U.S. patent application number 13/009289 was filed with the patent office on 2012-07-19 for fuel additives and gasoline containing the additives.
This patent application is currently assigned to Afton Chemical Corporation. Invention is credited to Xinggao Fang, Jason Lagona, Michel Nuckols, May Duffield Thomas.
Application Number | 20120180382 13/009289 |
Document ID | / |
Family ID | 45442981 |
Filed Date | 2012-07-19 |
United States Patent
Application |
20120180382 |
Kind Code |
A1 |
Fang; Xinggao ; et
al. |
July 19, 2012 |
Fuel Additives and Gasoline Containing the Additives
Abstract
The present disclosure relates to a gasoline additive
concentrate including a reaction product of (a) 1,8-naphthalic
anhydride; and (b) a reaction product of a hydrocarbyl-substituted
succinic anhydride with a polyamine. Fuel compositions containing
the additive concentrate are also disclosed. Method of reducing
greenhouse gas emissions is also disclosed.
Inventors: |
Fang; Xinggao; (Richmond,
VA) ; Lagona; Jason; (Richmnd, VA) ; Nuckols;
Michel; (Midlothian, VA) ; Thomas; May Duffield;
(Richmond, VA) |
Assignee: |
Afton Chemical Corporation
Richmond
VA
|
Family ID: |
45442981 |
Appl. No.: |
13/009289 |
Filed: |
January 19, 2011 |
Current U.S.
Class: |
44/342 ;
44/347 |
Current CPC
Class: |
C10L 1/221 20130101;
C10L 2270/023 20130101; C10L 10/02 20130101; C10L 1/2383 20130101;
C10L 1/14 20130101; C10L 2200/0423 20130101; C10L 10/18 20130101;
C10L 1/1616 20130101; C10L 1/224 20130101 |
Class at
Publication: |
44/342 ;
44/347 |
International
Class: |
C10L 1/232 20060101
C10L001/232 |
Claims
1. A gasoline additive concentrate comprising: the product of
combining: (a) a 1,8-naphthalic anhydride; and (b) a reaction
product of a hydrocarbyl-substituted succinic anhydride with a
polyamine, wherein (a) and (b) are present in a molar ratio of
0.5:1 to 1:0.5 wherein the product of (a) and (b) is a gasoline
additive concentrate.
2. The concentrate of claim 1, wherein the polyamine is selected
from the group consisting of N-dodecyl propanediamine,
N-aminopropyl piperazine ethanolamine, N-ethanol ethylene diamine,
propylene diamine, dipropylene triamine,
di-(1,2-butylene)-triamine, tetra-(1,2-propylene)pentaamine,
ethylene diamine, diethylene triamine, triethylene tetraamine,
tetraethylene pentamine, pentaethylene hexaamine, heavy polyamine,
and mixtures thereof.
3. The concentrate of claim 1, wherein the polyamine is
tetraethylene pentamine.
4. The concentrate of claim 1, wherein the hydrocarbyl substituent
is polyisobutylene.
5. The concentrate of claim 4, wherein the polyisobutylene has a
molecular weight ranging from about 200 to about 5000.
6. The concentrate of claim 1, wherein the concentrate is a
reaction product of 1,8-naphthalic anhydride and a polyisobutylene
succinic anhydride-tetraethylene pentamine.
7. (canceled)
8. The concentrate of claim 1, wherein the hydrocarbyl-substituted
succinic anhydride and the polyamine are present in a molar ratio
of about 1:1 to about 1:1.
9. The concentrate of claim 1, further comprising at least one of a
Mannich base detergent and a carrier fluid.
10. A fuel composition comprising: (1) a minor amount of the
gasoline additive concentrate of claims 1; and (2) a major amount
of a hydrocarbon fuel boiling in the gasoline range.
11. The composition of claim 10, further comprising at least one of
a Mannich base detergent and a carrier fluid.
12. The composition of claim 10, wherein the hydrocarbyl
substituent is polyisobutylene.
13. The composition of claim 12, wherein the polyisobutylene has a
molecular weight ranging from about 200 to about 5000.
14. The composition of claim 10, wherein the polyamine is selected
from the group consisting of N-dodecyl propanediamine,
N-aminopropyl piperazine ethanolamine, N-ethanol ethylene diamine,
propylene diamine, dipropylene triamine,
di-(1,2-butylene)-triamine, tetra-(1,2-propylene)pentaamine,
ethylene diamine, diethylene triamine, triethylene tetraamine,
tetraethylene pentamine, pentaethylene hexaamine, heavy polyamine,
and mixtures thereof.
15. The composition of claim 10, wherein the polyamine is
tetraethylene pentamine.
16. The composition of claim 10, wherein the concentrate is a
reaction product of 1,8-naphthalic anhydride and a polyisobutylene
succinic anhydride-tetraethylene pentamine.
17. The composition of claim 10, wherein the
hydrocarbyl-substituted succinic anhydride and the polyamine are
present in a molar ratio of about 1:1.
18. The composition of claim 10, wherein the additive concentrate
can be used in the gasoline composition in an amount of 0.1 ptb to
about 10 ptb
19. A method to reduce the amount of deposits in direct injection
gasoline engines, said method comprising: adding to a gasoline to
be combusted in the direct injection gasoline engine a gasoline
additive concentrate comprising: the product of combining: (a) a
1,8-naphthalic anhydride; and (b) a reaction product of a
hydrocarbyl-substituted succinic anhydride with a polyamine,
wherein (a) and (b) are present in a molar ratio of 0.5:1 to 1:0.5
to form a gasoline composition, then combusting said gasoline
composition.
20. A method for reducing greenhouse gas emissions, said method
comprising: adding to a gasoline to be combusted in the direct
injection gasoline engine a gasoline additive concentrate
concentrate comprising: the product of combining: (a) a
1,8-naphthalic anhydride; and (b) a reaction product of a
hydrocarbyl-substituted succinic anhydride with a polyamine,
wherein (a) and (b) are present in a molar ratio of 0.5:1 to 1:0.5
to form a gasoline composition, then combusting said gasoline
composition.
Description
FIELD OF THE DISCLOSURE
[0001] The present disclosure relates in one embodiment a gasoline
additive concentrate comprising the product of combining a
1,8-naphthalic anhydride and a reaction product of a
hydrocarbyl-substituted succinic anhydride with a polyamine. A fuel
composition comprising the gasoline concentrate is also disclosed.
Moreover, there is also disclosed a method for reducing greenhouse
gas emissions comprising adding to a gasoline the disclosed
additive and combusting the fuel composition in an engine.
[0002] This invention materially enhances the quality of the
environment by contributing to the restoration or maintenance of
the basic life-sustaining natural elements. In particular, this
invention materially contributes to greenhouse gas emission
reduction.
BACKGROUND OF THE DISCLOSURE
[0003] Gasoline fuel requires additives to maintain optimal
performance for machineries that use gasoline fuel. Common fuel
additives include a reaction product of hydrocarbyl phenol with
formaldehyde and amines, which are generally known as Mannich base
products or dispersant/detergents. Additives could also include
hydrocarbons and alkyl polyols, which are commonly known as carrier
fluids. One critical performance requirement of machinery such as
automobile engines is maintaining a clean fuel delivery system.
Additives mentioned above could mitigate the problem of fouling
fuel delivery system. Yet there is always a need for additives that
could afford better performance.
[0004] Over the years considerable work has been devoted to
additives for controlling (preventing or reducing) deposit
formation in the fuel induction systems of spark-ignition internal
combustion engines. In particular, additives that can effectively
control fuel injector deposits, intake valve deposits and
combustion chamber deposits represent the focal point of
considerable research activities in the field and despite these
efforts, further improvements are desired.
[0005] In addition, more sophisticated engines are being developed
to increase automobile performance including increasing fuel
economy, reducing emission. An example is direct injection gasoline
(DIG) engine. These newer engines demand more effective additives
to keep the fuel delivery systems from being clogged and to clean
up the clogged fuel delivery systems. However, direct injection
gasoline engines can encounter problems different from those of the
conventional engines due to the direct injection of gasoline into
the combustion chamber.
[0006] Current generation DIG technologies have experienced deposit
problems. Areas of concern are fuel rails, injectors, combustion
chamber (CCD), crankcase soot loadings, and intake valves (IVD).
Deposits in the intake manifold come in through the pressure
control valve and exhaust gas recirculation (EGR). Because there is
no liquid fuel wetting the back of the intake valves, these
deposits build up quite quickly.
[0007] The additives which work well as detergents in multi-port
injection engines will not necessarily work well in DIG engines,
and as such additional detergents prepared especially for DIG
engines may be required as a "top-treat" type additive or as an
after-market fuel supplement.
[0008] One approach to reducing deposits has been to introduce a
small amount of the reaction product of hydrocarbyl succinic
anhydride (HSA) with polyamines (PAM) of about one to one molar
ratio. However there is still a need for additives that offer
improved performance.
[0009] It has been known to combine certain aromatic anhydrides and
ethylene carbonate post-treated dispersants to improve dispersancy
in an engine oil. In particular, the post reaction of
polyisobutylene succinimide (PIBSI) with a so-called capping agent
is common in engine oil additives. Many capping agents, including
maleic anhydride, succinic anhydride, phthalic anhydride,
1,8-naphthalic anhydride, and boric acid are known. It has been
known to formulate an oil-soluble lubricating oil additive with a
naphthalic anhydride post-treated mono-succinimide derived from a
2300 MW polyisobutylene succhinic anhydride (PIBSA) and a heavy
polyamine. However, the ratio of the naphthalic anhydride capping
agent to the PIBSA was 0.60:1 and this compound was used in an
engine oil containing known engine oil additives. One of ordinary
skill in the art would know that engine oils contain additives that
are not suitable for use in fuels, such as zinc
dialkyldithiophosphate. Further, it is known to further treat with
a cyclic carbonate, which is not required by the present
invention.
[0010] It has also been known to prepare fuel compositions
comprising additives prepared by acylation of alkyl or alkenyl
succinimides with the polyether half-esters of dicarboxylic acids,
such as phthalic acid or 1,8-naphthalic acid. To be clear, the
polyether half-esters of dicarboxylic acids are grafted onto the
polyamine moiety of alkyl or alkenyl succinimides by reacting the
succinimide and the half-ester under conditions to form an amide
group. The succinimides and the polyamines are present in a ratio
of 2:1, thereby forming a bis compound.
[0011] Capping by other materials in diesel can be detrimental to
keeping injectors clean and contradictory to common sense. In
particular, when compounds made by reacting terminal amine moieties
with anhydrides are used in fuels, such as diesel, they generally
have a negative effect on the fuels performance. For this reason,
such compounds have not been used.
[0012] It has been surprisingly found that a class of material when
mixed into the additized gasoline fuels containing typical Mannich
base product or detergent and carrier fluid could enhance the
ability of the additized fuel in keeping a clean fuel delivery
system for advanced automotive engines.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] The accompanying drawings, which are incorporated in and
constitute a part of this specification, illustrate certain
embodiments of the invention and together with the description,
serve to explain the principles of the invention. In the
figures:
[0014] FIG. 1 is a graph of the Long Term Fuel Trim (LTFT) of a
conventional additized gasoline fuel comprising Mannich and carrier
fluid.
[0015] FIG. 2 is a graph of the LTFT for various comparative
compositions.
[0016] FIG. 3 is a graph of the LTFT of various inventive
compositions.
SUMMARY OF THE DISCLOSURE
[0017] In accordance with the disclosure, there is disclosed a
gasoline additive concentrate comprising the product of combining
(a) a 1,8-naphthalic anhydride; and (b) a reaction product of a
hydrocarbyl-substituted succinic anhydride with a polyamine.
[0018] In another aspect, there is disclosed a method to reduce the
amount of deposits in direct injection gasoline engines, the method
comprising adding to a gasoline to be combusted in the direct
injection gasoline engine a gasoline additive concentrate to form a
gasoline composition, then combusting the gasoline composition.
[0019] Moreover, there is disclosed a method to reduce greenhouse
gas emissions, the method comprising adding to a gasoline to be
combusted in the direct injection gasoline engine a gasoline
additive concentrate to form a gasoline composition, then
combusting the gasoline composition.
DESCRIPTION OF THE EMBODIMENTS
[0020] The present disclosure relates in one embodiment to a
gasoline additive concentrate comprising a product of combining (a)
a 1,8-naphthalic anhydride; and (b) a reaction product of a
hydrocarbyl-substituted succinic anhydride with a polyamine. It is
believed, without being limited to any particular theory, that the
reaction product forms an imide. The molar ratio of (a) to (b) is
about 1:1, for example ranging from about 0.95:0.05 to about
0.05:0.95, and as a further example from about 0.8:0.2 to about
0.2:0.8. In an aspect, the molar ratio is from about 0.5:1 to about
1:0.5.
[0021] The prior art teaches using a reaction product of PIBSA and
various amines in fuel and lubricant compositions, but an
improvement herein lies in top treating a gasoline composition with
a gasoline additive concentrate comprising a product of combining
(a) a 1,8-naphthalic anhydride; and (b) a reaction product of a
hydrocarbyl-substituted succinic anhydride with a polyamine.
[0022] There is disclosed (b) a reaction products obtained by
reacting a hydrocarbyl-substituted succinic anhydride, acid,
acid-ester or lower alkyl ester with an amine containing at least
two amino groups, such as a polyamine. Representative non-limiting
examples are given in U.S. Pat. Nos. 3,172,892; 3,202,678;
3,219,666; 3,272,746, 3,254,025, 3,216,936, 4,234,435; and
5,575,823. The hydrocarbyl-substituted succinic anhydride may be
prepared readily by heating a mixture of olefin and maleic
anhydride to about 180-220.degree. C. The hydrocarbyl is, in an
embodiment, a polymer or copolymer of a lower monoolefin such as
ethylene, propylene, isobutene and the like. In another embodiment,
the source of alkenyl group is from polyisobutene having a
molecular weight up to 10,000 or higher. In another embodiment, the
alkenyl is a polyisobutene group having a molecular weight of about
200-5,000, for example about 500-2,000, and as a further example
form about 700-1000. In another aspect, the polyisobutene group has
a molecular weight less than about 1000, such as about 950.
[0023] In an aspect, the hydrocarbyl substituent of the
hydrocarbyl-substituted succinic anhydride is a
polyisobutylene.
[0024] Amines which may be employed include any that have at least
two amino groups which can react to form an imide group. A few
representative examples are: N-dodecyl propanediamine,
N-aminopropyl piperazine ethanolamine, N-ethanol ethylene diamine
and the like. Preferred amines include the alkylene polyamines such
as propylene diamine, dipropylene triamine,
di-(1,2-butylene)-triamine, tetra-(1,2-propylene)pentaamine.
[0025] In one embodiment the amines are the ethylene polyamines
that have the formula H.sub.2N(CH.sub.2CH.sub.2NH).sub.nH wherein n
is an integer from one to ten. These ethylene polyamines include
ethylene diamine, diethylene triamine, triethylene tetraamine,
tetraethylene pentaamine, pentaethylene hexaamine, and the like,
including mixtures thereof in which case n is the average value of
the mixture. These ethylene polyamines have a primary amine group
at each end so can form mono-alkenylsuccinimides and
bis-alkenylsuccinimides. A heavy polyamine can also be used. In an
embodiment, the polyamine is tetraethylene pentamine.
[0026] The molar ratio of the hydrocarbyl-substituted succinic
anhydride to the polyamine is about 1:1, but may include other
ratios such as 5:1-1:5, and ranges in between.
[0027] Thus the reaction product (b) for use in the present
invention can also include the products of reaction of a
polyethylenepolyamine, e.g. triethylene tetramine or tetraethylene
pentamine, with a hydrocarbon substituted carboxylic acid or
anhydride made by reaction of a polyolefin, such as polyisobutene,
having a molecular weight of 250 to 5,000, for example 500 to 2000,
and as a further example less than about 1000, with an unsaturated
polycarboxylic acid or anhydride, e.g. maleic anhydride.
[0028] The gasoline additive concentrate can be used to top treat a
gasoline composition in any amount effective to reduce intake valve
deposits. In particular, the additive concentrate can be used in a
gasoline composition in an amount of 0.1 ptb to about 10 ptb, such
as 0.4 ptb to about 7 ptb, as a further example 1 ptb to about 6
ptb, and as a further example, 2 ptb to about 5.5 ptb.
[0029] The fuel compositions disclosed herein comprise a minor
amount of the disclosed gasoline additive concentrate and a major
amount of a hydrocarbon fuel in the gasoline boiling range. As used
herein "minor amount" means less than about 50% by weight of the
total weight of the fuel composition. As used herein, "major
amount" means greater than or equal to about 50% by weight of the
total weight of the fuel composition.
[0030] The fuel utilized in the practice of this disclosure can be
traditional blends or mixtures of hydrocarbons in the gasoline
boiling range, or they can contain oxygenated blending components
such as alcohols and/or ethers having suitable boiling temperatures
and appropriate fuel solubility, such as methanol, ethanol, methyl
tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), tert-amyl
methyl ether (TAME), and mixed oxygen-containing products formed by
"oxygenating" gasolines and/or olefinic hydrocarbons falling in the
gasoline boiling range. Thus this disclosure involves use of
gasolines, including the so-called reformulated gasolines which are
designed to satisfy various governmental regulations concerning
composition of the base fuel itself, componentry used in the fuel,
performance criteria, toxicological considerations and/or
environmental considerations. The amounts of oxygenated components,
detergents, antioxidants, demulsifiers, and the like that are used
in the fuels can thus be varied to satisfy any applicable
government regulations, provided that in so doing the amounts used
do not materially impair the improved ignition performance made
possible by the practice of this invention.
[0031] When formulating the fuel compositions of this invention,
the gasoline additive concentrate is employed in amounts sufficient
to reduce or eliminate injector deposits. Thus, the fuels will
comprise minor amounts of the gasoline additive, i.e., the reaction
product of (a) an aromatic anhydride or derivative thereof, and (b)
a hydrocarbyl amine or alcohol proportioned so as to prevent or
reduce formation of engine deposits, especially fuel injector
deposits, and most especially intake valve deposits.
[0032] The gasoline additive concentrate or fuel composition
further comprises other additives, such as a Mannich base detergent
such as those disclosed in U.S. Pat. No. 7,491,248. The Mannich
base detergents useful in embodiments of the present invention are
the reaction products of an alkyl-substituted hydroxy aromatic
compound, aldehydes and amines. The alkyl-substituted
hydroxyaromatic compound, aldehydes and amines used in making the
Mannich reaction products of the present invention may be any such
compounds known and applied in the art, such as those disclosed in
U.S. Pat. No. 7,491,248.
[0033] In another embodiment, the gasoline additive concentrate or
fuel composition further comprises a liquid carrier or induction
aid such as those disclosed in U.S. Pat. No. 7,491,248. Such
carriers can be of various types, such as for example liquid
poly-alpha-olefin oligomers, mineral oils, liquid poly(oxyalkylene)
compounds, liquid alcohols or polyols, polyalkenes, liquid esters,
and similar liquid carriers. Mixtures of two or more such carriers
can be employed.
[0034] Liquid carriers can include but is not limited to 1) a
mineral oil or a blend of mineral oils that have a viscosity index
of less than about 120, 2) one or more poly-alpha-olefin oligomers,
3) one or more poly(oxyalkylene) compounds having an average
molecular weight in the range of about 500 to about 3000, 4)
polyalkenes, 5) polyalkyl-substituted hydroxyaromatic compounds or
6) mixtures thereof.
[0035] The fuel compositions of the present invention may contain
supplemental additives in addition to the detergent(s), and carrier
fluids described above. Said supplemental additives include
additional dispersants/detergents, antioxidants, carrier fluids,
metal deactivators, dyes, markers, corrosion inhibitors, biocides,
antistatic additives, drag reducing agents, demulsifiers, dehazers,
anti-icing additives, antiknock additives, anti-valve-seat
recession additives, lubricity additives and combustion
improvers.
[0036] The additives used in formulating the preferred fuels of the
present invention can be blended into the base fuel individually or
in various sub-combinations. However, it is preferable to blend all
of the components concurrently using an additive concentrate as
this takes advantage of the mutual compatibility afforded by the
combination of ingredients when in the form of an additive
concentrate. Also use of a concentrate reduces blending time and
lessens the possibility of blending errors.
[0037] Other aspects of the present invention include a method to
reduce the amount of deposits in direct injection gasoline engines,
the method comprising adding to a gasoline to be combusted in the
direct injection gasoline engine a gasoline additive concentrate to
form a gasoline composition, then combusting the gasoline
composition.
[0038] Moreover, there is disclosed a method to reduce greenhouse
gas emissions, the method comprising adding to a gasoline to be
combusted in the direct injection gasoline engine a gasoline
additive concentrate to form a gasoline composition, then
combusting the gasoline composition.
EXAMPLES
[0039] The following examples further illustrate aspects of the
present disclosure but do not limit the present disclosure.
Example A
Synthesis of Comparative Additive (PIBSI)
[0040] An additive was produced from the reaction of
polyisobutylenesuccnic anhydride (PIBSA, from Afton Chemical) with
polyamine (PAM, in this case PAM is tetraethylenepentamine, TEPA)
in a molar ratio of PIBSA/PAM=1/1. A modified procedure of U.S.
Pat. No. 5,752,989 was used. PIBSA (551 g) was diluted in solvent
aromatic 150 (200 g) under nitrogen atmosphere. The mixture was
heated to 115 C. 112 g of TEPA was then added through an addition
funnel. The addition funnel was rinsed with additional solvent
aromatic 150 (50 g). The mixture was heated to 180.degree. C. for
about 2 hr under a slow nitrogen sweep. Water was collected in a
Dean-Stark trap. Product was obtained as a brownish oil. The FTIR
peak absorptions were at 1772 cm.sup.-1 and 1703 cm.sup.-1.
Example B
Synthesis of Inventive Additive--PIBSA-TEPA-NA
[0041] 1,8-naphthalic anhydride (27.7 g, 0.14 mol) was added to a
PIBSI (950 MW PIB), a reaction product of PIBSA with TEPA in about
1 to 1 molar ratio with a method disclosed in U.S. Pat. No.
5,752,989 (180.9 g, 0.164 mol). Solvent aromatic 150 (128 g) was
added. The mixture was heated to 175.degree. C. for 1.5 hr under a
slow nitrogen sweep. It was then filtered via celite 512 to afford
product as a brown oil. The FTIR peak absorptions were at 1702
cm.sup.-1 and 1664 cm.sup.-1. DIG test--An engine test measuring
fuel injector deposit is performed following a procedure disclosed
in Society of Automotive Engineer (SAE) International publication
2009-01-2641 "Test and Control of Fuel Injector Deposits in Direct
Injected Spark Ignition Vehicles". A mathematical value of Long
Term Fuel Trim (LTFT) is used to gauge the ability of the additive
to keep deposits from accumulating in the injectors, or keep the
injector clean. The higher the LTFT, the more deposit in the
injectors, the less effective the additive is in keeping the
injector clean. A 2008 General Motors Pontiac Solstice GXP equipped
with a DISI 2.0 liter turbocharged I-4 was used in the test.
TABLE-US-00001 TABLE 1 Injector Cleanliness as determined by Long
Term Fuel Trim (LTFT). TEST# additives LTFT 1 no top treat,
reference run 17.2% 2 PIBSA-TEPA 1.5 ptb 11.7% 3 PIBSA-TEPA 2 ptb
4.7% 4 PIBSA-TEPA-NA 2 ptb 0.8% 5 PIBSA-TEPA-NA 1 ptb 2.4%
Comparative Example 1
[0042] Dig test with conventional additized gasoline fuel
containing Mannich and carrier fluid. No additional additive was
used. The treat rate of the Mannich and carrier fluid was 38.4
pound additive per thousand barrel of gasoline fuel (ptb). The LTFT
was measured at 17.2%. Comparative example 2-PIBSI from Example A
was used at a treat rate of 1.5 ptb. The LTFT was measured at
11.7%.
Comparative Example 3
[0043] Same as comparative example 2 except that 2.0 ptb of active
PIBSI from example A was mixed into the fuel. The LTFT was measured
at 4.7%.
Inventive Example 4
[0044] 2 ptb of active material from Example B was used. The LTFT
was measured at 0.8%.
Inventive example 5
[0045] Same as inventive example 4 except that the amount of
additive was reduced to 1 ptb. The LTFT was measured at 2.4%.
[0046] The smaller the LTFT, the cleaner the fuel injector. So, the
data in Table 1 shows that inventive compositions 4-5 have a
smaller LTFT, i.e., cleaner injectors, as compared to comparative
composition 1-3. This demonstrates the unexpected and superior
performance of the PIBSA-TEPA NA in a fuel composition.
[0047] Ford 2.3-IVD test. Another test (a modified ASTM D620) was
conducted to determine the intake valve deposit-forming tendency of
gasoline using a Ford 2.3-Liter engine (short for Ford 2.3-IVD
test). The additive was mixed into gasoline to control the amount
of deposit in the intake valve. For this test, a 1994 Ford 2.3-L
dual spark plug engine on a dynamometer test stand was used. The
test cycle consists of:
[0048] 2,000 rpm and 230-mm Hg manifold absolute pressure for 4
minutes
[0049] 30-second ramp to 2,800 rpm
[0050] 2,800 rpm and 540 Hg manifold absolute pressure for 8
minutes
[0051] 30-second ramp back to 2,000 rpm
[0052] The cycle was repeated for 100 hours. Intake valve deposit
weights were reported
TABLE-US-00002 TABLE 2 Reduction in Intake Valve Deposit of Port
Fuel Injection Engine. Avg TEST Valve 1 Valve 2 Valve 3 Valve 4
IVD(mg) 8 106.4 159.7 85.4 123.8 118.8 ref 9 136.5 89.9 114.5 62.1
100.8 ref 10 76.8 82.9 101.4 27.3 72.1 2ptb PIBSA- TEPA-NA
[0053] The compositions in Table 2 were run in a test cycle CRC for
100 hours. Inventive composition 10 exhibited a reduction in intake
valve deposits as compared to Comparative compositions 8-9. The
additives in tests 8 and 9 were 28 ptb of a mixture of a typical
Mannich base and a typical carrier fluid. -cl Comparative example
8
[0054] Ford 2.3-IVD test with conventional additive Mannich and
carrier fluid. The average intake valve deposit (IVD) was at 118.8
mg.
Comparative example 9
[0055] Repeat of comparative example 8. The average IVD was 100.8
mg.
Inventive example 10
[0056] Same as comparative example 8 except that material from
example B was added at a treat rate of 2.0 ptb. The average IVD was
72.1 mg. The less the amount of deposit, the more effective the
additive was in reducing intake valve deposit. This also
demonstrates the unexpected and superior performance of the
PIBSA-TEPA NA in a fuel composition.
TABLE-US-00003 TABLE 3 Dirty, 2006 Buick Lacrosse with artificially
plugged injector, LTFT 4.7% Run No. FTP B1 (hot) FTP B2 FTP B3
HwFET US06 city US06 Hwy CO2 1 387.8023633 440.731 390.3925 262.904
564.6301 321.0167 g/mi 2 393.8057617 444.8809 391.3243 263.9494
563.2401 319.5851 3 393.6697355 448.6128 391.0601 262.5692 566.2071
310.4464 Avg 391.759 444.742 390.926 263.141 564.692 317.016 -2.42%
-1.76% -2.40% -3.08% -2.27% -3.44% Fuel 1 22.9279614 20.2136
22.7966 33.86581 15.65253 27.68976 Economy 2 22.5957295 20.01766
22.74065 33.70907 15.74413 27.80583 mi/gal 3 22.59947057 19.84532
22.75711 33.89471 15.68088 28.63305 Avg 22.708 20.026 22.765 33.823
15.693 28.043 2.59% 1.91% 2.50% 3.23% 2.91% 3.65%
[0057] As can be seen from the data in Table 3, there is about a 1
to 3% reduction in CO.sub.2 emission in gasoline powered vehicles
directly resulting from injector keep clean or clean up. The
emissions reduction can be measured and quantified in units of
grams/mile, and it is sustainable, so long as injectors are kept
clean with the inventive gasoline additive concentrate. Fuel
economy of the vehicle is improved by an equivalent amount, so
reduced gasoline consumption is yet another benefit.
[0058] At numerous places throughout this specification, reference
has been made to a number of U.S. patents, published foreign patent
applications and published technical papers. All such cited
documents are expressly incorporated in full into this disclosure
as if fully set forth herein.
[0059] For the purposes of this specification and appended claims,
unless otherwise indicated, all numbers expressing quantities,
percentages or proportions, and other numerical values used in the
specification and claims, are to be understood as being modified in
all instances by the term "about." Accordingly, unless indicated to
the contrary, the numerical parameters set forth in the following
specification and attached claims are approximations that can vary
depending upon the desired properties sought to be obtained by the
present disclosure. At the very least, and not as an attempt to
limit the application of the doctrine of equivalents to the scope
of the claims, each numerical parameter should at least be
construed in light of the number of reported significant digits and
by applying ordinary rounding techniques.
[0060] It is noted that, as used in this specification and the
appended claims, the singular forms "a," "an," and "the," include
plural referents unless expressly and unequivocally limited to one
referent. Thus, for example, reference to "an antioxidant" includes
two or more different antioxidants. As used herein, the term
"include" and its grammatical variants are intended to be
non-limiting, such that recitation of items in a list is not to the
exclusion of other like items that can be substituted or added to
the listed items.
[0061] It is to be understood that the reactants and components
referred to by chemical name anywhere in the specification or
claims hereof, whether referred to in the singular or plural, are
identified as they exist prior to coming into contact with another
substance referred to by chemical name or chemical type (e.g., base
fuel, solvent, etc.). It matters not what chemical changes,
transformations and/or reactions, if any, take place in the
resulting mixture or solution or reaction medium as such changes,
transformations and/or reactions are the natural result of bringing
the specified reactants and/or components together under the
conditions called for pursuant to this disclosure. Thus the
reactants and components are identified as ingredients to be
brought together either in performing a desired chemical reaction
(such as a Mannich condensation reaction) or in forming a desired
composition (such as an additive concentrate or additized fuel
blend). It will also be recognized that the additive components can
be added or blended into or with the base fuels individually per se
and/or as components used in forming preformed additive
combinations and/or sub-combinations. Accordingly, even though the
claims hereinafter may refer to substances, components and/or
ingredients in the present tense ("comprises", "is", etc.), the
reference is to the substance, components or ingredient as it
existed at the time just before it was first blended or mixed with
one or more other substances, components and/or ingredients in
accordance with the present disclosure. The fact that the
substance, components or ingredient may have lost its original
identity through a chemical reaction or transformation during the
course of such blending or mixing operations is thus wholly
immaterial for an accurate understanding and appreciation of this
disclosure and the claims thereof.
[0062] As used herein the term "fuel-soluble" or "gasoline-soluble"
means that the substance under discussion should be sufficiently
soluble at 20.degree. C. in the base fuel selected for use to reach
at least the minimum concentration required to enable the substance
to serve its intended function. Preferably, the substance will have
a substantially greater solubility in the base fuel than this.
However, the substance need not dissolve in the base fuel in all
proportions.
[0063] At numerous places throughout this specification, reference
has been made to a number of U.S. patents and published foreign
patent applications. All such cited documents are expressly
incorporated in full into this disclosure as if fully set forth
herein. This invention is susceptible to considerable variation in
its practice. Therefore the foregoing description is not intended
to limit, and should not be construed as limiting, the invention to
the particular exemplifications presented hereinabove. Rather, what
is intended to be covered is as set forth in the ensuing claims and
the equivalents thereof permitted as a matter of law.
[0064] Applicant does not intend to dedicate any disclosed
embodiments to the public, and to the extent any disclosed
modifications or alterations may not literally fall within the
scope of the claims, they are considered to be part of the
invention under the doctrine of equivalents.
* * * * *