SO 40 30 20
2 1 0.5 0.2 0.1 0.05 0.01
o
S-
U
O *-
(7) 0)
4->
0)
E
Q
0)
'J
k
re
o.
ro
(*)
MASS DISTRIBUTION
FIGURE 128
Run NO. 276T
Total in Particles of Diameter
-------
MAP ritUBABILITY 4B BU43
£• X 2 LOO CYCLES ..of in 11.1.1.
9999
99 98 95 90
2 1 O.S 0.2 0.1 0.05 0.01
o
s-
o
rs>
O
>J
E
ra
MASS DISTRIBUTION
FIGURE 129
Run No. 276A
Total in Particles of Diameter
-------
Enqine Stand
VEHICLE TYPE: 1972 Chevrolet
FUEL: Baseline + Fuel Additive A
CONVERTER: Monolith
DYNAMOMETER TEST
TABLE 24
Grams per 1.61 km (1 mile)
o
00
Vehicle Follow-up Glass Filter Millipore
lest Test lest Andersen glass Andersen 4- 142 mm 142 mm
No. Hours Miles Test Mode Sampler Filter Filter (Avq. of two)
279C
279F
279G
279X
279Y
279Z
3.7
18.0
18.6
135.7
138.0
138.6
SS - 60 MPH
ECUS
FCHS
SS - 60 MPH
FCHS
FCHS
.0147
--
--
.0116
—
.2900
--
--
.1792
—
.3047
--
--
.1808
--
.3117
.2053
.2835
.1974
.0733
.0812
.2867
.0879
.1026
.2074
.1907
.2347
-------
TABLF 24 (Cont'd)
EXHAUST GAS ANALYSIS
KJ
Vehicle
Test
No.
279C
279F
279G
279X
279Y
279Z
co2
6.5
9.0
6.0
6.4
10.2
10.25
9.5
9.5
% by V
°2
11.40
8.15
10.5
' 10.2
6.4
6.25
7.5
7.4
olume
81.0
82.0
82.6
82.45
82.55
82.6
82.2
82.2
Parts Per Million
CO
36.3
38.7
>250
>250
123.4
130.3
239.6
>250.0
Cg II. C.
4
5
26.0
28.0
22.0
20.0
35.0
40.0
N02
NO
718
969
640
676
1034
1019
540
604
"V Nx
. 978
1036
1170
1162
1235
1375
1009
104 81
-------
TABLE 24 (Cont'd)
ANALYSIS OF EXHAUST PARTICULATE
Vehicle
Test
No.
279 C
279 F&G
279 X
^J 279 Y&Z
0
Fe
.07
1.9
.03
.4
N1
<.01
<.05
<.01
<.05
Cu
.02
.7
.02
.3
Trac
AT
.02
.5
.03
.2
e Metals on Milllpore Filter (
Ca Mg Mn Cr Sn Zn
.14
7.4
.17.
3.6
.03
1.4
.04
.6
<.005
.09
<.005
.01
<.01
.1
<.01
.1
<.01
<.05
<.01
<.05
<.03
.5
<.03
.2
%)
Ti
<.01
.09
<.01
.02
P-b.
.2
.4
.1
.1
%SOA
Glass Fiber Filters
i
%C
1.05
6.05
1.49
28.18
-«H
2.06
1.01
2.41
8.92
*N
1-.19
4.19
1.25
3.05
PPM
BAP
1
2d
15
55
-------
X 2 UOOCYCLES «« .
KCUPPEL ft ESSER CO.
99.99
0.2 0.1 0.05 0.01
to
c
o
o
•I—
E
O
KJ 1_
01
E
9
O
0)
u
co
i
CD
MASS DISTRIBUTION
FIGURE 130
Run No. 279C
Total in Particles of Diameter
-------
99.99
99 98
95 90
80 70 60 50 40 30 70
10
0.5 0.2 0.1 0.05 0.01.
c/i
B
O
k
u
KJ fc.
0)
-(->
0>
£
IQ
•i—
O
0>
MASS DISTRIBUTION
FIGURE 131
Run No. 279X
Total in Particles of Diameter
-------
DYNAMOMETER TEST
Engine Stard
VEHICLE TYPE: 1972 Chevrolet
FUEL: Baseline + Fuel Additive B
CONVERTER: Monolith
TABLE 25
Grams per 1.61 km (1 mile)
Vehicle Follow-up Glass Filter Millipore
Test Car Test Andersen glass Andersen +• 142 mm 142 nun
No. Miles Hrs- Test Mode Sampler Filter Filter (Avq. of two)
272B
272D
272E
2721!
2720
272P
0
0
0
88
88
88
60 riPK SS
. FCHS
FCHS
60 MPH SS
FCHS
FCHS
.0185
—
--
.0179
--
.1551
--
--
.1795
--
.1734
—
—
.1974
—
.1402
.3666
.4008
.2072
.3960
.3764
.1781
.5280
.6453
.1876
.5570
.6453
-------
TABLE 25 (Cont'd)
EXHAUST GAS ANALYSIS
Vehi cle
Test
No.
272B
272M
co2
10.35
10.45
9.7
10.2
% by V
°2
6.3
6.2
7.2
6.4
ol ume
N2
82.45
82.45
82.3
82.5
Parts Per Million
CO
38.7
36.3
144.7
53.2
Cg H.C.
15
12
35
30
N02
. NO
875
942
792
646
N0x- Nx
. 1209
1398
1214
897
Start
Finish
Start
Finish
NJ
4=
-------
TABLE 25 Cont'd)
ANALYSIS OF EXHAUST PARTICIPATE
Vehicle
Test
No.
272 3
272 D
272 M
272 P
Fe
.03
.13
.02
.12
N1
<.01
<.01
<.01
<.01
Cu
.03
.16
.0-2
.13
Trace Metals on Milltpore Fil
Al Ca Mg Mn Cr Sn
<.01
.04
<.01
.04
.2
1.4
.16
.87
.07
.27
.05
.22
2.7
2.8
2.1
2.7
<.01
.02
<.01
.04
<.01
<.01
<.01
<.01
ter (
Zn
.03
.11
.03
.13
%)
Ti
<.01
.01
<.01
.02
Rb.
1.3
.3
1.2
.58
ISO.
Glass Fiber Filters
%C
1.67
3.46
0.83
18.45
-XK
3.34
3.17
2.40
5.15
XN
4,77
1 4.11
2.12
0.94
PPM
BAP
4
90
3
40
-------
99.99
99.9 99.8
99 98 95 90
80 70 60 50 40 30 20
10
2 1 0.5 0.2 0.1 0.05 0.01
MASS DISTRIBUTION
FIGURE 132
Run No. 272B
% Total in Particles of Diameter
-------
99.99
99.9 99.8
80 70 60 50 40 30 20
L 0.5 Oi2 0.1 0.05 0.01
-^r* t I i . I . 1
V)
C
o
J-
u
01
-M
-------
Engine Stand
VEHICLE TYPE: 1972 Chevrolet
FUEL: Baseline
CONVERTER: Beaded
DYNAMOMETER TEST
TABLE 26
Grams per 1.61 km (1 mile)
Vehicle Follow-up
Test Test Test Andersen glass Andersen +
No. Hours Miles Test Mode Sampler Filter Filter
2S6L
2S6H
2851
5; 2S6X
286 Y
2862
38.4
56.3
56.9
145.1
146.0
146.7
r
!
2 HRS SS
FCHS
FCKS
2 HRS SS
FCHS
FCHS
.0030
--
—
.0048
--
.0459
--
--
.0432
—
.0489
--
--
.0481
—
Glass Filter Millipore
142 mm 142 mm
(Avq. of two)
.0574
.061]
.0708
.0462
.0562
.0513
.0447
.0440
.0806
.0447
.0513
.0586
-------
TABLE 26 (Cont'd)
EXHAUST GAS ANALYSIS
Vehicle
Test
No.
286E
286H
2861
286X
NJ
IO
286Y
286Z
co2
10.4
10.1
9.8
10.7
10.3
9.95
10.3
9.85
% by V
°2
6.7
6.3
6.5
5.25
6.4
7.1
5.65
6.25
ol ume
N2
82.0
82.65
82.8
83.1
82.4
82.2
83.1
83.0
Parts Per Mi 1 1 ion
CO
33.9
33.9
133.1
208.1
48.4
36.3
186.4
850.0
c6 ii. c.
9
8
22
23
7
6
20
67
N02
NO
1506
983
557
1025
732
845
475
462
NV Nx
. 1975
1520
1141
1597
1054
1168
864
904'
Start
Finish
Start
Finish
-------
TAELF 26 (Cort'd)
ANALYSIS OF EXHAUST PARTICIPATE
Vehicle
Test
No.
286 E
286 I
286 X
286 Y
Fe
.04
.53
.06
.67
Ni
<.01
<0.1
<.01
<.05
Cu
.05
.38
.04
.53
Trace Metals on Millipore Fil
Al Ca Mq Mn Cr Sn
.04
.25
.02
.37
.45
3.9
.40
6.1
.10
.78
.09
1.4
<.00f
< .05
.00!
.03
.01
<0.1
.01
.17
<.01
<0.1
<.01
<.05
ter (
Zn
<.03
<0.3
<.03
.38
%)
Ti
.01
<0.1
<.01
.07
Rb.
<.03
<0.3
.03
_%so.
Glass Fiber Filters
1
XC
2.42
11.56
2.59
46.97
3.37
3.07
3.69
3.41
*N
5,09
' 3.31
7.01
7.46
PPM
BAP
15
<20
5
75
-------
KCUFPCL * Htl* CO.
95 90 80
0.5 0.2 0.1 0.05 0.01,
01
C
o
NJ
KJ
u
O)
-t-J
-------
99.99
99.9 99.8
99 98 85 90 80 70 60 50 40 30 20
c
o
u
'i-
E
Is)
NJ L.
KJ
-------
K>
UJ
Engine Stand
VEHICLE TYPE: 1972 Chevrolet
FUEL: Baseline + Fuel Additive A
CONVERTER: Beaded
DYNAMOMETER TEST
TABLE 27
Grams per 1.61 km (1 mile)
Vehicle Follow-up Glass Filter Millipore
Test Test Test Andersen glass Andersen + 142 mm 142 mm
Mo. Hours Miles Test Mode Sampler Filter Filter (Avq. of two)
2SSC
289F
239G
2S9X
289Y
239Z
20.0
33.7
34.3
142.9
145.0
145.6
120
7.5
7.5
120
7.5
7.5
2KRS 60 MPF
FCH?
FCIIS
2I-RS 60 npi:
FCKS
FCKS
.0027
--
--
.0042
--
.0197
--
--
.0207
--
.0224
--
—
.0249
--
.0217
.0440
.0342
.0219
.0875
.0586
.0170
.0366
.0293
.0192
.0220
.0220
-------
TABLE 27 (Cont'd)
EXHAUST GAS ANALYSIS
Vehicle
Test
No.
289C
289T.
289G
289X
289Y
289Z
co2
11.1
11.0
10.4
10.0
11.0
10.9
10.15
10.40
% by V
°2
5.65
5,70
4.3
4.7
5.15
5.35
5.10
4.90
ol ume
82.35
82.40
84.40
84.40
83.05
82.9
83.6
83.7
Parts Per Mi llion
CO
18.0
18.0
260
460
550
300
2270
780
Cg II. C.
9
9
23
23
12
12
79
38
N02
NO
1167
1387
345
347
990
1089
475
5S8
"V Nx
1387
1696
580
583
1321
1546
952'
1004
Start
Final
Start
Final
-------
TABLE 27 (Cont'd)
ANALYSIS OF EXHAUST PARTICIPATE
N>
KJ
in
Vehicle
Test
No.
289 C
289 F
289 X
289 Y
Fe
.15
1.50
.16
5.9
Ni
.02
<.l
.01
.14
Cu
.11
.86
.11
1.9
Trac
Al
.06
.73
.05
1.3
e Met
Ca
l.l
8.6
0.9
17.6
als o
Mq
.23
1.7
.17
3.2
n Milltpore Filter (
Mn Cr Sn Zn
.014
.12
.009
.70
.03
.26
.03
.53
<.01
<.l
<.o;
0.1
.07
.62
.07
1.4
%)
Ti
<.01
<.l
<.01
.17
Pb
.28
.98
.33
27.1
%so1
Glass Fiber Filters
1
XC
3.63
TRACE
1.39
1.80
-%K
3.33
5.23
2.72
TRACE
%H
7,. 58
•20.91
9.43
9.86
!
PPM
BAP
37
430
<7
75
-------
9" 99-8
99 98
KCUFFEL » CStCR CO.
95 90 80
70 60 50 40 30 20
10
1 0.5 0.2 0.1 0.05 0.01
10
MASS DISTRIBUTION
FIGURE 136
Run No. 289X
P
8
EE£
-i . . •
O
s_
O
-:-rf
U.
i_
01
4J 1-
.iUJ
111!
E
O
•t—
Q
9)
»~ • t.
S-
m
a.
co
i
-I L
t±tt±n
i±
M-lf
I !_L
T
% Total in Particles of Diameter
-------
K.
"
46 8043
MAPI IN U S. A.
KCUPPCL » ts»ER CO.
PROBABfLITY
X 2 LOG CYCLES
99.99
99 98
95
0.01
CO
c
o
o
i
01
$
E
<0
•r—
O
0)
U
•r-
4->
U
-------
Engine Stand
VEHICLE TYPE: 1972 Chevrolet
FUEL: Baseline + Fuel Additive B
CONVERTER: Beaded
DYNAMOMETER TEST
TABLE 28
Grams per K61 km (1 mile)
KJ
oo
Vehicle Follow-up Glass Filter Millipore
lest Test rest Andersen glass Andersen + 142 mm 142 mm
No. Hours Miles Test Mode Sampler Filter Filter (Avq. of two)
282C
282F
232G
2S2U
232V
282W
*Polyca
5.5
3
8
131.3
132.0
132.3
rbor.ate
?ilter.
60 I:PK ss
FCHS
FCHS
FCKS
FCKS
60 MPII SS
.0039
—
—
—
--
.0065
.0206
--
--
--
--
.0119
.0245
--
--
--
--
.0185
.0245
.0723
.0660
.0582
.0586
.0133
.0129
.0733
.0611
.0513
.0513
.0096
-------
TABLF 28 fCont'd)
ANALYSIS OF EXHAUST PARTICULATE
NJ
VO
Vehicle
Test
No.
282 C
282 F&G
282 U&V
282 W
Fe
.1
.7
.8
.2
N1
<.05
<.05
<.l
<.05
Cu
.1
.4
.7
.2
Tra<
Al
.06
.28
.35
.13
:e Mel
Ca
1.0
3.4
5.3
1.7
:als on Mi
Mq Mn
.3
.8
1.3
.5
14.0
6.0
8.3
18.0
Mpore Filter (
Cr Sn In
<.05
.09
.15
<.05
<.05
<.05
<.l
<.05
.2
.4
.6
.3
%)
Ti
<.05
.05
<.l
< .05
Rb
5.1
2.0
2.7
9.1
_%so4
Glass Fiber Filters
*C
0.95
2.84
2.87
3.33
-XH.
2.09
1.45
3.35
2.47
XN
4.35
0.95
1.10
1.37
PPM
BAP
24
160
10
60
-------
TABLE 28 (Cont'd)
EXHAUST GAS ANALYSIS
KJ
U)
Vehicle
Test
No.
282C
282F
282G
282L*
282V
282W
co2
11.10
9.95
10.4
10.6
10.1
10.0
10.4
9.2
% by V
°2
4.9
6.6
6.15
6.0
6.8
6.6
6.5
8.1
olume
83.0
82.5
82.55
82.6
82.1
82.6
82.3
81.8
Parts Per Mi 1 1 ion
CO
204.0
133.1
1150
495
360
675
121.1
111.3
Cg H.C.
16
16
75
50
55
68
30
30
N02
NO
946
1128
467
667
385
384
730
782
1
"V Nx
1058
1308
906
965
805
779
1272
1395'
Start
Finish
Start
Finish
-------
fcfO^ • —• . • -»>* ^v^-r_.
r\ C X 2 LOG CYCLES »ot i. u.«.«. •
KCUFFCL » E5SIR CO.
10.
9.
8.
7.
6_
5.
99.99
99.9 99.8
99 98 95 90
80 70 60 50 40 30 20
u
1 0.5 0.2 0.1 0.05 0.01
10
?
8
7
6
5
MASS DISTRIBUTION
FIGURE 138
No. 282C
''i
-TPT
.-
r, rlr-
4
V)
B
0
:.r
*)
ID
NJ
t.
0)
•414"
fl
r: o>
Q
0>
O
+» .5
(0
2_
I En
^
% Total in Particles of Diameter
-------
10.
9.
8.
7.
6..
5.
99.99
99.9 99.8
99 98 95 90
80 70 60 50 40 30 20
10
2 1 0.5 0.2 0.1 O.OS 0.01
MASS DISTRIBUTION
FIGURE 139
Run No. 282W
23±c
CL--—
10
3E^
— t-
c
o
s-
(J
Tffl
"-i^-
ffil
I
TT
S-
OJ
4->
ni
•r-
Q
OJ
U
I
-tll-
IlTu
Ifi
.9-
.8.
.7.
-T-:
++4-
-
1_
HI
" ~n~
i_L
11
LL
F
% Total in Particles of Diameter
• • i • i • ii i :: i i i i i i i t i i i i i i i i i i i i i j i i; i: • i i
i 1
-------
CHASSIS DYNAMOMETER TEST
U>
U)
CAR NUMBER: U-0435
VEHICLE TYPE: 1972 Tan Chevrolet
FUEL: Baseline No Fb.
CONVERTER: Beaded
TABLE 29
Grams per 1.61 km (1 mile)
Vehicle Follow-up
Test Car Test Andersen glass Andersen +
No. Miles Miles Test Mode Sampler Filter Filter
267A
267E
267C
267D
233A
2333
2£3C
233-D
2,871.0
2,991.0
2,998.5
3,006.0
8,755.0
•
i
11.5
120.0
7.5
7.5
11.5
120.0
7.5
•7.3
I
MFCCS
•GO MPi: SS
FCIIS
FCHS
MFCCS
2 H?»S SS
?c::s
.'.:ia
.1004
.0044
--
--
.0526
.0034
--
.0095
.0509
--
--
.01*3
.0646
--
.1100
.0554
--
--
.0669
.0680
--
Glass Filter Millipore
142 mm 142 mm
(Avq. of two)
.0286
.C806
.0293
.0391
.0454
.0746
.0256
.0342
.0813
.0311
.0293
.1173
.0286
.0749
.044C
.0586
-------
TABLE 29 (Cont'd)
ANALYSIS OF EXHAUST PARTICIPATE
w
jr
Vehicle
Test
No.
267 B
267 C
267 D
283 A
283 B
283 C
283 D
Fe
.06
.45
39
• J .x
.03
1.0
Only
N1
<.01
<.01
< 01
^ • w J.
<.01
'-1
283 E
283 L
Cu
.03
.22
22
• C £•
.02
.5
were
Trace Metals on Millipore Filter (
Al Ca Mq Mn Cr Sn Zn
.02
.2
_
.02
.52
anal
.24
2.7
2 fi
£. • \J
.2
5.2
/zed
.05
.6
6
.04
1.0
<.005
<.05
< ns
^ • \J -J
<.005
<.05
<.01
<-l
< 1
^- • A.
<.01
.15
<.01
<.l
< 1
x • X
<.01
<.l
.04
<0.3
< n 1
^ U • J
.03
.7
%)
Ti
<.01
<.l
s 1
^ • ±
<.01
.08
P-b
c.03
«0. 3
x A -3
"* U • J
<.03
1.8
%so1
Glass Fiber Filters
i
.45
2.40
11.50
23.77
-XK
2.71
4.22
6.30
3.73
*N
4. '2 6
7.03
3.10
0.28
P
E
<
<4
<6<
-------
TABLE 29 (Cont'd)
EXHAUST GAS ANALYSIS
tsj
U)
Vehicle
Test
No.
267A
267B
267C
267D
283A
283B
283C
233D
co2
8.9
8.9
11.2
11.7
9.1
8.9
9.3
9.2
11.4
12.15
9.35
9.10
55 by V
°2
8.3
8.4
4.9
. 4.4
7.8
8.3
7.65
7;8
4.7
3.6
7.5
7.9
ol ume
81.9
81.9
83.0
83.1
82.1
82.0
82.15
82.05
R3.0
83.35
82.2
82.05
Parts Per Mi llion
CO
>250
>250
15.7
18.1
215.3
123.4
8RP
198.5
7^.2
50. 8
9*. 4
186.4
C, H.C.
0
55
35
5
5
10
20
35
37
3
2
22
34
N02
NO
152
260
591
680
188
181
188
353
1152
1050
196
176
NV Nx
, 209
298
693
738
277
257
?80
458
1295
1204
362
305
23 Min.
41 Min.
Start
Finish
1390 Sec.
Last 505 Sec.
Start
Finish
-------
10.
9.
8-
7.
5.
99.99
99.9 99.8
99 98 95 90
80 70 60 50 40 30 20
10
? 1 0.5 0.2 0.1 0.05 0.01
-: ::.j v:.r .
^rti-r^.-i.-
MASS DISTRIBUTION
FIGURE 140
Run No. 267A
::d±
1
ft--. ::i
:T~
•Jt-
^^
B
SF
10
^SS>
•frn
•-.n
714-..—z^_-
g_._j___
::
11-
•^r
' * r_t
^F
.
.t-L
-.l
mj
£a
it^
^
H3J
to
c
o
J-
u
±ta
ge
:3B
ttttt
B
Efi
HS
TP
•
HTf'J
::.
uo
i
1
PM
**=
:xn
E
•«
.1
IPS
^ r ~ .- i' i
--\--~-
—-'1 1 —
L3
+-
SB
K
0)
•-
u
^fe^^iik^
&**
5..
s
^£
-E 131
li:
:'-
?B^
= 4"
:±t
^3
Fe
,TT
. 2_
.— 4.,
»
' '~T
£
~
ww
i_
444
:±
U4--.
ttt
.u
.
TT
_ 4.
II
wm
-I -r
% Total in Particles of Diameter
-------
K^C PWOBAB
°Z X 2 LOO
IUITT
CYCLES
KIUFPEL »
4O 0043
MIDI in u.». «. .
CO,
99.99
0.01
c
o
c_>
i
to -
00 O)
^J M
(V
E
Q
01
u
•r-
4J
i-
MASS DISTRIBUTION
FIGURE 141
Run No. 267B
% Total in Particles of Diameter
-------
10.
9.
8_
7.
6.
5.
99.99
99.9 99.8
99 98 95 90
80 70 60 50 40 30 20
10
1 0.5 0.2 0.1 0.05 0.01
MASS DISTRIBUTION
FIGURE 142
Run No. 283A
rin-g;
.. *
t±
10
= *
: s
o
s-
rr
-Hit
U4
n
OJ
o>
•M
E
re
o
m
o
•r—
•M
S.
I
.9-
. 8_
.7-
B
HI'
TTi~t"
TRT
itit
-U+4-
Tn
t
r*rr
It
iln
IT
i I I
r4^"
n
TTI
Total in Particles of Diameter
-------
»»ni in u i. *, •
99.99
KEUFF-CL » ES1ER CO.
95 90 80
0.2 0.1 0.05 0.01
(A
C
o
J-
U) O
t£> ^-»
U
0)
-I-)
01
!_
C_
MASS DISTRIBUTION
FIGURE 143
Run No. 283B
Total in Particles of Diameter
-------
CHASSIS DYNAMOMETER TEST
CAR NUMBER: D-0436
VEHICLE TYPE: 1972 Chevrolet
FUEL: Baseline + Fuel Additive A
CONVERTER: Beaded
TABLE 30
Grams per 1.61 km (1 mile)
Vehicle Follow-up Glass Filter Millipore
Test Car Test Andersen glass Andersen + 142 mm 142 mm
No. Miles Miles Test Mode Sampler Filter Filter (Avq. of two)
268A
26BB
268C
§ 268D
280C
280D
2,911.8
9,063.0
t
280£
28CF
11.5
120
7.5
7.5
11.5
7.5
7.5
120
MFCCS
. SS 60 MPK
FCKS
FCHS
KFCCS
FCHS
FCHS
2 I!RS SS
.0860
.0049
—
--
.0547
--
--
.0506
.0095
.0158
—
--
.0383
--
--
.1033
.0956
.0208
—
--
.0930
--
—
.1539
.0119
.0237
.0256
.0146
.0191
.0317
.0317
.1196
.0191
.0189
.0440
.0220
.0047
.0293
.0440
.1171
-------
TABLE 30 (Cont'd)
EXHAUST GAS ANALYSIS
Vehicle
Test
No.
268A
268B
268C
268D
280C
280D
280E
280F
co2
9.7
9.5
13.0
14.85
9.1
9.15
9.1
9.1
9.1
9.1
12.0
11.8
X by V
°2
7.3
7:3
2.55
0.3
8.1
7.9
7.8
8.0
8.0
8.0
3.8
4.1
olume
H2
82.2
82.4
83.65
84.2
81.95
82.0
82.1
82.0
32.0
82.0
83.3
83.2
Parts Per Million
CO
>250
210
193.6
>250
95.6
82.2
>250
>250
>250
>250
96.8
84 7
c6 ii. c.
35
25
2
2
15
12
50
140
30
55
2
2
N02
NO
178
328
990
1075
181
189
173
305
192
179
550
620
"V Nx
253
406
143
147
258
279
244
352
282
274
731
747
Part *1
Part ?2
Start
Finish (Over ten
1380 Sec.
505 Sec.
Start
Finish
-------
TABLE 30 (Cont'd)
ANALYSIS OF EXHAUST PARTICIPATE
Vehicle
Test
No.
268 B
268 C
280 F
£ 280 G&E
Fe
.16
1.6
.02
1.3
Ni
<0.1
<0.1
'.01
<.05
Cu
.13
1.2
.02
.9
Trac
Al
<.l
.5
.02
.6
e Met
Ca
.8
L1.2
.14
9.3
als o
Mq
.2
2.2
.02
1.8
n Milltpore Fil
Mn Cr Sn
c.05
.07
:.005
.05
.2
.2
<.01
.2
<0 . 1
<0 . 1
<.01
<.05
ter (
Zn
<0.3
.7
<.03
.9
«)
Ti
<0.1
.1
<.01
.1
Rk
.5
<0.3
<.03
.3
%so1
Glass Fiber Filters
XC
0.48
1.32 '
1.25
5.68
4.36
1.93
2.99
3.60
XN
14.43
1 4.93
1.24
0.0
P
B
i
7!
2
5(
-------
X 2 LOO CYCLES .'.oriii u.i"«. .
* ES*CR CO.
c:
o
S-
o
NO
U)
O)
+->
O)
E
Q
eu
o
MASS DISTRIBUTION
FIGURE 144
Run No. 268A
Hffiffir
iTi'TTTT
% Total in Particles of Diameter
-------
99.99
99 98 95 90
80 70 60 50 40 30 20
10
2 1 O.S 0.2 0.1 0.05 0.01
to
c
o
i.
u
•M
01
E
rt3
•r-
Q
0)
0
k
-1
a
MASS DISTRIBUTION
FIGURE 145
Run No. 268B
Total in Particles of Diameter
-------
0.01
X 2 LOG CYCLES .»( i. „.,.,. .
KCUFFEL » ESSC* CO.
MASS DISTRIBUTION
FIGURE 146
Run No. 280C
% Total in Particles of Diameter
-------
99.99
KCUPPEL » KS*tft CO.
95 90 80
O
i.
u
0)
E
n
•r-
Q
0>
u
• -
+J
,-r
Ct
1 0.5 0.2 0.1 0.05
MASS DISTRIBUTION
FIGURE 147
Run No. 280F
% Total in Particles of Diameter
-------
CHASSIS DYNAMOMETER TEST
CAR NUMBER: D-1585
VEHICLE TYPE: 1973 Chevrolet
FUEL: Baseline + Fuel Additive B
CONVERTER: Beaded
TABLE 31
Grams per 1.61 km (1 mile)
Vehicle Follow-up Glass Filter Millipore
Test Car Test Andersen glass Andersen + 142 mm 142 mm
No. Miles Miles Test Mode Sampler Filter Filter (Avg. of two)
275C
275D
275E
275F
296A
296B
296C
296D
2,529.0
9,120
11.5
120.0
7.5
7.5
11.5
7.5
7.5
120
MFCCS
60 MPK SS
FCHS
FCI:S
MFCCS
FCHS
FCHS
60 MPH SS
.1004
.0054
--
--
.0573
.0065
.0191
.0373
--
—
.0191
.0714
i
.1195
.0428
--
--
.0765
.0779
.0239
.0669
.0244
.0219
.0358
.0537
.0415
.1004
.0286
.0580
.0439
.0439
.0526
.0440
.0440
.0935
-------
TABLE 31 (Cont'd)
EXHAUST GAS ANALYSIS
Vehicle
Test
No.
275C
275D
275E
£ 275F
00
296A
296B
296C
296D
co2
9.55
9.30
11.20
11.35
9.8
9.65
9.2
10.0
10.65
10.75
10.95
11.10
% by V
°2
7.15
7. -50
4.9
4.85
6.90
7.25
7.75
6.55
5.80
5.70
5.45
5.15
ol ume
N2
82.4
82.3
83.05
82.95
82.3
82.15
82.15
82.5
82.6
82.75
82.75
82.85
Parts Per Million
CO
>250
>250
16.9
14.5
125.8
145.2
620
750
570
570
130.7
164.6
Cg H.C.
20.0
15.0
2.0
1.0
12.0
14.0
63
78
81
82
5
5
N02
NO
199
282
665
516
175
183
174
256
176
187
588
668
N0x- Nx
258
332
805
€26
253
243
210
286
225
240
660
773
23 Mm.
41 fir..
Start
Finish
Part 1
Part 2
Start
Finish
-------
D1585 Copper Chev.
TABLE 31 (Cont'd)
ANALYSIS OF EXHAUST PARTICIPATE
Trace Metals on MilHpore Filter («)
Glass Fiber Filters
Vehicle
Test
No.
275 C
275 D
275 E
275 F
NJ
1C
296A
296C
296D
Fe
Not
.07
.9
0.6
1.0
0.2
H1
Anal}
<.05
<.05
.06
<.01
Cu
zed
.04
.6
.34
.53
.01
Al
<.05
.3
.17
.29
.01
Ca
.2
8:7
3.8
8.6
.02
Mq
.09
1.6
1.2
1.5
.03
Mn
<.03
<.03
2.8
4.0
.08
Cr
<.05
.2
.13
.21
Sn
<.05
<.05
<.01
<.01
Zn
<.15
.5
.2
.4
<.03
Ti
<.05
.06
.02
.0
P-b.
<.15
<.15
.4
.7
.08
%SO,.
xc
1.78
6.60
12.8
41.9
0.275
3.79
3.20
0.60
>10.0
0.035
XN
' 5.12
0.0
0.0
1
12.4
2.65
PPM
BAP
60
480
<10
<70
< 2
-------
99.99
s
99.9 99.8
•^H-H-
99 98 95 90
"["i I il I
80 70 60 50 40 30 20
10
MASS DISTRIBUTION
FIGURE 148
Run No. 275C
2 1 O.S 0.2 0.1 0.05 0,01
10
:: •
- - . - I, —i- i -f •-; ' I ^
:: L
-i—r
to
c
o
s-
u
•r-
-4*
|T
tttt
I I
•M
OJ
E
Hi
£ • «--
Q
V
u
'—I—•-
a
•«-» .5,.
f«
Ou
434
t±t
ffl
._
::
FI:
i;
TT
III
% Total in Particles of Diameter
-------
K_,
46 8043
MAPt IH g.f.A.
KtUFFEL ft ESICft CO.
PROBABILITY
X 2 LOG CYCLES
99.99
0.01
to
c
o
s-
u
•o
en
S-
01
4-J
CD
E
-M
i-
MASS DISTRIBUTION
FIGURE 149
Run NO. 275D
% Total in Particles of Diameter
-------
99.99
2 1 0.5 0.2 0.1 0.05 0,01
99 98 95 90
80 70 60 50 40 30 20
MASS DISTRIBUTION
FIGURE 150
Run No. 296A
% Total in Particles of Diameter
-------
46 SO43
urn IN u.l. >.
KEUFFEL • HICK CO.
PROBABILITY
X 2 LOG CYCLES
99.99
99.9 99.8
99 98
95 90
80 70 60 50 40 30 20
10
1 0.5 0.2 0.1 0.05 0.01
5
MASS DISTRIBUTION
FIGURE 151
Run No. 296D
ni
3*3=
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REFERENCES
1. Mathematical Modeling of Catalytic Converter System,
J. C. Kuo, H. G. Lassen, C. R. Morgan, SAE Report
710289.
2. HC/CO Oxidation Catalysts for Vehicle Exhaust Emission
Control, K. I. Jagel, F. G. Dwyer, SAE Report 710290.
3. NO Reduction Catalysts for Vehicle Emission Control,
G. H. Meguerian, C. R. Lang, SAE Report 710291.
4. Catalytic Converter Vehicle Syst.em Performance: Rapid
Versus Customer Mileage, E. E. Hancock, R. M. Campau,
and R. Connolly, SAE Report 710293.
5. Thermal Reactor—Design, Development and Performance,
A. Jaimee, A. I. Roxmanith, D. E. Schneider, and J. W.
Sjoberg, SAE Report 710293.
6. Low Emission Concept Vehicles, R. M. Campau, SAE
Report 710294.
7. Effect of Fuel and Lubricant Composition on Exhaust
Emissions, A. I. Rozmanith, L. W. Mixon, and W. T.
Wotring, SAE Report 710295.
8. Small Engine—Concept Emission Vehicles, Y. Kaneko,
H. Kuroda, K. Tanaka, &AE Report 710296.
9. Fuel Lead and Sulfur Effects on Aging of Exhaust
Emission Control Catalysts, S. S. Hetrick and F. J.
Hills, SAE Report 730596.
10. Effects of Fuel Factors on Emissions/ S. S. Sorem,
SAE Report 710364.
11. Effects of Tetraethyl Lead on Catalyst Life and
Efficiency in Customer Type Vehicle Operation, E. E.
Weaver, SAE Report 690016.
12. Analytical Evaluation of a Catalytic Converter System,
John L. Warned, SAE Report 720520.
13. Low NO Emissions from Automotive Engine Combustion,
James G. Hansel, SAE Report 720509.
14. Field Test of an Exhaust Gas Recirculation System
for the Control of Automotive Oxides of Nitrogen,
J. C. Chipman, J. Y. Chao, R. M. Ingels, R. G. Jewell,
and W. F. Deeter, SAE Report 720511.
254
-------
15. A Comparison of Dynamic Exhaust Emissions Tests:
Chassis Dynamometer vs. Engine Dynamometer, J. F.
Cassidy, Jr., SAE Report 720455.
16. Application of Catalysts to Automotive NO Emissions
Control, L. S. Bernstein, K. K. Kearby, A? K. S. Ram
J. Vardi, and E. E. Wigg, SAE Report 710014.
17. A Well-Mixed Thermal" Reactor System for Automotive
Emission Control, Robert J. Lang, SAE Report 710608.
18. Buick's 1972 Exhaust Gas Recirculation System, A. L.
Thompson, SAE Report 720519.
19. An Analytical Framework for the Study of Exhaust Manifold
Reactor Oxidation, Richard C. Schwing, SAE Report 700109.
20. Studies of Catalyst Degradation in Automotive Emission
Control Systems, Joseph E. Hunter, SAE Report 720122.
21. Effect of Fuel and Oil Additive on Catalytic Converters,
J. C. Gagliardi, Carol S. Smith and E. E. Weaver,
Paper No. 63-72, Ford Motor Company.
22. Evaluation of CO/Hydrocarbon Oxidation Catalysts for
Automotive Emission Control Systems, David Liederman,
Sterling E. Voltz, and Stephen M. Oleck, Mobil Research
and Development Corporation.
23. Predicting NO Emissions and Effects of Exhaust Gas
Recirculation in Spark-Ignition Engines, Kunihiko
Komiyama and John B. Heywood, SAE Report 730475.
24. Poisoning of Monolithic Nobel Metal Oxidation Catalysts
in Automobile Exhaust Environment, M. Shelef, R. A.
Dalla Betta, J. A. Larson, K. Otto, and II. C. Yao,
Ford Motor Company.
25. The Control of Automotive Emissions with Dual Bed
Catalyst Systems, L. S. Bernstein, A. K. S. Raman
and E. E. Wigg, Esso Research and Engineering Company.
26. Automotive Particulate Emissions, J. S. Ninomiya, W.
Bergman and B. H. Simpson, Ford Motor Company.
27. Characterization and Control of Gaseous and Particulate
Exhaust Emissions from Vehicles, K. Habibi, E. S.
Jacobs, W. G. Kunz, Jr., and D. L. Pastell, D. I.
DuPont de Nemours & Co., Inc.
255
-------
28. Status Report on HC/CO Oxidation Catalysts for Exhaust
Emission Control, P. W. Snyder, W. A. Stover, and
H. G. Lassen, SAE Report 720479.
29. NO Reduction Catalysts for Vehicle Emission Control,
G. H. Meguerian, E. H. Ilirschberg, F. W. Rakowsky,
C. R. Lang, and D. N. Schock, SAE Report 720480.
30. Methods for Fast Catalytic System Warm-Up During Vehicle
Cold Starts, W. E. Bernhardt and E. Hoffmann, SAE
Report 720481.
31. Engine Testing of Catalysts—Conversion Versus Inlet
Conditions, P. Oser, D. H. Pundt and W. Buttergeit,
SAE Report 720482.
32. Mitsubishi Status Report on Low Emission Concept
Vehicles, Y. Kaneko and Y. Kiyota, SAE Report 720483.
33. Economical Matching of the Thermal Reactor to Small
Engine—Low Emission Concept Vehicles, H. Kuroda,
Y. Nakajima, Y. Kayashi and K. Sugihara, SAE Report
720484.
34. Fiat Status Report on Low Emission Concept Vehicles,
Carlo Pollone, SAE Report 720485.
35. Toyo Kogyo Status Report on Low Emission Concept
Vehicles, K. Tanaka, M. Akutagawa, K. Ito, Y. Higashi,
and K. Kobayashi, SAE Report 720486.
36. Toyota Status Report on Low Emission Concept Vehicles,
T. Inoue, K. Goto, and K. Matsumoto, SAE Report 720487.
37. Ford Durability Experience on Low Emission Concept
Vehicles, R. M. Campau, A. Stefan, and E. E. Hancock,
SAE Report 720488.
38. Reactor Studies for Exhaust Oxidation Rates, H. A. Lord,
E. A. Sondreal, R. H. Kadlec, and D. J. Patterson,
SAE Report 730203.
39. The Effect Lead, Sulfur, and Phosphorus on the
Deterioration of Two Oxidizing Bead-Type Catalysts,
R. A. Giacomazzi and M. F. Homfeld, SAE Report 730595.
40. Engine Dynamometers for the Testing of Catalytic
Converter Durability, J. P. Casassa and D. G.
Beyerlein, SAE Report 730558.
256
-------
41. Effects of Engine Oil Composition on the Activity of
Exhaust Emissions Oxidation Catalysts/ N. E. Gallopoulos,
J. C. Summers, and R. L. Klimisch, SAE Report 730598.
42. An Evaluation of the Performance and Emissions of a
CFR Engine Equipped with a Prechamber, D. B. Wimmer
and R. C. Lee, SAE Report 730474.
43. Fuel Effects on Oxidation Catalysts and Catalyst-
Equipped Vehicles, A. H. Neal, E. E. Wigg and E. L.
Holt, SAE Report 730593.
44. Durability of Monolithic Auto Exhaust Oxidation Catalysts
in the Absence of Poisons, K. Aykan, W. A. Mannion,
J. J. Mooney and R. D. Hoyer, SAE Report 730592.
45. Comparison of Catalyst Substrates for Catalytic
Converter Systems, J. L. Harned and D. L. Montgomery,
SAE Report 730561.
46. An Engine Dynamometer System for the Measurement of
Converter Performance, D. M. Herod, M. V. Nelson and
W. M. Wang, SAE Report 730557.
47. Thermal Response and Emission Breakthrough of Platinum
Monolithic Catalytic Converters, C. R. Morgan, D. W.
Carlson, and S. E. Voltz, SAE Report 730569.
48. Catalytic NO Reduction Studies, H. R. Jackson, D. P.
McArthur, ana H. D. Simpson, SAE Report 730568.
49. Nickel-Copper Alloy NO Reduction Catalysts for Dual
Catalyst Systems, L. S. Bernstein, R. J. Lang, R. S.
Lunt, G. S. Musser and R. J. Fedor, S7*E Report 730567.
50. Closed-Loop Exhaust Emission Control System with
Electronic Fuel Injection, R. Zechnall, G. Baumann
and H. Eisele, SAE Report 730566.
51. Cycle Simulation, E. H. Comfort, J. S. Howitt, and'J. W.
MacBeth, SAE Report 730559.
52. A Servo Vehicle Driver for EPA Emission Tests, A.
Levijoki, J. Ayres, R. Yu and M. Hammel, SAE Report
730532.
53. Variables for Emission Test Data analysis, W. H. Holl,
SAE Report 730533.
54. Assurance and Control of Vehicle Testing, M. L. Moore,
SAE Report 730534.
257
-------
55. Brake and Clutch Emissions Generated During Vehicle
Operation, M. G. Jacko, R. T. DuCharme and J. H. Somers,
SAE Report 730548.
56. Contribution of the Vehicle Population to Atmospheric
Pollution, C. E. Fegraus, C. J. Domke and J. Marzen,
SAE Report 730530.
57. A Laboratory for 1975-1976 Vehicle Emission Testing,
Arthur Brown and Norman Br«inard, SAE Report 730531.
58. Gasoline Lead Additive and Cost Effects of Potential
1975-1976 Emission Control Systems, M. G. Hinton, Jr.,
T. lura, J. Meltzer, and J. H.~~So"mers, SAE Report
730014.
59. Warmup Limitations on Thermal Reactor Oxidation,
D. J. Patterson, R. H. Kadlec and E. A. Sondreal,
SAE Report 730201.
60. Study of the Deactivation of Base Metal Oxide Oxidation
Catalyst for Vehicle Emission Control, E. C. Su and
E. E. Weaver, SAE Report 730594.
61. Catalyst Evaluation Procedures, Ford Motor Company.
62. Development of an Automotive Particulate Sampling
Device Compatible with the CVS System, G. S. Musser
and L. S. Bernstein, Eoso Research and Engineering
Company.
63. Application of Catalytic Converters for Exhaust
Emission Control of Gaseous and Liquid Fueled Engines,
K. I. Jagel, Jr., G. J. Lehmann, Engelhard Minerals and
Chemicals Corporation.
64. Sulfuric Acid Aerosol Emissions from Catalyst-Equipped
Engines, W. R. Pierson, R. H. Hammerle, and J. T.
Rummer, SAE Report 740287.
65. Measurement of Vehicle Particulate Emissions, M.
Beltzer, R. J. Campion, and W. L. Peterson, SAE Report
740286.
66. A Technique for Endurance Testing of Oxidation Catalytic
Reactors, R. A. Haslett, SAE Report 740246.
67. Factors Affecting Dual Catalyst System Performance,
R. J. Lan, W. R. Leppard, and L. S. Bernstein, SAE
Report 740252.
258
-------
68. Catalytic Converter Testing with Portable Engine
Dynamometers, B. D. Lockhart and S. L. Genslak, SAE
Report 740245.
69. Experimental and Theoretical Investigation of Turbulent
Burning Model for Internal Combustion Engines, N. C.
Blizard and J. C. Keck, SAE Report 740191.
70. Lube Effects on Exhaust Gas Oxidation Catalyst
Activity, R. A. Bouffard and W. E. Waddey, SAE Report
740135.
71. The Influence of Vehicle Parameters on Catalyst Space
Velocity and Size Requirements, J. G. Hansel, K. Aykan
and J. G. Conn, SAE Report 740274.
72. Flow Effects in Monolithic Honeycomb Automotive
Catalytic Converters, J. S. Howitt and T. C. Sekella,
SAE Report 740244.
73. Flow Through Catalytic Converters—An Analytical and
Experimental Treatment, C. D. Lemme and W. R. Givens,
SAE Report 740243.
74. Measurement of Vehicle Particulate Emissions, Morton
Beltzer, R. J. Compton, W. L. Peterson, SAE Report 740286
75. Sulfuric Acid Aerosol Emissions from Catalyst-Equipped
Engines, W. R. Pierson, R. H. Hammerle, J. T. Kummer,
SAE Report 740287.
259
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Appendix B3.18
Status of Mobile Source
Quality Assurance Programs
The various quality assurance and standard methods development programs
related to emission products from motor vehicles including sulfuric acid
and noble metals is now being implemented. This is a phased program through
the next two Fiscal Years. Highlights of current.status are as follows:
1. A contract was awarded to Midwest Research Institute in
June, '74 to carry out an in-depth single laboratory
evaluation of two ambient sulfate measurement methods.
2. On June 4, 1974, a contract was awarded to Olson Laboratories,
Inc. to develop:
a. Guidelines for quality assurance programs for measurement
systems for light duty gasoline vehicles (cars and trucks),
and
b. Guidelines for quality assurance programs for measurement
systems for heavy duty diesel engines.
The concerned pollutants in (a) are: hydrocarbons, carbon
monoxide and nitrogen oxides.
The concerned pollutants in (b) are all of those in (a)
plus smoke.
The work plan submitted by the contractor was approved on July 15,
1974. The schedule completion date for this work is June 1, 1975.
The contract may be extended to cover heavy duty gasoline engines
and light duty diesel engines and other pollutants.
3. On May 1, 1974 a cbntract was awarded to Research Triangle
Institute to develop Guidelines for Development of Quality Assurance
Programs for Measurement Systems for:
a. Laboratory method for determination of lead in gasoline,
b. Field method for determination of lead in gasoline, and
c. Laboratory method for determination of phosphorous in gasoline.
260
-------
The scheduled completion date for this work is February 1, 1975.
A tentative quality assurance plan for enforcement monitoring of the
unleaded regulation was developed in-house in conjunction with
OEGC. This plan includes the use of standard reference materials
as calibration checks and quality control reference samples for
further documenting the validity of data.
4. Both in-house and contract programs are underway to develop
analytical methods for platinum in tissues and large ambient
participate samples.
5. Standard reference materials are being developed for mobile source
sulfuric acid and noble metals. This is an in-house program iniated
in Third Quarter CY 74.
261
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NO
EPA-600/3-75-010 f
3.
1. REC.IPII-NTT- ACCESSION NO.
I TITIE AND SUBTITLE
ANNUAL CATALYST RESEARCH PROGRAM REPORT
Appendices, Volume V
G. PERFORMING ORGANIZATION CODE
7 AUTHORIS)
Criteria and Special Studies Office
0. PERFORMING ORGANIZATION REPORT NO.
9 PERFORMING OR"ANIZATION NAME AND ADDRESS
Health Effects Research Laboratory
Office of Research & Development
U.S. Environmental Protection Agency
Research Triangle Park, N.C. 27711
I?. SPONSORING AOENCY NAME ANO ADDRESS
Same as above
DATE
September 1975
10 riU'GMAM ELEMENT NO.
1AA002
1 I. CONTRACT/GRANT NO.
13 7 YPE OF REPORT AND PEUIOO COVERLO
Annual Program Status 1/74-9/7
l4~SPONSOmNG AGENCY CODE »
EPA-ORD
Ib. SUPPLE MEN fARY NOTES
This is the Summary Report of a set (9 volumes plus Summary).
See EPA-600/3-75-010a thru OlOe & OlOg thru OlOj. Report to Congress,
16. AOSTRACT
This report constitutes the first Annual Report of the ORU Catalyst Research
Program required by the Administrator as noted in his testimony before the
Senate Public Works Committee on November 6, 1973. It includes all research
aspects of this broad multi-disciplinary program including: emissions charac-
terization, measurement method development, monitoring, fuels analysis,
toxicology, biology, epidemiology, human studies, and unregulated emissions
control options. Principal focus is upon catalyst-generated sulfuric acid
and noble metal particulate emissions.
I 7
KEY WORDS AND DOCUMENT ANALYSTS
DEScnii'Tons
Catalytic converters
Sulfuric' acid
Uesul furization
Catalysts
Sul fates
Sulfur
Health
STA1 LMENf
Available to public
li lOENTIFIEHS/OftN ENDE.U TEMMS
Automotive emissions
Unregulated automotive
emissions
Health effects (public)
19 StCUHITY CLASS film Htpo'l)
26 SECumrY cLAssTr'i'J />«ir7
Unclassified
L. COSATI I ILlll/( .liillji
21. NO OF PAGES
263
22 PRICE
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