EFFECTS OF FUEL ADDITIVES
ON AIR POLLUTANT EMISSIONS
FROM
DISTILLATE-OIL-FIRED FURNACES
U. S. ENVIRONMENTAL PROTECTION AGENCY
-------
EFFECTS OF FUEL ADDITIVES
ON AIR POLLUTANT EMISSIONS
FROM DISTILLATE-OIL-FIRED
FURNACES
by
G. B. Martin
D. W. Pershing
and
E. E. Berkau
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Air Programs
Research Triangle Park, North Carolina
June 1971
For sals by the Superintendent o( Documents, U.S. Government Printing Office, Washington, D.C. 20402 - Price 50 cents
Slock Number 5503-0021
-------
The AP series of reports is issued by the Office of Air Programs, Environmental
Protection Agency, to report the results of scientific and engineering studies,
and information of general interest in the field of air pollution. Information
reported in this series includes coverage of Air Program intramural activities
and of cooperative studies conducted in conjunction with state and local
agencies, research institutes, and industrial organizations. Copies of AP reports
are available free of charge - as supplies permit - from the Office of Technical
Information and Publications, Office of Air Programs, Environmental Protec-
tion Agency, Research Triangle Park, North Carolina 27711.
Office of Air Programs Publication No. AP-87
-------
CONTENTS
Page
ABSTRACT v
INTRODUCTION 1
HISTORY 1
PURPOSE 1
SUMMARY 3
EXPERIMENTAL APPROACH 5
ADDITIVES 5
TEST PLAN 5
TEST FACILITY 7
FURNACE DESIGN 7
TEST CYCLE 10
STANDARD FUEL 10
ANALYTICAL PROCEDURES 10
TEST PROCEDURE 11
ADDITIVE CONCENTRATION 11
AIR-TO-FUEL RATIO 12
ADDITIVE TESTING 12
Test Series 12
Additive Tests 12
Background Checks 12
RESULTS 13
COMPLETE TABULATION 13
CONFIDENCE LIMITS 13
CARBON DIOXIDE AND OXYGEN 13
CARBON MONOXIDE AND HYDROCARBONS 13
OXIDES OF SULFUR 14
OXIDES OF NITROGEN 15
PARTICULATE MATTER 15
DISCUSSION OF RESULTS 17
METALLIC ADDITIVES 17
NON-METALLIC ADDITIVES 21
BURNER MODIFICATIONS 21
CONCLUSIONS 23
RECOMMENDATIONS 25
APPENDIX A. ADDITIVE LISTING 27
APPENDIX B. LIST OF ADDITIVE MANUFACTURERS 45
APPENDIX C. ANALYTICAL PROCEDURES 51
APPENDIX D. EXPERIMENTAL RESULTS 59
BIBLIOGRAPHY 85
ill
-------
ABSTRACT
The Office of Air Programs of the U.S. Environmental Protection Agency
has recently completed a study of the use of fuel additives to control air
pollution from distillate oil burning systems. The available literature was
surveyed, and samples of all known additives procured. Each additive was
analyzed for elemental composition to provide a basis for testing. A standard
screening procedure was established to test the effect of each additive on emis-
sions from fuel oil combustion. Screening tests were carried out on all distillate
soluble additives. The most promising additives were then subjected to a
rigorous examination. This report is a comprehensive summary of the entire
program.
The results show that fuel additives are not a promising way of reducing
air pollution from distillate oil combustion. A majority of the additives tested
had no beneficial effects on air pollutant emissions; in fact, some additives even
increased total particulate and NOX emissions. Several of the metal-containing
additives, e.g., Ferrocene, CI-2, and Fuelco S03, reduced total particulate emis-
sions; however, the unknown toxicity of new emissions they create makes their
use questionable. Further, there is evidence that for distillate oils, burner modi-
fications are a more suitable route to air pollution control.
-------
EFFECTS OF FUEL ADDITIVES ON AIR
POLLUTANT EMISSIONS FROM
DISTILLATE-OIL-FIRED FURNACES
INTRODUCTION
HISTORY
This investigation of the relationship of fuel additive technology to air
pollution control was begun with a literature survey and contacts with individ-
uals knowledgeable in the use of additives for specific situations. Additives for
all fuels except coal and gasoline were considered. The published literature
revealed little information on the effects of fuel additives in reducing, increas-
ing, or creating emissions of air pollutants. Contacts with the oil industry
revealed that proprietary work had been done in certain areas (primarily with
combustion improvers), but the information was not generally available. Publi-
cations collected after the initial literature survey only provided more informa-
tion on manufacturers' claims of additive effects. In this work all available
distillate soluble additives were examined. Many fuel additives are designed for
functions not related to combustion (for example, as dispersants) and, there-
fore, have little direct effect on reduction of air pollution. These compounds
may, however, add new types of air pollutants, such as metals, to the environ-
ment and were, therefore, included in the testing program.
This document is a final report on the investigation by the Air Pollution
Control Office of the U.S. Environmental Protection Agency into the use of
fuel additives as a means of reducing air pollutant emissions from the combus-
tion of distillate fuel oil. Mention of company and product names herein does
not constitute endorsement by the U.S. Environmental Protection Agency.
PURPOSE
This study was the first phase of a program to explore the possibility of
using additives to reduce the air pollution from fuel oil combustion. In this
phase additives for distillate oil were examined.
Questions to be answered by this study included the following: What are
the effects of additives on emissions of air pollutants from combustion proc-
esses? What additive concentrations are the most effective in reducing the
amount of emissions? Are those additives that are effective also practical in
terms of cost, toxicity, corrosion, and fuel and additive stability?
-------
SUMMARY
The results of this study show that in distillate oil most fuel additives
have no beneficial effects on the air pollution problem. Fewer than 10 percent
of the additives tested produced any pollutant reduction, whereas more than
20 percent increased emissions of at least one pollutant. In a few cases proprie-
tary metallic additives substantially reduced particulate emissions, but in no
case did an additive reduce the emissions of carbon monoxide, unburned
hydrocarbons, sulfur oxides, or nitrogen oxides.
From a cost/effectiveness viewpoint Ferrocene (Arapahoe Chemicals) and
CI-2 (Ethyl Corp.) have the greatest impact on total particulate emissions. CI-2
added to the distillate oil for a residential heating unit at a cost of about $2.00
per year could reduce particulate emissions 40 percent. Unfortunately,
however, both Ferrocene and CI-2 contain large amounts of metals; Ferrocene
is 20 percent iron, and CI-2 is 20 percent manganese. This causes a high
concentration of metal compounds in the flue gas, and the possible toxicity of
these new emissions makes the use of additives very questionable. Further,
properly designed flame retention devices can be easily added to standard oil
burners to produce greater reductions in particulate emissions than any
additive tested. Since such flame retention devices provide greater reductions
of particulate emissions, present no toxicity problems, and are currently
available at a cost of only about $25.00, it is recommended that none of the
fuel additives tested be used as a means of controlling air pollutant emissions
from distillate oil burning.
-------
EXPERIMENTAL APPROACH
ADDITIVES
With the cooperation of many manufacturers, samples of some 206
additives were collected for testing. Appendix A contains a listing of these
additives, along with company name for each, suggested fuel dose
(concentration), function and general composition. Names and addresses of
manufacturers are given in Appendix B. The additives collected were intended
for use in a variety of fuels. The major fuel types represented are distillate oil
(No. 1 and No. 2), heavy distillate (No. 4 and No. 5), residual oil (No. 6 and
Bunker C), and coal. Distillate oils also include kerosene and diesel fuel. In this
work all additives that were soluble in distillate oil were tested even though
many of them were not recommended for use in distillate oil. This policy was
formulated to ensure completeness of the testing program and will be main-
tained in the upcoming testing of the use of additives in a residual oil burner.
Most commercial additives are designated as performing certain functions
in the fuel. These functions are listed alphabetically (with synonyms) below:
1. Chelating agent (metal deactivator).
2. Combustion improver (combustion catalyst).
3. Corrosion inhibitor (rust inhibitor, acid neutralizer, oxidation in-
hibitor, antioxidant).
4. Demulsifying agent (antihaze).
5. Dispersant (emulsifier, surface active agent, detergent).
6. Gum inhibitor (antifouling agent).
7. Odor maskants.
8. Pour point depressant (cold flow improver).
9. Stabilizer (color stabilizer).
Additives intended to fulfill several of these functions are usually advertised as
multipurpose additives.
TEST PLAN
The experimental phase of the evaluation included characterizing the
chemical composition of the additive compounds and measuring their effects
on emissions of air pollutants. While these additive samples and related litera-
ture were being collected and analyzed, the oil-fired test systems was con-
structed, instrumented, and operated with a standard No. 2 fuel oil to establish
baseline operating performance over a range of air-fuel ratios.1 '2 Flue gas from
the test system was analyzed for particulate matter, smoke, carbon monoxide,
carbon dioxide, oxygen, total gaseous hydrocarbons, oxides of nitrogen, and
-------
oxides of sulfur. An operating air-fuel ratio that produced a moderate amount
of particulate matter (0.14 to 0.20 gram per kilogram of fuel) in the flue gas
was chosen for screening the additives. Additives effects were evaluated by
comparing emissions with additives with baseline performance data.
The additives tested were commercially available, proprietary formula-
tions. Since knowledge of the elemental composition of the proprietary
additives was required, each product was analyzed for elemental constituents
by an independent laboratory. Based on analysis the additives were then sub-
categorized either as metallic or non-metallic and a uniform dose rate estab-
lished. In cases wherein the measured composition varied from the manufac-
turers claims, the measured values were used. Additives that showed promise in
this screening study were evaluated more thoroughly at a variety of concentra-
tions.
EVALUATION OF FUEL OIL ADDITIVES
-------
TEST FACILITY
FURNACE DESIGN
The experimental furnace is illustrated in Figure 1. Schematics of the test
facility are shown in Figures 2 and 3. The combustion chamber design provides
a residence time of 0.60 second at 20 percent excess air. (Typical residence
times are 0.36 second at 20 percent excess air for a residential furnace burning
No. 2 oil and 1.5 to 2.0 seconds for larger boilers.) The experimental furnace
has a standard high-pressure atomizing gunburner that feeds fuel at a rate of
1.0 gallon per hour through an 80-degree hollow cone nozzle. The air-cooled,
EXHAUST
SAMPLING AREA
COOLING AIR
WING WALL
I V-
AIR CHOKED
NOZZLE
HEAT EXCHANGER
COMBUSTION
CHAMBER
27 in.
FUEL OIL
Figure 1. Experimental furnace interior detail.
-------
oo
W
>
r
>
H
H- I
O
TI
d
w
r
o
K-I
r
>
a
a
w
C/3
FLUE GAS
COMBUSTION
AIR IN
COOLING
AIR IN
WARM
A'IR OUT f 6_
FLAME
THERMOCOUPLE
ENTRY
POINTS
FILTER L~
TO ANALYTICAL
INSTRUMENTS
• COMBUSTION
y— AIR BLOWER
'ON'CYCLE
COMBUSTION AIR
BLOWER CONTROL
LAMINAR
FLOW-
ELEMENT
POWERSTATS
'OFF' CYCLE AIR
BLOWER CONTROL
COMBUSTION
AIR RATE
MANOMETER
WEIGH
MAIN
FUEL
SUPPLY
STAINLESS STEEL
FUEL SUPPLY
SYSTEM
Figure 2. Experimental furnace schematic.
-------
TO WET NOX(FIGURE C-2)
TO WET SOX (FIGURE A-3)
o
h"»«
TEFLON
LINE
HEATED'
MOLECULAR
o SEIVE
(3A -CLAY BASE)
STAINLESS
STEEL-
SILICA
GEL TRAP
PARA
MAGNETIC 02
ANALYZER
FIBER-GLASS
INDUSTRIAL
FILTER
WATER
TRAP
GLASS
WOOL
0 FILTER
FLAME-
IONIZATION
H/C
ILICAGEL STACIU
TRAP
FLUE
GAS
PARTICULATE
n FILTER:
FLOW
CONTROL
SEQUENTIAL
TAPE
SMOKE
SAMPLER
ANALYZER
Figure 3. Analytical system.
-------
steel heat exchanger is a shell-and-tube type with combustion gases on the tube
side. A baffled stack provides a homogeneous gas mixture for sampling. Com-
bustion air is measured with a laminar flow element and regulated by a blower
controlled by a powerstat to produce the designated excess air level. Fuel
weight is determined by mounting the fuel tank on a scale.
TEST CYCLE
The furnace was operated on an average of 10 minutes "on" followed by
20 minutes "off." This cycle was chosen to allow investigation of the effects of
startup and shutdown interactions on emissions. During the burner-off period,
an auxiliary powerstat regulated the blower to provide a reduced flow of air
into the furnace for heat removal and pollutant sampling. A programmed cam
timer regulated this cyclic operation. For reporting purposes, each "burner-on"
period was defined as a "run."
STANDARD FUEL
To provide uniform test fuel with a low background of metal contami-
nants, a large quantity of a No. 2 oil was obtained and stored under a pure
nitrogen blanket. This distillate oil was from a Gulf Coast crude stock, contain-
ing a mixture of straight distilled and cat-cracked products. API gravity was
36°; aromatic content, 25 percent; sulfur content, 0.1 percent; nitrogen
content, 0.01 percent; and mass ratio of carbon to hydrogen, 6.62:1 (molecu-
lar formula CH^ .8j).
ANALYTICAL PROCEDURES
Sampling and analytical procedures were identical to those used in earlier
studies by Martin and Wasser1 -2: paramagnetic oxygen analysis, flame ioniza-
tion detection for unburned hydrocarbons, nondispersive infrared for carbon
monoxide and dioxide, sequential smoke sampler, Combustion Engineering-
Shell method for sulfur oxides, phenol disulfonic acid method for oxides of
nitrogen, and collection of filterable and condensable particulate. A detailed
discussion of these procedures is provided in Appendix C. In a modified
method, a woven silver filter was used to collect filterable particulate matter
from selected runs to simplify chemical analysis of the particulate matter. Solid
particulate matter was analyzed for metals content and ultimate constituents
(C, H, N, S, and 0) to determine changes in composition caused by the
additive. Condensable particulate matter was collected on selected runs where
it was necessary to quantify a specific additive element.
10 EVALUATION OF FUEL OIL ADDITIVES
-------
TEST PROCEDURE
ADDITIVE CONCENTRATION
One factor that had to be established was the range of additive-to-fuel
ratios that would be effective in reducing air pollutants. Each manufacturer
specifies the concentration for his particular additive; however, for the pur-
poses of comparison it is often desirable to base the concentration on some
component of the additive, such as a certain metal or organic specie. The
approaches used in this study are outlined below.
In most cases where the additive contained a large amount of metal
(>0.1 wt %), two methods were used to determine the test concentration.
First, the additive was tested at the level specified by the manufacturer.
Second, it was tested at a concentration set on a standard basis involving the
metal content of the additive. The data of Riggs3 were used to select a metal
concentration of 0.5 millimole of metal per kilogram of fuel as an appropriate
starting point for evaluating effects on particulates. This level of metal in the
fuel also results in a reasonable level of metallic emissions, at least as compared
with the overall mass of the particulate. In this study, all metals present in the
additive were summed as the basis for arriving at 0.5 millimole metal per
kilogram of fuel. The differences in concentration that result from use of these
methods depend on the amount and type of metal in the additive. Normally
manufacturers' suggested concentrations range from 1:1000 to 1:8000 for a
metal content greater than 0.1 weight percent. The potential variation in con-
centration based on the moles of metal is 1:1000 to 1:25,000. If the "stan-
dard" concentration was different from the one recommended by the
manufacturer by more than a factor of 4, the additive was tested at both
concentrations.
Note that most of the additives that contain less than 0.1 weight percent
metal would require an additive concentration greater than 1 percent by weight
to produce the 0.5-millimole level. From a purely economic standpoint these
additives were grouped as non-metals.
The available literature did not indicate any method for choosing a stan-
dard concentration for non-metallic additives. One method considered involved
basing the additive concentration on the elemental composition, specifically
oxygen, nitrogen, sulfur, and halogen. This method was not selected because it
related only to potentially detrimental effects, e.g., increased pollutant emis-
sions due to conversion of additive constituents to NOX, SOX, or HC1, or
inhibition of combustion by halogens. The method chosen was to base the test
concentration on the manufacturer's recommendation.
11
-------
AIR-TO-FUEL RATIO
To eliminate the effect of excess air variation on pollutant emissions, all
tests were conducted at the same air-fuel ratio. The ratio was chosen to dupli-
cate operation of a furnace at a marginal condition from the standpoint of
particulate and smoke emissions (0.14 to 0.20 gram per kilogram of fuel). This
loading was chosen so that enough material would be provided for accurate
determination of additive-related changes in soot and for accurate chemical
analysis without creating a soot-fouling problem in the furnace. For the test
furnace the air-fuel ratio chosen was'approximately 1.2 times stoichiometric,
i.e., a ratio that would provide 20 percent excess air.
ADDITIVE TESTING
Test Series
A complete test consisted of 15 half-hour cycles or runs. Oxygen,
gaseous hydrocarbon, carbon monoxide, and carbon dioxide were determined
continuously; oxides of nitrogen and sulfur were determined on six cycles; and
particulate emissions, on selected cycles.
Additive Tests
For an additive test series, the furnace was brought to operating equilib-
rium by burning blank oil for six cycles. The next cycle was defined as a
"blank run," during which pollutant data were collected. The fuel supply was
switched to one containing the additive, and one purge cycle was used to clear
the fuel line and burner of blank oil. The additive test consisted of the next 10
cycles. Tests were completed with a purge cycle and two blank cycles.
The monitoring instruments recorded data continuously on all cycles.
Oxides of nitrogen and sulfur were determined on four additive cycles spaced
to cover the entire test period and on two blank cycles, one in the morning,
and the other in the afternoon. Particulate matter was collected on all cycles,
and the weight of filterable particulate was determined. The silver filters were
used on two blank cycles and three additive cycles. Fuel weights were taken,
and excess air was controlled for all blank and additive cycles.
Background Checks
To check the operation of the furnace, background runs were made
periodically with the standard fuel oil (blank) through all 15 cycles. Data were
compared with baseline data previously collected to detect any change in fur-
nace operation.
12 EVALUATION OF FUEL OIL ADDITIVES
-------
RESULTS
COMPLETE TABULATION
The numbers in the second column of Appendix A denote the additives
that were tested in distillate oil. Moreover, these numbers have been used to
index the complete tabulation of all results in Appendix D. For each additive,
this appendix shows the concentrations tested, the resulting effect on emis-
sions, and the chemical analysis of the additive. Each emission number
(columns 3-6) is the ratio of emissions with the additive in the fuel to emissions
without the additive (i.e., emissions from the pure fuel). A ratio less than 1.0
represents an improvement of performance attributable to the additive.
CONFIDENCE LIMITS
To ensure a completely fair evaluation program, several precautions were
taken. First, in an effort to preclude any day-to-day variations in furnace
operation, the performance of each additive was based on the data from stan-
dard fuel runs on that particular day. Further, all-day pure fuel tests were made
periodically throughout the entire program to check burner performance. A
detailed statistical analysis revealed that the following standard deviations were
inherent within the system: particulate ratios ±7 percent, SOX ratios ±3 per-
cent, and NOX ratios ±7 percent. Thus, there is 95 percent certainty that a
ratio less than 0.85 is significant.
CARBON DIOXIDE AND OXYGEN
The amount of carbon dioxide produced by burning a given weight of
fuel can be calculated from a stoichiometric equation based on the composi-
tion of the fuel. The amount of oxygen required can be determined in a similar
manner; and, therefore, the exit oxygen level can be calculated. Throughout
the entire work the measured concentrations of CO2 and 02 were extremely
close to the theoretically calculated ones. That is, no additive had any notice-
able effect on the efficiency of combustion.
CARBON MONOXIDE AND HYDROCARBONS
Carbon monoxide and unburned hydrocarbons are emitted in flue gas in
accordance with the concentration-time patterns shown in Figure 4. When the
burner first fires, an emission peak is caused by the relatively cold firebox.
13
-------
BURNER
ON
BURNER
OFF
o
o
o
o
TINIER
Figure 4. Startup and shutdown effects on
hydrocarbon and carbon monoxide
concentration patterns.
Emissions then decrease to an equilibrium level (zero in the case of the hydro-
carbons) during the firing cycle. After burner shutoff, a second peak is caused
by partial oxidation of heated fuel dripping through the nozzle to the hot
firebox. The nature of initial and final peak emissions appears to preclude any
reduction of these emissions as a result of using additives. The equilibrium
emission level in the CO curve was not reduced by any additive tested, nor
were the peak values for CO and hydrocarbons affected by any additive tested.
OXIDES OF SULFUR
The sulfur in the fuel is oxidized to produce sulfur dioxide and sulfur
trioxide. In emissions from the test furnace, the sulfur trioxide concentration
was less than 0.5 ppm and the sulfur dioxide averaged about 45 ppm, repre-
senting approximately 6 ppm less than the theoretical SO2 concentration cal-
culated from the sulfur in the fuel. None of the additives tested appeared to
produce an effect on either of the sulfur oxide emissions.
14
EVALUATION OF FUEL OIL ADDITIVES
-------
OXIDES OF NITROGEN
Emissions of oxides of nitrogen are attributable to two sources, isother-
mal fixation of atmospheric nitrogen at high temperatures and oxidation of
nitrogen in the fuel or the additive. No additive tested decreased nitrogen oxide
emissions; however, in a few cases NOX emissions were increased as a result of
oxidation of nitrogen contained in the additives.
PARTICULATE MATTER
Another product of incomplete combustion is particulate matter, pri-
marily carbon soot formed by thermal cracking of the fuel hydrocarbons. The
greatest additive effects were expected and realized with this pollutant.
Columns 3 and 4 in Appendix D show the effect each additive had on
particulate emissions. Total particulate refers to the total amount of solid
material collected from the flue gas. Carbon particulate is the amount of car-
bon in the total material collected. In the case of pure fuel, these numbers are
the same because chemical analyses revealed that essentially all of the particu-
late matter is carbon; however, with some additives, a noticeable amount of
metallic oxide was collected causing a difference in the two weights and
therefore in their respective emission ratios.
About 10 percent of the proprietary additives tested reduced total
particulate, whereas nearly 20 percent increased total particulate to some ex-
tent. The particulate collected was analyzed for metals content, and the results
were compared with the metals content of the additive. The apprent recovery
of metals from the additives ranged from 15 to 100 percent.
Results 15
-------
DISCUSSION OF RESULTS
METALLIC ADDITIVES
The chemical analyses of the additives (Appendix D) revealed that almost
half had a total metal content greater than 0.1 percent. Based on information
in the literature, probable forms are: organo-metallics, Metallic sulfonates, and
metal oxide slurries. These compounds represent a total of 14 different metals;
however, only additives containing at least one of the transition metals; iron,
manganese, or cobalt significally reduced particulate emissions. Table 1 shows
Table 1. DISTILLATE FUEL-OIL ADDITIVES THAT SUBSTANTIALLY
REDUCED TOTAL PARTICULATE EMISSIONS
Additive
Arapahoe Ferrocene
Ethyl CI-2
Commercial Chemical
Improsoot
Gamlen
DP 231
Fuel Combustion Corp.
Fuelco SOs
Commercial Chemical
Formula LSD
Industrial Chemicals
Watcon 130
Concentration
Weight
1:7150
1:9000
1:150
1:110
1:500
1:200
1:500
Molar2
0.50
0.36
0.50
0.50
0.10
0.40
0.05
Composition
20% Fe
18.0%Mn
0.3% Ca
0.1%Ca
0.2%Mn
0.1%Fe
0.25% Mn
0.9% Co
0.15%Fe
Total
particulate
ratio
0.53
0.56
0.57
0.61
0.64
0.68
0.69
flMillimoles per kilogram.
17
-------
the seven most outstanding additives in distillate oil. Once the field was nar-
rowed to these seven additives, concentration studies were conducted. Each of
the additives was tested over a wide range of concentrations to determine an
optimum concentration for particulate reduction. Figure 5 is a plot of particu-
late emissions versus concentration for CI-2 and is typical of all the results.
Total particulate emissions decreased with increasing additive concentration up
to a point. Beyond this point, the carbon particulate often continued to de-
crease, but total particulate emissions increased as a result of the increasing
concentration of additive metal. As Table 1 shows, the optimum weight con-
centration is highly dependent upon the specific additive; however, it is
interesting that each of the four most effective additives was most effective at a
total metal concentration of 0.5 millimole per kilogram. This suggests a com-
mon chemical mass action mechanism.
The cost of using each additive was another important consideration in asses-
sing the potential of fuel additives for reduction of pollutant emissions. Table 2
shows the smallest amount of each additive necessary to treat 10,000 gallons of
distillate fuel oil and achieve a 35 percent reduction of particulate emissions.
The cost figures are based on the best numbers available for additives in
500-pound lots f.o.b. the point of supply. This table points out very clearly
that a purely economic point of view would favor Ferrocene, CI-2, and Fuelco
SO3. Further, it shows that using fuel additives is not extremely expensive,
since it would take the average residental user between 10 and 20 years to burn
0.010 0.020
ADDITIVE, wt %
0.030
Figure 5. Particulate reduction versus
Cl 2 additive concentration.
18
EVALUATION OF FUEL OIL ADDITIVES
-------
Table 2. COST OF TREATING 10,000 GALLONS OF FUEL
OIL TO GIVE 35 PERCENT REDUCTION IN PARTICIPATE
EMISSIONS
Additive
Arapahoe Ferrocene
Ethyl CI-2
Commercial Chemical Improsoot
GamlenDP231
Fuel Combustion Corp. Fuelco S03
Commercial Chemical Formula LSD
Industrial Chemicals Watcon 1 30
Amount
needed, Ib
6
8
350
640
95
350
140
Approximate
cost,$
36
17
125
200
34
100
60
10,000 gallons of fuel oil, e.g., using CI-2 would cost less than $2.00 per year.
From a cost-effectiveness viewpoint Ferrocene and CI-2, are outstanding; how-
ever, if an additive is to be truly beneficial for control of air pollution, it must
not add pollutants to the atmosphere.
Fortunately, the chemical structure of neither Ferrocene nor CI-2 is
confidential.4'5 Ferrocene is dicyclopentadienyl iron, and CI-2 contains
methylcyclopentadienyl manganese tricarbonyl. Both compounds are sandwich
transition metal complexes.
A preliminary toxicological investigation revealed that cyclopentadienyl man-
ganese tricarbonyl is toxic at low concentrations and has marked cumulative
properties.6 Little specific information is available on dicyclopentadienyl iron;
however, animal feeding experiments have shown an almost complete absence
of toxicity.7 These facts make Ferrocene more desirable from the standpoint
of handling.
From an air pollution viewpoint the form of the metals emitted is im-
portant. An analysis of the particulate forms emitted revealed that in nearly all
cases metals in additives are emitted as metal oxides. Table 3 shows the
amounts of metal and metal oxide emissions that result from using nine differ-
ent additives. Unfortunately, use of either Ferrocene or CI-2 causes a high
metal concentration in the flue gas. Although the iron oxides from Ferrocene
do not appear to be highly toxic (7), they do catalyze certain undesirable S02
reactions. Data indicate that manganese emissions are hazardous in themselves8
and probably should be avoided.
Discussion of Results
19
-------
Table 3. METAL EMISSIONS RESULTING FROM USE OF VARIOUS ADDITIVES
Additive
Improsoot
Formula LSD
Ferrocene
Ethyl CI-2
Fuel CO S03
GamlenDP231
Wat con 130
Dose
1:150
1:200
1:7150
1:9000
1:750
1:111
1:500
Composition
0.3% Co
0.1% Ca
0.9% Co
20 %Fe
18.0%Mn
0.25% Mn
0.2% Mn
0.1%Fe
0.15%Fe
Metal emissions/7
Mg/m3
1,219 Co
406 Ca
2,744 Co
l,706Fe
l,219Mn
300 Mn
l.lOSMn
554 Fe
831 Fe
Metal emissions,0
mg/kg fuel
20.0 Co
6.7 Ca
45.0 Co
28.0 Fe
20.0 Mn
3.3 Mn
13.3 Mn
6.7 Fe
3.0 Fe
Metal oxideb
emissions,
mg/kg fuel
25.4CoO
8.4 CuO
57.0CoO
40.0Fe203
31.6Mn02
5.2Mn02
21.0Mn02
9.6 Fe2 Ob
4.3 Fe203
rfl
>
r
>
H
h-S
O
G
W
O
h— <
r
>
a
o
w
CX3
aThis column shows the amount of metal emitted, probably in the form of an oxide.
b A standard burner emits about 200 milligrams of carbon particulate per kilogram of fuel burned.
-------
NON-METALLIC ADDITIVES
Any additive with a total metal content less than 0.1 percent was con-
sidered a non-metal. These ashless organic compounds were probably of the
following types: amines, nitrates, oxygen-containing, nitrogen and/or sulfur in
combination with oxygen, and halogen containing. The active ingredients in
most non-metallic additives are apprently dissolved or suspended in mineral oil,
light fuel oil, or other bases compatible with fuel oils. None of the non-metallic
additives reduced total particulate emissions significantly at economically
practical concentrations. Even at impractically high concentrations, only
moderate reductions were noted.
BURNER MODIFICATIONS
During the time the fuel additive testing was being conducted, Howe-
kamp9'10 also tested several burner modifications and demonstrated that three
flame retention devices substantially reduced particulate emissions. Martin11
subsequently compared the most effective burner modifications with the most
effective additives. Burner modification appears to offer more promise for
particulate reduction, In addition one of these devices also reduced NOX emis-
sions significantly; no additive tested showed any promise in this area. Figure 6
o
-------
permits comparison of the effects of additives and burner modifications on
particulate emissions. At a given excess air setting, carbon particulate matter
emitted by the-modified burner with pure fuel is considerably less than that
emitted by the standard burner or the standard burner with CI-2 in the fuel.
These flame retention burners retail for about the same as a standard burner
($70); a modification kit for use on existing burners is available for $25. It
should be noted that the optimum burner design for reduction of particulate
matter and NOX emissions has not yet been achieved.
22 EVALUATION OF FUEL OIL ADDITIVES
-------
CONCLUSIONS
1. In distillate oil no additive reduced NOX or SOX emissions, and only 17 out
of 206 reduced particulate emissions. None of the 206 additives reduced
unburned hydrocarbons or carbon monoxide.
2. Only proprietary metallic additives containing cobalt, iron, or manganese
appreciably reduced particulate emissions. There is no evidence that a combina-
tion of metals in an additive offers any advantage over a single metal in an
additive. Although a few non-metallic compounds seemed to reduce particulate
emissions moderately, the concentrations required were too large to make
them practical.
3. The most effective weight concentration for particulate reduction is highly
dependent upon the specific additive; however, it appears that 0.5 millimole of
total metal per kilogram of fuel is the optimum molar concentration and will
be investigated further.
4. Arapahoe's Ferrocene and Ethyl's CI-2 reduced particulate emissions the
most at practical concentrations. Further, Ferrocene, CI-2, and Fuelco SO3
(from Fuel Combustion Corporation) are the most economical of the effective
additives. From a cost-effectiveness viewpoint Ferrocene and CI-2 are the most
promising; however, the unknown toxicity of the metallic emissions they pro-
duce makes their use questionable. Moreover, commercially available flame
retention devices can reduce particulate emissions more than any additive
tested.
23
-------
RECOMMENDATIONS
1. Fuel additives should not be used as a means of controlling air pollutant
emissions from distillate oil burning unless the metallic emissions they produce
can be shown to be completely harmless.
2. Corrosion, fuel and additive stability, and long-term effects in addition to
toxicity are areas of additive research that need detailed investigation before
any general use could be recommended.
3. Fundamental research should be conducted to determine the mechanisms
through which the most effective additives function and thereby gain an insight
into the nature of the "optimum" fuel additive in terms of current knowledge.
25
-------
APPENDIX A.
ADDITIVE LISTING
The information contained in this appendix was compiled from manufac-
turers' promotional material. Listing in this section does not constitute an
endorsement by the Air Pollution Control Office. An effort was made to make
this listing reasonably comprehensive, but a few manufacturers and specific
additives may have been overlooked.
The test numbers shown in the second column correspond with the
number found in column 1 of Appendix D. Note that some additives listed
were not tested because of unavailability of samples. Note also that all dose
figures are volume per volume unless indicated otherwise.
KEY TO SYMBOLS IN ADDITIVE LIST
AF Antifouling D
AH Antihaze DE
AN Acid Neutralizing E
AO Anti-Oxidant GI
CA Chelating Agent 01
CC Combustion Catalyst PPD
CI Combustion Improver RI
CrI Corrosion Inhibitor S
CS Color Stabilizer SAA
Dispersant
Demulsifying Agent
Emulsifier
Gum Inhibitor
Oxidation Inhibitor
Pour Point Depressant
Rust Inhibitor
Stabilizer
Surface Active Agent
27
-------
ts>
00
W
$
C
FUEL ADDITIVES
Manufacturer
Test
No.
Additive
Acheson Colloids 1 Oil Dag
Oil Dag 170
Aetna Chemical
Actene A
Type fuel
2-6
2-6
1-6
Dosefl
0.1 to 1.0%
0.1 to 1.0%
1:2000-1:4000
§
^
s
fl
2
r
o
h-H
ti
3
C/5
A+LLabs
Alb en Daniels
Chemical Corp.
Alken-Murray
Alox
Corporation
Actene C
Actene D-60
Actenite
3 Inferno
Econodyne
Micheldyne
4 Evenflo910
5 Evenflo910E
6 Evenflo HFS
7 Alox 488
8 Alox 1 643
9 Alox 1846
R
R
Heavy
No. 1 and 1
2-6
2-6
Bunker C
Bunker C
Bunker C
Gasoline and
diesel
Residual
Light dist.-
jet fuel
Apply to firebox
1:1000
1:3000
1:1000
1:4500- 1:7000
1:4500- 1:7000
1:6000-1:10,000
6 oz of 20% add.
in oil per 10
gal of gas
1:2000-1:4000
4-20 Ib per
lOOObbl
CI
D,E,CrI
CI
VA-S inhibitor
D,E,CrI
CI
D,S,CrI
CI
D
D, S,OI,DE
D,S,OI,DE
E,D
Lubricity
D
CI
Description"^
Colloidal graphite-in.
oil dispersion 10%
solids
Semi-colloidal graphite-
in-oil dispersion 40 %
solids
Nonacid, noncaustic
Oxygen releasing solid
SAA-organic nitrogen
SAA-organic nitrogen
SAA-organic nitrogen
Ashless mixture of or-
ganic acids, oxy-acids,
lactones, esters, and
other oxygenated hydro-
carbons
-------
.
§
3
a
5'
>
^
a
&
S-'
M**
l_
1~t-
5'
w
American Sand- Sabanol
Baunum
10
Amoco Petrofina 1 1 SLD
SA
Amyloid Pyrocat-E
Pyrocat-F
Pyrocat-NA
Pyrocat-SS
Pyrocat-I
Pyrocat-HV
Andrew Rolfe 12 Rolfite 404N
Chemical
Company Rolfite 10 IN
No-Smogg
No. 4, 5, and 6
Diesel, No. 1 and 2
Bunker C
High S-Va
No. 6 and
Bunker C
Residual-
HighNA
Heavy oils
Heavy oils
Heavy oils
2-6
Heavy oils, light
oils in gas turbines
Gasoline and
Diesel
1:4000
1:8000
1:10,000
1:8000- 1:10,000
1:8000-1:10,000
1:10,000
1:5000
1 :4000
1:25,000
1:650
1:1000
D,CI,,GI
Va and sulfur
inhibitor
D,CI,GI,Va
and sulfur in-
hibitor
Cl.slag
inhibitor
CI,slag
inhibitor
Cl.slag
inhibitor
S,CI
S,CI
SOs reduction
Va-2 inhibitor
S03 inhibitor
Va-S inhibitor
SOa inhibitor
CI,D
Cl.Crl
Aromatic organic, emul-
sifying agent
Rust inhibitor and agent
to lower soot combus-
tion temp.
Metal chelates
Metal chelates plus
sodium complexing
agent
Organic
Metal chelates
Slurry—basic metal oxide
Rolfite CI
Special
flAs taken from manufacturers' literature. No attempt at verification was made by the Air Pollution Control Office.
-------
FUEL ADDITIVES (Continued)
OJ
0
tn
>.
r
c
jj>.
H
h-H
0
z
o
>n
*ri
c
tn
r
kH
r
o
D
3
tn
1/3
Manufacturer
An-Pol
Apollo
Arapahoe
Arol
Baroid
(National Lead)
Basic Chemical
Company
Test
No.
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
Additive
AnPolD
AnPolG
AnPolB
AnPolR
DSD -2
SDI - 40
MC-7
SSI -3
CC-2
VCI-4
Ferrocene
Allite FS-12
Sludge Solvent
Allite FOT
P-D-5 Comb.
Cat.
Coat 907
Liquimag
Mark VII
Type fuel
D
G
1-2
Residual
Distillate
Distillate
Residual
Hi-S residual
Diesel
Hi-VaandNa
residual
No. 6
No. 6
No. 6
No. 6
Jet, diesel, No. 1,
gas
Bunker C
Dose0
1:2000
1:1000
1:4000-1:6000
1:2000
1 gal per 600 -
800 bbl
1:4000
1:1000
1:4000
10 - 25 ppm
1 :4000
App. 0.1 -0.5
wt %
Function0
S,E,D,CI
E, D, CI
D
D, S, CI
D,CI,GI
S, OI
Va and sulfur
inhibitor, CI
CrI,CI,D
SOX inhibitor
D,CI,CrI
Va and sulfur
inhibitor, D
CI,GI
CI
CrI
CrI, Va and S
inhibitor, SO3
reduction
Description0
Multipurpose catalyst
Multipurpose catalyst
Metallic compounds
Dicyclopentadienyl iron
Polar organic salts
Magnesium oxides and
other metallic oxides in
oil 68%. massMgO,8. 6
Ib/gal, balance SiO2,
CaO.
-------
>
13
n
CL
S'
•
^
CL
CL
E±
re
r*
K"
3"
00
Bell Labs
Berrymand
Brilco Labs
Bryton
Butler Engineer-
ing Association
Bystroms
Cabot
ATAKA and Co
LTD (KAMEI
Carbogen Ltd)
Carbo-Solv
Lubricate
30
31
32
33
34
35
36
37
38
39
40
41
42
43
Atom IX
DEE - ZOL
B - 12 Chem-
tool
Sludge Solvent
Hybase
Hybase C-300
Hybase M-400
Sul-Van-
Kontrol
SK-3
TK-5
Bycosin
Alon
Blue Sky
(Carbogen)
Fuel Oil
Saver
Diesel F. OS.
No. 4, 5, and 6
Diesel
Diesel
Distillate
Diesel
Crankcase
Diesel
Crankcase
G.D.1-6
G
No. 1 through
No. 6
Diesel
1:2500
1:25-1:50
1:4000
0.01 - 0.05% (vol)
15 -20% (vol)
1 - 5% (vol)
15 - 20% (vol)
1 - 5% (vol)
1:1000- 1:2500
1:1500- 1:3000
1:2000
1:2000
D,E,GI,CI
D,CI
E, D, CI
D,E,S
D
CrI
CrI
SAA,D
Slag inhibitor
CI
AN,D,CI
CrI,E
AN,CI,D,E
Non-petroleum, all
organic
14.5% (wt) Ba, 2% (wt)
S, barium sulfonate
11.6%(wt)Ca,2%(wt)
S, calcium sulfonate
7.2%Mg,2.0%(wt)S,
magnesium sulfonate
1.22% ash (9 9% iron
oxide)
Fumed alumina
Camphor oil, SAA
o-dichlorobenzene
Alkaline, 27% CI2
aAs taken from manufacturers' literature. No attempt at verification was made by the Air Pollution Control Office.
-------
FUEL ADDITIVES (Continued)
w
^
r
d
H
o
z
o
d
tn
o
I—I
I"1
O
0
a
H
h-l
tn
Gfl
Manufacturer
Carter Chemical
Company
Castroleum
Catalin
Celanese
Chemical
Specialties
Columbia-
Bedford
Combustion Cat.
Corp.
Commercial
Chemicals
Test
No.
44
45
46
47
48
49
50
51
52
53
54
55
56
57
Additive
Coal Treat
Diesel Treat
Fuel Treat
"S"
Fuel Treat
"2"
Casta Lube D
CAO-6
Methylal
CH-22
Klenn
Glo-Klen
Improsoot
Formula LSD
Improsite
Dispersite
Dispersoot
Type fuel
Coal
Diesel
Residual
Distillate
Diesel
Petroleum
Diesel
Hi Va-S
residual
Residual
Residual
All grades
All grades
All grades
Coal
Dose*7
1:320
0.5% (wt)
0.25-2.0%
1:2000
1:1000-1:8000
1:4000-1:8000
1:4000-1:8000
2 lb/ 100 boiler hq
Function2
AO
Deposit
reduction
CrI, S03
CI,S03
inhibitor
D,E,CrI
CI
D,CI
D,E,CrI
S
D, S
Soot remover
Description2
Degummed castoroil
9% (wt) sulfur. Aro-
matic sulfur organic
CH3 - 0 - CH2 - 0 - CH3
MgO/Al203 = 10/l,CaO,
SiO2,Fe203<1.5%each
Clay(Si,Na,Al,P)
Organic solvents,
emulsifiers, catalysts
Organic solvents,
catalysts
Organic solvents,
emulsifiers
-------
CrowleyTar 58 Cyclo-Flo No. 6
Products 59 Vanadaban No. 6
CD
I
X
>
Cb
CL
I
c
CO
ft
1:1000
1 gal per
11 to 176 bbl
D
Va inhibitor
60
61
62
63
64
65
66
67
68
69
70
Heating Oil
Catalysts
FE4
FE6
Gand
(No Name)
Kryda
Sootrol
FOA-2
FOA-3
DMD
Tenamene 60
Open flame
burners
Diesel and
kerosene
No. 6
Fuel oils
No. 6
Distillate and
residual
Diesel and
fuel oils
Diesel and
fuel oils
1:1000
1:1280
1:1280
1:40-1:1000
1:1000
1:1000-1:6000
mass basis
10 gal per
lOOObbl
5 - 60 Ib per
1000 bbl
1 -lOlbper
1000 gal
1/4 to 2 Ib
per 1000 bbl
CI
CI
CI
E, S02
reduction
S03 inhib-
itor, D, DE
D
D,E
OA, AH, S
Cooper de-
activator
Metal de-
activator
Petroleum base
Mg, Al, Zr compounds
petroleum base-40%
active
All organic
Copolymeric amine
C, H, + N only
(amine)
N, N' - disalicylidene
1,2- proponediamine
N, N' - disalicylidene
1,2- proponediamine
°As taken from manufacturers' literature. No attempt at verification was made by the Air Pollution Control Office.
-------
FUEL ADDITIVES (Continued)
OJ
4^
w
<
>
r
c
>
H
O
2
0
>n
HH
-*-J
c
w
t"1
o
1— 1
r
>
o
HH
H
HH
s
CO
Manufacturer
Enjay
Erlen
Ethyl
Fuel Activator
Chemical Corp.
Fuel
combustion
Corp.
Gamlen
Chemical
Company
No.
71
72
73
74
75
76
77
78
79
80
81
82
83
84
Additive
Paradyne 4
Paradyne 5
Paradyne 6
No. 150 FOA
DB-36
DII -2
MPA-D
CI-2
Fuel
Activator
Diesel F.A.
FUELCO
FUELCO SO3
VASCONOL 3
VASCONOL 4
DP 231
Type fuel
Distillate
Distillate and
residual
No. 1 - No. 6
Diesel
Diesel
Diesel
No. 2 dis-
tillate
G
D
6
6
H, Va - S residual
H, Va - S residual
D, 1 -6
Dosea
0.002- 0.0 l%(wt)
0.002-0.01% (wt)
10-501bper
lOOObbl
1:4000-1:6000
fvon
VVVJ1V
1% (vol)
1% (vol)
200 - 400 ppm
1 g Mn per gal
1:1280
1:3000
1:2000
1:1000-1:3000
1:1000-1:3000
Function0
S
S,DE
DE,D
SAA, D, CrI
Cetane im-
prover
Cetane
improver
GI, D,
detergent
CI
E, D, CI
D,CI
E, AN,D
CrI, DI
CrI, CI, SO3
inhibitor
CrI, CI, S03
inhibitor
CI, CrI, Va -
S-SO3 inhibitor
Description5
Ashless
Ashless
Ashless polymer
Amyl nitrate
Hexyl nitrate
Surface active organic
24.7wt%Mn,C9
H^OoMn
fj \j 3 -i-'-1"1*
Mg pet. sulfonate
Cresol and pet. deriv-
atives, no halides
-------
>
"O
•o
S
2t
>
>.
CL
&
<'
r1
55'
3'
tw
Gibraltar
W. R. Grace
Harco Chernical
Harlou
Hoko Chemical
Company
Hy-Test 303
Corp.
Industrial
Chemical
Company
Industrial
Chemicals,
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
Gamlenol
Regular
Diesel F. A.
Dearsol 25
Dearsol 30
Dearsol 35
FT-1
Oil Stabilizer
HCC
STAB + HCC
Harcoite Z
Fuel Oil Add.
BHA
Heat NRG
Fortifier
INDUCO
Supreme
INDUCO Elite
INDUCO Diesel
INDUCO Delux
INDUCO BX 400
Watcon 130
Watcon 140
R
Diesel
Fuel oil
Industrial fuel oil
Residual
Coal
Residual
Residual
Residual
6
Residual
Residual
No. 2
G
D
R
Fuel oils
Coal, oil
1:1000-1:400
1:320-1:400
1:4000
1:4000
1:8000
1:5000
1:5000
50 ppm
1:4000
1:480
1:480
1:1000
1 Ib per 400 -
D
D,CI
E,GI
Va and S inhibi-
tor, CI, DE
Va and S inhibi-
tor, CI
S, SAA, E
CI,CrI,Vaand
Sinhib.
Both of above
CI
CI
S oxidation ac-
celerator, CI
CrI, D, E,
D,E,CI
CI,D
D
CI
Cresol and pet. deriv-
atives
Combustion catalyst
Contains zirconium
Organic Enzyme
OJ
"As taken from manufacturers' literature. No
Chlorides, sulphates,
attempt at verification was made by the Air Pollution Control Office.
-------
FUEL ADDITIVES (Continued)
UJ
ON
w
<
r
c
h-^
0
z
0
V
>n
w
r
o
I-H
f
>
o
H
HH
m
cc
Manufacturer
Incorporated
Lone Star
Lubal Mfg. and
Dist. Company
Lubrication
Engineering
Lubrizol
Marine
Electrolysis
Eliminator
Metropolitan
Petroleum and
Petrochemical
Corp.
Test
No.
105
106
107
108
109
110
111
112
113
114
115
116
117
118
119
Additive
Texon
Combusto
Lubal D
Lubal Super D
DCI
520
560
585
565
Red Devel
Soot Remover
456
456 SV
Metlite
Metlite 2D+
Metspray
Type fuel
Diesel
Diesel
Diesel
Diesel
No. 4, 5 and 6
Middle distillate
Diesel
Kerosene to
Bunker C
No. 4, 5, 6 and
heavy
No. 4, 5, 6 and
heavy
No. 2
Diesel
Coal
Dose*
600 gal
1:480
1:1000
1:4000
1:150
7 - 1 0 gal per
lOOObbl
15 -SOlbper
lOOObbl
1:400-1:2000
1:1250
1:3000
1:3000
1:3000
1:1500
Function0
D,S,DECrI,CS
D,DI,CrI
Detergent
CrI, detergent
CrI,CI,D,CS
D,S,CI
DE, CrI, CI
S,CS,D
D
CI
D,E,CrI,CI
D,E,S,CI
Va and S
inhibitor
CI,DE,D
CI.GI
Description"
carbonates, and stearates
of Zn, Na, and Cu. Cel-
lulose and lignin
Alkaline
Alkaline, organometal-
lic soap
Alkaline, organometallic
Metal Organic
-------
13
re
a
x"
re
C
3
os
N. A. Mogul
Monsanto
Nalco
Nalco (cont'd)
120
121
122
123
124
125
126
127
128
129
130
131
132
133
134
Fuel Oil Treatment
DP-2
Santolene K
151
152
155
156-C
158
158-D
159
160-M
160-T
161
165 -AC
262
All fuel oils
Cat-cracked
fuel oils
Diesel and
fuel oils
Coal
Coal
Residuals
Coal
Residuals
Residuals
Diesel and
Residuals
Distillate
Distillate
Petroleum proc-
ess equipment
Petroleum proc-
ess equipment
Petroleum proc-
ess equipment
1:1000
1:1000
20 - 30 Ib per
lOOObbl
1 Ib per 3 - 6 tons
1 Ib per 3 - 6 tons
1:1000-1:4000
1 Ib per 3 - 6 tons
1:2000- 1:4000
1:2700-1:8000
1:1000-1:8000
2-151bper
lOOObbl
5 - 40 ppm
5 - 20 ppm
2 - 5 ppm
>10 ppm
(20 avg)
D
S,D
D,CrI
CI
Slag removal
AF, D, CI CrI
D,CrI,AF
D, S, CrI
CrI
CrI
CrI
D,CrI
CrI
AF
Non-metallic; mildly
toxic
Combustion catalyst
Combustion catalyst
Organic liquid, phenolic
ordor
Organic, aromatic odor,
alkaline
Organo-metallic blend
in sulfur free hydro-
carbon
Organic liquid
Organic
HMW polar organic
liquid, no metals
Hydrocarbon
N=3%, no halogens,
HMW polor organic
/•__1_ 1 \
"As taken from manufacturers' literature. No attempt at verification was made by the Air Pollution Control Office.
-------
FUEL ADDITIVES (Continued)
VJ
oo
tn
>
r
c
>
a
o
l~>
^
>n
T3
S
m
r
o
h-l
r
>
a
3
!~1
^H
w
CO
Test
Manufacturer No.
135
136
137
138
139
140
141
New Surpass 142
143
Nitro Nobel AB
R. S. Norris and 144
Associates
145
146
Additive
303 -AC
305
D-1887
D-1955
D-1976
D-1991
D-2015
Surpanate
960
Surpanate
960C
IPN
Barsad
FOA-2
Barsad MN
Barsad S
Type fuel
Distillate
Jet and rocket
fuel
Furnace oils
Distillate
Distillate
Distillate
Distillate
Motor oil
Motor Oil
D
Diesel and
residual
No. 6
No. 6
Dosea
5 Ib per 1000 bbl
minimum
5 - 30 Ib per
1000 bbl
(17 - 100 ppm)
1:8000
2 Ib per 1000 bbl
21bper 1000 bbl
2 Ib per 1000 bbl
1 Ib per 1000 bbl
1:200
1:3000
1 gal per 300 bbl
Function0
S,D,CrI
AO
E, D, deter-
gent, CrI,CC
CS
CS,D
C.S.D
D
D,CrI
D,CrI,SO2-
SOs neutralier
Cetane im-
prover
D,CI
SO3rinhibitor
SO3 inhibitor
Description0
Polymeric aliphatic
amine, formaldehyde
As 303 AC
As 303 AC and amine
dispersant
As 303 AC and amine
dispersant
Aromatic solvent and
amine dispersant
2.7 wt%Ca; calcium
petroleum sulfonate
Calcium petroleum sul-
fonate; colloidal Ca COs
(total Call. 5%)
Contains isopropylni-
trate
Contains calcium
Contains Mn
Contains Mg
-------
T3
T3
CL
r
3'
Norsemen
Olin
Oxi-Kor
Corporation
Parke-Hill
Perolin
147
148
149
150
151
152
153
154
155
156
157
158
159
160
161
SP
Hydrazine
Kor
Blue Heat
Sludge Ban
Triple-X-100
Van Sul Ban
Parko D-5
PFOT 617-GM
PFOT 626-DA
PFOT 644-EM
PFOT 646-SP
PFOT 687-SD
Petrosene A
Petrosene C
Petrosene PM
Cord wood oil,
and gas
No. 1 -No. 6
Distillate
Residual
Residual
Residual
Diesel
Gas turbine
residual
Residual
Residual
Residual and
distillate
Diesel
No. 2 and 4
No. 6
Distillate and
Residual
100 g per ton fuel
1/2 Ib per 5000
gal oil
1:4000
1:1000
1:1000
Hi S3: 10,000
Hi V 1:2000
1:3000-1:4000
1:4000
1:2500-1:4000
1:2500
1:8000
1:4000
1:4000
1:2000
Soot destruction
D,CI
CrI, CI, D, E
E, CrI, D
D,CrI
D,CrI
S and Va inhibitor
CI
CrI,Va-Na-S
inhibitor
CrI, slag inhibitor;
Va, Na inhibitor
D,CrI,E,CI,
Va-S inhibitor
CI,CrI,D,S
CI
CI, D, CrI
D,CrI
SO3 inhibitor
Applied to fire box
OJ
VO
"As taken from manufacturers' literature. No attempt at verification was made by the Air Pollution Control Office.
-------
FUEL ADDITIVES (Continued)
>
H
HH
O
C
M
o
o
w
C/3
Manufacturer
Poly Phase
Power Dynamics
Power Dynamics
(cont'd)
Rohm and Haas
H. E. Sanson
Sir Michael
Thomas
Chemicals Ltd.
Solval
Engineering
Test
No.
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
178
179
Additive
RX-613
Anticor AC6-2
Polyblend
Polymag
Polyphase F 106
Powerdyne 10
Powerdyne 12
Powerdyne 32
Powerdyne 77
Powerdyne 102
Powerdyne 105
Powerdyne 505
Acryloid 917
Primene81-R
SYN-SOLV.
T-H-R-U-S-T
SI 12 Concentrate
Pride
DC 25
APC30
Type fuel
Coal
Coal and fuel oil
Fuel oil
Fuel oil
Light oil
Heavy oil
Light oil
Coal
Coal
Heavy oil
Motor oil
Heating oil
All fuel oil
Fuel oil
Heavy oils
No. 4 and 6
2-4
2-4
Dosefl
1 Ib per 10 tons
1 Ib per 10 tons
1:2000
1:1250
10 to 30 Ib
per lOOObbl
1:5000-1:16000
1:8000
1:3000
Spot cleaner
1:1000 - 1:4000
Function0
CrI, Va and S03
inhibitor
D,E,CI
CI,D
CI,D
Sa-Va inhibitor
D,DET,CICrI
CI
CI
S-Va inhibitor
D,PPD
AO,S
D
E.Crl
SOX inhibitor
Soot reduction,
D
D
Soot reduction,
D
Description0
Each additive contains
one of the following:
organo metallics, metal
slurries, amine types
Methacrylate ester
Organic amine
Solvent
-------
T3
13
p.
^
*
a-
CL
I—"
r-f-
m
w"
a
<{Q
Studebaker
Corp.
United
Lubricants Ltd.
United (Oil
Tech. Corp.)
United (Oil Tech.
Corp.) (cont'd)
UOP
R. T. Vanderbilt
Company,
180
181
182
183
184
185
186
187
188
189
190
191
STP-Diesel
Blitz
Isotane
Technol
Technol D
Technol G
Polyflo 100
Polyflo 120
Polyflo 121
Polyflo 122
Polyflo 130
Polyflo 135
Polyflo 140
Vanlube PC
Vanlube 601
No. 1 diesel
Diesel
No. 6
No. 4
Diesel
Gasoline
No. 2
1 -2
Distillate
Diesel and
distillate
Distillate
Crude
Distillate
Distillate
Pet. fuels
1:800
1:1000
1:2000
1:300-1:400
1:300-1:350
0.0005 -
0.005 wt%
14-56g
perm3
14-28g
perm3
0.0005 -
0.10wt%
0.0005 -
0.005 wt%
10-40ppm
10-1000ppm
0.02 - 0.2%
D,CI deterge:
Smoker in-
hibitor
CI, D, DET
PPD
CI.DET
CI, DET
D,S,PPD,D
CS,DE,PPD
CS,DE,PPD
CA
01, CS, AF
CI,AH
CI,D,S,PPD
AF,OI
AF,S,PPD
OI
CA.CI
Incorporated.
100% petroleum; no
sulfur
Isoprophyl nitrate
Petroleum products, and
hydrocarbons, no salts
or metals
Ashless polymeric
amine
As 100 plus demulsifier
Poloyflo 120 w copper
deactivator added
Similar to above
Replace Polyflo 100
Polymeric amine and
antioxidant
Improved 100 and 130
Substituted phenol
Heterocyclic nitrogen-
sulfur
°As taken from manufacturers' literature. No attempt at verification was made by the Air Pollution Control Office.
-------
FUEL ADDITIVES (Continued)
w
m
<
r
d
H
I-H
O
2!
O
Tl
G
W
r
o
HH
r
j^
o
H
<
w
c«
Manufacturer
R. T.Vanderbilt
Company Incor-
porated (cont'd)
W-6, Inc.
Witco
Whitnor
Wonder-King
Chemical
Company
Wynn
Test
No.
192
193
194
195
196
197
198
199
200
201
Additive
NA-SUL AS
NA-SUL EDS
NA-SUL LP
Cuvan 80
W-6
300 Base Cal-
cium petronate
W-2
Methyl High-Test
Sludge Klean
Bunker fuel add
Type fuel
Pet. fuels
Pet. fuels
Distillate
Distillate
D, 1 -6
Gasoline and
diesel
Fuel Oil
No. 2, 4, 5
and 6
Bunker
Dose0
0.5-121b
per 1000 bbl
1:4000
0.025 - 01 wt%
lgal(50%w-2
and 50% Napth-
enic oil) per
4000 gal
1:1000-1:4000
Function0 Description0
RI Chain-ring organic with
S03 NH4;50%in
mineral oil
RI, CI Chain-ring organic, dia-
mine and SO 3 , 50% in
kerosene
CI Chain-ring organic, dia-
mine and S03 , 50% in
kerosene
CA, S Cycle diamine, 80% in
org. sol
D,CrI,CI
3% Ca; Ca sulfonate
45%; 0.25% Ob; 0.1%
Na
D,CrI
G.D.DI
D
D,S,CI,AN
-------
TJ
n
Cu
Wynn (cont'd)
Zep
W. E. Zimmie,
Inc.
202
203
205
206
Furnace Fuel
Conditioner
Formula 221
204 Comb. Cat 405
Fuel Oil Stabi-
lizer ZF 400
Zimmite 455
Distillate
Fuel oil
Oil
Coal
Residual
1:000-1:2000
1:400-1:10,000
1:500-1:7000
1:4000
1:4000
D, DE, CrI, CI,
SOX reduction
D, E, CrI
CI,CC,S03
inhibitor
CI,CrI,D,E
Hydrocarbon fraction,
SAA ethane oxide,
monoethanol amine
Combined 400 and 405
a
CL
r
B"
OJ
taken from manufacturers' literature. No attempt at verification was made by the Air Pollution Control Office.
-------
APPENDIX B.
LIST OF ADDITIVE MANUFACTURERS
Company
Acheson Colloids
Aetna Chemical Corp.
Alben Daniels Chemical
Corp.
Alken-Murray Corp.
Alox Corp.
American San Banum
Company
Amoco Petrofma SA
Amyloid, Inc.
Andrew Rolfe Chemical
Company
An Pol
Apollo Chemical Corp.
Arapahoe Chemicals
Arol Chemical Products
Company
Address Phone
Port Huron, Mich.
Wallace St. Extension
East Patterson, N. J. 796-0230
P.O. Box 148
Hyattsville, Md.
111 Fifth Avenue
New York, N.Y. 10003 777-6560
P.O. Box 517
Niagara Falls, N.Y. 14302 282-1295
1 Merrick Avenue
Merick, N.Y. 11566
33 Rue De La Loi
Bruxelles 4, Belgium
322 Main Street
Stamford, Conn. 06901
900 Bedford Street
Stamford, Conn. 06902
P.O. Box 20259
Long Beach, Calif. 90801
250 Delawanna Avenue
Clifton, N.J. 07014
2855 Walnut Street
Boulder, Colo. 80302
371-81 Wayne Street
Jersey City, N.J. 07302
378-3390
12.01.60.10
Lignes
324-9788
327-3151
436-1297
472-5400
442-1926
432-4710
45
-------
Company
Address
Phone
Baroid Division National
Lead Company
Basic Chemicals
Bell Laboratory
Berryman Products, Inc.
Brilco Laboratories
Bryton Chemical
Company
Butler Engineering
Assoc.
Carbo-Solv Lubricite
Corp.
Carter Chemical
Company
Castroleum
P.O. Box 1675
Houston, Texas 77001 524-6381
845 Hanna Building
Cleveland, Ohio 44115 241-5000
2421 Kilgore Avenue
Orlando, Fla. 32803 422-2568
P.O. Box 1016
San Jose, Calif. 95108
1553 63rd Street
Brooklyn, N.Y. 11219 236-3812
9 Rockefeller Plaza
New York, N.Y. 10020 586-2510
764 Ramsey Avenue
Hillside, N.J. 07205 688-3300
4144 Sheridan Road
Chicago, 111. 60613 935-4548
31 Fullerton Avenue
Yonkers, N.Y. 10704 476-7210
Catalin Corp.
1 Park Avenue
New York, N.Y. 10016
683-2100
Celanese Chemical
Company
245 Park Avenue
New York, N.Y. 10017
867-2000
Chemical Specialities
Corp.
75 Hillside Road
Fairfield, Conn. 06430
255-2804
Columbia-Bedford
Corp.
44 Whitehall Street
New York, N.Y. 10025
269-1457
Combustion Catalyst
Corp.
1731 Munsey Building
Baltimore, Md. 21202
685-2484
46
EVALUATION OF FUEL OIL ADDITIVES
-------
Company
Address
Phone
Crowley Tar Products
Desmul Chemical
Company
Dexson Chemical
Corp.
DiBattista, Charles
Ditta Francesco Ferrerio
RDona
Dryden Oil Company
271 Madison Avenue
New York, N.Y. 10016 683-1040
Pier 66
Seattle, Wash. 98121 623-6356
407 Weatherly Building
Portland, Ore. 97214 233-6422
716 Willow Street
Cranford, N.J.
10-12ViaDonatello
Milano, Italy
Braddish Avenue and WMRR
Baltimore, Md. 21216
DuPont Petroleum Lab. Wilmington, Del. 19898
Eastman Chemical
Products
Enjay Chemical Company
Eden Products
Ethyl Corp.
Fuel Activator Chemical
Corp.
Fuel Combustion Corp.
Gamlen Chemical
Company
Gibraltar Refining and
Chemical Company
W. R. Grace and Company
Chemicals Division
Kingsport, Tenn. 37662
60 West 49th Street
New York, N.Y. 10020
700 South Flower Street
Burbank, Calif. 91502
100 Park Avenue
New York, N.Y. 10017
745 Fifth Avenue
New York, N.Y. 10002
11 Broadway
New York, N.Y. 1000
Manor, Penn. 15665
Merchandise Mart. Plaza
Chicago, 111. 60654
200.281
233-2000
299-5000
246-2111
849-6591
679-2000
753-0078
863-3400
527-3273
Appendix B. List of Additive Manufacturers
47
-------
Company
Address
Phone
Harco Chemical Company
Harlou Products Corp.
Hoko Chemical Company
Hy-test 303 Corp.
Industrial Chemical
Company
Industrial Chemicals,
Inc.
Lone Star Chemical
Company
Lubal Mfg. and Dist.
Company
Lubrication Engineers
Lubizol Corp.
338 North Avenue E.
Cranford, NJ. 07016 276-1096
23-37 51st Avenue
Long Island City 1, N.Y. 784-9340
341 Daigiri, Fujisawa-shi,
Kanagawa Prefecture, Japan
9 Meadow Road
Rutherford, N.J. 07105 933-0300
P.O. Box 78
Cupertino, Calif. 95014
2215 South Main Street
South Bend, Ind. 46613 287-3397
P.O. Box 26777
Houston, Texas 77032 643-9406
375 West Rich Street
Columbus, Ohio 43223 221-4674
3851 Riverside Freeway
Fort Worth, Texas 76111 834-6321
29400 Lakeland Blvd.
Cleveland, Ohio 44117 943-4200
Marine Electrolysis
Eliminator
1137 SWHanford Street
Seattle, Washington 98134
624-2266
Metropolitan Petroleum
Petrochemicals
235 East 42nd Street
New York, N.Y. 10017
867-4141
North American Mogul
Products Company
Standard Building
Cleveland, Ohio 44113
Monsanto Company
Nalco Chemical Company
800 N. Lindbergh Blvd.
St. Louis, Mo. 63166
180 North Michigan Avenue
Chicago, 111. 60601
694-1000
48
EVALUATION OF FUEL OIL ADDITIVES
-------
Company
Address
Phone
New Surpass. Petrochemical
Ltd.
Nitro Nobel A. B.
R.S. Norris and Assoc.
Norsemen Chemical Ltd.
Oil Technology Corp.
Ohn Chemicals
Oxi-Kor Corp.
Parke Hill Chemical
Corp.
Perolin Company
Poly Phase Chemical
Service
Power Dynamics Corp.
Rohm and Hass Company
H. E. Sanson and Sons,
Inc.
Sir Michael Thomas, Ltd.
Solval Engineering Corp.
36 Upton Road
Scarborough, Ontario, Can. 751-6100
Stockholm, Sweden
26 Valley Road
Larchmont, N.Y. 10538 834-4195
P.O. Box 16
Rungsted Kyst, Denmark 864121
99 E. Hawthorne Avenue
Valley Stream, N.Y. 11580 593-3711
460 Park Avenue
New York, N.Y. 10022 572-3000
600 West 9th Avenue
Gary, Indiana 46401 883-8567
29 Bertel Avenue
Mont Vernon, N.Y. 10550 688-7220
350 Fifth Avenue
New York, N.Y. 10001 947-8987
180 Hempstead Turnpike
W. Hempstead, L.I., N.Y. 485-6161
11552
P.O. Box 145
Boston, Mass. 02101 542-7634
Independence Mall West
Philadelphia, Penn. 592-3000
2215-25 North American St.
Philadelphia, Penn. 19133 426-7723
Musk Lane, Lower Gornal, Dudley
Worchestershire, England 3852454
Massey Hill Road
E. Swanzey, N.H. 03446
352-4879
Appendix B. List of Additive Manufacturers
49
-------
Company
Studebaker Corp.
United Lubricants, Ltd.
UOP Process Division
R. T. Vanderbilt Company
W - 6, Inc.
Witco Chemical Company
Whitnor Chemicals
Wonder King Chemical
Corp.
Wynn Oil Company
Zep Manufacturing
Company
W. E. Zimmie, Inc.
Address Phone
635 South Main Street
South Bend, Inc. 46618
Address Unknown
Assumed Defunct.
30 Algonquin Road
Des Plains, 111. 60016 763-6000
230 Park Avenue
New York, N.Y. 10017 686-6864
P.O. Box 3146
Inglewood, Calif. 90304 677-5345
75 E. Wacker Drive
Chicago, 111. 346-2960
Model City, N.Y. 14107 754-4008
31 New Haven Railroad Street
Mount Vernon, N.Y. 688-4078
1151 West 5th Street
Azusa, Calif. 91703
334-0231
1310 Seaboard Industrial Blvd. NW
Atlanta, Ga. 30301
810 Sharon Drive
Westlake, Ohio 44145
871-9660
50
EVALUATION OF FUEL OIL ADDITIVES
-------
APPENDIX C.
ANALYTICAL PROCEDURES
PARTICULATE MATTER
The particulate sampling train consisted of a Pryex glass probe (1-7/16-
inch i.d.) with an integral filter. A fiber glass filter paper (MSA 1106BH) 2
inches in diameter was used with a sintered-glass back-up plate. The filter was
followed by an air-cooled section of glass tubing, which was connected to a
series of three glass water bubblers and one dry trap. The bubblers and trap
were immersed in a water bath at 32° F. The trap was followed by a second
fiber glass filter.
Gas flow rates were measured with a calibrated orifice and manometer;
isokinetic sampling rates were maintained. A dry-gas meter was used to mea-
sure the total sample volume. Preliminary tests were made to locate a point in
the sampling stack where average particulate concentrations could be obtained.
After sampling, material inside the probe was combined with the filtered
solids. Filter temperatures were not controlled, but were somewhat below the
flue gas temperatures. Condensation on the filter was not encountered.
The weight of the material collected in the bubblers and trap, referred to
as condensables, was also determined in some cases.
Each particulate determination for air-fuel ratios of 1.50 and higher was
an integrated sample accumulated over six cycles. Particulate emissions were so
much greater at stoichiometric ratios of 1.0 and 1.10, that each 10-minute
"burner on" period had to be divided into five 2-minute sampling periods.
Thus, five separate, consecutive samples were required to cover the 10-minute
"burner on" period.
SMOKE
Smoke levels were determined automatically with a sequential tape
sampler incorporating a light transmission recorder. The instrument was modi-
fied to take samples equivalent to the smoke number measurements of the
Shell-Bacharach index, which is widely used to evaluate the performance of oil
burners. The flue gas sample was drawn through a water-cooled probe with a
condensate trap. Each smoke spot was taken in 48 seconds (12 seconds being
required to advance the tape between samples). Ten smoke measurements were
made during each 10-minute "burner on" period.
51
-------
The tapes were later scanned with a Shell-Bacharach index to give a visual
light reflectance reading for comparison with the light transmission readings. A
graph relating the smoke index to Cohs per 1000 feet from the light transmis-
sion meter is shown in Figure C-l. The upper limit of measurements for the
Shell-Bacharach index12 corresponds to a value of 425 Cohs per 1000 feet.
Approximately 1200 Cohs per 1000 feet is the upper limit for the transmission
instrument. At every smoke number reading there was an overlap with smoke
density at the next higher and lower smoke numbers. For a given smoke
density, a range of Bacharach smoke index is shown in Figure C-l and is
attributable to the variation in visual evaluation of the Bacharach smoke index.
CARBON DIOXIDE, OXYGEN, CARBON MONOXIDE, AND
GASEOUS HYDROCARBONS
Automatic instruments were used to continuously record the concentra-
tions of C02, 02, CO, and gaseous hydrocarbons in the flue gas. C02 was
measured by a nondispersive infrared analyzer; 02 was measured by a
paramagnetic-type instrument; CO was measured by a nondispersive infrared
analyzer; gaseous hydrocarbons were measured by a flame ionization analyzer.
The instrument ranges available were 0 to 16 percent for C02; 0 to 21 percent
of 02; 0 to 500 ppm, 0 to 1500 ppm, and 0 to 2 percent for CO; and 0 to 100
ppm and up for gaseous hydrocarbons (calibrated as propane).
.0123456789
BACHARACH No.
Figure C-1. Bacharach No. ver-
sus smoke density.
52
EVALUATION OF FUEL OIL ADDITIVES
-------
OXIDES OF NITROGEN
Total nitrogen oxide concentrations were measured from 2-liter inte-
grated samples taken over the 10-minute "burner on" period. Since sulfur
dioxide was present in the sample gas, the phenoldisulfonic acid method13 was
chosen for the analysis. During the later stages of the work, this method was
checked with long-path nondispersive infrared analysis and the agreement was
quite satisfactory. Instrument ranges available were 0 to 150 ppm, 0 to 750
ppm, and 0 to 1500 ppm.
A stainless steel sampling prob (1/4-in. o.d. by 14 inches long) was used
in the testing. The collection flask was a 2-liter round-bottom flask with an
outer 24/40 joint for integrated samples. Figure C-2 shows the details of the
orifice assembly. A flow rate of about 1 liter per minute was maintained. The
spectrophotometer used in this work was a Beckman Model B.
The analytical testing required several different reagents, which are
described below.
1. 30 percent Hydrogen Peroxide (reagent grade).
2. *3 percent Hydrogen Peroxide. Dilute 30 percent H2O2 with water
at 1:10 ratio. Prepare fresh daily.
3. Concentrated Sulfuric Acid.
4. 0.1N (approximate) Sulfuric Acid. Dilute 2.8 ml concentrated
H2SO4 to 1 liter with water.
5. Absorbing Solution. Add 12 drops 3 percent H202 to each 100 ml
0.1N H2 SO4. Make enough for required number of tests.
PROBE
ORIFICE ASSEMBLY
-STAINLESS STEEL
PROBE GLASS
TEFLON CAPILLARY
SLEEVE TUBE-7
GLASS-FIBER /YGON
.FILTER /SLEEVE
112/5
'119/38 ^THREE-WAY
STOPCOCK
MERCURY
MANOMETER
2 - liter FLASK
TO VACUUM
PUMP
Figure C-2. Integrated sample apparatus with detail of critical
orifice assembly.
Appendix C. Analytical Procedures
53
-------
6. IN (approximate) Sodium Hydroxide. Dissolve 40 g NaOH pellets
in water and dilute to 1 liter.
7. Concentrated Ammonium Hydroxide.
8. Fuming Sulfuric Acid. 15-18 weight percent free sulfuric anhydride
(oleum).
9. Phenol (reagent grade).
10. Phenoldisulfonic Acid Solution. Dissolve 25 g of pure white phenol
in 150 ml concentrated H2S04 on a steam bath. Cool and
add 75 ml fuming sulfuric acid. Heat to 100° C for 2 hours.
Store in a dark, stoppered bottle. This solution should be
colorless if prepared from quality reagents.
11. Potassium Nitrate (reagent grade).
12. Standard Potassium Nitrate Solution. Solution A: Dissolve 0.5495
g KN03 and dilute to 1 liter in a volumetric flask. Solution
B: Dilute 100 ml of Solution A to 1 liter. One ml of Solution
A contains the equivalent of 0.250 mg N02 and of Solution
B, 0.0250 mgN02.
Following a sampling period, the collection flask was shaken for 15
minutes and allowed to stand overnight. The contents were then transferred
into a beaker, and the flask washed three times with 15-milliliter portions of
H20. These washings were then added to the solution in the beaker. For a
blank, 25 milliters of absorbing solution and 15 milliters of H20 were added to
a beaker. From this point on, both the blank beaker and the test beaker were
processed according to the following scheme.
1 N NaOH was added to the beaker in question until the solution showed
just alkaline on litmus paper. Next the solution was evaporated to dryness on a
water bath, and 2 milliliters of phenoldisulfonic acid solution was carefully
added to the dried residue. Four drops of concentrated H2SO4 and 2 milliliters
of H2 0 were then added.
After the solution was allowed to cool, 25 milliliters of H20, 10 ml
concentrated NH4OH was added dropwise, and the solution allowed to cool
again. All samples were filtered, diluted with water, and thoroughly mixed.
Finally, the absorbency was read for each sample at 420 millimicrons. If the
absorbancy was higher than 0.60, a suitable dilution was made. The final
calculations were made by using the following formula.
where C = concentration of N02, mg from a calibration chart
V5 = gas sample volume in ml at 70° F and 29.92 in Hq
OXIDES OF SULFUR
Concentrations of sulfur dioxide and sulfur trioxide were measured from
25 -liter integrated samples taken over a 10-minute "burner on" period. Sulfur
54 EVALUATION OF FUEL OIL ADDITIVES
-------
trioxide was collected by the Combustion Engineering condensation tech-
nique14 in which the temperature is maintained below the,dew point of S03
and above that of water. Sulfur dioxide was collected in hydrogen peroxide
solution in a bubbler. Analysis of the SO3 and S02 was done by the Shell
method.1 s Interference from particulate matter, which may contain metal
sulfates, cations that complex with the indication as coprecipitate barium, or
phosphates, was eliminated by means of a silica wool filter.
The sampling equipment used in this work is shown in Figure C-3. The
reagents that were used in the analysis are listed below along with a description
of how to prepare them.
1. Isopropyl alcohol, anhydrous.
2. 80% Isoproyl Alcohol. Dilute anhydrous isoprpyl alcohol 4 to 1
with distilled water.
3. 3% Hydrogen Peroxide. Dilute 30% hydrogen peroxide 1 to 9 with
distilled water.
4. Standard 0.00500 Formal Barium Perchlorate. Dissolve 1.9516 g
barium perchlorate, Ba(C104). 3H20, in 200 ml distilled
water and dilute to 1 liter with anhydrous isopropyl alcohol.
Standardize this solution against standard 0.0IN sulfuric acid
containing 80% isopropyl alcohol in its final volume.
5. Standard 0.01N Sulfuric Acid (0.005 formal in sulfate ion). Pipet
100 ml purchased, prestandardized 0.1N H2S04 into a 1-liter
volumetric flask and, add 100 ml distilled water. Make up to
1 liter with anhydrous isopropyl alcohol.
6. Thorin Indicator. l-(O-arsonophenylazo) 2-naphthol-3,6-disulfonic
acid, disodium salt. Dissolve 0.2 g thorin in 100 ml distilled
water. Store in polyethylene container. Thorin solution
deteriorates if stored in glass container.
The sampling procedures that were given to the technicians for use in this
work are listed below for completeness. The analytical method is from
Shell Development.
SAMPLING PROCEDURE
Set up apparatus as shown in Figure C-3. Wrap the fritted disk up to the
inlet of the bubbler with asbestos tape; any water condensation would be likely
to contain some S02 as sulfurous acid, which would, if oxidized, be mistaken
as S03. Evacuate the tank(s) and check for leaks. Record manometer readings,
temperature, and barometric pressure. Sample at a rate of 2 to 3 liters per
minute. At end of test, again record manometer readings and temperature.
Disassemble sampling train. Save the silica wool filter used at the tip of the
Appendix C. Analytical Procedures 55
-------
Os
HOT WATER TO DRAIN
W
H-(
o
2!
O
>n
>r)
c
m
r
o
r
>
o
o
w
1/3
STACK
WAL
TO VACUUM PUP/IP
HOT WATER IN (130°-160° F)
SILICA WOOL
3% H202 SOLUTION
SILICA GEL DRYING TUBE
Figure C-3. Sulfur oxides sampling apparatus.
ROTAMETER
(3 liter/in)
VACUUM
TANK
(1 ft3)
(TWO
REQUIRED)
36-in. Hg
MANOW1ETER
-------
condenser for reuse. Flue gas conditioning of a fresh filter plug is desirable to
prevent S03 adsorption.
ANALYSIS
Sulfur Trioxide
Mount the condenser in a vertical position, as shown in Figure C-4, with
a graduated Erlenmeyer flask as a receiver on the lower end. Apply a vacuum at
this end, and rinse condenser with one 20-milliliter portion followed by two
10-milliliter portions of distilled water from a graduated cylinder. Add in a way
that ensures that the entire fritted disk is contacted. To the 40 milliliters of
rinsings in the flask, add 160 milliliters of anhydrous isopropyl alcohol (to
obtain an 80 percent alcohol solution) and 2 or 3 drops of thorin indicator
(enough to give a yellow color). Titrate with standard barium perchlorate to
the pink endpoint. Run a blank determination in parallel.
Sulfur Dioxide
Pour the bubbler contents into an Erlenmeyer flask and rinse the bubbler
with distilled water to obtain approximately 40 milliliters of solution total.
Add 4 times this amount of anhydrous isopropyl alcohol (160 ml) to obtain an
80 percent alcohol solution. Add 2 or 3 drops of thorin indicator, and titrate
to the pink endpoint with standard barium perchlorate. Run a blank determi-
nation in parallel.
DISTILLED WATER RINSE
ADDED FROM GRADUATED
CYLINDER
TO VACUUM
4: \ ERLENMEYER FLASK
Figure C-4. Sulfur trioxide sampler.
Appendix C. Analytical Procedures
57
-------
APPENDIX D.
EXPERIMENTAL RESULTS
This section contains the actual experimental results of this program.
Additives may be identified by referring to the corresponding number in
Appendix A.
59
-------
o\
o
TEST RESULTS AND ADDITIVE ANALYSIS
Add.
No.
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
Test dose
NTb
NT
1:370
1:4500
1:4500
1:475
1:6000
NT
1:2000
1:12,600
NT
1:2360
Pollutant ratio
Total part.
ratio
1.0
1.0
1.0
1.0
1.0
1.35
0.84
1.25
Carbon
part, ratio
1.0
ND
ND
1.0
1.0
ND
ND
1.0
SOV ratio
j\
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
NOX ratio
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
Additive composition, wt%
C
86.4
87.7
81.3
85.8
71.2
67.8
83.5
85.1
78.7
90.2
53.1
H
10.9
12.1
11.7
10.8
9.0
7.7
13.0
13.1
12.7
7.4
8.4
N
<0.1
<0.1
<0.1
0.2
0.3
<0.1
<0.1
<0.1
0.7
0.5
<0.1
s
0.3
0.2
0.8
<0.1
<0.1
0.3
<0.1
<0.1
0.3
0.5
0.9
Hai.
NDC
ND
ND
ND
0.1
<0.1
ND
ND
ND
ND
ND
Od
2.4
nil
6.2
3.2
19.4
22.5
3.5
1.8
7.6
0.6
9.6
Ash
<0.2
<0.2
<0.2
<0.2
<0.2
1.7
<0.2
<0.2
<0.2
0.8
28.
Metals
Na = 0.42
K = 0.34
Na = 0.34
Pb = 0.48
Ba = 16.2
r
c
O
2!
O
w
r
o
r
>
o
D
H
-------
12.
13.
i£
•a
n
i— >
o.
X 14-
P
W
X
"rt
i-i
1'
1 15.
SL
7* 16.
C/l
C
S 17.
1:1000
1:500
1:4000
1:2000
1:1000
1:500
1:250
1:125
1:2000
1:1500
1:1000
1:750
1:500
1:250
1:1000
1:1000
1:860
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
0.78
0.83
0.86
1.0
1.0
1.0
1.0
ND
ND
ND
1.0
1.0
ND
ND
ND
ND
ND
ND
0.83
0.86
0.74
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
84.6
83.5
83.7
83.0
83.5
71.4
12.4
12.4
12.1
12.4
12.6
10.2
0.2
0.6
0.5
0.4
0.3
0.6
0.6
<0.1
<0.1
<0.1
<0.1
0.2
ND
ND
ND
ND
ND
ND
1.8
3.3
3.7
4.0
3.4
11.6
0.4
0.2
<0.1
0.2
0.2
6.0
Mn = 0.2
Ba = 0.1
Ba = 0.1
Ba = 0.1
Pb = 0.9 Ca = 0.48
Mn = 0.6 Sn = 0.30
Ba = 0.6 Si = 0.18
aThis value was determined by difference.
bNT = Not tested.
CND = Not determined.
-------
ON
$
r
G
TEST RESULTS AND ADDITIVE ANALYSIS (continued)
Add.
No.
18.
19.
20.
21.
22.
23.
Test dose
1:11,200
1:5,600
1:2,240
1:1,120
1:560
1:13,600
1:9100
1:920
1:21,500
1:28,600
1:11,900
1:8,925
1:7,150
Pollutant ratio
Total part.
ratio
1.0
1.0
1.0
1.0
1.68
1.0
1.0
1.0
1.0
1.0
0.65
0.68
0.55
Carbon
part, ratio
NDC
ND
ND
0.89
ND
1.0
1.0
0.89
1.0
1.0
0.59
0.59
0.46
SOX ratio
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
N0xratio
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
Additive composition, wt%
C
67.0
33.7
39.0
80.1
39.8
65.6
H
10.4
5.8
5.5
11.7
7.7
5.8
N
0.7
0.3
0.1
0.1
<0.1
<0.1
S
1.6
04.
0.4
0.4
0.3
0.1
Hal.
ND
ND
0.3
ND
0.1
ND
Oa
2.3
7.8
37.7
2.5
17.1
1.5
Ash
18.
52.
17.
5.2
35.
27.0
Metals
Ba = 7.2 Pb = 0.05
Ca -0.18
Mn = 24.8 Fe = 1.0
Ba = 6.9 Si = 2.4
Al= 1.3 Ca = 0.41
Mg = 10. Mn = 0.85
Ba = 0.85 Sb = 0.34
Zn - 3.0
Ba= 1.0
Mg = 10. Sb = 0.34
Mn = 0.85 Ca = 0.21
Fe = 20.
Tl
C
w
r
o
H^
r
>
o
u
H
-------
24.
25.
£ 26.
•o
a 27.
x"
a
in 28-
X
1 29.
fD
W
» 3°-
| 31.
f-r-
32.
1:5,360
1:3,775
1:4000
1:4000
1:4000
1:4000
1:4000
NTb
1:2500
1:1000
1:50
1:1000
1:50
0.64
0.53
1.15
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
0.44
0.34
ND
ND
ND
1.0
ND
ND
ND
ND
ND
ND
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
40.6
73.6
77.8
80.4
81.5
35.5
85.9
86.0
74.3
5.0
9.4
8.0
11.8
13.8
5.3
14.0
14.0
10.9
<0.1
0.1
<0.1
<0.1
0.2
<0,
<0.1
<0.1
<0.1
0.1
<0.1
<0.1
<0.2
<0.1
<0,
0.1
0.1
0.2
24.3
1.4
1.2
ND
ND
ND
ND
ND
ND
30.1
15.6
13.0
5.8
4.5
5.2
nil
nil
14.6
<0.2
<0.2
<0.2
2.0
<0.2
54.
<0.2
<0.2
<0.2
Zr= 1.0
Pb = 0.04
Mg = 35. Al = 0.5
Ca=1.5 Fe = 0.25
Se= 1.0 Pb = 0.15
ON
aThis value was determined by difference.
bNT = Not tested.
CND = Not determined.
-------
ON
TEST RESULTS AND ADDITIVE ANALYSIS (continued)
Add.
No.
33.
34.
35.
36.
37.
38
39.
40.
41.
Test dose
1:4000
1:1900
1:6000
1:4650
1:440
1:400
1:420
1:1000
1:193
1:1000
1:118
Pollutant ratio
Total part.
ratio
1.0
1.0
1.0
1.16
1.27
1.0
1.42
1.0
1.26
1.0
1.16
Carbon
part, ratio
NDC
1.0
1.0
1.0
1.24
ND
1.24
ND
0.72
1.0
1.16
SOX ratio
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
NOX ratio
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
Additive composition, wt%
C
89.8
62.2
58.6
62.8
86.5
86.1
83.4
85.0
83.1
H
7.6
9.8
9.0
10.1
12.2
13.3
12.3
14.0
12.3
N
0.7
<0.1
<0.1
<0.1
0.1
<0.1
<0.1
<0.1
0.5
S
0.7
3.1
1.7
1.9
<0.1
<0.1
<0.1
<0.1
0.1
Hal.
ND
ND
ND
ND
ND
ND
ND
ND
ND
Oa
1.2
nil
8.7
11.2
0.3
0.6
0.4
0.1
3.7
Ash
<0.2
25.
22.
14.
0.9
<0.2
3.9
0.9
0.3
Metals
Ba = 13.0
Ca - 0.05
Ca = 12
Mg - 5.6
Mg = 0.4 Pb = 0.07
P = 0.1 Co = 0.05
Mg = 0.2
Pb = 2.4
Fe = 0.5
Na = 0.09
Si = 0.045
w
>
r
c
o
z
o
^
^
w
r
o
HH
r
>
o
o
tn
-------
42.
43.
44.
"d
•d
re
3 45.
*'
46.
m
•d
re
|- 47.
re
3
£ 48.
58
re
g 49.
5?
50.
1:2000
1:2000
NTb
1:1175
1:1070
1:1210
1:320
1:200
1:400
1:50
0.77
1.0
1.0
1.0
1.0
1.0
1.0
1.0
0.71
ND
ND
0.87
0.84
0.85
ND
ND
1.0
0.71
1.0
1.0
1.0
1.0
1.0
1.0
1.4
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
60.5
60.5
3.7
76.5
79.2
77.0
86.8
73.1
46.5
9.3
9.3
1.4
10.9
9.0
10.8
12.7
8.3
10.4
<0.1
<0.1
3.8
<0.1
<0.1
<0.1
0.2
<0.1
<0.1
<0.1
<0.1
<0.1
0.4
0.3
0.4
<0.1
6.5
<0.1
30.0
30.0
ND
ND
ND
ND
ND
ND
ND
nil
nil
11.1
0.6
0.7
nil
0.3
11.1
43.1
0.2
0.2
80.0
11.6
10.8
11.8
<0.2
1.0
<0.2
K = 0.025
Na = 0.075
K = 0.025
Na = 0.075
Ca = 0.2 Mg = 50.
Fe = 2.0 Na = 0.5
Pb = 6.0 Mn = 0.4
Ba = 3.0
Pb = 5.5 Mn = 0.3
Ba = 2.8
Pb = 6.0 Mn = 0.4
Ba = 3.0
Fe = 0.01
aThis value was determined by difference.
bNT = Not tested.
Si CND = Not determined.
-------
TEST RESULTS AND ADDITIVE ANALYSIS (continued)
Add.
No.
51.
52.
53.
54.
55.
Test dose
1:5500
Cannister
Cannister
1:150
1:4000
1:1070
1:535
1:340
1:214
1:107
1:81
1:54
1:4000
Pollutant ratio
Total part.
ratio
1.0
1.0
1.0
0.57
1.0
1.0
1.0
0.67
0.68
0.80
1.0
1.0
1.0
Carbon
part, ratio
.87
NDC
ND
0.47
1.0
1.0
1.0
0.65
0.62
0.57
0.60
0.51
ND
SOX ratio
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
NOX ratio
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
Additive composition, wt%
C
70.2
5.0
87.4
86.6
91.6
H
10.4
3.2
8.0
7.8
7.6
N
<0.1
<0.1
0.2
0.1
<0.1
S
<0.1
0.1
<0.1
<0.1
<0.1
Hal.
ND
ND
ND
ND
ND
Oa
6.4
19.7
3.4
2.8
0.8
Ash
13.
72.
1.0
2.7
<0.2
Metals
Mg = 6.0 Ca = 0.045
Al -0.6
Si = 20.0 K = 3.0
Al = 10.0 Na = 3.0
Fe = 3.0 P = 3.0
Mg= 1.0
Ca= 1.0
Co = 0.3
Ca = 0.1
Co = .9
Ca = 0.01
ON
o\
W
>
S
o
z
o
c!
W
r
o
P
>
a
o
w
CO
-------
56.
57.
58.
•o
a.
x"
a
60.
W
x
"§ 61.
1 62.
£
£ 63.
??
H 64-
VI
1:4000
NTb
1:1000
1:26,600
1:1000
1:1000
1:1000
1:1000
1:50
1:8800
1:2000
1:1000
1.2
1.0
1.0
1.0
1.0
1.0
1.25
1.26
1.0
1.0
1.0
ND
ND
1.0
ND
ND
ND
1.25
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
88.5
0.3
92.3
37.6
80.5
82.5
84.6
80.0
29.8
11.4
0.1
7.7
5.6
13.0
9.6
9.9
12.3
10.4
<0.1
<0.1
<0.1
<0.1
0.3
0.9
1.0
<0.1
0.4
<0.1
<0.1
<0.1
0.4
0.1
1.0
0.9
<0.1
<0.1
ND
ND
ND
ND
ND
ND
ND
ND
ND
nil
39.6
nil
3.4
6.1
6.0
3.6
7.7
38.4
<0.2
60.0
<0.2
53.
<0.2
<0.2
<0.2
<0.1
21.
Na = 30.0 Ca = 0.2
Zn = 10.0
Fe = 1.0
Mg = 30.0
Ca = 1.5 Fe = 0.5
Al = 0.5 Si = 0.5
Na = 10.
Al = 0.02 Si = 0.1
aThis value was determined by difference.
bNT = Not tested.
CND = Not determined.
-------
ON
00
TEST RESULTS AND ADDITIVE ANALYSIS (continued)
Add.
No.
65.
66.
67.
68.
69.
70.
71.
72.
73.
Test dose
1:1000
1:1000
1:5000
1:5000
1:4000
1:50
1:4000
1:4000
1:1000
1:10,000
1:10,000
1:10,000
Pollutant ratio
Total part.
ratio
1.0
1.0
1.0
1.0
1.0
1.2
1.0
1.0
1.0
1.0
1.0
1.0
Carbon
part, ratio
NDC
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
SOX ratio
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
NOX ratio
1.0
1.0
1.0
1.0
1.0
1.2
1.0
1.0
1.0
1.0
1.0
1.0
Additive composition, wt%
C
62.3
76.1
83.0
83.1
74.5
70.4
77.8
78.0
83.2
H
6.9
11.8
11.6
12.3
7.0
6.3
14.0
14.3
11.4
N
4.2
0.1
0.4
0.5
8.0
7.8
5.4
5.2
0.7
S
0.2
<0.1
0.1
0.1
<0.1
<0.1
<0.1
<0.1
<0.1
Hal.
0.1
ND
ND
ND
ND
ND
ND
ND
ND
Oa
26.3
3.7
4.9
3.7
10.5
15.5
2.8
2.5
4.7
Ash
<0.2
8.3
<0.2
0.3
<0.2
<0.2
<0.2
<0.2
<0.2
Metals
Ba = 3.2
P = 0.4
Na = 0.09
Si = 0.045
d
M
r
o
i— i
r
>
o
o
H
N-I
w
-------
74.
75.
76.
77.
§ 78.
a
x"
p
tn
x
8 79.
3
1 80.
£.
PO 81.
a>
E.
on
1:4000
1:100
1:100
1:100
1:13,100
1:9000
1:6550
1:4920
1:3280
1:1280
1:3000
1:2000
1:1500
1:1000
1:1000
1:750
1:500
1:250
1.0
1.0
1.0
1.0
0.74
0.56
0.62
0.64
0.74
1.0
1.0
1.0
1.0
1.0
0.72
0.72
1.0
1.0
ND
ND
ND
ND
.72
ND
0.56
0.56
0.52
ND
ND
ND
ND
ND
ND
ND
ND
ND
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.98
1.77
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
78.2
44.9
49.5
69.7
50.3
73.0
56.4
84.4
11.5
8.6
9.2
10.6
3.4
7.8
5.7
12.8
0.2
10.3
9.3
<0.1
<0.1
0.3
<0.1
0.2
0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
nil
ND
ND
<0.1
ND
13.6
15.6
ND
9.8
36.2
32.0
19.5
23.3
5.3
22.3
2.6
0.2
<0.2
<0.2
0.2
23.
<0.2
<0.2
<0.2
Cu = 0.01
Al = 0.02
Mn = 24.8
Mn = 0.01
aThis value was determined by difference.
bNT = Not tested.
CND = Not determined.
-------
TEST RESULTS AND ADDITIVE ANALYSIS (continued)
Add.
No.
82.
83.
84.
85.
Test dose
1:1000
1:750
1:500
1:100
1:1750
1:1000
1:660
1:440
1 :330
1:220
1:110
1:4000
1:3000
1:2000
1:1000
1:500
1:250
Pollutant ratio
Total part.
ratio
0.78
0.65
0.64
0.64
1.15
1.0
1.0
1.0
1.0
0.88
0.72
1.0
1.0
1.0
1.0
1.0
1.0
Carbon
part, ratio
NDC
ND
0.51
0.38
1.0
1.0
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
SOX ratio
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
NOX ratio
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
Additive composition, wt%
C
84.8
80.8
86.1
86.8
H
13.1
9.8
10.2
9.8
N
0.1
<0.1
<0.1
3.0
S
<0.1
0.6
<0.1
0.1
Hal.
ND
ND
ND
ND
Oa
1.5
4.3
3.2
0.3
Ash
0.5
4.5
0.5
<0.2
Metals
Mn = .25
Ca = 0.05
Mg = 2.0
Fe = 0.1
Mn = 0.2
tfl
S
O
2!
O
r
o
i—i
r
>
o
a
-------
86.
87.
88.
£ 89.
1
~ 90.
P
| 9L
| 92.
3. 93.
£2-
8 94.
c
S? 95.
96.
1:400
1:4000
NTb
NT
NT
1:8000
1:5000
1:5000
1:1000
1:300
1:1000
1.0
1.0
1.0
1.0
1.0
1.26
1.0
1.4
ND
ND
ND
ND
ND
ND
0.73
ND
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
85.4
80.0
77.8
81.3
0.3
83.3
71.1
78.8
76.0
85.6
84.5
14.1
13.5
10.9
10.8
1.7
11.4
10.3
8.7
16.0
8.1
13.7
0.2
0.8
0.4
<0.1
5.8
0.9
0.4
<0.1
0.2
<0.1
0.1
1.5
0.5
<0.1
<0,
<0.1
0.2
0.1
0.4
<0.1
ND
ND
ND
ND
ND
ND
11.3
5.5
ND
ND
ND
nil
4.2
9.3
6.8
59.2
4.4
7.3
6.4
7.9
3.2
1.8
0.2
<0.2
1.1
1.1
33.
<0.2
<0.2
<0.2
<0.2
2.5
<0.2
Ca = 0.04
Cu = 0.6
P = 0.04
Cu = 0.6
P = 0.04
Na = 20. Cu = 0.2
Zn =5. Ca = 0.1
Cr = 0.02
Fe = 0.05
Ba = 0.4
aThis value was determined by difference.
bNT = Not tested.
CND = Not determined.
-------
TEST RESULTS AND ADDITIVE ANALYSIS (continued)
Add.
No.
97.
98.
99.
100.
101.
102.
103.
104.
105.
Test dose
1:525
1:480
1:480
1:480
1:480
1:480
1:2800
1:1000
1:500
1:250
1:125
1:625
NTb
1:480
Pollutant ratio
Total part.
ratio
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
0.69
0.69
0.78
0.85
1.0
Carbon
part, ratio
0.82
NDC
ND
ND
1.0
1.0
1.0
1.0
0.66
0.63
0.70
0.67
ND
SOX ratio
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
NOX ratio
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
Additive composition, wt%
C
79.4
86.3
86.5
86.2
81.6
86.6
87.5
4.0
85.6
H
12.3
13.5
13.4
13.8
14.0
13.4
10.7
0.6
13.6
N
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
0.1
<0.1
<0.1
s
0.1
0.1
0.1
<0.1
<0.1
<0.1
0.1
<0.1
<0.1
Hal.
ND
ND
ND
ND
ND
ND
ND
ND
ND
Oa
1.7
0.1
nil
nil
4.4
nil
1.1
21.4
0.8
Ash
6.5
<0.2
<0.2
<0.2
<0.2
<0.1
0.5
74.
<0.2
Metals
Pb = 3.0 Ca = 0.18
Ba = 0.6
Fe = 0.15
Na = 20. Cu = 3.0
Zn = 10.
M
>
r
>
H
^H
O
G
Pfl
r
o
H^
t-1
H
)-H
$
t/3
-------
106.
107.
108.
109.
1 110-
1
X
a in-
I 112'
n
g. 114.
M
50
I US.
5*
1:1000
1:1000
NT
1:150
1 :4000
1:1050
NT
1:3000
1:2760
1:2080
1:6000
1:1000
1.0
1.0
2.0
1.29
1.44
1.0
1.45
1.0
0.80
1.0
ND
ND
ND
1.21
1.19
1.0
.81
1.0
0.77
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
72.1
75.5
71.2
74.7
70.1
67.2
57.7
75.1
73.3
79.2
9.0
10.5
9.1
11.8
11.1
9.8
8.8
12.3
11.8
10.2
0.5
0.4
0.4
0.2
<0.1
5.9
1.1
<0.1
<0.1
0.1
<0.1
<0.1
<0.1
<0.1
0.1
<0.1
0.3
0.4
0.1
1.0
16.9
11.0
1.3
ND
ND
0.5
ND
ND
ND
ND
1.5
2.6
18.0
3.3
0.7
16.6
nil
0.2
9.0
nil
<0.2
<0.2
<0.2
10.
18.
<0.2
33.
12.
5.8
9.9
Ba = 4.0
Ba = 7.2
Ba = 18.9
Ba = 4.8
P= 3.6
Ba = 0.6
Pb = 3.0
Ba = 5.2
Pb = 0.1
aThis value was determined by difference.
bNT = Not tested.
CND = Not determined.
-------
TEST RESULTS AND ADDITIVE ANALYSIS (continued)
Add.
No.
116.
117.
118.
119.
120.
121.
122.
Test dose
1:3000
1:3000
1:2000
1:1000
1:750
1:1000
Canister
1:535
1:1000
1:10,000
Pollutant ratio
Total part.
ratio
1.0
1.0
1.0
1.0
1.0
0.88
1.25
1.43
1.0
1.57
Carbon
part, ratio
NDC
ND
ND
ND
ND
ND
ND
1.43
ND
1.57
SOX ratio
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
NOX ratio
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
Additive composition, wt%
C
63.9
71.0
70.7
3.0
83.0
85.4
71.4
H
9.0
8.8
9.9
1.2
12.1
14.3
12.5
N
0.1
0.1
0.1
1.0
<0.1
0.1
4.4
S
0.8
0.5
0.5
0.3
1.0
<0.1
<0.1
Hal.
ND
ND
ND
ND
ND
ND
ND
Oa
4.2
3.6
3.8
13.5
1.6
0.2
10.3
Ash
22.0
16.
15.
81.
2.3
<0.2
1.4
Metals
Pb = 12. Mn = 0.2
Ba = 8.0 Si =0.1
Ba = 2.9 Pb = 3.0
Mn = 0.15
Pb = 4.5
Ba = 2.9
Mn = 0.15
Mg = 47.9
Fe = 1 .0
Na = 0.6
Si = 0.014
K = 0.1 Ni = 0.05
P = 0.4 Mg = 0.03
Ca = 0.03
H
HH
O
21
O
r
o
D
O
HH
H
HH
<
-------
123.
> 124
£
TS
3 125.
Cu
*' 126.
P
1
1 127.
3
g 128.
E
£ 129
£
(-K
cn
130
131
1:1000
1:400
NTb
NT
1:156
NT
1:2000
1:3500
1:700
1:1000
1:1000
1.15
1.17
1.28
1.0
1.0
1.0
1.18
1.0
ND
1.14
1.24
ND
1.0
1.0
ND
ND
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
<0.1
80.4
0.3
84.8
64.8
80.9
82.7
81.1
1.4
0.6
12.5
0.3
9.4
11.0
13.3
11.0
11.5
4.2
2.2
0.1
0.2
0.3
0.1
0.1
0.4
1.6
<0.1
<0.1
<0.1
0.3
<0.1
1.7
0.1
<0.1
<0.1
ND
ND
ND
ND
ND
ND
ND
ND
ND
20.4
13.2
6.4
2.9
5.5
11.4
4.0
5.9
5.5
73.
84.
0.6
96.
<0.2
11.0
1.6
<0.2
0.3
Na = 30.
Cu = 3.0
Na = 25. Cu = 3.0
Zn = 5.0 Fe=1.0
Cu = .5
Mg = 40. Si = 0.3
Cu =1.0 Al = 0.1
Ca = 1.0
Na = 3.0 Al = 0.2
Si= 1.0
Mn = 0.8
P = 0.64
aThis value was determined by difference.
bNT = Not tested.
--J
<-" ND = Not determined.
-------
TEST RESULTS AND ADDITIVE ANALYSIS (continued)
Add.
No.
132.
133.
134.
135.
136.
137.
138.
139.
Test dose
NTb
NT
NT
1:1000
1:8000
1:6000
1 :4000
1:2000
1:1000
1:500
1:8000
1:110
1:1000
1:1000
Pollutant ratio
Total part.
ratio
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.28
1.0
1.28
Carbon
part, ratio
NDC
ND
ND
ND
ND
ND
ND
1.0
1.0
ND
ND
SOX ratio
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
NOX ratio
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.1
1.0
1.0
Additive composition, wt%
C
79.6
88.4
83.2
82.5
77.9
66.7
78.0
78.4
H
9.4
10.2
11.1
10.9
13.2
10.6
10.8
10.6
N
1.2
1.2
1.1
3.8
2.9
1.5
5.5
6.3
S
<0.1
<0.1
1.2
<0.1
<0.1
<0.1
<0.1
<0.1
Hal.
ND
ND
ND
ND
ND
7.4
ND
ND
Oa
9.8
0.2
3.4
2.8
6.0
13.2
5.7
4.2
Ash
<0.2
<0.2
<0.2
<0.2
<0.2
0.6
<0.2
0.5
Metals
Pb = 0.24 Cu = 0.03
Si = 0.06 Al = 0.018
Ni = 0.042
o
w
r
o
HH
r
>
o
a
H
w
en
-------
140.
141.
142.
143.
« 144-
CL
X 145.
O
146.
W
X
"rt I47-
| 148.
o? H9-
i.
150.
1:1000
:1000
NT
NT
1:1000
NT
NT
NT
1 :4000
1:1000
1:1000
1.0
1.0
1.0
1.0
1.24
1.0
ND
ND
0.79
ND
1.0
ND
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.1
1.0
1.0
1.0
1.0
79.9
80.3
76.5
61.2
82.2
68.8
66.6
1.2
61.2
76.3
86.4
10.9
10.2
12.1
8.0
12.0
11.4
11.4
0.7
9.7
8.9
8.4
5.8
3.7
<0.1
<0.1
<0.1
0.2
15.3
<0,
<0.1
<0.1
<0.1
<0.1
2.5
1.8
1.2
2.0
1.8
7.3
<0,
<0.1
<0.1
ND
ND
ND
ND
ND
0.1
18.0
ND
nil
ND
ND
3.4
5.8
0.2
8.0
nil
12.8
37.3
28.8
5.9
5.2
<0.2
<0.2
8.7
21.
4.8
4.7
2.9
38.
0.3
8.9
<0.2
Ca = 3.6
Ca = 12.
Ca = 2.0
Mn = 2.0
Mg = 1.0
K= 30.
K = 0.03
Na = 0.075
Pb = 5.4
Si = .45
aThis value was determined by difference.
bNT = Not tested.
CND = Not determined.
-------
TEST RESULTS AND ADDITIVE ANALYSIS (continued)
Add.
No.
151.
152.
153.
154.
155.
156.
157.
158.
159.
Test dose
1:65
NTb
1:1000
NT
NT
1:4000
1:2500
1:780
1:3750
1:1800
Pollutant ratio
Total part.
ratio
1.0
1.0
1.0
1.0
1.0
1.0
1.0
Carbon
part, ratio
0.84
1.0
1.0
1.0
1.0
1.0
1.0
SOX ratio
1.0
1.0
1.0
1.0
1.0
1.0
1.0
NOX ratio
1.0
1.0
1.0
1.0
1.0
1.0
1.0
Additive composition, wt%
C
77.3
37.3
77.2
52.6
31.4
90.4
78.6
60.4
67.6
H
8.7
8.6
8.3
10.0
8.2
8.1
9.8
7.2
10.1
N
<0.1
<0.1
<0.1
0.1
<0.1
0.4
0.1
<0.1
<0.1
S
<0.1
0.3
<0.1
0.5
0.4
<0.1
0.3
<0.1
0.5
Hal.
ND
ND
12.5
ND
0.1
ND
ND
0.4
ND
9.1
24.8
2.0
7.8
30.9
0.5
2.2
nil
2.8
Ash
4.9
29.
0.2
29.
29.
0.6
9.0
32.
19.
Metals
Pb = 03.0 Ni.= 0.05
Si = 0.25
Cu = 0.25
Mg = 12. Si = 0.3
Ca = 0.6 Al=0.15
Mg=18. Al = 0.3
Ca = 0.9
Al= 12.
Na = 0.15
Ca = 0.4
Pb = 6.0
Si = 14.6
P = 0.36
Pb = 13.3
Ca = 1.0
oo
M
h-H
O
W
r
o
HH
r
>
o
o
-------
160.
161.
| 162.
a
O 163.
T3
|- 164.
n
1
M 165'
tW
£ 166.
167.
1:9800
1:4000
1:1600
1:21,000
NT
NT
1:850
NT
1:1250
1:1000
1.0
1.0
1.0
1.0
0.86
1.0
1.23
1.0
1.0
1.0
1.0
0.85
1.0
NDC
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
78.8
31.0
10.5
10.6
78.3
37.6
83.1
80.1
11.8
6.5
2.2
1.5
12.5
5.6
12.9
9.4
0.5
<0,
2.2
3.6
<0.1
<0,
<0.1
0.1
1.9
0.4
<0,
<0.1
0.6
0.1
0.9
<0.1
ND
0.1
ND
ND
ND
ND
ND
ND
nil
27.0
24.1
26.3
5.5
2.7
0.5
10.4
7.3
35.0
61.
58.
3.1
54.
2.6
<0.2
Ca = 3.2
Na = 0.04
Mg= 17.5
Zn = 15.0 Si = 2.5
Na = 30. Cu = 3.0
Zn = 3.0
Mg = 20. Fe = 4.0
Na=3.0 Ca=15.
Cu = 3.0
Na = 0.6 P = 0.18
Cu = 0.45 Mg = 0.09
Mg=2.7 Ca=1.6
Cu = 2.7 Si =1.1
Pb = 0.03
Na= 1.4
10
aThis value was determined by difference.
bNT = Not tested.
CND = Not determined.
-------
oo
o
W
>
r
I
TEST RESULTS AND ADDITIVE ANALYSIS (continued)
Add.
No.
168.
169.
170.
171.
172.
173.
174.
175.
176.
Test dose
1:185
1:480
1:1420
NTb
NT
1:1000
1:1000
1:8000
1:5000
Pollutant ratio
Total part.
ratio
1.28
1.0
1.0
1.0
1.0
1.0
1.19
Carbon
part, ratio
1.18
1.0
1.0
ND
ND
ND
ND
SOX ratio
1.0
1.0
1.0
1.0
1.0
1.0
1.0
NOX ratio
1.0
1.0
1.0
1.0
1.0
1.0
1.0
Additive composition, wt%
C
84.5
70.6
77.0
2.7
5.1
70.3
82.1
74.2
90.6
H
9.9
8.1
10.4
0.7
0.8
9.2
13.3
13.3
7.4
N
<0.1
<0.1
1.8
<0.1
<0.1
2.4
0.4
7.1
0.5
S
<0.1
0.1
0.1
0.3
0.1
<0.1
<0.1
<0.1
0.7
Hal.
ND
0.1
ND
ND
ND
0.1
ND
ND
ND
Oa
4.8
18.9
7.0
16.3
21.0
18.0
4.2
5.4
0.8
Ash
0.8
2.3
3.7
80.
73.
<0.2
<0.2
<0.2
<0.2
Metals
Cu = 0.24
Mn = 0.24
Zn = 0.8 Mg = 0.2
Pb = 0.6
Mg= 1.6
Ca = 0.16
Na = 20. Si = 4.0
Zn = 10. Al = 2.0
Ca=5.0 B=1.0
Fe= 1.0
Zm = 20. Si = 5.0
Ma = 10. Al = 3.0
Ca =10. B= 1.0
r
o
h-H
r
m
t/3
-------
177.
178.
179.
> 180.
1 18L
x"
p
w
X
1 182-
£ 183.
| 184.
K"
185.
186.
1:685
1:1000
1:1000
1:800
1:2000
1:1500
1:1000
1:750
1:500
1:250
1:1000
1:1000
1:1000
1:1000
1:20,000
1.14
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.17
1.26
1.22
1.19
1.0
1.0
1.14
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
83.8
64.8
74.6
77.2
61.1
81.7
71.3
71.9
72.9
8.3
9.5
12.6
8.3
8.2
11.7
13.3
12.8
12.5
0.4
1.6
7.0
<0.1
<0.1
<0.1
6.2
6.5
6.0
0.7
<0.1
<0.1
<0.1
<0,
<0.1
<0.1
<0.1
<0.1
ND
21.9
ND
12.5
9.1
ND
nil
nil
ND
4.9
2.2
5.8
2.0
21.6
5.0
9.2
8.8
8.6
1.9
<0.2
<0.2
<0.2
<0.2
1.6
<0.2
<0.2
<0.2
Mg = 0.6 Si = 0.04
Na = 0.4
Pb = 0.6 P = 0.1
oo
aThis value was determined by difference.
bNT = Not tested.
CND = Not determined.
-------
00
W
H
O
1
w
o
H-(
r
W
C/5
TEST RESULTS AND ADDITIVE ANALYSIS (continued)
Add.
No.
187.
188.
189.
190.
191.
192.
193.
194.
195.
196.
197.
198.
199.
Test dose
1:20,000
1:20,000
1:20,000
1:1000
1:1000
1:1000
1:1000
1:1000
1:1000
1:4000
1:5000
1:1000
1:1000
Pollutant ratio
Total part.
ratio
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
Carbon
part, ratio
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1.0
ND
ND
SOX ratio
1.0
1.0
1.0
1.0
1.12
1.0
1.0
1.0
1.0
1.0
l.Q
1.0
1.0
NOX ratio
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
Additive composition, wt%
C
79.3
78.8
84.8
81.4
74.0
77.2
70.8
65.9
65.8
87.3
59.6
76.4
90.2
H
10.8
9.1
13.1
11.2
10.9
11.3
10.5
9.5
5.9
11.9
8.9
12.9
8.2
N
3.5
1.0
0.1
0.1
4.3
1.6
1.5
1.5
8.6
<0.1
0.1
<0.1
0.3
S
<0.1
<0.1
<0.1
0.3
9.1
3.5
<0.1
2.6
0.1
0.1
1.7
<0.1
0.3
Hal.
ND
5.6
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.1
ND
Oa
6.4
5.5
1.5
6.7
1.7
6.4
17.2
20.5
19.6
0.7
8.7
10.6
0.8
Ash
<0.2
<0.2
0.5
0.3
<0.2
<0.2
<0.2
<0.2
<0.2
<0.2
21.
<0.2
0.2
Metals
Mn = 0.25
Ca = 10.
-------
200.
201.
.
"O
T5
0>
3
~ 202.
a
tn
a>
i-t
§' 203.
re
EL
50
1 204.
5?
205.
206.
:1000
:2000
:1500
:1000
1:750
1:500
1:185
1:1500
1:1000
1:500
1:370
1:185
1:500
1:302
1:151
1:4000
1:4000
1 :4000
1.0
1.0
1.0
1.0
1.0
1.0
1.33
1.0
0.82
1.0
1.17
1.59
1.0
1.0
1.0
1.0
1.0
1.0
ND
1.0
0.76
0.81
0.88
1.0
1.0
ND
ND
ND
ND
1.0
1.0
ND
ND
ND
ND
ND
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
91.8
76.2
78.2
80.7
75.3
79.2
75.0
8.2
11.7
7.4
10.4
11.1
7.1
8.8
<0.1
<0.1
1.2
0.3
<0.1
0.5
0.2
<0.1
0.2
<0.1
1.4
<0.1
<0.1
<0.1
ND
ND
0.2
ND
nil
3.2
8.7
nil
2.6
12.0
6.3
13.4
10.0
7.1
<0.2
9.3
1.0
0.9
0.2
<0.2
0.2
Ba = 4.5 P = 0.9
Fe = 0.27
Mn = 0.5
Fe = 0.4
Sn = 0.05
Fe = 0.06 Pb = 0.01
Cr = 0.02
00
OJ
aThis value was determined by difference.
bNT = Not tested.
°ND = Not determined.
-------
BIBLIOGRAPHY
1. Wasser, J. H., R. P. Hangebrauck, and A. J. Schwartz. Effects of air-fuel
stoichiometry on air pollutant emissions from an oil-fired test furnace.
JAPCA. 18(5):332-37.May 1968.
2. Wasser, J. H., G. B. Martin, and R. P. Hangebrauck. Effects of combus-
tion gas residence time on air pollutant emissions from an oil-fired test
furnace. IniProc. 1st National Oil Fuel Institute New and Improved Oil
Burner Equipment Workshop. Linden, N. J. Sept. 17-18, 1968. NOFI
Tech. Publ. 106 Ed. pp. 110/1 110/13.
3. Riggs, R. J., T. J. Wilkison, and H. R. Wolfe. Combustion improvers for
fuel oils. Ethyl Corporation Publication. 1966.
4. Arapahoe Chemical Catalog. Arapahoe Chemicals. Division of Syntex
Corp. Boulder, Colo.
5. "Ethyl" Combustion Improver Literature. Ethyl Corporation. New York.
6. Litton Systems, Inc. Preliminary air pollution survey of manganese and
its compounds: a literature survey. Oct. 1969. Contract No. PH
22-68-25, Air Pollution Controll Office. Raleigh, N. C. Pub. No. APTD
69-39.
7. Litton Systems, Inc. Preliminary air pollution survey of iron and its
compounds: a literature survey. Oct. 1969. Contract No. PH 22-68-25,
Air Pollution Control Office. Raleigh, N. C. Pub. No. APTD 69-38.
8. Sax, N. I. Dangerous Properties of Industrial Materials. Reinhold Publish-
ing Corporation. New York. 1963.
9. Howekamp, D. P., and M. H. Hooper. Effects of combustion-improving
devices on air pollutant emissions from residential oil-fired furnaces. Air
Pollution Control Office. Cincinnati, Ohio. 1970.
10. Howekamp, D. P. Flame retention effects on air pollution. NOFI Annual
Convention. Atlantic City, N. J. June 1970.
11. Martin, G. B. Use of Fuel additives and combustion improving devices to
reduce'air pollution emissions from domestic oil furnaces. Air Pollution
Control Office. Cincinnati, Ohio. 1970.
85
-------
12. Colborne, W. G. Performance of intermittently fired oil furnaces. Heat,
Piping, and Air Cond. p. 147-150. April 1957.
13. Chass, R. L. et al. A joint project, emissions of oxides of nitrogen from
stationary sources in Los Angeles County. Report No. 1. p. 24-34. Los
Angeles County Air Pollution District. Los Angeles. February 1960.
14. Lisle, E. S., and J. D. Sensenbaugh. The determination of SO3 and acid
dew point in flue gases. Combustion, 36:12-16. January 1965.
15. Shell Development Company Analytical Department. Determination of
sulfur dioxide and sulfur trioxide in stack gases. Emeryville, Calif. 1959.
86 EVALUATION OF FUEL OIL ADDITIVES
------- |