U.S. patent application number 11/104898 was filed with the patent office on 2005-10-20 for fuel compositions and methods thereof.
Invention is credited to Fernandes, Joseph Bedtal.
Application Number | 20050229479 11/104898 |
Document ID | / |
Family ID | 36678033 |
Filed Date | 2005-10-20 |
United States Patent
Application |
20050229479 |
Kind Code |
A1 |
Fernandes, Joseph Bedtal |
October 20, 2005 |
Fuel compositions and methods thereof
Abstract
Anti-knock gasoline fuel compositions are provided including
anti-knock additives and mixtures thereof. The octane quality of
fuel for an internal combustion engine improved with the anti-knock
additives.
Inventors: |
Fernandes, Joseph Bedtal;
(Arlington, VA) |
Correspondence
Address: |
SHAILAJA SHIRODKAR
2 CHESTER MILL COURT
SILVER SPRING
MD
20906
US
|
Family ID: |
36678033 |
Appl. No.: |
11/104898 |
Filed: |
April 13, 2005 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
60562028 |
Apr 14, 2004 |
|
|
|
60643620 |
Jan 13, 2005 |
|
|
|
Current U.S.
Class: |
44/329 |
Current CPC
Class: |
C10L 1/30 20130101; C10L
1/308 20130101; C10L 1/1824 20130101; C10L 1/1608 20130101; C10L
1/14 20130101; C10L 1/232 20130101; C10L 1/224 20130101; C10L
1/1852 20130101; C10L 1/226 20130101; C10L 1/2608 20130101; C10L
1/202 20130101; C10L 1/203 20130101; C10L 1/1855 20130101; C10L
10/10 20130101; C10L 1/223 20130101; C10L 1/305 20130101; C10L 1/28
20130101; C10L 1/2437 20130101; C10L 1/19 20130101; C10L 1/1241
20130101; C10L 1/1857 20130101; C10L 1/198 20130101; C10L 1/1828
20130101; C10L 1/238 20130101; C10L 1/143 20130101; C10L 1/1881
20130101; C10L 1/2225 20130101 |
Class at
Publication: |
044/329 |
International
Class: |
C10L 001/24 |
Claims
1) An anti-knock gasoline fuel composition suitable for combustion
in an automotive engine comprising: a) a compound of Formula I:
34wherein each of A, B and C is independently selected from the
group consisting of alkyls, alkenes, aryls, heterocyclyls, aryloxy,
cycloalkyls, cycloalkenyl, heteroaryls, esters, amides, ethers,
aldehydes, ketones, carbonates, diazenes, aldehydic acids,
alcohols, oxides, ketonic acids, othroesters, diesters, phenols,
glycol ethers, glycols, alkyl carbonates, dialkyl carbonates,
di-carbonates, organic and inorganic peroxides, hydroperoxides,
carboxylic acids, amines, nitrates, di-nitrates, oxalates, boric
acids, orthoborates, hydroxyacids, orthoacids, anhydrides,
acetates, acetyls, benzoic acids, nitrates, di-nitrates, and
nitro-ethers; and X is polyalkyl, polyalkoxy, polyether,
polyterphthalate or polycarbonate chain of from about 400 to 3600
g/mol; and b) optionally at least one or more additives.
2) The composition according to claim 1, wherein X is selected from
the group consisting of butyl, isobutyl, pentyl, hexyls, octyl,
nonyl, dodecyl, docosyl, polyethylene, polypropylene,
polyisobutylene, ethylene-propylene copolymer, chlorinated olefin
polymer, polyether, paraffin and oxidized ethylene-propylene
copolymer.
3) The composition according to claim 1, wherein X is
polyisobutylene.
4) The composition according to claim 3, wherein the
polyisobutylene has a number average molecular weight of from about
400 to about 3600 g/mol.
5) The composition according to claim 3, wherein the
polyisobutylene is substituted, the substituents selected from the
group consisting of alkoxy, hydroxyl, halo, alkyl, substituted
alkyl, and nitro.
6) The composition according to claim 1, wherein X is paraffin.
7) The composition according to claim 1, wherein each of A, B or C
are independently selected from the group consisting of: 35
8) The composition according to claim 1, wherein the substituted
aryloxy is a dye moeity.
9) The composition according to claim 7, wherein the dye moiety is
selected from the group consisting of reactive dye, direct dye,
pigment powder, napthols, and basic dye.
10) The compound according to claim 7, wherein the dye moeity is
selected from the group consisting of oil yellow, oil orange, oil
orange R, oil red, oil green, oil cyanine green, oil violet, oil
brilliant blue, and oil pink.
11) The composition according to claim 10, wherein the dye is
selected from the group consisting of oil orange R, oil brilliant
blue, and indoineblue.
12) The composition according to claim 1, wherein the additive is
selected from the group consisting of fulvenes, alkyl carbonates,
phenyl carbonates, dyes, aromatics, dye-polymer conjugates,
ester-polymer conjugates, dye-paraffin conjugate, norbornadienes,
organometallics and oxygenates.
13) The composition according to claim 1, wherein the additive is
selected from the group consisting of ferrocene, ruthenocene,
chromocene, osmocene, methyl cyclopentadienyl manganese
tricarbonyl, napthacenes, methylferrocene, cobaltocene,
nickelocene, titanocene dichloride, zirconocene dichloride,
uranocene, decamethylferrocene, decamethylsilicocene,
decamethylgermaniumocene, decamethylstannocene,
decamethylphosocene, decamethylosmocene, decamethylruthenocene,
decamethylzirconocene, silicocene, and decamethylsilicocene.
14) The composition according to claim 1, wherein the additive is
selected from the group consisting of alcohols, esters, ethers,
carboxylic acids and mixtures thereof.
15) The composition according to claim 14, wherein the additive is
ethanol, methanol, t-butyl alcohol, methyl tertiary butyl ether
(MTBE), ethyl tertiary butyl ether(ETBE), tertiary amyl methyl
ether(TAME), tetrahydrofuran or mixtures thereof.
16) The composition according to claim 1, wherein the concentration
of compound of Formula I is less than 1500 ppm.
17) The composition according to claim 1, wherein the concentration
of additive is less than 500 ppm.
18) The composition according to claim 1 wherein the concentration
of additive is less than 49%.
19) A compound of claim 1 selected from the group consisting of
compounds of the following formulae: 36
20) An anti-knock gasoline fuel composition suitable for combustion
in an automotive engine consisting of: a) an organic compound
selected from the group consisting of alkenes, aldehydes, esters,
ketones, alkyl carbonates, aryl carbonates, aminoaryls, cycloalkyl,
aromatics, dye-polymer conjugates, ester-polymer conjugates, and
dye-paraffin conjugates; b) optionally an organometallic compound
selected from the group consisting of ferrocene, ruthenocene,
chromocene, osmocene, methyl cyclopentadienyl manganese
tricarbonyl, nickelcarbonyls, organosilicon metallocene, alkyltin,
and derivatives thereof; and c) optionally an oxygenate selected
from the group consisting of alcohols, esters, ethers, furans and
mixtures thereof.
21) The composition according to claim 20 wherein the organic
compound is selected from the group consisting of fulvenes, alkyl
carbonates, phenyl carbonates, dyes, dye-polymer conjugates,
ester-polymer conjugates, and dye-paraffin conjugate.
22) The composition according to claim 20 wherein the
organometallic compound is selected from the group consisting of
ferrocene, chromocene, and cyclopentadienyl manganese
tricarbonyl.
23) The composition according to claim 20 wherein the oxygenate
compound is selected from the group consisting of ethanol and
tetrahydrofuran.
24) The composition according to claim 20 wherein the concentration
of organic compound less than 1500 ppm.
25) The composition according to claim 20 wherein the concentration
of organometallic is less than 500 ppm.
26) The composition according to claim 20 wherein the concentration
of oxygenate is less than 49%.
27) The composition according to claim 20, wherein the composition
further comprises a second additive, or mixture of two or more
additives.
28) The composition of claim 20, wherein the organic compound is
present in an amount from about 1 ppm by weight to about 1500 ppm
by weight based on the total weight of the composition.
29) A method for improving the antiknock property of a gasoline
fuel, the method comprising admixing an effective amount of at
least one composition of claim 1 with the gasoline fuel.
30) The composition as claimed in claim 29, wherein the composition
further comprises dyes, detergents, dispersants, demulsifiers,
antioxidants, corrosion inhibitors, or stabilizers and other
antiknock additives.
Description
CLAIM OF PRIORITY
[0001] This application claims the benefit of filing date of U.S.
Provisional Application Ser. Nos. 60/562,028 filed on Apr. 14, 2004
and 60/643,620 filed on Jan. 13, 2005, which are incorporated by
reference in their entirety.
FIELD OF INVENTION
[0002] The present invention relates to anti-knock gasoline fuel
compositions and methods of increasing octane index of the gasoline
fuel. The invention also relates to methods of improving anti-knock
of gasoline fuel by admixing the above-referenced compositions
without significant environmental consequences.
BACKGROUND OF INVENTION
[0003] Fuels, particularly gasoline grade fuels have undergone many
changes over the years in order to improve engine performance and
reduce engine emissions. Many octane improving compounds used for
improving engine performance and extending fuel supplies, such as
tetraethyl lead, aromatic compounds, methylcyclopentadienyl
manganese tricarbonyl, methyl tertiary butyl ether ("MTBE") and
other such additives, have fallen into disfavor because of concerns
about adverse environmental consequences arising from their
use.
[0004] The octane requirement increase effect exhibited by internal
combustion engines, e.g., spark ignition engines, is well known in
the art. If the engine is operated with a gasoline fuel, which has
a lower octane number than the minimum requirement for the engine,
"knocking" can occur. Knocking occurs when a gasoline fuel
spontaneously and prematurely ignites or detonates in the engine
prior to spark plug initiated ignition. This effect is coincidental
with the formation of deposits in the region of the combustion
chamber of the engine.
[0005] During the initial operation of a new or clean engine there
is a gradual increase in octane requirement, i.e., fuel octane
number required for knock-free operation, which is observed with an
increasing build up of combustion chamber deposits until a stable
or equilibrium octane requirement level is reached. This level
appears to correspond to a point in time when the quantity of
deposit accumulation on the combustion chamber and valve surfaces
no longer increases but remains relatively constant. This so-called
"equilibrium value" is normally reached between 3,000 and 20,000
miles or corresponding hours of operation. Further accumulation of
deposits on the intake valves of internal combustion engines,
however presents problems. The accumulation of such deposits is
characterized by overall poor drivability including hard starting,
stalls, and stumbles during acceleration and rough engine idle.
[0006] Several additives when added to hydrocarbon fuels can
prevent or reduce deposit formation, or remove or modify formed
deposits, in the combustion chamber and on adjacent surfaces such
as intake valves, ports, and spark plugs, which in turn causes a
decrease in octane requirement. Organometallic compounds, which
possess antiknock activity, have been proposed to replace
tetraethyl lead. For example, methylcyclopentadienyl manganese
tricarbonyl (MMT) is known to be an effective antiknock additive
(See U.S. Pat. Nos. 2,818,417; 2,839,552; and 3,127,351), and is
currently used in unleaded fuels in Canada and in leaded gasoline
in the U.S.
[0007] Numerous non-metallic compounds have also been suggested as
antiknock additives. Examples of such compounds include 1,4 and
1,3-diaminobutanes (See U.S. Pat. No. 4,445,909), 2-dimethylamino
methyl-4-fluorophenol (See U.S. Pat. No. 4,378,231), norbornadiene
(See U.S. Pat. No. 4,387,257), and alkyl carbonate (See U.S. Pat.
No. 4,600,408). Particularly preferred antiknock compounds are
aniline and certain of its alkyl derivatives such as
2,6-dimethylaniline, n-methylaniline, n-alkyl toluidines (See U.S.
Pat. No. 4,294,587), and o-aminoazides (See U.S. Pat. No.
4,266,947).
[0008] Other anti-knock compounds have included fulvene
derivatives. For example, U.S. Pat. No. 4,264,336 discloses use of
halogenated fulvenes as antiknock compounds. However, the use of
chloro or fluoro compounds, as antiknock agents may be
environmentally undesirable due to their detrimental effect on the
ozone layer. U.S. Pat. No. 3,706,541 discloses the use of certain
aminofulvenes such as 6-dimethylamino fulvene as antiknock
additives. More recently, 6-dimethylamino fulvene has been reported
to be among the most active non-metallic antiknock additives (See
S. Stournos et al. 199th National ACS Meeting, Boston, Mass., Apr.
22, 1990).
[0009] U.S. Pat. No. 5,607,486 describes engine fuel additives
comprising terpenes, aliphatic hydrocarbons and lower alcohols.
Hydrocarbon component containing one or more hydrocarbons such as
five to eight carbon atoms straight-chained or branched alkanes
have been described in U.S. Pat. No. 6,712,866.
[0010] WO8905339 relates to a gasoline mixture containing between
75 to 95% unleaded gasoline, 5 to 25% oxygenated hydrocarbons such
as alcohols of less than 5 carbons, between about 0.05 g to 4 g
Pb/gal. and between about 0.005 g to 0.15 g Mn/gal.
[0011] RU2161639 relates to a gasoline additive which contains by
wt %: aromatic amine 6-20, crotonic aldehyde 0.1-1.5, acetic
aldehyde 0.2-2.0, water 0.5-1.5, and organometallic additive
0.1-4.0. As an aromatic amine, N- methylaniline or toluidine
mixture, or xylidine mixture is used and, as organometallic
additive, methylcyclopentadienylmanganese tricarbonyl or
dicyclopentadienyliron derivative is used. Such additive is
contained in gasoline composition in concentrations 5 to 15 wt %.
Enhanced octane number is obtained without worsening environmental
properties and reducing CO and CH formation in internal combustion
engines.
[0012] GB802181 relates to a fuel composition including an
aliphatic oxygen compound which is not an aldehyde or an acid and a
gasoline blend, the gasoline blend being such that when it contains
2.3 c.c. of tetraethyl lead per U.S. gallon it has a research
octane rating of at least 6 octane numbers more than the research
octave rating of a 75 per cent recovered distillate (clear)
obtained from the gasoline blend. The blend may consist of a light
virgin naphtha having a final boiling-point below 350 DEG F. and a
research octave rating below 70, and a heavy catalytic reformate,
which may be an ultraformate, platformate, or fluid hydroformate,
with a research octave rating above 85. The oxygen compound may be
an alcohol, such as ethyl alcohol, isopropyl alcohol or an oxo
alcohol, a ketone, an acetal, an ester, an ether, or a cyclic
ether, such as furan and its derivatives. Compositions described
contain ethanol, isopropyl alcohol, isopropyl ether, di-methyl
furan, a mixture of alcohols obtained by oxidation of a virgin
naphtha, and tetraethyl lead.
[0013] U.S. Pat. No. 5,288,393 to Unocal relates to a method of
reducing NO.sub.x, CO and/HC-hydrocarbons by controlling properties
of a gasoline fuel. Preferred properties were Reid vapor pressure
(RVP) no greater than 7.5 psi, essentially zero olefins and a 50%
distillation point greater than 180 degree C. Action of other
properties are increase in octane, decrease in 10% distillation
point, increase in aromatics.
[0014] There are several limitations to the above described
compounds as anti-knock fuel additives, for example, high cost,
relatively low antiknock quality, hydrolytic, thermal or oxidative
instability, low solubility in gasoline, environmental concern or
high solubility in water. Accordingly, there is continuing interest
in the development of antiknock fuel additives, which provide
enhanced engine performance, reduced pollution and can be used to
extend fuel supplies through the use of renewable fuels such as
ethanol without adversely affecting the environment.
SUMMARY OF THE INVENTION
[0015] The present invention relates to anti-knock fuel
compositions and methods of increasing the octane index of gasoline
using compounds of Formula I and optionally other additives. The
invention also relates to methods of making high-octane gasoline or
super octane refinery stream by admixing naphtha or low octane
gasoline with above-referenced compositions without significant
environmental consequences. A gasoline mixture can include organic
compounds, oxygenates, organometallics, and solvents. The actual
percentages of in the gasoline mixture can be optimized as needed
to produce the desired increase in octane, using empirical methods.
Octanising technology of the present invention can be applicable in
both up-stream and down-stream of a refinery by using naphtha as a
base fuel for up-stream and a sub-grade gasoline is a base fuel for
downstream.
[0016] In one aspect, an anti-knock gasoline fuel composition
suitable for combustion in an automotive engine is described
comprising:
[0017] i) a compound of Formula I: 1
[0018] wherein each of A, B and C is independently selected from
the group consisting of alkyls, alkenes, aryls, heterocyclyls,
aryloxy, cycloalkyls, cycloalkenyl, heteroaryls, esters, amides,
ethers, aldehydes, ketones, carbonates, diazenes, aldehydic acids,
alcohols, oxides, ketonic acids, othroesters, diesters, phenols,
glycol ethers, glycols, alkyl carbonates, dialkyl carbonates,
di-carbonates, organic and inorganic peroxides, hydroperoxides,
carboxylic acids, amines, nitrates, di-nitrates, oxalates, boric
acids, orthoborates, hydroxyacids, orthoacids, anhydrides,
acetates, acetyls, benzoic acids, nitrates, di-nitrates, and
nitro-ethers; and X is a polyalkyl, polyalkoxy, polyether, or
polycarbonate chain of from about 400 to 3600 g/mol; and
[0019] ii) optionally at least one or more additives.
[0020] In another aspect, an anti-knock gasoline fuel composition
is described suitable for combustion in an automotive engine
consisting of:
[0021] a) an organic compound selected from the group consisting of
alkenes, aldehydes, esters, ketones, alkyl carbonates, aryl
carbonates, aminoaryls, cycloalkyl, aromatics, dye-polymer
conjugates, ester-polymer conjugates, and dye-paraffin
conjugates;
[0022] b) optionally an organometallic compound selected from the
group consisting of ferrocene, ruthenocene, chromocene, osmocene,
methyl cyclopentadienyl manganese tricarbonyl, nickelcarbonyls,
organosilicon metallocene, alkyltin, and derivatives thereof;
and
[0023] c) optionally an oxygenate selected from the group
consisting of alcohols, esters, ethers, and mixtures thereof.
[0024] In another aspect, a method for improving the antiknock
property of a gasoline fuel is described, the method comprising
admixing an effective amount of at least one composition of Claim 1
with the gasoline fuel.
[0025] Embodiments of the invention may have one or more of the
following advantages. The composition advantageously provides
improved anti-knock properties. The composition of the present
invention can provide antiknock additives for fuels as a refinery
stream additive or in gasoline fuels used for internal combustion
engines. The compositions of this invention can potentially replace
fossil fuel up to 49% with renewable ethanol while providing
significant boost in octane number. The composition can address
formulation of clean fuels, increase octane requirement, increase
compliance to emission standards, and use renewable fuel in
conventional gasoline formulations.
[0026] Other features and advantages of the invention will be
apparent from the following detailed description.
DESCRIPTION OF DRAWINGS
[0027] FIG. 1 is an illustration of the working principle of Zeltex
meter.
[0028] FIG. 2 is a graph of octane rise (dRON) vs. concentration
(g/L).
[0029] FIG. 3 is a graph illustrating synergistic interaction
between compounds.
[0030] FIG. 4 is a graph showing synergistic effect of ethanol with
organic compound.
[0031] Like reference symbols in the various drawings indicate like
elements.
DETAILED DESCRIPTION OF THE INVENTION
[0032] A gasoline fuel composition can be formulated to provide
anti-knock property in an internal combustion engine. The fuel
composition can be blended in a refinery stream to increase octane
performance or added as an additive to increase octane performance
of a hydrocarbon fuel in an internal combustion engine.
[0033] Octane rating of hydrocarbons is determined by the structure
of the molecule, with long, straight hydrocarbon chains producing
large amounts of easily-autoignitable pre-flame decomposition
species, while branched and aromatic hydrocarbons are more
resistant. Unburnt "end gases" ahead of the flame front encounter
temperatures up to about 700.degree. C. due to compression and
radiant and conductive heating, and commence a series of pre-flame
reactions. These reactions occur at different thermal stages, with
the initial stage (below 400.degree. C. ) commencing with the
addition of molecular oxygen to alkyl radicals, followed by the
internal transfer of hydrogen atoms within the new radical to form
an unsaturated, oxygen-containing species. These new species are
susceptible to chain branching involving the HO.sub.2 radical
during the intermediate temperature stage (400-600.degree. C.),
mainly through the production of OH radicals. Above 600.degree. C.,
the most important reaction that produces chain branching is the
reaction of one hydrogen atom radical with molecular oxygen to form
O and OH radicals.
[0034] The addition of compositions of Claim 1 and oxygenates can
significantly affect the pre-flame reaction pathways. Antiknock
additives work by interfering at different points in the pre-flame
reactions, with the oxygenates retarding undesirable low
temperature reactions, and the compositions of Claim 1 react in the
intermediate temperature region to deactivate the major undesirable
chain branching sequence. The antiknock ability is related to the
"autoignition temperature" of the hydrocarbons. The combination of
vehicle and engine can result in specific requirements for octane
that depend on the fuel. If the octane is distributed differently
throughout the boiling range of a fuel, then engines can knock on
one brand of 87 (RON+MON)/2, but not on another brand. This "octane
distribution" is especially important when sudden changes in load
occur, such as high load, full throttle, acceleration. The fuel can
segregate in the manifold, with the very volatile fraction reaching
the combustion chamber first and, if that fraction is deficient in
octane, then knock will occur until the less volatile, higher
octane fractions arrive.
[0035] Anti knocks delay the pre-ignition of fuel. The ignition
delay of pre-ignition occurs when accumulated energy needed for
detonation has not the reached the minimum energy needed for
detonation. The delay of accumulation of energy may be because of
reactions involving initiation, propagation of free radicals such
as HO2., OH. involved in the oxidation of fuel hydrocarbons.
Interventions in the chains of the hundreds of oxidation reactions
can be caused by regulating the initiation and propagation steps in
the chain. Following interventions have been found to be
influencing positively and in occasional circumstances negatively:
these interventions are Base RON, oxygenates such as ethyl alcohol,
impurities in fuel processing and anti knocks agents. Since all of
these are important and also dependant on the components in fuel
and fuel additives (even smaller amount of impurities especially
metallic impurities) could in occasional cases have
intervention.
[0036] Unless indicated otherwise, the following definitions apply
throughout the present specification and claims. These definitions
apply regardless of whether a term is used by itself or in
combination with other terms. For example, the definition of
"alkyl" also applies to the "alkyl" portion of "alkoxy". It should
also be noted that any of the moieties can be further substituted
by substituents well known to one skilled in the art, for example,
alkyl further substituted, with for example, alcohol or halide.
[0037] The term "polyalkyl" or "paraffin" means a group having a
carbon atom directly attached to the remainder of the molecule and
having a hydrocarbon or predominantly hydrocarbon character within
the context of this invention. Such groups include the
following:
[0038] (1) Purely hydrocarbon groups; That is, aliphatic, (e.g.,
alkyl or alkenyl), alicyclic (e.g., cycloalkyl or cycloalkenyl),
aromatic, aliphatic- and alicyclic-substituted aromatic,
aromatic-substituted aliphatic and alicyclic groups, and the like,
as well as cyclic groups wherein the ring is completed through
another portion of the molecule (that is, any two indicated
substituents may together form an alicyclic group). Non-limiting
examples include methyl, ethyl, octyl, decyl, octadecyl,
cyclohexyl, and phenyl;
[0039] (2) Substituted hydrocarbon groups; that is, groups
containing non-hydrocarbon substituents which do not alter the
predominantly hydrocarbon character of the group. Non-limiting
examples include include hydroxy, nitro, cyano, alkoxy, acyl, etc.;
and
[0040] (3) Hetero groups; that is, groups which, while
predominantly hydrocarbon in character, contain atoms other than
carbon in a chain or ring otherwise composed of carbon atoms.
Non-limiting examples include nitrogen, oxygen and sulfur.
[0041] "An effective amount" means to describe an amount of
compound of the present invention or another agent effective to
reduce knock and thus producing the desired effect.
[0042] "Alkyl" means an aliphatic hydrocarbon group, which may be
straight or branched and comprising about 1 to about 20 carbon
atoms in the chain. Alkyl groups can contain about 1 to about 12
carbon atoms in the chain. More specifically, alkyl groups can
contain about 1 to about 6 carbon atoms in the chain. Branched
means that one or more lower alkyl groups such as methyl, ethyl, or
propyl, are attached to a linear alkyl chain. Non-limiting examples
of suitable alkyl groups include methyl, ethyl, n-propyl,
isopropyl, n-butyl, t-butyl, n-pentyl, heptyl, nonyl, and
decyl.
[0043] "Alkylaryl" means an alkyl-aryl- group in which the alkyl
and aryl are as described herein. Preferred alkylaryls comprise a
lower alkyl group. Non-limiting examples of suitable alkylaryl
groups include o-tolyl, p-tolyl and xylyl. The bond to the parent
moiety is through the aryl.
[0044] "Aryl" means an aromatic monocyclic or multicyclic ring
system, wherein at least one ring is aromatic, comprising about 6
to about 14 carbon atoms, or from about 6 to about 10 carbon atoms.
Non-limiting examples of suitable aryl groups include: phenyl,
naphthyl, indenyl, tetrahydronaphthyl, indanyl, anthracenyl, and
fluorenyl.
[0045] "Aryloxy" means an aryl-O- group in which the aryl group is
as previously described. Non-limiting examples of suitable aryloxy
groups include phenoxy and naphthoxy. The bond to the parent moiety
is through the ether oxygen.
[0046] "Cycloalkyl" means a non-aromatic mono- or multicyclic ring
system comprising about 3 to about 10 carbon atoms, or from about 5
to about 10 carbon atoms. Cycloalkyl rings can contain about 5 to
about 7 ring atoms. Non-limiting examples of suitable monocyclic
cycloalkyls include cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl, cycloheptyl and the like. Non-limiting examples of
suitable multicyclic cycloalkyls include 1-decalin, norbornyl,
adamantly and the like.
[0047] "Cycloalkenyl" means a non-aromatic mono or multicyclic ring
system comprising about 3 to about 10 carbon atoms, preferably
about 5 to about 10 carbon atoms which contains at least one
carbon-carbon double bond. Preferred cycloalkenyl rings contain
about 5 to about 7 ring atoms. The cycloalkenyl can be optionally
substituted with one or more "substituents" which may be the same
or different, and are as defined above. Non-limiting examples of
suitable monocyclic cycloalkenyls include cyclopentenyl,
cyclohexenyl, cycloheptenyl, and the like. Non-limiting example of
a suitable multicyclic cycloalkenyl is norbornylenyl.
[0048] "Heterocyclyl" means a non-aromatic saturated monocyclic or
multicyclic ring system (i.e., a saturated carbocyclic ring or ring
system) comprising 3 to 10 ring atoms (e.g., 3 to 7 ring atoms), or
5 to 10 ring atoms, in which one or more of the atoms in the ring
system is an element other than carbon, for example nitrogen,
oxygen or sulfur, alone or in combination. There are no adjacent
oxygen and/or sulfur atoms present in the ring system.
Heterocyclyls can have 5 to 6 ring atoms. The prefix aza, oxa or
thia before the heterocyclyl root name means that at least a
nitrogen, oxygen or sulfur atom, respectively, is present as a ring
atom. The nitrogen or sulfur atom of the heterocyclyl can be
optionally oxidized to the corresponding N-oxide, S-oxide or
S,S-dioxide. Non-limiting examples of monocyclic heterocyclyl rings
include: piperidyl, pyrrolidinyl, piperazinyl, morpholinyl,
thiomorpholinyl, thiazolidinyl, 1,3-dioxolanyl, 1,4-dioxanyl,
tetrahydrofuranyl, tetrahydrothiophen-yl, and
tetrahydrothiopyranyl.
[0049] "Heteroaryl" means an aromatic monocyclic or multicyclic
ring system comprising 5 to 14 ring atoms, or 5 to 10 ring atoms,
in which one or more of the ring atoms is an element other than
carbon, for example nitrogen, oxygen or sulfur, alone or in
combination. Heteroaryl can contain 5 to 6 ring atoms. The prefix
aza, oxa or thia before the heteroaryl root name means that at
least a nitrogen, oxygen or sulfur atom respectively, is present as
a ring atom. A nitrogen atom of a heteroaryl can be optionally
oxidized to the corresponding N-oxide. Non-limiting examples of
heteroaryls include: pyridyl, pyrazinyl, furanyl, thienyl,
pyrimidinyl, isoxazolyl, isothiazolyl, oxazolyl, thiazolyl,
pyrazolyl, furazanyl, pyrrolyl, pyrazolyl, triazolyl,
1,2,4-thiadiazolyl, pyrazinyl, pyridazinyl, quinoxalinyl,
phthalazinyl, imidazo[1,2-a]pyridinyl, imidazo[2,1-b]thiazolyl,
benzofurazanyl, indolyl, azaindolyl, benzimidazolyl, benzothienyl,
quinolinyl, imidazolyl, thienopyridyl, quinazolinyl,
thienopyrimidyl, pyrrolopyridyl, imidazopyridyl, isoquinolinyl,
benzoazaindolyl, 1,2,4-triazinyl, and benzothiazolyl.
[0050] The fuel composition, as described above, provides a
synergistic increase in octane number of the additive composition
and fuel over what would be expected based on the octane number of
the components. For the purposes of this invention, the octane
number is defined as (R+M)/2 wherein R is the research octane
number and M is the motor octane number. The designation dRON is
the difference between the RON of the base fuel and RON of the same
base fuel with the antiknock additive. It is noted that the
compounds of the present invention were used with or without
further purification.
[0051] The inventive compositions, in one embodiment, are also
useful in reducing intake valve deposits as anti-knocks, thus
improving quality of combustion in the engine. In one embodiment,
the compositions provide fuel economy by controlling octane of
gasoline fuels. An anti-knock gasoline fuel composition suitable
for combustion in an automotive engine includes:
[0052] A. Compounds of Formula I:
[0053] i) a compound of Formula I: 2
[0054] wherein each of A, B and C is independently selected from
the group consisting of alkyls, alkenes, aryls, heterocyclyls,
aryloxy, cycloalkyls, cycloalkenyl, heteroaryls, esters, amides,
ethers, aldehydes, ketones, carbonates, diazenes, aldehydic acids,
alcohols, oxides, ketonic acids, othroesters, diesters, phenols,
glycol ethers, glycols, alkyl carbonates, dialkyl carbonates,
di-carbonates, organic and inorganic peroxides, hydroperoxides,
carboxylic acids, amines, nitrates, di-nitrates, oxalates, boric
acids, orthoborates, hydroxyacids, orthoacids, anhydrides,
acetates, acetyls, benzoic acids, nitrates, di-nitrates, and
nitro-ethers; and
[0055] X is a polyalkyl, polyalkoxy, polyether, polyterphthalate or
polycarbonate chain of from about 400 to 3600 g/mol; and
[0056] ii) optionally at least one or more additives.
[0057] Each of A, B or C can be an aryloxy moiety which can be a
dye. The dye can be, for example, a reactive dye, direct dye,
pigment powder, napthols, and basic dye. For example, the dye can
be a substituted diazene, for example, a oil yellow, oil orange,
oil orange R, oil red, oil green, oil cynanine green, oil violet,
oil brilliant blue, and oil pink. Suitable dyes include group
consisting of oil orange R, oil brilliant blue, and
indoineblue.
[0058] Each of A, B, or C can be an acid. Non limiting examples of
acids, include but not limited to benzoic acid derivatives e.g.
2,4-dimethyl benzoic acid, methyl red, p-tert-butylbenzoic acid,
2-(1-methylethyl)benzoic acid, benzoic acid anhydride, 4-benzoyl
benzoic acid, 2,4-dihdroxy benzoic acid, 2,4-dimethyl-benzoic acid,
3-ethoxy benzoic acid, 2-hydroxy-4-methyl benzoic acid, 2-hydroxy
benzontrile, 4-methoxy benzotrile, acetic acid derivatives, e.g.
anhydride acetic acid, chloroacetic acid, decyl ester acetic acid,
dibromoacetic acid, and the like, may be employed. Non-limiting
examples of salts include binary, ternary and higher metallic acid
salts, hydroxy acids, etc. Other non-limiting compounds acids are
set forth below and include for example, oxamic acid, lithium
acetate acid, lithium salt acetic acid, propanoic acid lithium
salt, cyclohexanebutyric acid lithium salt, aminobenzole acid
lithium salt, borate ester, dimethyl borate, di-n-butyl borate,
dicyclohexyl borate, didodecylborate, di-p-cresyl borates, boric
acids, orthoborates, henylboronic acid, diphenylboronic acid,
o-tolylboronic acid, p-tolylboronic acid, m-tolylboronic acid,
cylohexylboronic acid, cylohexenylboronic acid, cyclopentylboronic
acid, methylphenylboronic acid, methylcylohexyl-boronic acid,
methylcyclopentylboronic acid, methylbenzylboronic acid,
dimethylphenylboronic acid, dimethylcylohexylboronic acid,
dimethylcyclopentylboronic acid, dimethylbenzylboronic acid,
diphenylboronic acid, dibenzylboronic acid, dicylohexylboronic
acid, dicylohexenylboronic acid, dicyclopentylboronic acid,
mgethyldiphenylboronic acid, bis[(methyl)cylohexyl]boronic acid,
bis[(methyl)cyclopentyl]boronic acid, bis[(methyl)benzyl]boronic
acid, bis[(dimethyl)phenyl]boronic acid,
bis[(dimethyl)cylohexyl]boronic acid,
bis[(dimethyl)cyclopentyl]boronic acid, or
bis[(dimethyl)benzyl]boronic acid.
[0059] In the alternative, A, B or C can be an alcohol moiety.
Non-limiting examples of alcohols include ethanetriols,
propanetriols, butanetriols, 1,2,3 butanetriol, pentanetriols,
1,2,3 pentanetriol, 2,3,4 pentanetriol, hexanetriols,
septanetriols, octanetriols, or tertraethylene glycol, triethylene
glycol, 1-octene, high flash point ketone, naphthalenes,
triethylene glycol, trimethylene glycol, isopropyl acetone,
diisopropyl acetone, diisopropyl diacetone, diethylene acetate,
diethylene diacetate, ethylene acetate compound, phenol, or other
flash point temperature reducing co-solvent set forth in
aforementioned PCT Applications. Co-solvents should not be
corrosive or hazardous to fuel systems.
[0060] In the alternative, each of A, B or C can be an aldehyde.
Non-limiting examples of amides include any aliphatic or aromatic
amide. For example, A, B or C can be substituted or unsubstituted
benzaldehyde or anisaldehyde. Alternatively each of A, B or C can
be 3
[0061] Examples of X group include butyl, isobutyl, pentyl, hexyls,
octyl, nonyl, dodecyl, docosyl, polyethylene, polypropylene,
polyisobutylene, ethylene-propylene copolymer, chlorinated olefin
polymer, polyether, paraffin and oxidized ethylene-propylene
copolymer. The X moiety can be polyisobutylene. The polyisobutylene
can have a number average molecular weight of 400 to 3600 g/mol.
The polyisobutylene can be substituted, the substituent can be, for
example, alkoxy, hydroxyl, halo, alkyl, substituted alkyl, and
nitro. Alternatively, X can be a paraffin.
[0062] A fuel composition can be formulated to include a mixture of
a major amount of liquid hydrocarbon diluents and minor amount of a
composition of Claim 1.
[0063] The composition can include, for example, compounds 4
[0064] or mixtures thereof.
[0065] Alternatively, fuel compositions can include
[0066] (a) a compound represented by Formula II: 5
[0067] wherein each of D and E is selected from the group
consisting of aryl, aryloxy, heteroaryl, or diazene;
[0068] Y is --CH--, --C(.dbd.O)O--, --C(.dbd.O); and
[0069] (b) a hydrocarbon diluent. For example, each of D and E can
be cyclopentadiene, substituted phenyl, and 6
[0070] B. Additives:
[0071] The composition can include optionally at least one or more
additives, for example, a dye or mixture of two or more additives.
The additive can be a dye, for example, oil orange R dye or
brilliant blue dye. The dye can be present in an amount from about
1 ppm by weight to about 500 ppm by weight based on the total
weight of the composition. Liquid hydrocarbon diluents and/or fuels
can be a gasoline fuel or diesel fuel. Suitable hydrocarbon
diluents are mixtures of hydrocarbons with a boiling range of from
about 25.degree. C. to about 232.degree. C. and include saturated
hydrocarbons, olefinic hydrocarbons, and aromatic hydrocarbons. For
example, the diluent can have a saturated hydrocarbon content of
from about 40 to about 80 percent, an olefinic hydrocarbon content
from about 0 to about 30 percent volume and an aromatic hydrocarbon
content from about 10 to about 60 percent volume.
[0072] The additives can include fulvenes, aldehydes, esters,
ketones, alkyl carbonates, phenyl carbonates, dyes, aromatics,
dye-polymer conjugates, ester-polymer conjugates, and dye-paraffin
conjugates, organometallics and oxygenates.
[0073] The additives include fulvenes, for example, dimethyl
carbonate fulvene, anisaldehyde fulvene, ethyl anisate fulvene;
dyes, for example, oil orange R dye, oil brilliant blue MBA; esters
and carbonates, for example, ethyl anisate, 2-ethyl furoate,
tert-butyl acetate, ethyl nicotinate, dimethyl carbonate;
dye-attached to polymer to form conjugates, for example, oil orange
R-PIB conjugate ["dye-PIBA"], oil orange R-multibrominated PIB
conjugate; esters attached to polymer to form ester-polymer
conjugate, for example, ethyl anisate-PIBA ("EA-PIBA"]; ester
attached to dye, for example, ethyl anisate-oil orange R dye
conjugate, dye attached to paraffin, for example, kerosene-oil
orange R dye conjugate; oxygenate attached to paraffin, for
example, kerosene-ethanol conjugate. Representative examples of
additives include: 7
[0074] ii) Aldehyde, Esters & Ketone:
[0075] Aldehydes can include, for example, anisaldehyde and
benzaldehyde. Esters can include, for example, ethyl Anisate. 8
[0076] Ketones can include, for example, benzophenone.
[0077] iii) Alkyl &/or phenyl carbonate:
[0078] Akyl carbonates can include, for example, dimethyl carbonate
9
[0079] or phenyl carbonate. Suitable example of phenyl carbonate is
diphenyl carbonate
[0080] iv) Dyes: Any dye can be used as an additive. Examples of
dyes are listed in Table 1.
1TABLE 1 Name Structure Oil orange R 10 Acid Blue 40 Alizarin
Direct Blue A2G 11 Alizarin Mordant Red 11 12 Cresol Red o-
Cresolsulfonephthalein 13 Phenol Red Phenolsulfonephthalein 14
Chicago Sky Blue 6B Direct Blue 1 15 CongoRed Direct Red 28 16
Direct Red 81 Sirius Red 4B 17 Evan's Blue Direct Blue 53 18
Indolene-50 19 Indoine Blue Basic Blue 16 20
[0081] v) Aromatics, for example, 21
[0082] Additives can include alkyl toluidene, for example, 4-methyl
benzamine. Additives can include, fluorophenol, or
2-dimethylaminomethyl-4-methoxyphenol
[0083] 22
2-dimethylaminomethyl-4-fluoroxyphenol
[0084] 23
[0085] vi) Norbornadiene: 24
[0086] vii) Organometallics: Alternatively, additives can include,
organometallic compounds, for example, ferrocene, ruthenocene,
chromocene, osmocene, methyl cyclopentadienyl manganese tricarbonyl
and derivatives thereof.
[0087] a. Ferrocene 25
[0088] eg: Iron tetracarbonyl, Fe.sub.3(CO).sub.12
[0089] eg: Iron pentacarbonyl, Fe(CO).sub.5
[0090] eg: Novel carboxylic ferrocene
[0091] b. Methyl cyclopentadienyl manganese tricarbonyl (MMT)
26
[0092] c) Nickel for example, nickel pentacarbonyl, eg:
Ni(CO).sub.5
[0093] d) Silicon eg., organosilicon metallocene compound
[0094] e) Tin eg., tetraethyl tin.
[0095] f) Ruthenocene, napthacenes, methylferrocene, cobaltocene,
nickelocene, titanocene dichloride, zirconocene dichloride,
uranocene, decamethylferrocene, decamethylsilicocene,
decamethylgermaniumocene, decamethylstannocene,
decamethylphosocene, decamethylosmocene, decamethylruthenocene,
decamethylzirconocene, silicocene, and decamethylsilicocene.
[0096] viii) The composition can include an additive, or mixture of
two or more additives, for example, the additive can be a dye. The
compounds can include ethyl anisate-cyclopentadiene conjugate
(EA--CPD) and ethyl anisate-dye conjugate (EA-Dye). 27
[0097] xi) Oxygenates: In the alternative, oxygenates can be
additives. Oxygenates can be selected from the group consisting of
alcohols, esters, ethers, acetates and mixtures thereof.
[0098] a. Alcohols: Methanol, ethanol, butanol etc
[0099] b. Ethers: methyl tert-butyl ether, ethyl tert-butyl
ether
[0100] c. Ester: Ethyl acetate, Methyl acetate, polyvinyl acetate
etc
[0101] d. Carboxylic acid: Formic acid, Acetic acid etc
[0102] The oxygenates can include, for example, ethanol, methanol,
t-butyl alcohol, methyl tertiary butyl ether (MTBE), ethyl tertiary
butyl ether (ETBE), tertiary amyl methyl ether(TAME),
tetrahydrofuran or mixtures thereof. The concentration of oxygenate
can be at least hundred times that of organic compound of Formula
I. The additives can further include dyes, detergents, dispersants,
demulsifiers, antioxidants, corrosion inhibitors, or stabilizers
and other antiknock additives. Concentration of each of the
compounds of Formula I in compositions of Claim 1 can be minute,
for example, less than 1500 ppm. The concentration of the additive
in compositions of Claim 1 can be less that, for example, 49% by
weight of gasoline fuel. Some of the components in composition of
Claim 1 can be chemically bound and gives greater rise to the
octane number than the individual components. For example,
oxygenates when mixed with compounds of Formula I and
organometallic compounds, an unexpected rise in greater octane
number is observed.
[0103] The fuel compositions of the present invention may
additionally include additives such as dyes, detergents,
dispersants, demulsifiers, antioxidants, corrosion inhibitors, or
stabilizers. Furthermore, the fuel composition may additionally
include other anti-knock additives. The compositions of Claim 1 can
be present in less than about 10% of fuel. Suitable concentration
from about 1 ppm by weight to about 1500 ppm, or less than 300 ppm
by weight based on the total weight of the composition. The
compounds of Formula I can be used in a gasoline fuel, or
alternatively, for example, in a diesel fuel, naphtha or residual
oil. Surprisingly, there is a synergy between the compounds of
Formula I and selected additives. Thus, the compositions give a
synergistic rise in octane number, wherein the octane rise is
greater than the sum of octane rise by individual components of
compounds of Formula I and additives.
[0104] In the compositions according Claim 1, there exists a
synergy within the molecules of compounds of Formula I, as shown
below Table 2. [See also FIG. 3]
2TABLE 2 Wt of O Sr No Compound in gm RON dRON 1 SF.sup.1 0 88.2 **
2 SF + EA 2 88.6 0.3 3 SF 0 88.4 ** 4 SF + PIBA 2 88.4 0.4 5 SF 0
88.2 ** 6 SF + EA-PIBA 2 90.6 2.4 .sup.1SF = Synthetic fuel; EA is
ethyl anisate; and EA-PIBA is ethyl anisate-polyisobutylene
conjugate
[0105] The results of the above table show that research octane
number of ethyl anisate-polyisobutylelene amine conjugate which is
more than the sum of individual research octane numbers of ethyl
anisate and polyisobutylene. Here, the research octane number for
SF and EA-PIBA conjugate blend is 2.4 instead of the additive sum
of 0.7 based on SF and PIBA blend (dRON 0.4) and SF and EA blend
(dRON 0.3), leading to an increase of unexpected synergistic
increase of 1.7.
[0106] The fuel compositions described above can improve antiknock
property of a hydrocarbon base fuel. The efficiency of the
antiknock compounds for improving anti-knock properties of liquid
hydrocarbons was tested as shown in Table 3. The octane enhancing
property of the above referenced compositions can be measured by
Waukesha Engine [ASTM D2699(RON), D2700(MON), D4815(Oxygen)]. In
the following table, the composition was blended with a synthetic
reference fuel (SF) in a blend of 1% by volume reference fuel and
100% by volume product. Compounds Dye-polyisobutylene (Dye-PIB) and
ethyl anisate-polyisobutylene conjugate (EA-PIBA) were tested
against dimethyl fulvene in variety of fuels. Significant increases
in dRON were observed for Dye-PIB and EA-PIBA.
3TABLE 3 Quantity Base Final tti- Compound (gm) % EtOH Fuel Type
RON RON dRON Dimethyl 1.5 0 SF 82.8 86.4 3.6 fulvene Dimethyl 1.5 0
SF 84.7 87.6 2.9 fulvene Dimethyl 1 0 SF 84.7 87.1 2.4 fulvene
Dimethyl 0.75 0 SF 84.7 86.6 1.9 fulvene Dye-Pib 1.5 0 SF 82.7 85.5
2.8 Dye-Pib 1.5 0% Regular 92.6 94 1.4 0 0 0 SF 82.7 83.1 0.4
Dimethyl 1.5 10% SF 84.7 93.8 9.1 fulvene Dimethyl 1.25 10% SF 84.7
92.8 8.1 fulvene Dimethyl 1 10% SF 84.7 92 7.3 fulvene Dye-Pib 1.5
SF 82.8 95.7 12.9 Dye-Pib 1.5 SF 82.8 84.3 9.8 Dye-Pib 1.5 10% SF
82.8 92.6 9.8 Dye-Pib 1.5 10% SF 82.7 92.1 9.4 Dye-Pib 1.5 10%
randum 96.2 99.9 3.7 Dye-Pib 1.5 10% regular 92.6 97.2 4.6 Dye-Pib
1.5 10% naphtha 86.4 91.5 5.1 Dye-Pib 1.5 MTBE-10% regular 91.1
94.5 3.4 Dye-Pib 1.5 1% regular 92.6 94.1 1.5 0 0 1% regular 91.1
91.2 0.1 0 0 10% SF 84.5 89.1 4.6 Dye-Pib 0.5 10% SF 84.5 90.4 5.9
0 0 20% SF 70.4 82.3 11.9 Dye-Pib 1.5 20% SF 70.4 92 21.6 0 0 30%
naphtha 56 78.2 Dye-Pib 1.5 30% naphtha 56 91.6 35.6 0 0 1% SF 91.8
93.1 1.3 Dye-Pib 0.5 1% SF 91.8 93.2 1.4 0 0 10% SF 84.5 89.1 0 0
30% naphtha 56 78.2 EA-PIBA 0.4 30% naphtha 56 88.8 32.8 EA-PIBA
..25 30%-- naphtha 56 74.6 18.6 acetone EA-PIBA 0.4 30%-- naphtha
56 77.9 21.9 acetone EA-PIBA 0.25 30%--MTBE naphtha 56 74 18
EA-PIBA 0.4 30%--MTBE naphtha 56 83.6 27.6 EA-PIBA ..25 40% naphtha
56 85.6 EA-PIBA 0.4 40% naphtha 56 97.6 41.6 EA-PIBA ..25 40%-MTBE
naphtha 56 80 24 EA-PIBA 0.4 40%-MTBE naphtha 56 87.9 31.9 EA-PIBA
0.4 1% regular 91.8 93.3 1.5 EA-PIBA 0.4 1% regular 91.8 93.1 1.3
EA-PIBA 0.4 10% naphtha 56 68.4 12.4 EA-PIBA 0.4 25% naphtha 56
82.1 26.1 EA-PIBA 0.4 50% naphtha 56 88.9 32.9 EA-PIBA 0.4 75%
naphtha 56 102.7 46.7 EA-PIBA 0.4 85% naphtha 56 112.1 56.1 0 0
5.11% Arco-reg 91.8 na na 0 0 5.11% Arco-reg 91.7 na na EA-PIBA 0.4
5.11% Arco-reg 91.8 95.6 3.8 EA-PIBA 0.4 5.11% Arco-reg 91.7 95.5
3.8 5.65% 2.2 blended 92 na na regular gasoline EA-PIBA 0.1 5.65%
2.2 blended 92 92.4 0.4 regular gasoline 5.65% RBOB gasoline 89.3
na na W/2.2% oxygen EA-PIBA 0.4 5.65% RBOB gasoline 89.3 93.4 4.1
W/2.2% oxygen EA-PIBA 0.4 11.8(3.5)% Arco regular 93 cal 97.4 4.4
gasoline
[0107] Without being bound to a particular theory, Applicant
believes that physical features of chemical molecules, for example,
polarity, ionization, electron density, size, shape and
physico-chemical properties such as electron delocalization,
influence the anti-knock activity of the composition.
[0108] The above results in Table 3 show that the fuel additive
compositions of the invention have a substantially higher octane
number as compared to the synthetic fuel alone. Any increase in RON
as indicated by the .DELTA.RON is advantageous to fuel economy,
engine operability and the reduction of pollutants.
[0109] The octane enhancing property of the above referenced
compositions can also measured by a Zeltex meter as shown in Table
4. Zeltex meter is a portable octane analyzer of all grade of
unleaded gasoline, which works on the principle of near IR. It
shows the results of analysis in 20 second only directly in printed
form or on screen along with optical data of absorption of applied
infrared light. The Zeltex meter measures the research octane
number (RON), motor octane number (MON) and pump octane number
(RON+MON)/2. The Zeltex reading is accurate and provides
repeatability equivalent to ASTM-approved CFR engines. The working
principle of the Zeltex meter is that near IR light is applied to
the sample kept in sample holder, the light energy that enters the
sample is scattered and absorbed within the sample. The Zeltex
meter measures the spectra of existing sample and directly display
the results. [See FIG. 1] Here on the basis of data, accuracy of
Zeltex meter readings and their equivalency to ASTM-test method for
octane, we have used the Zeltex meter for octane testing of some of
the compounds. For testing purpose and initial screening of
potential high performance antiknocks, we have used ZX-101C model
of Zeltex meter provided by Zeltex INC. [See also FIG. 2].
4 TABLE 4 TEST ON SYNTHETIC FUEL By Zeltex Meter Sr No. Compounds
Gm/liter RON MON R + M/2 dRON I Reference compounds: A Fulvene 1
Dimethyl fulvene SF 88.4 83.2 85.8 5 88.8 82.3 85.5 0.8 10 89.5
82.1 85.8 1.5 2 SF + methyl ethyl fulvene SF 88.1 82.9 85.9 5 88.6
83.2 86.1 0.5 10 88.8 83.4 86.1 0.7 15 89 83.2 86 0.9 20 89 83.2 86
0.9 30 89.2 83.1 86.1 1.1 B Alkylaldehyde & ester 3 SF + TBA SF
88.3 82.5 85.4 5 88.4 83 85.7 0.1 10 88.9 83.2 86 0.6 15 89.1 83.3
86.2 0.8 20 89.6 83.6 86.6 1.3 50 90 84 87 1.7 4 SF + EA SF 88.1
82.9 85.9 5 88.3 82.8 85.6 0 10 88.6 82.7 85.7 0.3 15 88.7 82.9
85.8 0.4 20 88.9 82.9 85.9 0.6 25 89.2 82.8 86 0.9 30 89.2 83 86.1
0.9 35 89.5 83.2 86.3 1.2 C Alkyl phenyl Carbonate 5 Dimethyl
carbonate SF 88 82.2 85.1 10 88.6 82.7 85.6 0.6 II Present
invention: A Cyclopentadiene derivative 1 SF + DMC: CPD SF 88.3
82.5 85.4 5 88.3 82.8 85.5 0 10 88.7 82.6 85.6 0.4 15 89 82.8 85.9
0.7 20 89.4 82.5 85.9 1.1 25 90 82 86 1.7 2 Dimethyl carbonate
Cyclopentadiene conjugate Not miscible 3 Anisaldehyde
Cyclopentadiene conjugate Not miscible B Dyes 4 OIL Brilliant blue
SF 88.4 83.2 85.8 100 mg 88.9 83 85.9 0.5 250 mg 89.2 82.8 86 0.8
500 mg 90.2 82.3 86.3 1.8 750 mg 90.9 81.9 86.5 2.5 1000 mg 91.7
81.8 86.7 3.3 5 Oil orange R dye SF 88 82.2 85.1 100 mg 88.2 82.4
85.2 0.2 250 mg 88.5 82.5 85.5 0.5 500 mg 88.5 82.3 85.4 0.5 750 mg
88.7 82.2 85.4 0.7 1000 mg 89 82.1 85.6 1 6 Polysol yellow 100 mg
88.1 88.2 85.1 0.1 250 mg 88.1 88.2 85.1 0.1 500 mg INSOLUBLE C
Esters 7 SF + ethyl nicotinate SF 88.1 82.9 85.4 5 88.8 83.1 86 0.7
10 89.2 83 86.1 1.1 12.5 89.5 83.1 86.3 1.4 8 SF + ethyl furoate SF
88.1 82.9 85.4 5 88.5 82.9 85.8 0.4 10 88.6 82.9 85.8 0.5 20 88.9
82.9 85.9 0.8 25 89 83.2 86 0.9 30 89 83.2 86 0.9 40 89.1 83.1 86.1
1 D Dye-polymer conjugation 9 SF + dye-PIB SF 88.3 82.5 85.4 1 88.5
82.5 85.5 0.2 2 88.5 82.5 85.5 0.2 3 89.3 82.6 85.9 1 4 90.7 82.1
86.4 2.4 E Ester-poly isobutyl amine conjugation 10 SF + EA-PIBA SF
88.3 82.5 85.4 5 88.4 82.9 85.6 0.1 10 88.8 82.9 85.8 0.5 15 89.3
82.7 86 0.9 20 89.7 82.9 86.3 1.3 F Ester-dye conjugate 11 EA-Dye
(oil orange R) Not miscible G Dye attached to paraffin 12 SF +
kerosene-dye SF 88.3 82.5 85.4 (oil orange R) 1 88.8 82.6 85.7 0.5
2 89.6 82.3 86 1.3 3 90.4 82.2 86.3 2.1 H Oxygenate-polymer 13 SF +
mPIB-ethanol SF 88.2 86.3 87.2 1.25 89.3 85.9 87.6 1.1 2.5 90.6
85.3 88 2.4 3.75 92 84.7 88.4 3.8 5 93.6 84.3 88.9 5.4
[0110] In yet another embodiment, an anti-knock gasoline fuel
composition suitable for combustion in an automotive engine
includes:
[0111] a) an organic compound selected from the group consisting of
alkenes, aldehydes, esters, ketones, alkyl carbonates, aryl
carbonates, aminoaryls, cycloalkyl, aromatics, dye-polymer
conjugates, ester-polymer conjugates, and dye-paraffin
conjugates;
[0112] b) optionally an organometallic compound selected from the
group consisting of ferrocene, ruthenocene, chromocene, osmocene,
methyl cyclopentadienyl manganese tricarbonyl, nickelcarbonyls,
organosilicon metallocene, alkyltin, and derivatives thereof;
and
[0113] c) optionally an oxygenate selected from the group
consisting of alcohols, esters, ethers, and mixtures thereof.
[0114] Yet another embodiment is a method of improving the
antiknock property of a hydrocarbon base fuel, the method
comprising adding an effective amount of at least one composition
of Claim 1.
[0115] Yet another embodiment is a method of improving the
antiknock property of a hydrocarbon base fuel, the method
comprising adding an effective amount of at least one composition
of Claim 20.
[0116] A method for controlling octane requirement increase is
contemplated, comprising admixing at least composition of Claim 1.
Some of the polymers of formula I, such as poly ether amines,
polyisobutylene amines have an amine attached to the molecule.
Amination of polymers can also be carried out for the antiknocks
that do not have the amine moiety. Hence, the polymers will become
multifunctional. In addition to the molecule being primarily an
antiknock, other functional groups attached to the molecule will
enhance the molecule's function as a detergent for cleaning intake
valve deposits and the combustion chamber deposits. Reapited use of
the enhanced molecule will remove the combustion chamber deposits
and lower the ORI.
[0117] A method comprising a fuel composition admixing in the
refinery stream, the composition of Claim 1. When compositions of
the present invention are used on base fuels, the lower the octane
of the base fuel, higher is the synergetic increase in octane.
Hence, it is advantageous to use compounds of Claim 1 upstream in
the refinery.
[0118] A method for decreasing intake valve deposits in an internal
combustion engine is described, the method comprising burning in
the engine the composition of Claim 1.
[0119] A method for decreasing volatility of refinery blends is
described comprising: blending a downstream refinery blend with an
effective amount of compound of Claim 1.
[0120] A method of decreasing volatility of a refinery blend is
described comprising: blending an upstream refinery blend with an
effective amount of compound of Claim 1. The upstream refinery
hydrocarbon blends can be naphtha, residual oil. Ethanol can be
admixed to the blend.
[0121] A method for monitoring the octane number of a fuel is
described comprising: measuring a parameter associated with engine
knock by rapid compression machine (RCM); continuously outputting a
signal indicative of the parameter; and mathematically converting
the signal to an output signal indicative of the octane number.
[0122] The invention disclosed herein is exemplified by the
following preparations and examples, which should not be construed
to limit the scope of the disclosure. Alternative preparations and
analogous structures may be apparent to those skilled in the
art.
EXAMPLE 1
[0123] A mixture of 15 gm of oil orange dye, 24.15 gm of
polyisobutelene bromide and 100 ml diphenyl ether was refluxed for
8-10 hrs under stirring with elimination of HBr. The reaction
monitored by TLC. After completion, reaction mixture was dumped in
200 ml water to remove acidity. Solvent was removed azeotropically
and residue is distilled at reduced pressure. The yield of oil
orange dye-polyisobutelene-oil orange dye conjugate reaction
product was 52%. 28
EXAMPLE 2
[0124] A mixture of 15 gm of free base of dye (indoine blue), 18.3
gm of Polyisobutelene bromide and 50 ml of diphenyl ether was
refluxed for 4 hrs under stirring with elimination of HBr. The
reaction monitored by TLC. After completion, the reaction mixture
was dumped in water, solvent was removed azeotropically and residue
was distilled at reduced pressure. The yield of indoine blue
dye-polyisobutelene-indoine blue dye conjugate reaction product was
96%. 29
EXAMPLE 3
[0125] A mixture of anisic acid (5 gm), 2 ml of concentrated
sulphuric acid and 55 ml of absolute ethanol was refluxed at
80.degree. C. for 8 hrs under stirring. The reaction monitored by
TLC. After completion, reaction mixture was dumped in cold water
and oily layer was separated. The aqueous layer was extracted with
dichloromethane. This extracted layer and oily layer were combined
and washed with 5% sodium bicarbonate solution to remove unreacted
anisic acid. The dichloromethane was removed and residue was
distilled at reduced pressure. The yield of ethyl anisate was 86%.
30
EXAMPLE 4
[0126] A mixture of ethyl anisate (5.81 gm), 34.56 gm of
Polyisobutelene amine, 2 gm of ammonium chloride as catalyst and 75
ml of toluene was refluxed for 8-10 hrs under stirring. The
reaction was monitored by TLC. After completion solvent and ethanol
were removed from the product. The yield of ethyl anisate-PIB
conjugate reaction product was 90%. 31
EXAMPLE 5
[0127] A mixture of oil orange R dye (30 gm), 26.06 gm of
multibrominated polyisobutelene bromide and 120 ml diphenyl ether
was refluxed for 10-12 hrs under stirring with elimination of HBr.
Reaction was monitored by TLC. After completion, reaction mixture
was dumped in 200 ml water to remove acidity. Solvent removed
azeotropically and residue was distilled at reduced pressure. The
yield of oil orange R dye-polyisobutelene-oil orange R dye
conjugate reaction product was 25%. 32
EXAMPLE 6
[0128] A mixture of appropriate aldehyde or ketone and 20 gm of
freshly distilled cyclopentadiene is added to a solution of 6.9 gm
of sodium in 75 ml of distilled methanol. After 3 hrs of stirring
under nitrogen completion of reaction is monitored by TLC, then
reaction mass is poured into 250 ml of water. The organic phase is
extracted in dichloromethane and washed with water until the pH of
aqueous washes is neutral. It is then dried over anhydrous sodium
sulphate and filtered. The dichloromethane is removed and residue
is distilled at reduced pressure. The yield of respective fulvene
is indicated in the Table 5.
[0129] The general formula of fulvene is
5TABLE 5 33 Ex. Aldehyde/ YIELD No FULVENE R1 R2 Ketone (%) 6-13
6-(4- --H --C.sub.6H.sub.4.OMe Anisaldehyde 89 methoxy- (40.8 gm)
phenyl) fulvene 6-2 6,6- --OMe --OMe Dimethyl Dimethoxy carbonate
fulvene
EXAMPLE 7
[0130] This example describes the preparation and evaluation of the
blends in gasoline fuel. See Tables 6 and 7. Blends were prepared
by mixing the measured components as specified in the blends below,
at room temperature and pressure. The RON values were measured by
ASTM D2699.
6 TABLE 6 Blend No. Compound Quantity RON Blend 1 Naphtha 0.25 L 99
Commercial Grade 0.25 L Ethanol Ethylanisate-PIB 0.20 mg
conjugate.sup.1 t-butylalcohol 0.086 mg Blend A n-heptane (lab.
0.33 L Grade) Iso-octane 0.42 L Blend B Ethanol (Lab grade) 0.25 L
Blend A 0.25 L Blend 4 Blend B reference 101.3 Blend 5 Blend B 0.5
L 101.3 Ethylanisate-PIB 0.20 mg conjugate.sup.1 t-butylalcohol
0.086 mg Blend 6 Commercial grade 0.25 L 101.6 Ethanol n-heptane
0.11 L (lab. grade) Iso-octane (lab. 0.14 L Grade) Blend 7
Commercial grade 0.25 L 99.0 ethanol Naphtha 0.25 L
Ethylanisate-PIB 0.20 mg conjugate.sup.1 t-butylalcohol 0.086 mg
.sup.1(containing 0.02 mg impurities?)Additional 0.02 mg
impurities
[0131]
7TABLE 7 Blend No. Compound Quantity Base RON Final RON dRON 1
Ethylanisate- 0.4 gram.sup.1 56 97.6 41.6 Polyisobuttylene
conjugate t-butyl alcohol 0.167 gram Ethanol 0.4 L n-heptane 0.264
L Iso-octane 0.336 L 2 Ethylanisate- 0.4 gram.sup.1 56 68.4 12.4
Polyisobuttylene conjugate t-butyl alcohol 0.167 gram Ethanol 0.1 L
n-heptane 0.396 L Iso-octane 0.504 L 3 Orange Dye- 0.4 gram.sup.1
84.7 92.6 7.9 Polyisobutylene 3 Orange Dye- 0.4 gram.sup.1 84.7
92.6 7.9 Polyisobutylene conjugate Ethanol .1 L Synthetic Fuel .9
L
[0132] Several scenarios have changed in the fuel sourcing, prices,
policies for renewables, upcoming tighter emission standards. The
present invention incorporates use of renewable ethanol and an
organic antiknock that raises the octane far beyond the
compositions and the method of uses known to one skilled in the
art. Use of ethanol can raise the RVP. Methods of use suggested in
this invention screen the organic anti-knocks for suitability with
the fuel mixture of heavy straight chain (hence low RVP), naphtha
and ethanol using IR, followed by ASTM tests. Blends of heavy
naphtha or single component liquids derived from coal liquefaction
(will be cheaper under the present scenario of high price of crude)
will enhance the ability of present invention to reduce RVP,
aromatic content and T90, increase the content of paraffins and
simultaneously to reduce pollution (mixture of many hydrocarbons is
replaced by single component.). Use of single component hydrocarbon
and ethanol will automatically reduce olefins, T50, sulfur, T10 and
also T90.
[0133] It is contemplated, and will be apparent to those skilled in
the art from the foregoing specification, and examples, that
modifications and/or changes may be made in the embodiments of the
invention. Accordingly it is expressly intended that the foregoing
are only illustrative of the preferred embodiments and modes of
operation, not limiting thereto, and that the true spirit and scope
of the present invention be determined by reference to the appended
claims.
* * * * *