Note: Descriptions are shown in the official language in which they were submitted.
i60'7
Technical Field
The present invention relates to improving the
performance of internal combustion engines, both
ga~oline and diesel; and, more particularly, to the
formulation and use of fue:L additives and fuels
which burn more e~ficiently and with reduced noxious
emissions. : :
BackqL~und Art
Prior investigations involving the use of
platinum group metals in internal combustion engines
have led to the developmen~ of the catalytic
converter for emissions reduction. Reliance upon
costly mechanical equlpment, while less than ldeal
~3~
or desirable, has become standard despite the
efforts of the prior art to accomplish the same
result through less costly combustion improvements
in terms of better combustion conditions through
engine design and fuel additives. The efforts in
engine design have provided significant
improvemen~s, but the twin objectives of improved
operating efficiency and reduced noxious emissions
are difficult to achieve simultaneously.
E~perience to date with fuel additives has been
less successful, due in part to the complicated
eguipment necessitated for their introduction into
the fuel supply and in part to their cost where they
include more exotic catalytic materials. For
example, in U.S. Patent 4,295,816, Robinson
discloses an elaborate delivery system for
introducing water-soluble platinum group metal salts
through the air intake of internal combustion
engines to deliver platinum group metal catalysts to
the combustion chamber at a level no greater than 9
mg catalyst per kilogram of ~u~
In U.S. Patents 2,086,77!; and 2,-15l,432, ~yons
and McKone disclose addiny from O.OOl to 0.085~
(i.e., from lO to 850 part~; per million) of an
organometallic comp~und or mi~ture to a base fuel
such as gasoline, benzene, fuel oil, kerosene, or
blends to improve various aspects of engine
performance. Among the metals disclosed in U.S.
2,086,775 are cobalt, nickel, manganese, iron,
copper, uranium, molybdenum, vanadium, zirconium,
beryllium, platinum, palladium, chromium, aluminum,
thorium and ~he rare earth metals, such as cerium.
~.311~
~mong those disclosed in U.S. 2,151,432 are
selenium, antimony, arsenic, bismuth, cadmium,
tellurium, thallium, tin, barium, boron, cesium,
didymium, lanthanum, potassium, sodium, tantalum,
titanium, tungsten and zinc. In both di~closures,
the preferred organometallic compounds were beta
diketone derivati~es and their homologues, such as
the metal acetylacetonates, propionylacetonates,
formylacetonates, and the like. Such compounds
typically provide oxyyen-to-metal ratios in the
range of 1:1 to 1:10, and no essential feature
linked to the presence of oxygen is disclosed.
The Lyons and McKone disclosures state that
concentrations of from 0.001 to 0.04% (i.e., from 10
to 400 parts per million) are not effective to
improve combustion efficiency as introduced, but may
become so upon prolonged use as catalytically active
deposits are built up in the combustion chamber.
The disclosure further states that about 0.01%
(i.e., 100 ppm) of the organometallic compound is
usually suf~icient, once the requisite amount of
catalytically active depositE: has been built up, to
; perpetuate that amount of deposits by replacement of
losses therefrom. The compounds disclosed ware,
therefore, not capable o~ generating any instanta-
neous catalytic effect at low concentxations. U.S.
Patent 2,460,780 to Lyons and Dempsey, which relates
principally to water-soluble catalysts, confirms
this at column 1, lines 11-36. Further, no
indication was made for preferred oxidation states
for the ~etals disclosed.
Neither of the Lyons and McKon~ patents
disclose the use of oxygenated solvents or point to
the importance of high oxygen to metal ratios. In
Demonstration 15 in U.S. Patent ~,086,775, palladium
i6()7
- 4
acetylacetonate wa~ added to a fuel ~not specifi-
cally identified, but presumably the leaded 65
octane gasoline employed in ~emons~ration 1) at a
level of 0.002% (20 ppm). The weight ratio of
oxygen to palladium was not mentioned, although by
calculation it is found to be about 1 to 3, and the
level of palladium is found to be about 10 ppm. No
improvement in combustion was noted until after
substantial driving.
The above-noted U.S. Patent 2,460,780 to Lyons
and Dempsey relates principally to employing
catalysts which are soluble in water or other
l'internal li~uid coolants" such as alcohol, water~
soluble glycols or aqueous solutions of ~hese.
While catalyst levels based on the weight of metal
compounds as low as 0.001% are disclosed, it is
stated that for immediate catalytic effect the
catalyst compounds for useful effect may be present
at a level of at least 1% of the weight o the
;20 operating fuel charge. In some Examples, fuel-
~`soluble cobalt, cerium and c~hromium catalysts are
added to the fuel at total catalyst. levels of 0.01%.
No disclosure is given of fuel-soluble catalysts at
levels below 0.01% or with oxygenated solvents.
Moreo~er, where alcohol and glycols are employed
with water-soluble catalysts, they are disclosed
principally as solubilizing carriers for the
catalrysts and for their known internal cooling
function at high load.
In German Offenlegungsschrift 2,500,683, Brantl
discloses that a wide variety o catalytic metals
may be add~d to hydrocarbon fuels to reduce nitrogen
monoxide and oxidize carbon monoxide at the moment
of combustion in internal combustion engines. The
disclosure states that organometallic or Grignard
~L3C)~(3~17
- _ 5 _
compounds of the metals lithium, sodium, lead,
beryllium, magnesium, aluminum, gallium, zinc,
cadmium, tellurium, selenium, silicon, boron,
germanium, antimony and/or tin can be added to the
fuel individually or as a mixture. Similarly, the
metal complexes of the metals scandium, titanium,
vanadium, chromium, manganese, iron, cobalt, nickel,
copper, zinc, ruthenium, rhodium, palladium, osmium,
iridium, platinum, silver, gold, gallium,
molybdenum, lead and mercury, with different
ligands, can be added to the fuel individually or as
a mixture. For the platinum group metals osmium,
iridium, and platinum, broad concentrations of from
0.347 to 3.123 grams per liter of fuel are suggested
for the various compositions listed in the
disclosure, with the range for particularly
favorable results being from 0.868 to 1.735 grams
per liter of fuel. Considering the cost of these
metals and the compositions containing ~hem, there
is a negative incentive for employing them at the
high levels state~ by the disclosure to be
effective. Moreover, the tetramethyl platinum
compound is not known to exist..
In U.S. Patent 2,402,427, ~iller and Lieber
~5 disclose the use of cPrtain diesel-fuel-soluble
organic or oryanometallic compounds as ignition
~ promoters at concentrations of from 0.02 to 3%
; (i.e., 200 to 30,000 parts per million). No
platinum group metal compounds are identified and no
indication is given that the disclosed compounds at
the disclosed or lower levels would improve
combustion in a gasoline internal combustion engine.
Othex work done, in which cylinders of a diesel
engine were coated with platinum metal, showed
reductions in no~ious emissions, but the coating
wore off in a number of hours.
:~3C~5i6~:1'7
Disclosuxe of Inve tion
The present invention comprises the application
of certain platinum group metal compounds which are
directly soluble in engine fuels, such as diesel
fuel or gasoline, or solvents for use in internal
combustion gasoline and diesel engines. The
compounds, preferably in combination with a solvent
for them which is also miscible in the uel, are
emplsyed at very small, but catalytically effective
levels of from 0.01 to about 1.0 parts of platinum
group metal per one million parts of fuel ~ppm).
For the purposes of this description, all part per
million figures are on a weight to volume basis,
i.e., mg/liter, and percentages are given by weight,
unless otherwise indicated.
Accordi.ng to one its aspects, the invention
provides gasoline and diesel fuel additive
compositions comprising a solution of a fuel-soluble
platinum group metal compound in a solvent miscible
in the fuel, the platinum group metal compound being
present in an amount sufficient to supply from 0.01
to 1.0 parts pex million of the platinum group metal
when added to a predetermined amount of fuel.
Preferred solvents are oxygenated hydrocarbons
such as ethanol, tetrahydrofuran, and methyl
tertiary butyl ether, and will preferably be
emp7oyed in amounts of less than 5% of the weight o
the fuel. The oxygenated solvents will preferably
be employed in amounts sufficient to supply oxygen
at a weight ratio to the platinum group metal of at
least 1000.1.
~ mong the preferred platinum group metal
compounds are platinum group metal coordina-tion
compounds comprising a platinum group metal having a
- 7 -
~2 or +4 coordination state with at least one
coordination site in the compound beiny occupied by
a functional group containing at least one
unsaturated carbon-to-carbon bond with an olefinic,
acetylenic or axomatic pi bond configuration.
Especially preferred compounds are those of the
formula:
L~ \R
wherein M is a platinum group metal and R is benzyl,
phenyl or nitrobenzyl.
According tv another aspect of the invention,
ga~oline and diesel fuel compositions of improved
properties are provided, which comprises gas~line or
diesal fuel and an additive composition dissolved
therein, said additiye composition comprising a
fuel-soluble platinum group metal compound in an
amount effective to supply from 0.01 to 1.0 parts of
-the platinum group metal per million parts of ~uel.
According to a further aspect of the present
invention, there is provided a method of increasing
20 the utilizable energy of gasoline or diesel fuel for
powering internal combustion engines, comprising
admixing with said gasoline or diesel fuel an
additive composition cumprising a fuel-soluble
platinum grsup mekal compound in an amount effective
to supply from O.01 to 1.0 parts of the platinum
group metal per million parts of fuel.
The additive compositions accordiny to the
invention improve operating efficiency of gasoline
~3~5~ 7
and diesel internal combustion engines in term~ of
increas~d power outpu~ per unit of gasoline burned
and reduce the emissions of particulates and noxious
gases such as carbon monoxide and nitrogen monoxide.
The additives provide beneficial results upon
immediate use and over long periods of continuous
use.
For the purposes of this description, gasoline
is defined as a mixture of volatile hydrocarbons for
use in a spark-ignited internal co~bustion engine
and ha~ing an octane rating [(Research ~ Motor)/2]
of at least ~0, typically about 87 to 89 or above,
and according to the more preferred aspects of the
invention as having less than 1.4 grams per gallon
of lead. Most preferably, the gasoline will be
"unleaded" and contain no more than 0.05 grams of
lead per gallon and no more than 0.1% of sulfur.
Gasoline typically has a BTU value of about 19,700
calories per pound.
The gasoline additive compositions of this
invention achieve the most :reproducible effect in
engines operated under lean conditions, namely an
air to fuel ratio of about 14.7:1, and at
compression ratios from about 7:1 to 9~
~iesel fuels, ~or the purposes of this
: description, are defined as fuel oil number 2
petroleum distillates of volatility and cetane
number characteristics e.~fective for the purpose o.
fueling internal combustion diesel engines.
. 30 ~s indicated above, the preferred platinum
: group metal compounds are coordination compounds.
These compounds, especially those coordinated with
certain high molecular weight (preferably above 100
daltons) olefinic functional groups~ are stable in
~3~5~0'7
the presence of moisture. This is extremely
important due to the amounts of watsr present in
gasoline and diesel fuels. Gasoline, for example,
will typically contain dissolved water in amount;s on
the order of 30 ppm and frequently contains higher
levels of dispersed and bulk water.
Few, if any, platinum group mekal coordination
compounds which are directly soluble in gasoline or
diesel Euel are available commercially. Compounds
which are available often contain objectionable
functional groups containing halogen and phosphorus
and, therefore, are less ~han preferred for many
internal combustion applications. Preferably, the
~" compounds according to the present invention will
; 15 have no phosphorus or have low levels which are free
of significant disadvantages. We have discovered
that certain platinum group metal compounds can be
prepared which are soluble and stable in the fuels
and actively catalyze the combu~tion of gasoline and
diesel fuel in internal combustion engines and
reduce noxious emissions when in~roduced as an
I integra~ part of~the fuel.
;~ The preferred class of materials used include
platirlum group metal coordination states Il and IV.
Compounds in the lower (II)~state of ox.idation are
preferred due to their function in generating the
catalytic effect. A significant feature o~ the
~' invention is the use of platinum ~roup metal II
coordi~ation compound having at least one
coordination site occupied by a functional group
containing an unsaturate~ carbon-to-carbon bond of
the olefinic, acetylenic or aromatic pi bond
configuration. Preferably, two or more of the
; coordination sikes will be occupied by such
functional groups since the stability and solubility
6~
-- 10 --
in gasoline and diesel Euel of compounds having such
multiple functional groups are improved. While
wishing not to be bound ~o any particular theory, it
is believed that such preferxed compounds in the
lowest possible oxidant state are the most
beneficial for producing instantaneous catalytic
effect.
Occllpation of one or more coordination sites
with the following unsaturated functional groups
have been found useful:
1. Benzene and analogous aromatic compounds
such as anthracene and naphthalene.
2. Cyclic dienes and homologues such as
cyclooctadiene, methyl cyclopentadiene,
lS and cy~lohexadiene.
3. Olefins such as nonene, dodecene, and
polyisobutenes.
4. Acetylenes such as nonyne and dodecyne.
These unsaturated functional groups, in turn,
can be substituted with nonhalogen-, substituents
such as alkyl, carboxyl, amino, nitro, hydroxyl and
alko~yl groups. Other coordination sites can be
directly occupied by such groups.
The general formula ~or the preferred
coordination II compounds is:
~ \ ~ B
where M xepresents the platinum group metal, with
13~$~
a valence of +2, where A, B, ~, and E are groups
such as alkoxy, carboxyl, etc. described above,
where (C = C)x and (C = C~y represent unsaturated
functional groups coordinated with the platinum
group metal, and where x ~nd y are any integer.
Platinum group metals include platinum,
palladium, rhodium, ruthenium, osmium, and iridium.
Compounds including platinum, palladium and rhodium
are preferred in the practice of this invention.
The most preferred platinum group coordination
compound~ are those represented by the following
formula:
~' R
R
(
wherein M is a platinum group metal and R is benzyl,
phenyl or nitrobenzyl.
The platinum group metal compound will be added
to gasoline or diesel ~uel in an amount effective to
improve engine performance in terms of operating
- efficiency or emissions reduction. Typically, the
~, compound will supply an amount of the metal within
.
~ 20 the range o~ from 0.01 to 1.0 parts of the platinum
'i, group metal per one million parts of gasoline
(ppm w/v). A more preferred range is from 0O05 to
O.S ppm, and mos~ preferably, ~he platinum group
metal will be supplied at a level of from 0.10 to
0.30 ppm on this same basis.
The ~uel additive composition will preferably
include a solvent which is miscible in the intended
`~ fuel, be it gasoline or diesel fuel. Certain of the
- ~3~5~3'7
- 12 -
solvents provide enhancements in the effectiveness
of the platinum group metal compound and are
preferred for this rea~on. Among the preferred
solvents are oxygenated hydrocarbons, such as
alcohols, heterocyclic oxygen compounds and ethers.
Particularly pxeferred compounds are: 1 to 4 carbon
alcohols, especially ethanol; te~rahydrofuran; and
methyl tertiary butyl ether. Some of these
compounds, as will be seen from the examples which
follow, show especially strong enhancements with
particular platinum group metal coordination
compounds. Octyl nitrate functions well in diesel
fuel additives.
The solvent will preferably be employed at a
concentr~tion of up to 5% of the fuel and typically
greater than 0.25%. Solvent concentrations of from
0.25 to 2.5% are preferred, and are most preferably
1.0% or less, and in some cases show surprising
improvements in additive performance when employed
at these levels.
The preferred fuel additives will employ
suficient amounts of platinwn group metal compounds
and oxygenated solvent to prc~vide a weight ratio of
oxygen to platinum group met:al of from 1,000:1 to
100,000:1, preferably greater than 3,500:1. More
preferred oxygen to platinum group metal weight
ratios are from S,000:1 to 35,000:1.
The fuel additive compositions can con~ain
other additives such 2S deter~ents, antioxidants and
octane improvers which are known as beneficial, but
the use of such is not an essential feature of the
invention.
The following examples are presented for the
purpose of further illustrating and explaining the
present invention and the best mode for carrying it
out, and are not to be taken as limiting.
~3~ t7
13 -
Example 1
Dibenzyl cyclooctadiene Pt II was used as a
catalyst in unleaded gasoline supplied to an
automobile engine.
5Production of dibenzyl cyclooctadiene platinum
II was accomplished by slurrying 24.0 grams
(0.06~ mole) cyclooctadienyl Pt II dichloride in 200
milliliters of ~ylene. To the resultant mixture was
added 0.5 mole benzyl magnesium chloride in diethyl
ether (300 milliliters). The Grignard reaction was
continued overnight, followed by hydrolysis with
saturated ammonium sulfate solution in an ice bath.
Following hydrolysis, the mixture was shaken
vigorously and the layers were then allowed to
separate. The organic phase was collected, dried
over anhydrous sodium sulfate, and the residual
diethyl ether was removed, leaving a solution of the
product in xylene. This product has the structure:
. .
:
The xylene solution of the platinum compound
(0.17% by weight platinum) was admixed with other
fuel additive components set forth in Table lA
~elow.
~3~5t~
- ~4 -
A series of dynamometer -tests were conducted,
in which a 1984 Buick V 6 spark ignition engine was
connected to and loaded by an eddy current
dynamometer. The engine had the follot~ing
sp~cifications:
Engine Type Buick 90~V~6
Bore and Stroke 3.800 x 3.400
Piston Displacement 231 cu. in.
Compression Ratio 8.0:1
Carburetor T~pe 2 BBL-ROCH
Air - Fuel/Ratio 14.7:1
Data gathered during comparative engine tests
run on the Buick V-6 engine using unleaded Indolene
gasoline with a platinum-based fuel additive
formulation basad on the fol.Lowing ingredients with
a ~uel employing all compone~nts of the formulation
; except the platinum compound:
Table IA
Percent by
' Weight
Xylene 58.6
Methyl Tertiary Butyl Ether 40.5
Detergen~ (Ethyl MPA-448) 0.9
~. 25 Platinum Coordination`Compound as
:, p~epared above 0.012
. This platinum co~pound has the
l following elemental breakdown:
i Platinum 40.2~ :
Carbon 54.4~
'. Hydrogen 5-4Z
,i _
Th~ engine was run under steady conditions for about
ninety t90) minutes per run at about 1300 rpm and
~3~t56~)7
was loaded to about 79 ft. lb. torque by a dynamo-
meter ~o develop, on an average, 19.6 horsepower
throughout each run.
During each of these runs, the time the engine
took to consume a measured 900-milliliter quantity
of gasoline with and without the platinum compound
was recorded. For each run, such time readings were
taken on three occasions and the time averaged. The
product of the horsepower and average time ~in
minutes) to use 900 milliliters of fuel gave numbers
representing work. The results are summarized below
in Table lB.
Tabl~ lB
Ba~eline Run WorkRun with Additive Work
1 176.4 1 186.2
2 178.3 2 182.7
3 176.1 3 ~.84.1
4 175.8 4 181.5
20 5 179.2 5 184.0
6 178.8 6 189.5
7 180.0 7 184.3
: 8 177.1 8 1~3.0
9 180.5 9 183.3
2510 178.8 10 182.4
11 179.7 11 183.5
12 182.7
13 181.8
._
The consumption times for 900 milliliters of
gasoline containing 0.1 ppm of platinum supplled by
the platinum compound wera generally longer than the
consump~ion times without the platinum compound.
The average time wlth the platinum compound was 9.39
- 16 -
minutes, and withou~ was 9.11 minutes. This
improvement of fuel consumption due to the platinum
compo~lnd was 3.1%.
Fuel flow measurements showed a range of fuel
efficiency gains of three percent (3%) to six
percent (6%) with the platinum-based addi.tive
compared to the fuel additive formulation minus the
platinum-based compound in a series of similar
tests.
Exa~ple 2
The procedure of Example 1 was repeated, but
this time employing 5% ethanol in addition to the
fuel additi~e of Example 1 (at O.2 ppm of platinum
: w/v). Baseline data was collected for 2 days and
15 test data was noted on 12 day~ after an initial five
days of op~ration employing the additive. The test
engine was run at ~hree rpm's (1300, 1800 and 2100)
, in sequence ~n each test da~, all at a torque of 55
1~ lb . ft. The data collected for fuel flow and
20 hydrocarbon and carbon monoxide emissions are
summarized below in Table 2~
: :
..
Table 2
I Fuel FlowMydrocarbons Carbo~ Mo~oxide (O
`:i! 25(ml/see~ ~ppm w/v)
With : With With ~ :
RP~ Baseline Additive Baseline Additive Baseline Additive
:, 1300 1.12 1.07 210 135 1.79 0.6~
1800 1.~2 1.76 169 113 1.05 ~.40
~ 30 2100 2.20 2.15 l20 73 0.53 0.17
:; '
~3~S60~7
- 17 -
ExamE~le 3
Additive testin~ was performed with a Buick
engine having the specifications described in
Example 1, mounted on a Superflow SF-901 water brake
S dynamometer. Superflow data collection capabilities
included automatic measuring and recording of rpm
torque, horsepower, as well as various temperatures,
pressures, and flow rates.
~o of the engines spark plugs were fitted with
Kistler spark plug pressure adapters (Model 640) and
Kistler high impedance pressure transducers (Model
6001). An A.V.L. optical shaft encoder was mounted
on the test engine which generated signals for
bottom dead center and every half degree of crank
angle.
Pressure and crank angle data were collected,
stored and processed by a Colu~bia computer IModel
4220). Individual samples consisted of two pressure
measurements for every hal de-gree o shaft rotation
over eighty firing cycles.
Each additive set forth in Table 3 below was
-te~ted in the ~ollowing manner. A baseline test was
performed w~thout fuel treatment, followed by a test
in which additive was present in the fuel, and
~inally ~he baseline test was repeated. Two
pressure samples were collected during each test
run. Tests were twelve and one half minutes in
duration, wi~h 20 minutes run time between tests to
allow for conditioning or purging. The test engine
was run at 2100 rpm and 55 lb. t. of torque.
Superflow data collection was sampled at ten second
intervals. Standard deviation of horsepower was
produced after each test in order to confirm engine
)'7
- 18 -
stability and repeatability. Typical standard
deviations averaged .06, for twelve and one half
minutes of test engine run time.
The base fuel in each of the formulations
S tested was AMOCO unleaded regular gasoline having an
octane rating of 87. In each case where ethanol
(ETOH) or tetrahydrofuron (THF) was employed, its
concentration was 0.25%. The DIBENZYL PT(II)
referred to in -the table was dibenzyl cyclooctadiene
platinum II as prepared in Example 1; and, the
NITROBENZYL PT(II) was similarly prepared but having
nitrobenzyl in place of the two benzyl groups shown
in ~he formllla set forth in Example 1. Each of
these platinum compounds, when employed, was used at
a level sufficient to provide 0.15 ppm platinum,
except where noted as being otherwise, e.g.,
c = 0.1, c = 0.2, or c = 0.3 ppm. (The notation
(all) indicates that this t2~1e summari~es data at
all ethanol levels.)
For each test run which consisted of a
baseline-additive-baseline sequence, the pressure
measurements were plotted automatically as described
above.
For each plot obtained, three parameters were
studied:
1. Peak - ~he maximum pressure achieved in
~, the aylinder during combustioll.
~:!
~i 2. Distance - A physical measurement of the
horizontal distance between the top dead
center axis and the peak of the pressure
curve. Shorter distances between top dead
center and peak pressure achieved indicate
faster propagation of the flame fron~
across the cylinder.
3L3~5~iO~
- 19 -
3. MIP - The mean indicated pressure is the
average pressure achieved after ignition
at top dead center and is an indication of
the total work release achieved by
combusting the fuel.
In evaluating pressure curves with additive
increases in peak pressure and MIP and decreases
(shorter) distances were interpreted as a beneficial
effect produ~ed by the additive in terms of fuel
utilization and useful work derived from combusting
the fuel.
The nature of the effect of an additive
treatment to fuel was studied by using the Analysis
of Variance model otherwise ~nown as (ANOVA). The
assumptions that were made for this model have the
followin~ features:
1. There are two factor levels under study;
-~ baseline and treatecl conditions.
i`
~~~ 2.~i For ~each factor, the probability ~s~ :~
distribution of the data is normal.
~` 3. AIl probability distributions of ~he
~ factors have constant variance.
;~ 4. The mean for ~he data at each factor le~el
may dif~er, reflecting the various effects
`~ 25 of ~he txeatment.
~~,
A statistical test can be performed to determine
whe~her the means of the two factors are equal. If
they are not, ~hen further analysis is required.
, . . . .
~3~6~'7
- ~o --
This analysis involves the construction of an
interval estimation of the mean response for a given
factor, and comparison of mean responses for
different factor~. St~tistical inferences can be
made by using the interval estimation, i.e., it can
be estimated with 80 or 90 percent confidence that
the mean increase of the peak, dist or MIP are
between the lower limit and the upper limit of the
interval constructed. The interval estimation
depends on the confidence level, the total nllmber of
points in the data as well as the variance of the
difference of the two means. Thus conclusions can
be made about the effect of the fuel treatment
compared to nontreatment.
Table 3
Confidence
ev~l Low~r ~imit Upper Limit
ETOH vs BL~NK
80% Peak 0.75% 2.40%
Dist -0.39% 0.03%
MIP -0.43% 0.17~
90% Peak 0.42~ 2.72%
Dist -0.47% 0.12%
MIP -0.55% 0.29
DIBENZYL PTtII) vs BLANK
80~ Peak -0.11~ 1.05~
Dist 0.10% 0.58%
~IP -1.23% 0~64%
90% Peak -0.34% 1.27%
~ist 0.01% 0.67%
~IP -1.59% 1.01%
Confidence
Level _ Lower Limit Upper Limit
ETOH~DIBENZYL PT(II) vs BLANK
80% Peak 3.50% 6.34%
5 Dist -0.93% 0.39%
MIP -0.22% 0.45%
90% Peak 2.94% 6.89%
Dist -1.19% 0.64%
MIP ~0.35% 0.59%
THF vs BLANK
80% Peak 0.13% 1.05~
Dist -0.29% 0.11%
MIP -1.29% -0.69%
90% Peak -0.05% 1.23%
15 Dist -0.36% 0-19b
, MIP -1.41% -0.57%
;
NITROBENZYL PT(II) vs BLANK
80% Peak -O. 96% o . 76%
Dist -0.39~ 0.28%
MIP -1.21% -0.52%
90% Peak -1.30% 1.09%
Dist -0.53% 0.41%
MIP -1.34~ -0.39%
' :
NITROBENZYL PT~ THF vs BLANK
2580% Peak 1.09% 1. 39h
~ Dist -0.83% -0.05%
:: MIP -0.91% 0.36%
90% Peak 0.92~ 2.16%
Dist -0.98% 0.10~
MIP -1. 16% o . 60~b
~`' .
.
:13~S6~'7
- 22 -
Co~fidence
Level Lower Limit Upper Limit
ET DIBENZYL PT~II) vs ETOH ~c=O.l)
80% Peak -3.22% 3.69%
Dist-1.12% 0.98%
MIP -1.15% 1.17%
90% Peak -5.11% 5.59%
Dist -1.69% 1.56%
MIP -1.78% 1.80%
ETOH~DIBENZYL PT~II) vs ETOH (c=0.2)
80% Peak -2.54% 4.45%`
Dist -1.51% 0.53%
MIP -0.40% 0.10%
90~ Peak -4.46% 6.36%
Dist-2.07% l.09%
MIP -0.54% 0.24%
ETOH~DIBENZYL PT(II) vs ETOH (c=0.3)
:
80% Peak -2.49% 4.22%
: Dist-1.51% 0.67%
MIP -0.23% 0.62%
90~ Peak -4.33% 6.05h
Dist-2.10% 1.261G
MIP~0.47% 0.86%
ETOH*DIBENZYI PT(II) vs ETOH (ALL)
; 25 BO% Peak 0.56% l.Bl%
Dist-0.47% -0.04Gb
MIP O.lZ% 0.72%
90% Peak 0.36% 2.01%
Dist-0.54% 0.03%
MIP 0.03% 0.81%
-
13C~ '7
- 23 ~
E~ample 4
Following the test procedure of Ex2mple 3, (1)
osmium (II) tris (acetylacetonate) and (2) bis
(cyclopentadienyl) osmium (II) were tested against
the base fuel with no additive as sat forth in
Example 3. The e~fect of each compound on peak, MIP
and distance compared to base fuel was evaluated
with the results as set forth in Table 4:
Table 4
% Chan~e
Compound Tested Peak MIP Distance
: (1) +0.125 -0.029 ~0.07g
(2) ~5.86 ~0.847 0
Example S
This e~ample evaluates the pexformance o a
diesel ~uel additive according to the invention in
reducing light duty diesel emission~ and improving
fuel economy. The fuel additive had the formulation
set Eorth in Table SA:
Table SA
Ingredient ~ Parts by We~
Diphenyl Cyclooctadiene Platinum II
- Coordination Compound0.0170
~thyl Dii-3 Octyl Mitrate28.4
Ethyl EDA-2 Detergent 3.5
Xylene 2.6
E~xon LOPS ~ineral Spirits 65.5
_
lff~fff~ff~fffuf7
- 2~ -
Tff~fst Methodology
A 1984 Volvo GLE 760 diesel with five speed
transmission and approximately 30,000 miles was
selected as a test vehicle to provide data on a
newer, but well broken-in, die6el engine.
The vehicle was driven to Scott Environmental
Laboratories in PIumsteadville, Pennsylvania and
allowed to stabilize for twelve hours prior to
chassis dynamometer testing.
Baseline testing was conducted according to
U.S. EPA Federal Test Procedures (urban cycle) and
Highway Fuel Economy Test procedures. These
procedures call for the dynamometer to bfe loaded to
-~ a prescribed setting and the vehicle to be driven
through a series of acceleration, shifting, braking
and stopping patterns as emissions and fuel economy
da~a are collected. Data are collected over a
series of runs and analyzed through a computer
I software program to arrive at a composite numbfer fcffr
;! 20 emissions and fuel economy performance.
, ~ Fo~lowing bfaseline tesl~ing, the vehicle was
i treatad with additive at thef~ rate of seven ounces
per twenty gallons of fuel and relea~ed to
accumulate on-the-road mileage. The ~vehicle~ ;~
2S ~accumula~ed 1,600 miles ~fefore it was retested.
ff Treatmant was maintained durlng mileage accumulation
through the use of pfre packaged additive introduced
into the vehicle's~fuel tank at each fuel fill-up to
give an average concentration of platinum of f~bfout
30 0.15 ppm. Treated ~fuel testing followed the same
procedures as those for baseline testing.
The data is summar~`zed in Tabfle 5B.
~3~$~iO'7
- 25 -
Table 5B
Federal Emission Test Data
Baseline Treated % Increase % Decrease
.
C2 343.44 303.98 11.~9
HC 0.14 0.17 21.43
C0 0.83 0.34 59.04
N0 1.00 0.48 52.00
Partic~late 0.32 0.30 6.25
MPG 25.69 29.07 13.16
___ _________________________________________ __~_____________
~ighway Fuel Economy_Test Data
Baseline Treated~ % I~crease % Decrease
C2 231.88 199.55 13.~4
HC 0.09 0.04 S5.56
C0 0.53 0.46 13.21
: N0 0.61 0.33~ 45.90
Particulate -- -- --
MPG 43.68 50.78 16.25
20 _ :
'
Ex~ e 6
~: :
Two diesel passanger automobiles (a Peugeot a~d
~- a Vo1kswagen Dasher~ were fitted with on-board
computers to record trip data and road tested over a
~S~Oti'
- 2~ -
200-mile highway route. In these demonstrations,
route and load were held relatively constant,
measuring fuel consumption with and without the
additive of the invention. The road tests
accumulated data for over 7,000 miles driven with
untreated fuel and 6,400 miles for fuel treated with
the additive detailed in Table 5A to give a platinum
metal content of 0.15 ppm. From plots of the
regression curves ~mpg versus mph~ a numerical
integration was performed to determine the area
under baseline and treated curves. The difference
between the two areas was calculated in order to
arrive at a percentage figure to describe the
increase in mileage due to traatment with the fuel
~- 15 additive.
The results are summariæed in Table 6.
'
Table 6
Peugeot Li~ear R~gr~s~ion 6.55~ increas~
Quadratic Regr~ession 8.49~ increase
:' VW-Dasher Linear Regression 6.16% increase
Quadratic Re~r,ession 6.78% increase
:, :
~ E~ample 7
~j
;? 25 '~rials were conducted over a three-day period
~ to evaluate the performan e of the additive detailed
-~ in Table 5~ in a Ruston GAPC medium speed diesel
engine under closely controlled laboratory
conditions. The engine was operated at a constant
speed of 750 rpm within a power range of 35 to 85%
of maximum continuous rating (MCR).
~L3~ 7
- 2~ -
Baseline fuel tests were perfo~ned on the first
day, prior to additive introduction on the first and
second days. On the first day, baseline fuel f]ow
readings were recorded at power ratios of 35%, 50%,
62.5%, 75% and 85% MCR. Subseguently, additive was
introduced in the ratio of one part additive to 250
parts fuel and the power reduced through the above
range at hourly intervals. Fuel consumption was
recorded at five~minute intervals. At the end of
the day's testing, the engine was shut down with
additive remaining in the fuel system. The engine
had no preconditioning or "seasoning" time on
additive.
On the second say the engine was warmed up and
testing began using additive in a concentration of
one part to 400. Engine power was progressively
increased at hourly intervals through the same
points as on the first day, with fuel consumption
again recorded at five-minute intervals. An
additional baseline (untreatedL fuel) te~t was run on
the third day.
Analysis of the data collected on the first day
presented in Table 7A indicate a reduction in fuel
consumption of 3.1% to 5.3% when using the additive.
Treated data acqu'isition progressed from high lo d
(420 kw) to low load (220 kw~. Absolute reduction
in fuel consumption is noted to improve from no
reduction initially (first treated data point) to a
5.3% reduction at the end of the sequence.
Data presented in Table ~B represent a
comparison of treated data collected on the second
day versus the bAseline data of the first day.
Percentage reduction in fuel consumption ranged from
3.3% to 4.0% when using the additive. Absolute
reduction in fuel consumption is noted to improve
from 2.4 kg/hr to 3.3 kg/hr, which follows the trend
~30$~ 7
- 28 -
towards increased time of txeatment durincJ the
pro~ression from low load operation ~275 kw~ to high
load operation ~475 kw) on the second day.
Data collected on the third day (not ~hown) for
untr~ated operation app~ar identical to those ~or
treated operation the second day. This is probably
the result of a residual effect of additive
deposited on cylinder parts and lube oil comp~nents
during treatment.
10 __
Table 7A
Comparison Gf Baseline Fuel Consumption vs.
Treated Fuel Consu~ption at Indicated ~oads
(First Day Data)
Reduction in
Fuel Consumption
Treated Fuel Untreated with
Power Consumption Fuel Consumption Additive Reduction
~kw)(kg/hr)tkg/hr)(kg/hr) b
42086.8 86.8
3~571.5 73.8 2.3 3.1
28058.7 61.3 2.5 4.2
22~46.5 49.1 2.6 5.3
Table 7B
Comparison of Baseline~Fuel Consumption vs.
Treated Fuel Consump~ _at Indicated Loads
~Second Day Data)
Reduction in
: Fuel Consumption
~ Treated Fuel Untreated with
- Power Consumption Fuel Consumption Additive Reduction
kw) (kg/hr)(kg/hr~(kg/hr) %
27557.6 60.0 2.4 4.0
34771.2 7~.2 3.0 4.0
41084.3 87.1 3.1 3.6
47595.9 99.2 3.3 3.3
-
~15~1~7
~9
Example 8
This test evaluates the effect of the additive
detailed in Table 5A on the fuel economy and
horsepower output of a commercially-operated,
diesel-powered truck tractor.
On the first day o testing, baseline ~no
additive) chassis dynamometer tests were conducted.
The vehicle tested was a tandem tractor powered by a
Cummins NHC-250 engine~ The vehicle was supplied by
an independen~ owner-operator and was normally used
in highway construction hauling. The engine had
accumulated 8,003 miles since rebuild.
Following baseline testing and treatment at a
rate o:E one gallon of additive to four hundred
gallons of fuel, the vehicle was released to
accumulate approximately 1000 miles of over-the-road
treated data before being retested on the chassis
dynamometer.
During over-the-road inileage accumulation,
treatment was maintained by the driver according to
a~treatment schedule which prOVjJ~i. for~J,a ~ o
- do age rate. Product was supplied in one-gallon
containers along wi~h a ~raduated beaker for
accurate measurement. Daily record sheets were
completed by the driver to record miles driven and
fuel and additive consumed.
During dynamometer testing, the tractor was
secured to a CIayton water-brake dynamometer and run
for four minute intervals at settings of 2100 rpm
and full power, 2000 rpm and full power and 1900 rpm
and full power. Readings were taken every minute
from the dynamometer's gauges, recording the actual
rear wheel horsepower. A separate tachometer was
installed in the cab. The one in the tractor was
~L~(35~)'7
- 30 -
found to "bounce". The speed and horsepower balance
were maintained at the rear wheels from the cab.
Simultaneously, fuel measurements were taken at the
same intervals. A thirty gallon drum of fuel was
placed on an accurate digital scale and -the
reduction in the weight of the fuel was recorded.
Recirculation was returned to the drum to measure
only that fuel consumed. The combined rear wheel
horsepower was found to be equal to factory
specifications, i.e., 70% o~ rated 250 horsepower,
equal to 175. Prior to testing the engine was
checked by the manufacturer to be sure that the fuel
flow and fuel pressure agreed with the
manufacturer's specifications for the fuel pump.
Two test runs were conducted on each test date
to assure the repeatability of results. Each test
consisted of three minutes of stabiliæed run time at
each of the three rpm settings with one minute in
between to allow for stabilization and transition to
the next rpm level.
The averages of three readings for each rpm
,~ setting are summarized in Table 8~ for untreated and
treated data. Table 8A provides a comparison of
horsepower (output) versus fuel flow (i~put) at a
-
~`25 given engine rpm for untreated and treated data.
Horsçpower increases following additive treatment
;avexaged 2.6% to 5.2% improvement over baseline.
Table 8B provides a comparison of actual
horsepower increase using the additive versus
untreated data. Actual horsepowex increases ~anged
rom 4.5 hp to 9.0 hp ollowing additive treatment.
.: .
.
6lu 7
- 31 -
Table 8A
Horsepower and Fuel Flow Data
at Indicated RPM
----UNTREATED---- -----TREATED-----
Run 1 Run 2 ~ Run 1 Run 2 Avg
(2100) hp 170 174 172 181 181 181
Fuel Flow (lb/min) 1.6 1.6 1.6 1.6 1.6 1.6
(2000) hp 172 173 172.5 180 180 180
Fuel Flow (lb/min) 1.5 1.6 1.55 1.5 1.6 1.55
(1900) hp 173 173 173 177 178 177.5
Euel Flow (lb/min) 1.5 1.5 1.5 1.5 1.5 1.5
-
:
Table 8B
Actual HP Improvement Resulting from
Additive Treatment
RPM Untreated Treated HP Change
(2 run avg) (2 run avg)
2100 172 181 9.0
2000 172.5 180 7.5
1~00 173 177.5 4.5
Ave~age HP Improvement: 7.0
: :
Fu~l flow remained nearly constant;dur:ing the
tests, while actual horsepower measured by~ the
d~namometer increased for ~he treated runs. Actual ~ :
horsepower improvement a~eraged 7.0 hp for~ the
treated runs over :~he ~hree rpm settinqs. This
3Q corr~ponds to a 4.0~ increaee in horsepower over
baseline horsepower.
The dynamometer was not equipped to:run treated
te=ts at equivalent ba eline hor=ePower in order to~
13~560'~
- 32 -
monitor decrease in fuel flow; however, a
calculation of brake specific fuel consumption
(BSFC) is one means of recording the fact that more
work is produced per unit of fuel when using the
additive. Therefore, if power requirements were
held constant, less~ fuel would be consumed when
using the additive. The data provided in Table 8C
represent BSFC, pounds of fuel consumed per
horsepowex-hour for untreated and treated data. The
improvement using additive ranged from 2.5% to 5.0%.
Emissions measurelaents were not quantified
during these tests; however, a reduction in visible
smoke emissions was observed when running on treated
fuel at start-up, idle and loaded conditions.
Table 8C
Brake Specific Fuel Consumption
vs. ~PM
~BSFC in lb per h]p-hr)
----U~rREATED---- ----T~EATED-~
RPM Run 1 Run 2 ~ Run 1 lRun 2 A~ Improvement
2100 0.564 O.S51 0.558 0.530 0.530 0.530 5. 0b
2000 0.523 0.554 0.539 0.500 0.533 0.517 4.1~
1900 0.520 0.520 0.520 0.508 0.505 0.507 2.5%
Example 9
This test evaluates the efectiveness of the
diesel fuel additive set forth in Table 5A in a high
elevation test on large tractors presently used for
hauling. Two tractors were selected -- a new
Kenworth with a 400 horsepower Caterpillar engine
~30~ '7
(31,000 total miles) and a Kenworth with a 475
horsepower Cummins twin-turbo engine (172,000 total
miles).
Testinq Method (Over-the-Road?
Baseline data from previous months' records was
listed indicating date, miles driven, gallons of
fuel used and then miles per gallon was calculated.
The two selected vehicles were then tested on a
chassis dyn~mometer for baseline determination (see
Testing Method-Chassis Dynamometer). After the
dynamometer tests, the tractors were treated with
the fuel additive and returned to their commercial
routes. The next two months (treated data) were
then lis-ted and compared to the original (untreated)
baseline data.
Testing Method (Chassis Dynamometer~
Both Kenworth tractors ~were tested on an
Ostradyne Model UI30TT chassis dynamometer. The
specifications of the unit are~horsepower limit 500,
torque limit 1500 lb. ft., maximum rear wheel speed
was 60 mph.
The tractors were driven onto the dynamometer
such that the rear driving wheels of the tractor
turned a set of rollers. These rollers are
connected to a braking system. The force~required
on the turning rollers to load the tractor's rear
drivin~ wheels is indicated on various meters
located on the dynamometer's control panel. The
meters consisted ~of horsepower, torque, speed
~calibrated in miles per hour~ and also a separat~
panel with controls to adjus~ for barometric
pressure, humidlty, etc.
~3L3~5~,V~
- 34 -
The test consisted of selecting three basic
rpm ' s in the upper scale of the tractor's
capability. The tractor was then fully loaded
maintaining the specific rpm and the meters on the
dynamometer were recorded every minuts ~or 5
minutes.
Fuel flow was measured by filling a 20 gallon
pail with diesel fuel from the tractor's saddle
tanks. The 20 gallon pail was placed on an accurate
electronic scale. During the 5 minute load tests,
minute readings wexe taken from the scale so an
accurate accounting of the fuel usage în pounds o
fuel per minute was recorded.
Data Evaluation (Over~the-Road~
The over-the-road data for both tractors is
summarized in q'ables 9A ancl 9B. Both tractors
sh~wed improvements in excess of S.6% in MPG whil~
under treatment; with a discernable trend towards
continued improvement with time under trea~ment.
_ _ __ ~_
Table 9A
enworth-Caterpillar
Baseline ~ Treated
Day ~ MPG D~y MPG
1 4.13 1 ~.60
2 4.15 2. 4.63 :
: 3 4.11 : 3 4.86
4 4.20 4 4.67
3.84: 5 4.~5
6 4.7~ 6 5.02
7 4.15
8 : 4.19
. _____ _ ___ ___ _______ __~_ _______________ ______
N: 8.00 N: 6.00
AVG: 4.189 AVG: 4.788
STD: : 0.23: STD: 0.16
Improveme~t with Treatment = 0.599 mpg or 14.300%
'7
- 35 -
Table 9B
B eline Treated
Day MPG Day MPG
1 4.65 1 4.~7
2 4.43 2 4.64
3 4.75 3 4.87
4 5.20
____. ___________________________________ ________ __
10 N: 3.00 N: 4.00
AVG: 4.610 AVG: 4.895
STD: 0.134 STD: 0.200
Improvement with Treatment = 0.285 mpg o~ 6.18Z
The above description is for the purpose of
teaching the person of ordinary skill in the art how
to practlce the present i.nvention and is not
intended to detail all those obviou~ modifications
and variations of it which w:ill become apparent to
the skil;led worker upon reading the description. It
is intended, however, tha-t all such obviou~
modifications and variations be included within the
scope of ~he present invention which is defined by
the following claims.
:,
:
