CA2089833A1 - Gasoline composition - Google Patents
Gasoline compositionInfo
- Publication number
- CA2089833A1 CA2089833A1 CA 2089833 CA2089833A CA2089833A1 CA 2089833 A1 CA2089833 A1 CA 2089833A1 CA 2089833 CA2089833 CA 2089833 CA 2089833 A CA2089833 A CA 2089833A CA 2089833 A1 CA2089833 A1 CA 2089833A1
- Authority
- CA
- Canada
- Prior art keywords
- gasoline
- ppmw
- alkyl
- molecular weight
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 50
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001412 amines Chemical class 0.000 claims abstract description 14
- -1 poly(oxyalkylene) Polymers 0.000 claims abstract description 14
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 239000007859 condensation product Substances 0.000 claims abstract description 10
- 239000012141 concentrate Substances 0.000 claims abstract description 8
- 239000003254 gasoline additive Substances 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002485 combustion reaction Methods 0.000 claims abstract description 7
- 229920005862 polyol Polymers 0.000 claims abstract description 6
- 150000003077 polyols Chemical class 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 5
- 239000000376 reactant Substances 0.000 claims abstract description 5
- 125000003277 amino group Chemical group 0.000 claims abstract description 4
- 239000003085 diluting agent Substances 0.000 claims description 6
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 2
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 229920002866 paraformaldehyde Polymers 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims 1
- 239000000446 fuel Substances 0.000 description 22
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- 239000000654 additive Substances 0.000 description 11
- 230000000996 additive effect Effects 0.000 description 11
- 239000002585 base Substances 0.000 description 10
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000003599 detergent Substances 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000005529 alkyleneoxy group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- CREXVNNSNOKDHW-UHFFFAOYSA-N azaniumylideneazanide Chemical group N[N] CREXVNNSNOKDHW-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ANHQLUBMNSSPBV-UHFFFAOYSA-N 4h-pyrido[3,2-b][1,4]oxazin-3-one Chemical group C1=CN=C2NC(=O)COC2=C1 ANHQLUBMNSSPBV-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 125000005228 aryl sulfonate group Chemical group 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical class O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- FSWDLYNGJBGFJH-UHFFFAOYSA-N n,n'-di-2-butyl-1,4-phenylenediamine Chemical compound CCC(C)NC1=CC=C(NC(C)CC)C=C1 FSWDLYNGJBGFJH-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000003443 succinic acid derivatives Chemical class 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
Landscapes
- Solid Fuels And Fuel-Associated Substances (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
ABSTRACT
GASOLINE COMPOSITION
The invention provides a gasoline composition comprising a major amount of a gasoline and a minor amount of a mixture of (a) from 75 ppmw to 450 ppmw of a condensation product of (1) a high molecular weight sulfur-free alkyl-substituted hydroxyaromatic compound wherein the alkyl group has a number average molecular weight from 600 to 3000, (2) an amine which contains an amino group having at least one active hydrogen atom, and (3) an aldehyde, wherein the respective molar ratio of reactants is 1 : 0.1-10 :
0.1-10; and (b) from 75 ppmw to 175 ppmw of an oil-soluble poly(oxyalkylene) alcohol, glycol or polyol or mono or di ether thereof, wherein the weight ratio of (a) to (b) in the mixture is at least 0.43, all amounts (ppmw) being based on the gasoline composition; a gasoline additive concentrate for use in preparing said composition; and a method of operating a spark-ignition internal combustion engine using said composition.
GASOLINE COMPOSITION
The invention provides a gasoline composition comprising a major amount of a gasoline and a minor amount of a mixture of (a) from 75 ppmw to 450 ppmw of a condensation product of (1) a high molecular weight sulfur-free alkyl-substituted hydroxyaromatic compound wherein the alkyl group has a number average molecular weight from 600 to 3000, (2) an amine which contains an amino group having at least one active hydrogen atom, and (3) an aldehyde, wherein the respective molar ratio of reactants is 1 : 0.1-10 :
0.1-10; and (b) from 75 ppmw to 175 ppmw of an oil-soluble poly(oxyalkylene) alcohol, glycol or polyol or mono or di ether thereof, wherein the weight ratio of (a) to (b) in the mixture is at least 0.43, all amounts (ppmw) being based on the gasoline composition; a gasoline additive concentrate for use in preparing said composition; and a method of operating a spark-ignition internal combustion engine using said composition.
Description
GASOLINE COMPOSITION
The present invention relates to a gasoline composLtion, a gasoline additive concentrate for use in preparing the gasoline composition and B method of operating a spark-ignition Lnternal combustion engine using the gasoline composition.
Gasoline compositions have traditionally been formulated to improve the performance of csrburetor and throttle body in;ected engines. Beginning in about 1984, electronic port fuel in;ected engines were commonly introduced by auto~obile manufacturers.
Shortly thereafter, in about 1985, problems began to be reported 10 with intake valve deposits in electronic port fuel injected engines, which problems are characterized by hard starting, stalls, snd stumbles during acceleration and rough engine idle.
Accordingly, it would be desirable to have fuel compositions which reduce or eliminate such undesirable intake valve deposits in 15 electronic port fuel in~ected engines. Also, since some carburetor and throttle body in~ector engines will still be in use for the foreseeable future, it would be desirable if such fuels could also be compatible with these engines.
Condensation products of a hydroxyaromatic compound, an 20 amine, and an aldehyde are known to improve detergent properties of fuels used in carburetor and throttle body type engines. U.S.
Patent No. 4,231,759 teaches the use of the condensation product of a hydroxyaromatic compound, an amine, and an aldehyde in a carrier of polyolefin, mineral oil, or phenol compounds for removing and 2~ preventing deposits on carburetor surfaces and intake valves.
Such compositions have reduced effectiveness in electronic port fuel in~ected engines where the carrier appears to act li~e a diluent, reducing the effectiveness of the detergent which lt had enhanced in carbureted engines.
-U.S. Patent No. 4,116,644 discloses a concentrate for use in liquid hydrocarbon fuel boiling in the gasoline boiling range containing (I) as detergent additive, from about 35 to about 50 weight percent of the reaction product of:
(A) one mole part of an alkylphenol having the formula.
OH
~3 (Rl)n wherein n is an integer from 1 to 2, and Rl is an aliphatic hydrocarbon radical having an average molecular weight of from 15 about 400 to 1500;
(B) from 1-5 mole parts of an aldehyde having the for~ula:
H
wherein R2 i9 selected from hydrogen and alkyl rad~cal~ containing 1-6 carbon ato~s; ant (C) from 0.5-5 mole parts of an amine having at least one active hydrogen atom bonded to an amino nitrogen atom, and (II) from about 1.4 to about 5.6 weight percent of a demulsifying agent containing:
(A) at least one oil-soluble amine, ammonium, alkaline earth metal, or alkali metal salt of an aryl sulfonic acid;
(B) at least one oil-soluble polyether characterized by the presence within its structure of a group of the formula:
(-O-A-)x wherein A is an alkylene group containing from 2 to about 7 carbon 2~89833 atoms and wehre x has an average value of from about 5 to about 200; and (C) an oxyalkylated phenol formaldehyde resin of the formula:
(OA)moH
~C112 R
wherein A represents an alkylene group containing from about 2 to about 10 carbon atoms, where m has an average value of from about 4 to about 200, and where R i9 an alkyl group of about from 1 to about 20 carbon atoms.
(III) from about 20 to about 25 weight percent of a mono~ùclear or dinuclear aromatic hydrocarbon solvent, (IV) from about 20 to about 35 weight percent of an alkanol having from 4 to 10 carbon atoms, and (V) from about 3 to about 5 weight percent of a corrosion inhibitor.
The demulsifying agent may contain from about 2 to about 10 parts by weight of aryl sulfonate, from about 0.25 to about 4 parts by weight of polyether glycol, and from about 0.25 to about 4 parts by weight of oxyalkylated phenol formaldehyde resin.
The amount of detergent additive added to the gasoline is said to be in the range from about 3 to 2000 ppm. The amount of demulsifying agent added to the gasoline is said to be dependent, to a degree, upon the concentration of the deterge~t additive in the gasoline. From about 0.02 to 0.2~ ppm of demulsifying agent are added for every one ppm of detergent additive.
Gasolines containing the concentrate are indicated to be advantageous on the basis that they do not suffer from water/gasoline emuls~on problems.
U.S. Patent No. 4,398,921 discloses a fuel comprising a major amount of gasoline, a minor amount of ethanol and a detergent amount (about l.O to about 100 ppm) of an additive composition comprising:
(I) from about 20 to about 40 weight percent of the reaction product of:
(A) one mole psrt of an alkylphenol hav~ng the formula:
OH
~} (Rl)n wherein n is an integer from 1 to 2, and Rl is an aliphatic hydrocarbon radical having an average molecular weight of from about 400 to 1500;
(B) from l-S mole parts of an aldehyde having the formula:
H
wherein R2 is selected from hydrogen and alkyl radicals containing 1-6 carbon atoms; and (C) from 0.5-5 mole parts of an amine having at least one active hydrogen atom bonded to an amino nitrogen atom, and (II) from about 3.0 to about 6.0 weight percent of a demulsifying agent containing:
(A) at least one oil-soluble polyether characterized by the presence within its structure of a group of the formula:
(-O-A-)x wherein A is an alkylene group containing from 2 to about 7 carbon atoms and where x has an a~erage value of from a~out S to about 200; and 208~33 (B) an oxyalkylated phenol formaldehyde resin of the formula:
(OA)moH _ (OA)moH
t ~ C~ ~
R x R
wherein A represeDts an alkylene group containin~ from about 2 to about 10 carbon atoms, where ~ has an average ~alue of from about 4 to about 200, and where R is an alkyl group from about 1 to about 20 carbon atoms, and x is an integer greater than 1, (III) from about 40 to about 70 weight percent of a mononuclear or dinuclear aromatic hydrocarbon solvent, and (IV) from about 5.0 to about 15.0 weight percent of a corrosion inhibitor selected from a hydrocarbyl succinic acid or anhydride having from 12 to 30 carbon atoms (50% in oil).
Such fuels are indicated to be advantageous on the basls that they do not suffer from water/gasolins emulsion problems.
In accordance with the present invention, there is provided a gasoline composition comprising a ma~or amount of a gasoline and a minor amount of a mixture of (a) from 75 ppmw to 450 pp~w of a condensation product of (1) a high molecular weight sulfur-free alkyl-substituted hydroxyaromatic compound wherein the alkyl group has a number average molecular weight from 600 to 3000, (2) an amine which contains an amino group having at least one active hydrogen atom, and (3) an aldehyde, wherein the respective molar ratio of reactants is 1 : O.l-10 : 0.1-10; and (b) from 75 ppmw to 175 ppmw of an oil soluble poly(oxyalkylene) alcohol, glycol or polyol or mono or di ether thereof, wherein the weight ratio of (a) to (b) in the mixture is at least 0 43, all amouAts (ppmw) being based on the gasoline composition.
The condensation product is prepared by condensing in the usual manner under Mannich reaction conditions: (1) an alkyl-substituted hydroxyaromatic compound, whose alkyl-substituent 20~9833 has a number average molecular weight in the range from 600 to 3000, preferably from 750 to 1200, e.g. a polyalkylphenol whose polyalkyl substituent is derived from l-mono-olefin polymers having number average molecular weight from 600 to 3000, preferably from 750 to 1200; (2) an amine containing at least one >NH group, preferably an alkylene polyamine of the formula NH2-(A-NH)X-H
wherein A i9 a divalent slkylene radicsl hsving 2 to 6 carbon atoms and x is an integer from 1 to 10; B particularly preferred amine being one selected from the group consisting of dimethylamine, dimethylaminopropylamine, tetraethylenepentamine, trie~hylenetetramine, diethylenetriamine and admixtures thereof;
and (3) an aldehyde, preferably an aldehyde selected from the group conslsting of formaldehyde, paraformaldehyde and admixtures thereof. The condensat~on product and its preparation are described in further detall in U.S. Patent No. 4,231,759. The amount of condensstion product used in the gasoline will be in the range fro~ 75 ppmw up to 450 ppmw, prefersbly up to 400 ppmw, more preferably up to 2S0 ppmw, and especially up to 200 ppmw. Highly effective results have been realized when the condensation product is present in 140 ppmw to 180ppnw, especially 170 ppmw. The ratio of (a) to (b) is at least 0.43, preferably in the range from 0.~ to 1.4, and is especially in the range from 1.2 to 1.4.
Component (b) can be a carrier for component (a) but its presence also aids the effectiveness of the gssoline for control of deposits and engine operation and helps prevent low temperature intake valve sticking. Component (b) is used at concentrations from 75 ppmw up to 175 ppmw, preferably up to 150 ppmw, and especially up to 125 ppmw.
The polymeric carr~er used in the present invention, i.e., the oil soluble poly(oxyalkylene) alcohol, glycol or polyol or mono or di ether thereof, i9 well known in the art.
Component (b) is preferably a polyoxyalkylene compound of the formula Rl 0 (R20)n R3 wherein each of Rl and R3 independently represents a hydr~gen atom ~r an aliphatic, cycloaliphatic or aromatic hydrocarbon radical containing up to 40 20~'983~
carbon atoms, R2 represents an alkylene radical containin~ up to 12 carbon atoms, and n represents an integer of at least 7, preferably at least 20 when R20 is a ',2-propyleneoxy group. In the polyoxyalkylene chain - (R20) -, the group R2 can be any alkylene group. The polyoxyalkylene chain can contain two or more dissimilar alkyleneoxy groups, preferably an alkyleneoxy gro~p of 2 to 8 carbon atoms, especially an ethyleneoxy or 1,2 propyleneoxy group. These groups can be distributed randomly throughout the chain or can be arranged in a pre-determined pattern of units or blocks, each containing one or a plurality of alkyleneoxy groups.
In one embodiment of the invention, at least one of Rl and R3 is an alkyl or alkylphenyl group containing up to 20 carbon atoms, for example, a propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, octylphenyl or nonylphenyl group. Preferably, Rl is hydrogen and R3 is an alkyl group, more preferably, R3 i5 a dodecyl group or a mixture of C12-C15 alkyl groups.
Suitable carrSers include polyoxypropylene glycols and the glycol~ containing both ethyleneoxy and 1,2-propyleneoxy groups in the polyoxyalkylene chain as well as the mono- and di-alkyl ethers of such glycols.
The commercially available polyoxyalkylene compounds are generally mixtures of compounds in which the values for n and the molecular weight of such mLxtures being only average values. The values of n of typical compounds are usually between 7 and 100, preferably between 8 and 80. The molecular weights vary from 400 to 6000, preferably from 500 to 4000 and more preferably fro~ 1000 to 2000.
The gasoline compos~tion according to the invention comprises a ma~or amount of a gasoline (base fuel) suitable for use in internal combustion engines. This includes hydrocarbon base fuels boiling essentially in the gasoline boiling range from 25'C (77'F) to 232C ~450F). ~hese base fuels may comprise mixtures of saturated hydrocarbons, olefinic hydrocarbons and aromatic hydrocarbons. Preferably the base fuel has a saturated hydrocarbon content in the range from 40 to 80 percent volume, an olefinic 2~9~33 hydrocarbon content in the range from 0 to 30 percent volume and an aromatic hydrocarbon content in the range from 10 to 60 percent volume. The base fuel can be derived from straight run gasoline, polymer gasoline, natural gasoline, dimer or trimerized olefins, synthetically produced aromatic hydrocarbon mixtures from thermally or catalytically reformed hydrocarbons, or from catslytically cracked or thermally cracked petroleum stocks, or mixtures of these. The hydrocarbon composition and octane level of the base fuel are not critical. The octane level, (R+M)/2, will generally be above 85. Any conventional motor base fuel may be employed in the practice of this invention. Thus, in the gasoline, hydrocarbons can be replaced by up to substantial amounts of conventional alcohols, or ethers, con~entionally known for use in fuels. The base fuels are desirably substantially free of water, since water may impede a smooth combustion.
Preferably, the gasolines used in the present invention are lead-free, but may contain minor smounts of blending agents such as methanol, ethanol and methyl tertiary butyl ether at from 0.1 to 15% volume of the base fuel. The gasolines can also contain antioxidants such as between 1 ppmw and 40 ppmw phenolics, e.g., 2,6-di-tert-butylphenol or phenylensdiamines, e.g., N,N'-di-sec-butyl-p-phenylenediamine; dyes; metal deactivators;
dehazers such as polyester-type ethoxylated alkylphenol-formaldehyde resins; corrosion inhibLtors, such as a polyhydric alcohol ester of a succinic acid derivative having on at least one of its alpha-carbon atoms an unsubstituted or substituted aliphatic hydrocarbon group having from 20 to S00 carbon atoms, for example, pentaerythritol diester of polyisobutylene-substituted succinic acid, the polyisobutylene group ha~ing a number average molecular weight of 950, in an amount of l to lO00 ppmw; and antiknock compounds such as methyl cyclopentadienylmanganese tricarbonyl or ortho-azidophenol.
The additive mixture (a) plus (b) used in the present invent~on can be introduced iDto the combustion zone of the engine in a varlety o~ ways to prevent buildup of deposits, or to 2 ~ 3 3 g accomplish reduction or modification of deposits. Thus, the additive mixture can be in~ected into the intake manifold intermittently or substantially continuously, preferably in a hydrocarbon carrier having a final boiling point (by ASTM D86) lower than 232C (450~). A preferred method is to add the additive mixture to the gasoline. For example, the additive mixture can be added separately to the gasoline or blended with other gasoline additives Accordingly, the present ~nvention further provides a gasoline additive concentrate comprising a ma~or amount of a mixture of (a) from 75 pbw (parts by weight) to 450 pbw of a condensation product of (1) a high molecular weight sulfur-free alkyl-substituted hydroxyaromatic compound wherein the alkyl group has a number average molecular weight from 600 to 3000, (2) an amine which contalns an ami.no group having at least one active hydrogen atom, and (3) an aldehyde, wherein the respective molar ratio of reactants is 1:0.1-10:0 1-10; and (b) from 75 pbw to 175 pbw of an oil soluble poly(oxyalkylene) alcohol, glycol or polyol or mono or di ether thereof, wherein the weight ratio of (a) to (b) in the mixture is at least 0.43, preferably in the range from 0.8 to 1.4, most preferably in the range from 1.2 to 1.4, and a minor amount of a gasoline compatible diluent, e.g. a gasoline compatible diluent boiling in the range from 50 to 232C.
Suitable gasoline-compatible diluents are hydrocarbona and mixtures of hydrocarbons wlth alcohols or ethers, such as methanol, ethanol, propanol, 2-butoxyethanol or methyl tert-butyl ether.
Preferably the diluent is an aromatic hydrocarbon solvent such as toluene, xylene, mixtures thereof or mixtures of toluene or xylene with an alcohol.
The present invention still further provides a method of operating a spark-ignition internal combustion engine which comprises introducing to said engine a gasoline composition according to the present invention.
The invention will be further understood from the following 3S illustrative example.
- 2~9833 Example Intake valve detergency is generally defined by the BMW NA
standard of intake valve cleanliness for unlimited mileage, which is an established correlation of driveability and intake valve depos~t weight of 100 milligrams or less. Intake valve deposit tests were conducted at Southwest Research Institute in 1985 model BMU 318i cars equipped with the 1.8-liter, four-cylinder engine, and were operated for 10,000 miles on the test fuel. Before the test started, deposits were removed from the cylinder head, intake manifold and piston tops and new intake valves were weighed and installed. The oil and filter were changed, new spark plugs installed and the fuel in~ectors flow checked. Mileage was accumulated on public roads using trained drivers. The test route consisted of about 10% city driving, 20% on secondary roads and 70 highway driving (maximum speed of 65 mph).
The primary test data are the intake valve deposit (IVD) weights at the end of the 10,000-mile test. IVD weight~ are also determined at 5,000 miles, where tests can be terminated if the results are not promising. BMW's pass criteria are as follows: an sverage deposit weight of 100 milligrams per valve or less at the conclusion of the test meets BMW require~ents for unlimited mileage acceptance: an average deposit weight of 250 mg per valve or less at the conclusion of the test meets BMW requirement for 50,000-mile service.
The Table below lists the additive compositions used in regular unleaded base gasolines and the average intake valve deposit weights at the end of the test (10,000 miles).
Table Composition BMW 318i Compo~ent Compo~ent Results (a> (b) Ratio Ave Deposit Test ~w ppmw (a)/(b) ~ei~ht, m~
l(in~ention) 170 125 1.36 0 2 170 125 1.36 46 2~9833 In test l, "a" is a Mannich condensation product of an alkyl-substituted hydroxyaromatic compound, amine and aldehyde available from Amoco as "Amoco 596" gasoline additive; in test 2, "a" is N-polyisobutenyl-N',N'-dimethyl-1,3-diaminopropane, MW -1050.
Component "b" is a polyoxypropylene glycol mono ether of a mixed C12-C15 alcohol of average MW 1400.
Results of these tests demonstrate that the gasoline composition of the in~ention (1) passes the BMW unlimited mileage test and had no deposits whereas the other additive package did have deposits.
The present invention relates to a gasoline composLtion, a gasoline additive concentrate for use in preparing the gasoline composition and B method of operating a spark-ignition Lnternal combustion engine using the gasoline composition.
Gasoline compositions have traditionally been formulated to improve the performance of csrburetor and throttle body in;ected engines. Beginning in about 1984, electronic port fuel in;ected engines were commonly introduced by auto~obile manufacturers.
Shortly thereafter, in about 1985, problems began to be reported 10 with intake valve deposits in electronic port fuel injected engines, which problems are characterized by hard starting, stalls, snd stumbles during acceleration and rough engine idle.
Accordingly, it would be desirable to have fuel compositions which reduce or eliminate such undesirable intake valve deposits in 15 electronic port fuel in~ected engines. Also, since some carburetor and throttle body in~ector engines will still be in use for the foreseeable future, it would be desirable if such fuels could also be compatible with these engines.
Condensation products of a hydroxyaromatic compound, an 20 amine, and an aldehyde are known to improve detergent properties of fuels used in carburetor and throttle body type engines. U.S.
Patent No. 4,231,759 teaches the use of the condensation product of a hydroxyaromatic compound, an amine, and an aldehyde in a carrier of polyolefin, mineral oil, or phenol compounds for removing and 2~ preventing deposits on carburetor surfaces and intake valves.
Such compositions have reduced effectiveness in electronic port fuel in~ected engines where the carrier appears to act li~e a diluent, reducing the effectiveness of the detergent which lt had enhanced in carbureted engines.
-U.S. Patent No. 4,116,644 discloses a concentrate for use in liquid hydrocarbon fuel boiling in the gasoline boiling range containing (I) as detergent additive, from about 35 to about 50 weight percent of the reaction product of:
(A) one mole part of an alkylphenol having the formula.
OH
~3 (Rl)n wherein n is an integer from 1 to 2, and Rl is an aliphatic hydrocarbon radical having an average molecular weight of from 15 about 400 to 1500;
(B) from 1-5 mole parts of an aldehyde having the for~ula:
H
wherein R2 i9 selected from hydrogen and alkyl rad~cal~ containing 1-6 carbon ato~s; ant (C) from 0.5-5 mole parts of an amine having at least one active hydrogen atom bonded to an amino nitrogen atom, and (II) from about 1.4 to about 5.6 weight percent of a demulsifying agent containing:
(A) at least one oil-soluble amine, ammonium, alkaline earth metal, or alkali metal salt of an aryl sulfonic acid;
(B) at least one oil-soluble polyether characterized by the presence within its structure of a group of the formula:
(-O-A-)x wherein A is an alkylene group containing from 2 to about 7 carbon 2~89833 atoms and wehre x has an average value of from about 5 to about 200; and (C) an oxyalkylated phenol formaldehyde resin of the formula:
(OA)moH
~C112 R
wherein A represents an alkylene group containing from about 2 to about 10 carbon atoms, where m has an average value of from about 4 to about 200, and where R i9 an alkyl group of about from 1 to about 20 carbon atoms.
(III) from about 20 to about 25 weight percent of a mono~ùclear or dinuclear aromatic hydrocarbon solvent, (IV) from about 20 to about 35 weight percent of an alkanol having from 4 to 10 carbon atoms, and (V) from about 3 to about 5 weight percent of a corrosion inhibitor.
The demulsifying agent may contain from about 2 to about 10 parts by weight of aryl sulfonate, from about 0.25 to about 4 parts by weight of polyether glycol, and from about 0.25 to about 4 parts by weight of oxyalkylated phenol formaldehyde resin.
The amount of detergent additive added to the gasoline is said to be in the range from about 3 to 2000 ppm. The amount of demulsifying agent added to the gasoline is said to be dependent, to a degree, upon the concentration of the deterge~t additive in the gasoline. From about 0.02 to 0.2~ ppm of demulsifying agent are added for every one ppm of detergent additive.
Gasolines containing the concentrate are indicated to be advantageous on the basis that they do not suffer from water/gasoline emuls~on problems.
U.S. Patent No. 4,398,921 discloses a fuel comprising a major amount of gasoline, a minor amount of ethanol and a detergent amount (about l.O to about 100 ppm) of an additive composition comprising:
(I) from about 20 to about 40 weight percent of the reaction product of:
(A) one mole psrt of an alkylphenol hav~ng the formula:
OH
~} (Rl)n wherein n is an integer from 1 to 2, and Rl is an aliphatic hydrocarbon radical having an average molecular weight of from about 400 to 1500;
(B) from l-S mole parts of an aldehyde having the formula:
H
wherein R2 is selected from hydrogen and alkyl radicals containing 1-6 carbon atoms; and (C) from 0.5-5 mole parts of an amine having at least one active hydrogen atom bonded to an amino nitrogen atom, and (II) from about 3.0 to about 6.0 weight percent of a demulsifying agent containing:
(A) at least one oil-soluble polyether characterized by the presence within its structure of a group of the formula:
(-O-A-)x wherein A is an alkylene group containing from 2 to about 7 carbon atoms and where x has an a~erage value of from a~out S to about 200; and 208~33 (B) an oxyalkylated phenol formaldehyde resin of the formula:
(OA)moH _ (OA)moH
t ~ C~ ~
R x R
wherein A represeDts an alkylene group containin~ from about 2 to about 10 carbon atoms, where ~ has an average ~alue of from about 4 to about 200, and where R is an alkyl group from about 1 to about 20 carbon atoms, and x is an integer greater than 1, (III) from about 40 to about 70 weight percent of a mononuclear or dinuclear aromatic hydrocarbon solvent, and (IV) from about 5.0 to about 15.0 weight percent of a corrosion inhibitor selected from a hydrocarbyl succinic acid or anhydride having from 12 to 30 carbon atoms (50% in oil).
Such fuels are indicated to be advantageous on the basls that they do not suffer from water/gasolins emulsion problems.
In accordance with the present invention, there is provided a gasoline composition comprising a ma~or amount of a gasoline and a minor amount of a mixture of (a) from 75 ppmw to 450 pp~w of a condensation product of (1) a high molecular weight sulfur-free alkyl-substituted hydroxyaromatic compound wherein the alkyl group has a number average molecular weight from 600 to 3000, (2) an amine which contains an amino group having at least one active hydrogen atom, and (3) an aldehyde, wherein the respective molar ratio of reactants is 1 : O.l-10 : 0.1-10; and (b) from 75 ppmw to 175 ppmw of an oil soluble poly(oxyalkylene) alcohol, glycol or polyol or mono or di ether thereof, wherein the weight ratio of (a) to (b) in the mixture is at least 0 43, all amouAts (ppmw) being based on the gasoline composition.
The condensation product is prepared by condensing in the usual manner under Mannich reaction conditions: (1) an alkyl-substituted hydroxyaromatic compound, whose alkyl-substituent 20~9833 has a number average molecular weight in the range from 600 to 3000, preferably from 750 to 1200, e.g. a polyalkylphenol whose polyalkyl substituent is derived from l-mono-olefin polymers having number average molecular weight from 600 to 3000, preferably from 750 to 1200; (2) an amine containing at least one >NH group, preferably an alkylene polyamine of the formula NH2-(A-NH)X-H
wherein A i9 a divalent slkylene radicsl hsving 2 to 6 carbon atoms and x is an integer from 1 to 10; B particularly preferred amine being one selected from the group consisting of dimethylamine, dimethylaminopropylamine, tetraethylenepentamine, trie~hylenetetramine, diethylenetriamine and admixtures thereof;
and (3) an aldehyde, preferably an aldehyde selected from the group conslsting of formaldehyde, paraformaldehyde and admixtures thereof. The condensat~on product and its preparation are described in further detall in U.S. Patent No. 4,231,759. The amount of condensstion product used in the gasoline will be in the range fro~ 75 ppmw up to 450 ppmw, prefersbly up to 400 ppmw, more preferably up to 2S0 ppmw, and especially up to 200 ppmw. Highly effective results have been realized when the condensation product is present in 140 ppmw to 180ppnw, especially 170 ppmw. The ratio of (a) to (b) is at least 0.43, preferably in the range from 0.~ to 1.4, and is especially in the range from 1.2 to 1.4.
Component (b) can be a carrier for component (a) but its presence also aids the effectiveness of the gssoline for control of deposits and engine operation and helps prevent low temperature intake valve sticking. Component (b) is used at concentrations from 75 ppmw up to 175 ppmw, preferably up to 150 ppmw, and especially up to 125 ppmw.
The polymeric carr~er used in the present invention, i.e., the oil soluble poly(oxyalkylene) alcohol, glycol or polyol or mono or di ether thereof, i9 well known in the art.
Component (b) is preferably a polyoxyalkylene compound of the formula Rl 0 (R20)n R3 wherein each of Rl and R3 independently represents a hydr~gen atom ~r an aliphatic, cycloaliphatic or aromatic hydrocarbon radical containing up to 40 20~'983~
carbon atoms, R2 represents an alkylene radical containin~ up to 12 carbon atoms, and n represents an integer of at least 7, preferably at least 20 when R20 is a ',2-propyleneoxy group. In the polyoxyalkylene chain - (R20) -, the group R2 can be any alkylene group. The polyoxyalkylene chain can contain two or more dissimilar alkyleneoxy groups, preferably an alkyleneoxy gro~p of 2 to 8 carbon atoms, especially an ethyleneoxy or 1,2 propyleneoxy group. These groups can be distributed randomly throughout the chain or can be arranged in a pre-determined pattern of units or blocks, each containing one or a plurality of alkyleneoxy groups.
In one embodiment of the invention, at least one of Rl and R3 is an alkyl or alkylphenyl group containing up to 20 carbon atoms, for example, a propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, octylphenyl or nonylphenyl group. Preferably, Rl is hydrogen and R3 is an alkyl group, more preferably, R3 i5 a dodecyl group or a mixture of C12-C15 alkyl groups.
Suitable carrSers include polyoxypropylene glycols and the glycol~ containing both ethyleneoxy and 1,2-propyleneoxy groups in the polyoxyalkylene chain as well as the mono- and di-alkyl ethers of such glycols.
The commercially available polyoxyalkylene compounds are generally mixtures of compounds in which the values for n and the molecular weight of such mLxtures being only average values. The values of n of typical compounds are usually between 7 and 100, preferably between 8 and 80. The molecular weights vary from 400 to 6000, preferably from 500 to 4000 and more preferably fro~ 1000 to 2000.
The gasoline compos~tion according to the invention comprises a ma~or amount of a gasoline (base fuel) suitable for use in internal combustion engines. This includes hydrocarbon base fuels boiling essentially in the gasoline boiling range from 25'C (77'F) to 232C ~450F). ~hese base fuels may comprise mixtures of saturated hydrocarbons, olefinic hydrocarbons and aromatic hydrocarbons. Preferably the base fuel has a saturated hydrocarbon content in the range from 40 to 80 percent volume, an olefinic 2~9~33 hydrocarbon content in the range from 0 to 30 percent volume and an aromatic hydrocarbon content in the range from 10 to 60 percent volume. The base fuel can be derived from straight run gasoline, polymer gasoline, natural gasoline, dimer or trimerized olefins, synthetically produced aromatic hydrocarbon mixtures from thermally or catalytically reformed hydrocarbons, or from catslytically cracked or thermally cracked petroleum stocks, or mixtures of these. The hydrocarbon composition and octane level of the base fuel are not critical. The octane level, (R+M)/2, will generally be above 85. Any conventional motor base fuel may be employed in the practice of this invention. Thus, in the gasoline, hydrocarbons can be replaced by up to substantial amounts of conventional alcohols, or ethers, con~entionally known for use in fuels. The base fuels are desirably substantially free of water, since water may impede a smooth combustion.
Preferably, the gasolines used in the present invention are lead-free, but may contain minor smounts of blending agents such as methanol, ethanol and methyl tertiary butyl ether at from 0.1 to 15% volume of the base fuel. The gasolines can also contain antioxidants such as between 1 ppmw and 40 ppmw phenolics, e.g., 2,6-di-tert-butylphenol or phenylensdiamines, e.g., N,N'-di-sec-butyl-p-phenylenediamine; dyes; metal deactivators;
dehazers such as polyester-type ethoxylated alkylphenol-formaldehyde resins; corrosion inhibLtors, such as a polyhydric alcohol ester of a succinic acid derivative having on at least one of its alpha-carbon atoms an unsubstituted or substituted aliphatic hydrocarbon group having from 20 to S00 carbon atoms, for example, pentaerythritol diester of polyisobutylene-substituted succinic acid, the polyisobutylene group ha~ing a number average molecular weight of 950, in an amount of l to lO00 ppmw; and antiknock compounds such as methyl cyclopentadienylmanganese tricarbonyl or ortho-azidophenol.
The additive mixture (a) plus (b) used in the present invent~on can be introduced iDto the combustion zone of the engine in a varlety o~ ways to prevent buildup of deposits, or to 2 ~ 3 3 g accomplish reduction or modification of deposits. Thus, the additive mixture can be in~ected into the intake manifold intermittently or substantially continuously, preferably in a hydrocarbon carrier having a final boiling point (by ASTM D86) lower than 232C (450~). A preferred method is to add the additive mixture to the gasoline. For example, the additive mixture can be added separately to the gasoline or blended with other gasoline additives Accordingly, the present ~nvention further provides a gasoline additive concentrate comprising a ma~or amount of a mixture of (a) from 75 pbw (parts by weight) to 450 pbw of a condensation product of (1) a high molecular weight sulfur-free alkyl-substituted hydroxyaromatic compound wherein the alkyl group has a number average molecular weight from 600 to 3000, (2) an amine which contalns an ami.no group having at least one active hydrogen atom, and (3) an aldehyde, wherein the respective molar ratio of reactants is 1:0.1-10:0 1-10; and (b) from 75 pbw to 175 pbw of an oil soluble poly(oxyalkylene) alcohol, glycol or polyol or mono or di ether thereof, wherein the weight ratio of (a) to (b) in the mixture is at least 0.43, preferably in the range from 0.8 to 1.4, most preferably in the range from 1.2 to 1.4, and a minor amount of a gasoline compatible diluent, e.g. a gasoline compatible diluent boiling in the range from 50 to 232C.
Suitable gasoline-compatible diluents are hydrocarbona and mixtures of hydrocarbons wlth alcohols or ethers, such as methanol, ethanol, propanol, 2-butoxyethanol or methyl tert-butyl ether.
Preferably the diluent is an aromatic hydrocarbon solvent such as toluene, xylene, mixtures thereof or mixtures of toluene or xylene with an alcohol.
The present invention still further provides a method of operating a spark-ignition internal combustion engine which comprises introducing to said engine a gasoline composition according to the present invention.
The invention will be further understood from the following 3S illustrative example.
- 2~9833 Example Intake valve detergency is generally defined by the BMW NA
standard of intake valve cleanliness for unlimited mileage, which is an established correlation of driveability and intake valve depos~t weight of 100 milligrams or less. Intake valve deposit tests were conducted at Southwest Research Institute in 1985 model BMU 318i cars equipped with the 1.8-liter, four-cylinder engine, and were operated for 10,000 miles on the test fuel. Before the test started, deposits were removed from the cylinder head, intake manifold and piston tops and new intake valves were weighed and installed. The oil and filter were changed, new spark plugs installed and the fuel in~ectors flow checked. Mileage was accumulated on public roads using trained drivers. The test route consisted of about 10% city driving, 20% on secondary roads and 70 highway driving (maximum speed of 65 mph).
The primary test data are the intake valve deposit (IVD) weights at the end of the 10,000-mile test. IVD weight~ are also determined at 5,000 miles, where tests can be terminated if the results are not promising. BMW's pass criteria are as follows: an sverage deposit weight of 100 milligrams per valve or less at the conclusion of the test meets BMW require~ents for unlimited mileage acceptance: an average deposit weight of 250 mg per valve or less at the conclusion of the test meets BMW requirement for 50,000-mile service.
The Table below lists the additive compositions used in regular unleaded base gasolines and the average intake valve deposit weights at the end of the test (10,000 miles).
Table Composition BMW 318i Compo~ent Compo~ent Results (a> (b) Ratio Ave Deposit Test ~w ppmw (a)/(b) ~ei~ht, m~
l(in~ention) 170 125 1.36 0 2 170 125 1.36 46 2~9833 In test l, "a" is a Mannich condensation product of an alkyl-substituted hydroxyaromatic compound, amine and aldehyde available from Amoco as "Amoco 596" gasoline additive; in test 2, "a" is N-polyisobutenyl-N',N'-dimethyl-1,3-diaminopropane, MW -1050.
Component "b" is a polyoxypropylene glycol mono ether of a mixed C12-C15 alcohol of average MW 1400.
Results of these tests demonstrate that the gasoline composition of the in~ention (1) passes the BMW unlimited mileage test and had no deposits whereas the other additive package did have deposits.
Claims (10)
1. A gasoline composition comprising a major amount of a gasoline and a minor amount of a mixture of (a) from 75 ppmw to 450 ppmw of a condensation product of (1) a high molecular weight sulfur-free alkyl-substituted hydroxyaromatic compound wherein the alkyl group has a number average molecular weight from 600 to 3000, (2) an amine which contains an amino group having at least one active hydrogen atom, and (3) an aldehyde, wherein the respective molar ratio of reactants is 1 : 0.1-10 : 0.1-10; and (b) from 75 ppmw to 175 ppmw of an oil soluble poly(oxyalkylene) alcohol, glycol or polyol or mono or di ether thereof, wherein the weight ratio of (a) to (b) in the mixture is at least 0.43, all amounts (ppmw) being based on the gasoline composition.
2. A composition according to claim 1, wherein the number average molecular weight of the alkyl substituent is from 750 to 1,200.
3. A composition according to claim 1, wherein the alkyl-substituted hydroxyaromatic compound is an alkyl-substituted phenol.
4. A composition according to claim 1, 2 or 3, wherein the aldehyde is selected from the group consisting of formaldehyde, paraformaldehyde, and admixtures thereof.
5. A composition according to claim 1, 2 or 3, wherein the amine is selected from the group consisting of dimethylamine, dimethylaminopropylamine, tetraethylenepentamine, triethylenetetramine, diethylenetriamine, and admixtures thereof.
6. A composition according to claim 1, 2 or 3, wherein the ratio of (a) to (b) is in the range from 0.8 to 1.4.
7. A gasoline additive concentrate comprising a major amount of a mixture of (a) from 75 pbw to 450 pbw of a condensation product of (l) a high molecular weight sulfur-free alkyl-substituted hydroxyaromatic compound wherein the alkyl group has a number average molecular weight from 600 to 3000, (2) an amine which contains an amino group having at least one active hydrogen atom, and (3) an aldehyde, wherein the respective molar ratio of reactants is 1 : 0.1-10 : 0.1-10; and (b) from 75 pbw to 175 pbw of an oil soluble poly(oxyalkylene) alcohol, glycol or polyol or mono or di ether thereof, wherein the weight ratio of (a) to (b) in the mixture is at least 0.43, and a minor amount of a gasoline compatible diluent.
8. A gasoline additive concentrate according to claim 7, wherein the weight ratio of (a) to (b) is in the range from 0.8 to 1.4.
9. A gasoline additive concentrate according to claim 7, wherein the weight ratio of (a) to (b) is in the range from 1.2 to 1.4.
10. A method of operating a spark-ignition internal combustion engine which comprises introducing to said engine a gasoline composition according to claim 1, 2 or 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US83818092A | 1992-02-20 | 1992-02-20 | |
| US838,180 | 1992-02-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2089833A1 true CA2089833A1 (en) | 1993-08-21 |
Family
ID=25276482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2089833 Abandoned CA2089833A1 (en) | 1992-02-20 | 1993-02-18 | Gasoline composition |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2089833A1 (en) |
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| EP0647700A1 (en) * | 1993-10-06 | 1995-04-12 | Ethyl Corporation | Fuel compositions and additives therefor |
| US5634951A (en) * | 1996-06-07 | 1997-06-03 | Ethyl Corporation | Additives for minimizing intake valve deposits, and their use |
| US5697988A (en) * | 1991-11-18 | 1997-12-16 | Ethyl Corporation | Fuel compositions |
| EP0831141A1 (en) * | 1996-09-05 | 1998-03-25 | BP Chemicals (Additives) Limited | Detergents for hydrocarbon fuels |
| US5752989A (en) * | 1996-11-21 | 1998-05-19 | Ethyl Corporation | Diesel fuel and dispersant compositions and methods for making and using same |
| EP0870819A2 (en) * | 1997-04-10 | 1998-10-14 | Ethyl Corporation | Additives for minimizing intake valve deposits, and their use |
| US6210452B1 (en) | 2000-02-08 | 2001-04-03 | Hhntsman Petrochemical Corporation | Fuel additives |
| US6458172B1 (en) | 2000-03-03 | 2002-10-01 | The Lubrizol Corporation | Fuel additive compositions and fuel compositions containing detergents and fluidizers |
| US6514297B1 (en) | 1999-11-24 | 2003-02-04 | The Lubrizol Corporation | Detergents for use in preventing formation of iron complexes in hydrocarbon fuels |
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| US6800103B2 (en) | 2001-02-02 | 2004-10-05 | Ethyl Corporation | Secondary amine mannich detergents |
| US6835217B1 (en) | 2000-09-20 | 2004-12-28 | Texaco, Inc. | Fuel composition containing friction modifier |
| WO2006044892A1 (en) | 2004-10-19 | 2006-04-27 | The Lubrizol Corporation | Additive and fuel compositions containing detergent and fluidizer and method thereof |
| US7988749B2 (en) | 1999-10-06 | 2011-08-02 | Basf Se | Method for producing Mannich adducts that contain polyisobutylene phenol |
| US8016898B1 (en) | 1999-10-06 | 2011-09-13 | Basf Aktiengesellschaft | Method for producing Mannich adducts that contain polyisobutylene phenol |
| US8222180B2 (en) | 2005-08-01 | 2012-07-17 | Indian Oil Corporation Limited | Adsorbent composition for removal of refractory sulphur compounds from refinery streams and process thereof |
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| US10457884B2 (en) | 2013-11-18 | 2019-10-29 | Afton Chemical Corporation | Mixed detergent composition for intake valve deposit control |
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1993
- 1993-02-18 CA CA 2089833 patent/CA2089833A1/en not_active Abandoned
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| US5697988A (en) * | 1991-11-18 | 1997-12-16 | Ethyl Corporation | Fuel compositions |
| EP0647700A1 (en) * | 1993-10-06 | 1995-04-12 | Ethyl Corporation | Fuel compositions and additives therefor |
| US5634951A (en) * | 1996-06-07 | 1997-06-03 | Ethyl Corporation | Additives for minimizing intake valve deposits, and their use |
| EP0811672A2 (en) * | 1996-06-07 | 1997-12-10 | Ethyl Corporation | Additives for minimizing intake valve deposits, and their use |
| EP0811672A3 (en) * | 1996-06-07 | 1998-02-04 | Ethyl Corporation | Additives for minimizing intake valve deposits, and their use |
| US5876468A (en) * | 1996-09-05 | 1999-03-02 | Lubrizol Adibis Holdings (Uk) Limited | Detergents for hydrocarbon fuels |
| EP0831141A1 (en) * | 1996-09-05 | 1998-03-25 | BP Chemicals (Additives) Limited | Detergents for hydrocarbon fuels |
| US5752989A (en) * | 1996-11-21 | 1998-05-19 | Ethyl Corporation | Diesel fuel and dispersant compositions and methods for making and using same |
| EP0870819A2 (en) * | 1997-04-10 | 1998-10-14 | Ethyl Corporation | Additives for minimizing intake valve deposits, and their use |
| EP0870819A3 (en) * | 1997-04-10 | 1999-06-16 | Ethyl Corporation | Additives for minimizing intake valve deposits, and their use |
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| US8016898B1 (en) | 1999-10-06 | 2011-09-13 | Basf Aktiengesellschaft | Method for producing Mannich adducts that contain polyisobutylene phenol |
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