US3753670A - Hydrocarbon fuel compositions - Google Patents
Hydrocarbon fuel compositions Download PDFInfo
- Publication number
- US3753670A US3753670A US00051363A US3753670DA US3753670A US 3753670 A US3753670 A US 3753670A US 00051363 A US00051363 A US 00051363A US 3753670D A US3753670D A US 3753670DA US 3753670 A US3753670 A US 3753670A
- Authority
- US
- United States
- Prior art keywords
- fuel
- additives
- diamine
- additive
- carbon atoms
- 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.)
- Expired - Lifetime
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- 239000000446 fuel Substances 0.000 title claims abstract description 65
- 239000000203 mixture Substances 0.000 title claims abstract description 31
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 23
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 23
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 20
- 238000002485 combustion reaction Methods 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 239000003502 gasoline Substances 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 150000004985 diamines Chemical class 0.000 claims description 3
- 229920000768 polyamine Polymers 0.000 abstract description 25
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract description 21
- 239000007788 liquid Substances 0.000 abstract description 4
- 239000000654 additive Substances 0.000 description 54
- 238000012360 testing method Methods 0.000 description 22
- 230000000996 additive effect Effects 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 239000000460 chlorine Substances 0.000 description 10
- 125000004433 nitrogen atom Chemical group N* 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 7
- 150000002367 halogens Chemical class 0.000 description 7
- -1 polyethylene groups Polymers 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 239000012433 hydrogen halide Substances 0.000 description 5
- 229910000039 hydrogen halide Inorganic materials 0.000 description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 5
- 229920002367 Polyisobutene Polymers 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000003749 cleanliness Effects 0.000 description 4
- LFEUVBZXUFMACD-UHFFFAOYSA-H lead(2+);trioxido(oxo)-$l^{5}-arsane Chemical compound [Pb+2].[Pb+2].[Pb+2].[O-][As]([O-])([O-])=O.[O-][As]([O-])([O-])=O LFEUVBZXUFMACD-UHFFFAOYSA-H 0.000 description 4
- 239000006078 metal deactivator Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004129 EU approved improving agent Substances 0.000 description 3
- 239000000370 acceptor Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000003254 gasoline additive Substances 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- RURPJGZXBHYNEM-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]propyliminomethyl]phenol Chemical compound C=1C=CC=C(O)C=1C=NC(C)CN=CC1=CC=CC=C1O RURPJGZXBHYNEM-UHFFFAOYSA-N 0.000 description 2
- 239000004230 Fast Yellow AB Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 150000001844 chromium Chemical class 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- MLCJWRIUYXIWNU-OWOJBTEDSA-N (e)-ethene-1,2-diamine Chemical compound N\C=C\N MLCJWRIUYXIWNU-OWOJBTEDSA-N 0.000 description 1
- FDMXADMEKAUMIV-NSCUHMNNSA-N (e)-prop-1-ene-1,2-diamine Chemical compound C\C(N)=C/N FDMXADMEKAUMIV-NSCUHMNNSA-N 0.000 description 1
- QBIAZVPERXOGAL-OWOJBTEDSA-N (e)-prop-1-ene-1,3-diamine Chemical compound NC\C=C\N QBIAZVPERXOGAL-OWOJBTEDSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- CJYDNDLQIIGSTH-UHFFFAOYSA-N 1-(3,5,7-trinitro-1,3,5,7-tetrazocan-1-yl)ethanone Chemical compound CC(=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)CN([N+]([O-])=O)C1 CJYDNDLQIIGSTH-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- AVGFYOSXQXGHDL-UHFFFAOYSA-N C(C)(C)(C)C1(C=C(C=CC1O)C)C Chemical compound C(C)(C)(C)C1(C=C(C=CC1O)C)C AVGFYOSXQXGHDL-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 229910000737 Duralumin Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005263 alkylenediamine group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000004427 diamine group Chemical group 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- JMGZBMRVDHKMKB-UHFFFAOYSA-L disodium;2-sulfobutanedioate Chemical compound [Na+].[Na+].OS(=O)(=O)C(C([O-])=O)CC([O-])=O JMGZBMRVDHKMKB-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000010771 distillate fuel oil Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 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 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010763 heavy fuel oil Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical class CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 150000003870 salicylic acids Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000005017 substituted alkenyl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
Definitions
- the invention relates to fuel compositions having improved properties.
- it relates to gasoline compositions which effectively inhibit and/or prevent the fouling of the fuel and inlet system of internal combustion engines.
- crankcase ventilation is necessary to prevent dilution and contamination of the lubricating oil by unburnt or partly burnt gasoline components leaking from the combustion chamber along the piston and cylinder walls into the crankcase.
- the crankcase is ventilated by a forced draft as a result of whichcomponents known as blow-by gases, find their way into the atmosphere.
- blow-by gases find their way into the atmosphere.
- some engine manufacturers have provided the engine with means for returning the mixture of blow-by gases and air to the inlet system preceding the carburetor, for instance, to the air filter. This measure, however, causes fouling of the fuel and inlet system, which, in turn causes the engine to malfunction. This tends to increase the concentration of unburnt and partly burnt hydrocarbons in the exhaust gases.
- the fuels (called aviation turbine fuels) have to meet very stringent thermal stability requirements; they not These high temperatures further entail the risk of interreaction of the hydrocarbon components present in the aviation fuel composition with the resultant formation of products which may deposit on vital engine parts. This can cause serious problems, such as clogging of filters, control systems and fuel supply lines. Therefore, thermal stability constitues one of the major problems of fuels for supersonic aircraft.
- a class of polyamine compounds has now been found which, when incorporated as additives into the fuel in minor amounts, effectively act to inhibit and prevent engine fouling. When added to a gasoline, these polyamine compounds effectively counteract engine fouling and specifically inhibit fouling of the carburetor and to a certain extent also fouling of other parts of the fuel and inlet system, such as valves and valve rods.
- the compounds concerned are polyamines wherein at least one monovalent hydrocarbon group having at least 50 carbon atoms and at least one monovalent hydrocarbon group having at most five carbon atoms are bound directly to separate nitrogen atmos and wherein the number of hydrogen atoms which are bound to nitrogen is smaller than the number of nitrogen atoms present in the polyamine molecule.
- the invention therefore relates particularly to liquid hydrocarbon fuel compositions comprising a major proportion of a fuel and a minor proportion of one or more polyamines wherein at least one monovalent hydrocarbon group having at least 50 carbon atoms and at least one monovalent hydrocarbon group having at most five carbon atoms are bound directly to nitrogen and wherein the number of hydrogen atoms which are bound to nitrogen is smaller than the number of nitrogen atoms present in the polyamine molecules.
- the fuels to be used in the fuel compositions according to the invention may be distillate fuels, flashed distillates or residual fuels.
- distillate fuels such as diesel fuels, gasolines and aviation turbine fuels, the latter two being particularly preferred.
- Aviation turbine fuel can be defined as a hydrocarbon oil having a Reid vapor pressure below 3 lb/sq. inch at F and a final boiling point below 325C.
- Gasoline can be defined as a mixture of hydrocarbons having a boiling range determined according to ASTM method D 86 between about 30 and 210C.
- the additive according to the invention shows such excellent water-shedding properties especially in gasolines, since the water-shedding properties of very closely related compounds are so poor that these compounds are unsuitable, in this respect, as gasoline additives.
- an additive according to the invention e.g., a reaction product of one mole of a polyisobutenyl (PlB) chloride with one mole of N,N-dimethylpropylene-l,3-diamine is compared with the performance of a closely related compound, which, however, lies outside the scope of the present invention, e.g., a reaction product of one mole of the same polyisobutenyl chloride with one mole of tetraethylenepentamine, it appears that although both compounds have very good detergent properties, the former has excellent water-shedding properties, while the water-shedding properties of the latter are unacceptacle for a gasoline additive, since it tends to form undesirable water-gasoline emulsions when contacted by water.
- the terminal diamine structures of the additives according to the invention are tertiary having a more hydrophobic character rather than primary having a more hydrophilic character as in the PlB-tetraethylenepentamine coupled with the fact that the alkyl groups, according to the invention (.e.g, methyl) are too small to significantly effect the polar nature of the diami'ne, contribute, at least in part, to the advantageous use of the additives according to the invention.
- the polyamines which according to the invention are incorporated into the fuel compositions may contain, if desired, more than one of each of the above-mentioned types of hydrocarbon groups.
- the monovalent groups may be bound to the same nitrogen atom or to different nitrogen atoms.
- monovalent hydrocarbon groups should be understood a monovalent radical, built up substantially from carbon and hydrogen, in which, however, dependent on the chosen method of preparation of the additives, a minor amount of one or more other elements, e.g., halogen, may be present.
- hydrocarbyl groups are alkyl or alkenyl groups derived from alkanes or alkenes with a straight or a branched carbon chain, which may carry aromatic or cycloaliphatic hydrocarbon substituents.
- the hydrocarbon groups having at least 50 carbon atoms are preferably non-substituted alkenyl or alkyl groups, such as polyethylene groups, polypropylene groups, polybutenyl groups and polyisobutenyl groups, regularly branched being preferred.
- Additives containing less than 500 carbon atoms are preferred as hydrocarbon groups having at least 50 carbon atoms; particularly preferred are hydrocarbon groups having less than 200 carbon atoms.
- Polyisobutenyl groups are preferred most as hydrocarbon groups having at least 50 carbon atoms.
- the hydrocarbon groups having at most 5 carbon atoms are preferably alkyl groups with an unbranched carbon chain. Preferred are methyl, ethyl and propyl. Methyl groups are preferred most.
- the number of hydrogen atoms which are bound to nitrogen should be smaller than the number of nitrogen atoms present in the additives.
- the polyamines acting as carriers of the monovalent hydrocarbon groups in the additives according to the invention may be either aliphatic or aromatic polyamines. Both diamines and higher amines are suitable.
- suitable diamines are ethylene-1,2- diamine, propylene-1,2-diamine, propylene-1,3- diamine, N,N-dimethylpropane-l ,3-diamine, the butylene diamines and benzene-1,4-diamine.
- suitable higher amines are the polyalkylenepolyamines such as the polyethylenepolyamines, the polypropylenepolyamines and polybutylenepolyamines.
- Specific examples of the polyethylenepolyamines are diethylenetriamine, triethylenetetramine and tetraethylenepentamine, pentaethylenehexamine and higher polyamines with a molecular weight above 1000.
- alkylene diamines are preferred, especially polymethylene-a,m-diamine particularly propylenel ,3-diamine.
- the additives according to the invention may be prepared, for instance, by allowing a polyamine which already carries the desired number of monovalent hydrocarbon groups having at most five carbon atoms to react with a halogen-containing hydrocarbon having at least 50 carbon atoms in the molecule.
- a polyamine which already carries the desired number of monovalent hydrocarbon groups having at most five carbon atoms to react with a halogen-containing hydrocarbon having at least 50 carbon atoms in the molecule.
- One may very suitably start from a chlorine-containing hydrocarbon obtained by chlorination substitution of an alkene having at least 50 carbon atoms in the molecule and a double bond in the terminal position whose beta-carbon atoms carries a methyl group.
- the chlorination can very suitably be performed with an amount of chlorine that is just sufficient to convert the alkene into the corresponding alkenyl chloride.
- the reaction between the halogen-containing hydrocarbon and the polyamine is carried out at a temperature between 20 and 200C, preferably in the presence of an inert solvent.
- hydrogen halide is formed in addition to the desired additives.
- the hydrogen halide formed combines with the polyamine used as starting material. Therefore, unless special measures are taken, the polyamine has to be present in large excess.
- the reaction be carried out in the presence of a hydrogen halide acceptor that differs both from the polyamine used as starting material and from the additive formed.
- hydrogen halide acceptors suitable for use in the preparation of the present additives are, for instance, carbonates, bicarbonates, oxides and hydroxides.
- Favorable results are obtained by using sodium carbonate or potassium carbonate as the hydrogen halide acceptor.
- the molar ratio in which the halogen-containing hydrocarbon having at least carbon atoms in the molecule and the polyamine are reacted depends on the number of such hydrocarbon groups one wishes to introduce.
- the additives according to the invention are prepared by a process comprising the reaction of a halogen-containing hydrocarbon having at least 50 carbon atoms in the molecule with a polyamine in which one or more monovalent hydrocarbon groups with at most five carbon atoms are bound direct to nitrogen, very suitable products are produced from N,N- dimethylpropylenel ,3-diamine, N,N-diethylpropylenel ,3-diamine, N,N-dipropylpropylene-l ,Sdiamine, N,N-dibutylpropylene-l ,3-diamine, N,N- dipentylpropylene-1,3-diamine, N-methylpropylene- 1,3-diamine, N-ethylpropylene-l ,3-diamine, N-butylpropylene-l ,3-diamine, N-dienalpropylene-l ,3- diamine and the like.
- additives according to the invention were prepared wherein two lower-alkyl (one to four carbon atom alkyls), such as methyl groups and substantially one polyisobutenyl group having about 91 and 1 17 carbon atoms were bound direct to nitrogen and wherein the number of hydrogen atoms which were bound to nitrogen was substantially half the number of nitrogen atoms present in the additive.
- These compounds added in a small amount, for example to an aviation-turbine fuel, imparted to that fuel stability against high temperatures, as was shown by the performance of aviation turbine-fuel compositions according to the invention in a modified Fuel Coker Test.
- the aviation turbine fuels used may have been freed of sulfur by means of hydrotreating, or the sulfur compounds may have been converted by means of an acid (e.g., sulfuric acid) treatment.
- an acid e.g., sulfuric acid
- the compounds according to the invention were added in a small amount to a gasoline, they showed a high activity as cleanliness agents for the carburetor as well as for other parts of the inlet system, such as the inlet valves and the inlet valve rods. Moreover, their water-shedding properties were excellent.
- the concentration of the present additives in the fuel may vary within wide limits. in general, the desired stabilizing effect is obtained when the amount added is from 0.001 to 5%w preferably from 0.001 to 0.1%w.
- the additives may be added to the fuel as such or in the form of a concentrate with a small amount of hydrocarbon oil, such as a distillate fuel or lubricating oil.
- the fuel compositions according to the invention may contain minor amounts of other additives by which the quality of the fuel is further improved, such as agents improving the ingition, scavenging agents, anti-icing additives, antioxidants, conductivity improving agents, metal deactivating compounds.
- Suitable metal deactivators are compounds having the formula wherein R represents a heterocyclic radical containing a C N group in a five-membered or sixmembered ring and Y represents hydrogen or a cyclic or acyclic substituent, or the two Ys together with the group form acyclic structure.
- R represents a heterocyclic radical containing a C N group in a five-membered or sixmembered ring
- Y represents hydrogen or a cyclic or acyclic substituent, or the two Ys together with the group form acyclic structure.
- R group represents a thiazole, pyridine, quinoline or isopyrrole ring which may contain one or more substituents, and in particular compounds wherein this ring is attached to the nitrogen atom in the alpha-position.
- a very active metal deactivator, in particular copper deactivator, in this class of compounds is l,3-di(2'-pyridyl)- iminoisoin
- Especially suitable metal deactivators which may be used in the fuel compositions according to the invention are compounds belonging to the class of the N,N'- disalicylidene-l ,Z-diaminoalkanes. Preferred in this class of compounds is N,N'-disalicylidene-1,2- diaminopropane.
- the amount of metal deactivators which may be present in the fuel compositions according to the invention may vary within wide limits, between about 0.0001 and 0.01%w.
- Anitoxidants in particular alkylphenolic anitoxidants such as 2,6-di-tert-butyl-4-methylphenol and 2,4- dimethyl-o-tert-butylphenol may also be present in the 6 fuels according to the invention, preferably between about 0.005 and 0.05%w.
- Conductivity improving agents which decrease the tendency for self-inflammation during handling of fuels, in particular during pumping of aviation turbine fuels, may also be incorporated in the fuels.
- Suitable conductivity improving agents consist of a mixture of the calcium or barium salt of dialkyl (e.g., dioctyl) sodium sulfosuccinate, chromium salts of alkyl (e.g., C, --C, salicylic acids and a copolymer of alkyl methacrylates (e.g., lauryl and/or stearyl methacrylates) and a vinyl-pyridine (e.g., 2-methyl-5-vinylpyridino and/or 4 vinyl-pyridine).
- dialkyl e.g., dioctyl
- chromium salts of alkyl e.g., C, --C, salicylic acids
- alkyl methacrylates e.g., lauryl and/or stearyl methacryl
- Additive 2 Polyisobutene with a molecular weight of 1635 was chlorinated, in the same way as described for additive 1, to a product with a chlorine content of 2.0%w.
- a mixture of 140.6 g of this polyisobutenyl chloride, ml toluene and 10 g pulverized potassium carbonate was heated to C in a nitrogen atmosphere, with stirring and subsequently, while the mixture was being stirred, 10.5 g N,N-dimethylpropylene-1,3- diamine was added dropwise over a period of five hours. After that, an additional amount of 4 g pulverized potassium carbonate was added and the reaction mixture while being stirred was kept at 130C for 15 hours. The reaction mixture was finished in the same way as described for additive 1.
- the product obtained weighed 141.5,g and had a nitrogen content of 0.93%w. Analysis established it as being N,N-dimethyl-N'-polyisobutenyl-propylene-1,3- diamine.
- Additives A, B, C, and D (N-polyisobutenyltetraethylenepentamines)
- additives B, C, and D were prepared, starting from tetraethylenepentamine and polyisobutenes with molecular weights of 950, 1280, i380 and 1635, respectively.
- the preparation of these additives was carried out in a way substantially the same as described for the additives l and 2.
- Additive E and F Also for comparison, two commercial gasoline dispersants were incorporated into the testing program.
- Additive E is a reaction product of polyisobutenyl chloride, maleic anhydride and tetraethylenepentamine.
- Additive F is a mixture of alkylarnine salts of alkylphosphoric acids.
- EXAMPLE ii The additives 1, 2, A, D, E and F were tested as gasoline additives in a Sunbeam Talbot engine and in a Ford engine. The concentration of the additives in the gasoline was 0.01%w. For comparison, the two engine tests were also carried out with the same base gasoline containing no such additives. As base gasoline, a premium grade leaded gasoline was used.
- Ford E 105 engine test The extent of fouling of the carburetor was determined in a Ford E 105 engine equipped with a Solex B 30 lPSE carburetor.
- the carburetor was of the standard design except for the gas valve chamber having been bored and lined with a duralumin insert. After the test, the fouling of the carburetor was evaluated. in order to accelerate the formation of deposits, small, accurately metered amounts of blow-by gas from the engine and exhaust gas (representative of driving a car in heavy traffic) were returned to' the carburetor.
- the engine remained in operation for a total test period of 90 hours according to a scheme providing for operation in cycles consisting of running for 3.5 minutes at no load and running for 30 seconds with partly opened gas valve under conditions simulating driving on a road at normal load.
- Sunbeam Talbot engine test in this test, the inlet system fouling is determined on the basis of fouling of the inlet valves and the inlet valve rods.
- the test was carried out on a Sunbeam Talbot engine with a piston displacement of 2264 cm, a compression ratio of 6.45 1, and a maximum capacity of 70 bhp at 4000 rpm.
- the engine, including the two carburetors was cleaned whereupon the engine was kept in continuous operation for 32 hours, at a speed of 1500 rpm, a capacity of 15 bhp and a fuel consumption of 5.0 kg per hour. After the test had been finished, the fouling of the inlet valves and the inlet valve rods was evaluated.
- additive 1 and 2 and additives A-lF were determined in a test in which the fuel comprising 100 ppm (parts per million) additive is shaken with distilled water at ambient temperature under standard conditions. After adequate settling, the water content of a sample taken at a specified depth is determined by titration with Fischer reagent. The amount of free water is calculated from the total water content and basic solubility data.
- compositions according to the invention are thus shown to possess effective cleanliness properties and concomitantly excellent water-shedding characteristics.
- test fuel reservoir a stainless steel reservoir of 25 1 provided with a heating element was used wherein the fuel to be tested could be brought in one hour to 275F and kept at that temperature during the test in contact with the atmosphere.
- the preheater contained an aluminium preheater tube, which was internally supported by a stainless steel tube.
- the outer tube of the preheater was surrounded by a 3 cm thick layer of insulating material.
- the aviation turbine fuel compositions were tested for five hours at a preheater fuel outlet temperature of 4351F and a filter temperature of 525F, maintaining a fuel temperature of 275F in the reservoir.
- This modified version is considered to be a more severe test for the fuel than the ASTM D 1660 test proper, in view of the high preheater temperature and in view of the fact that the fuel to be tested is in contact with air at a high temperature.
- An aviation turbine fuels there were used an acid treated kerosene and a hydrodesulfurized kerosene both with a Reid vapor pressure of 0.1 lb/sq inch at lF and a boiling range from l50250C.
- drop Preheater treated to the 1,2-diam1n0- iminoisoimproving inc tube kerosine invention propane indoline additive mercury
- inventive compositions showed markedly superior thermal stability. Further, the addition of N,N- '-disalicylidene-1,2-diamino propane to the inventive compositions apparently enhanced their effectiveness.
- liquid hydrocarbon distillate fuel compositions containing polyamines according to the invention effectively counteract, nullify and/or inhibit fouling of vital parts of internal combustion engines.
- a method for reducing hydrocarbon exhaust gas emissions by operating an internal combustion engine 2.
Abstract
Liquid hydrocarbon fuel compositions, especially gasolines, containing certain hydrocarbyl polyamines, effectively nullify and/or inhibit fouling of vital parts of internal combustion engines.
Description
United States Patent Strang et al.
HYDROCARBON FUEL COMPOSITIONS Inventors: Aart Strang, Amsterdam,
Netherlands; Isaac C. H. Robinson, Chester, England Assignee: Shell Oil Company, New York, NY.
Filed: June 30, 1970 Appl. No.: 51,363
Foreign Application Priority Data June 30, 1969 Great Britain 32906/69 US. Cl. 44/72, 252/401 Int. Cl Cl0l 1/22 Field of Search 44/72, 73; 252/401 References Cited UNITED STATES PATENTS 4/1969 Honnen et al. 44/72 X FOREIGN PATENTS OR APPLICATIONS 931,436 7/1963 Great Britain 44/73 Primary Examiner-Daniel E. Wyman Assistant Examiner-W. J. Shine Attorney1-lenry C. Geller and Harold L. Dinkler [57] ABSTRACT Liquid hydrocarbon fuel compositions, especially gasolines, containing certain hydrocarbyl polyamines, effectively nullify and/or inhibit fouling of vital parts of internal combustion engines.
4 Claims, No Drawings HYDROCARBON FUEL COMPOSITIONS BACKGROUND OF THE INVENTION- The invention relates to fuel compositions having improved properties. In particular, it relates to gasoline compositions which effectively inhibit and/or prevent the fouling of the fuel and inlet system of internal combustion engines.
One means of combating air pollution is to reduce the emission of hydrocarbons by gasoline engines, due, inter alia, to crankcase ventilation. This ventilationis necessary to prevent dilution and contamination of the lubricating oil by unburnt or partly burnt gasoline components leaking from the combustion chamber along the piston and cylinder walls into the crankcase. The crankcase is ventilated by a forced draft as a result of whichcomponents known as blow-by gases, find their way into the atmosphere. To reduce this type of emission, some engine manufacturers have provided the engine with means for returning the mixture of blow-by gases and air to the inlet system preceding the carburetor, for instance, to the air filter. This measure, however, causes fouling of the fuel and inlet system, which, in turn causes the engine to malfunction. This tends to increase the concentration of unburnt and partly burnt hydrocarbons in the exhaust gases.
It is possible to counteract fouling of the engine by incorporating a minor amount of compounds with detergent properties into the fuel. These compounds, however, if they are to be effective for this purpose, must also possess good water-shedding properties. If the water-shedding properties of a fuel additive are poor, the additive promotes water pick-up and emulsion formation in the fuel. Fuels containing such additives are, inter alia, difficult to handle.
For non-surface vehicles such as supersonic aircraft, the fuels (called aviation turbine fuels) have to meet very stringent thermal stability requirements; they not These high temperatures further entail the risk of interreaction of the hydrocarbon components present in the aviation fuel composition with the resultant formation of products which may deposit on vital engine parts. This can cause serious problems, such as clogging of filters, control systems and fuel supply lines. Therefore, thermal stability constitues one of the major problems of fuels for supersonic aircraft.
Previous attempts have been made to solve these problems. As a rule, however, the usual oxidation inhibitors have proven entirely unsatisfactory. in certain cases inhibitors have even promoted the formation of deposits. in other cases where the additives possessed excellent antioxidant properties, they gave rise to the formation of gasoline-water-emulsions when brought into contact with water. For example, polyisobutenyl tetraethylene pentamine showed this disadvantage when contacted with water.
SUMMARY OF THE INVENTION A class of polyamine compounds has now been found which, when incorporated as additives into the fuel in minor amounts, effectively act to inhibit and prevent engine fouling. When added to a gasoline, these polyamine compounds effectively counteract engine fouling and specifically inhibit fouling of the carburetor and to a certain extent also fouling of other parts of the fuel and inlet system, such as valves and valve rods.
They possess excellent water-shedding properties and when incorporated into aviation fuels, they stabilize these fuels against deterioration at high tempeatures, and are able to minimize the formation of noxious products in the fuel system of the aircraft engine.
The compounds concerned are polyamines wherein at least one monovalent hydrocarbon group having at least 50 carbon atoms and at least one monovalent hydrocarbon group having at most five carbon atoms are bound directly to separate nitrogen atmos and wherein the number of hydrogen atoms which are bound to nitrogen is smaller than the number of nitrogen atoms present in the polyamine molecule.
The invention therefore relates particularly to liquid hydrocarbon fuel compositions comprising a major proportion of a fuel and a minor proportion of one or more polyamines wherein at least one monovalent hydrocarbon group having at least 50 carbon atoms and at least one monovalent hydrocarbon group having at most five carbon atoms are bound directly to nitrogen and wherein the number of hydrogen atoms which are bound to nitrogen is smaller than the number of nitrogen atoms present in the polyamine molecules.
DESCRIPTION OF THE PREFERRED EMBODIMENTS The fuels to be used in the fuel compositions according to the invention may be distillate fuels, flashed distillates or residual fuels. Preferred are distillate fuels such as diesel fuels, gasolines and aviation turbine fuels, the latter two being particularly preferred.
Aviation turbine fuel can be defined as a hydrocarbon oil having a Reid vapor pressure below 3 lb/sq. inch at F and a final boiling point below 325C.
Gasoline can be defined as a mixture of hydrocarbons having a boiling range determined according to ASTM method D 86 between about 30 and 210C.
it is very surprising that the additive according to the invention shows such excellent water-shedding properties especially in gasolines, since the water-shedding properties of very closely related compounds are so poor that these compounds are unsuitable, in this respect, as gasoline additives. If the performance of an additive according to the invention, e.g., a reaction product of one mole of a polyisobutenyl (PlB) chloride with one mole of N,N-dimethylpropylene-l,3-diamine is compared with the performance of a closely related compound, which, however, lies outside the scope of the present invention, e.g., a reaction product of one mole of the same polyisobutenyl chloride with one mole of tetraethylenepentamine, it appears that although both compounds have very good detergent properties, the former has excellent water-shedding properties, while the water-shedding properties of the latter are unacceptacle for a gasoline additive, since it tends to form undesirable water-gasoline emulsions when contacted by water.
Apparently, the fact that the terminal diamine structures of the additives according to the invention are tertiary having a more hydrophobic character rather than primary having a more hydrophilic character as in the PlB-tetraethylenepentamine coupled with the fact that the alkyl groups, according to the invention (.e.g, methyl) are too small to significantly effect the polar nature of the diami'ne, contribute, at least in part, to the advantageous use of the additives according to the invention.
The polyamines which according to the invention are incorporated into the fuel compositions (hereafter called the additives) may contain, if desired, more than one of each of the above-mentioned types of hydrocarbon groups. The monovalent groups may be bound to the same nitrogen atom or to different nitrogen atoms. Here, by monovalent hydrocarbon groups should be understood a monovalent radical, built up substantially from carbon and hydrogen, in which, however, dependent on the chosen method of preparation of the additives, a minor amount of one or more other elements, e.g., halogen, may be present. Examples of suitable hydrocarbyl groups are alkyl or alkenyl groups derived from alkanes or alkenes with a straight or a branched carbon chain, which may carry aromatic or cycloaliphatic hydrocarbon substituents. The hydrocarbon groups having at least 50 carbon atoms are preferably non-substituted alkenyl or alkyl groups, such as polyethylene groups, polypropylene groups, polybutenyl groups and polyisobutenyl groups, regularly branched being preferred. Additives containing less than 500 carbon atoms are preferred as hydrocarbon groups having at least 50 carbon atoms; particularly preferred are hydrocarbon groups having less than 200 carbon atoms. Polyisobutenyl groups are preferred most as hydrocarbon groups having at least 50 carbon atoms.
The hydrocarbon groups having at most 5 carbon atoms are preferably alkyl groups with an unbranched carbon chain. Preferred are methyl, ethyl and propyl. Methyl groups are preferred most.
In the additives according to the invention the number of hydrogen atoms which are bound to nitrogen should be smaller than the number of nitrogen atoms present in the additives. Preferred are additives wherein the number of hydrogen atoms which are bound to nitrogen is about half the number of nitrogen atoms present in the additive molecule.
The polyamines acting as carriers of the monovalent hydrocarbon groups in the additives according to the invention may be either aliphatic or aromatic polyamines. Both diamines and higher amines are suitable.
Examples of suitable diamines are ethylene-1,2- diamine, propylene-1,2-diamine, propylene-1,3- diamine, N,N-dimethylpropane-l ,3-diamine, the butylene diamines and benzene-1,4-diamine. Examples of suitable higher amines are the polyalkylenepolyamines such as the polyethylenepolyamines, the polypropylenepolyamines and polybutylenepolyamines. Specific examples of the polyethylenepolyamines are diethylenetriamine, triethylenetetramine and tetraethylenepentamine, pentaethylenehexamine and higher polyamines with a molecular weight above 1000. As carriers of the monovalent hydrocarbon groups in the additives according to the invention, alkylene diamines are preferred, especially polymethylene-a,m-diamine particularly propylenel ,3-diamine.
The additives according to the invention may be prepared, for instance, by allowing a polyamine which already carries the desired number of monovalent hydrocarbon groups having at most five carbon atoms to react with a halogen-containing hydrocarbon having at least 50 carbon atoms in the molecule. One may very suitably start from a chlorine-containing hydrocarbon obtained by chlorination substitution of an alkene having at least 50 carbon atoms in the molecule and a double bond in the terminal position whose beta-carbon atoms carries a methyl group. The chlorination can very suitably be performed with an amount of chlorine that is just sufficient to convert the alkene into the corresponding alkenyl chloride. One may start, for instance, from polyisobutene which in an inert solvent is converted, with a stoichiometric amount of chlorine, into polyisobutenyl chloride. The reaction between the halogen-containing hydrocarbon and the polyamine is carried out at a temperature between 20 and 200C, preferably in the presence of an inert solvent. In the reaction between a halogen containing hydrocarbon and a polyamine, hydrogen halide is formed in addition to the desired additives. The hydrogen halide formed combines with the polyamine used as starting material. Therefore, unless special measures are taken, the polyamine has to be present in large excess. Since it is desirable that the amount of polyamine required for the preparation be kept as small as possible, it is preferred that the reaction be carried out in the presence of a hydrogen halide acceptor that differs both from the polyamine used as starting material and from the additive formed. Examples of hydrogen halide acceptors suitable for use in the preparation of the present additives are, for instance, carbonates, bicarbonates, oxides and hydroxides. Favorable results are obtained by using sodium carbonate or potassium carbonate as the hydrogen halide acceptor.
The molar ratio in which the halogen-containing hydrocarbon having at least carbon atoms in the molecule and the polyamine are reacted depends on the number of such hydrocarbon groups one wishes to introduce. For the preparation of additives according to the invention in which substantially a single hydrocarbon group having at least 50 carbon atoms in bound direct to one of the nitrogen atoms of the polyamine, one preferably uses at most 2 gram molecules of the starting polyamine per gram atom of halogen-containing hydrocarbon.
lf the additives according to the invention are prepared by a process comprising the reaction of a halogen-containing hydrocarbon having at least 50 carbon atoms in the molecule with a polyamine in which one or more monovalent hydrocarbon groups with at most five carbon atoms are bound direct to nitrogen, very suitable products are produced from N,N- dimethylpropylenel ,3-diamine, N,N-diethylpropylenel ,3-diamine, N,N-dipropylpropylene-l ,Sdiamine, N,N-dibutylpropylene-l ,3-diamine, N,N- dipentylpropylene-1,3-diamine, N-methylpropylene- 1,3-diamine, N-ethylpropylene-l ,3-diamine, N-butylpropylene-l ,3-diamine, N-dienalpropylene-l ,3- diamine and the like. Especially preferred is N,N- dimethylpropylene-l,3-diamine.
Excellent results have been obtained by the reaction of polyisobutenyl chlorides in which the average number of carbon atoms amounted to about 91 and about 1 17 with an N,N-di lower-alkyl'lower-alkylene-mwdiamine, specifically N,N-dimethylpropylene-l,3- diamine, in which reaction about 1.3 gram molecules of polyamine were used per gram atom of chlorine, present in the polyisobutenyl chloride. in this way, additives according to the invention were prepared wherein two lower-alkyl (one to four carbon atom alkyls), such as methyl groups and substantially one polyisobutenyl group having about 91 and 1 17 carbon atoms were bound direct to nitrogen and wherein the number of hydrogen atoms which were bound to nitrogen was substantially half the number of nitrogen atoms present in the additive. These compounds, added in a small amount, for example to an aviation-turbine fuel, imparted to that fuel stability against high temperatures, as was shown by the performance of aviation turbine-fuel compositions according to the invention in a modified Fuel Coker Test. The aviation turbine fuels used may have been freed of sulfur by means of hydrotreating, or the sulfur compounds may have been converted by means of an acid (e.g., sulfuric acid) treatment. When the compounds according to the invention were added in a small amount to a gasoline, they showed a high activity as cleanliness agents for the carburetor as well as for other parts of the inlet system, such as the inlet valves and the inlet valve rods. Moreover, their water-shedding properties were excellent.
The concentration of the present additives in the fuel may vary within wide limits. in general, the desired stabilizing effect is obtained when the amount added is from 0.001 to 5%w preferably from 0.001 to 0.1%w. The additives may be added to the fuel as such or in the form of a concentrate with a small amount of hydrocarbon oil, such as a distillate fuel or lubricating oil.
In addition to a major amount of fuel and a minor amount of the present additives, the fuel compositions according to the invention may contain minor amounts of other additives by which the quality of the fuel is further improved, such as agents improving the ingition, scavenging agents, anti-icing additives, antioxidants, conductivity improving agents, metal deactivating compounds.
Suitable metal deactivators are compounds having the formula wherein R represents a heterocyclic radical containing a C N group in a five-membered or sixmembered ring and Y represents hydrogen or a cyclic or acyclic substituent, or the two Ys together with the group form acyclic structure. Examples are compounds of the above formula, in which the R group represents a thiazole, pyridine, quinoline or isopyrrole ring which may contain one or more substituents, and in particular compounds wherein this ring is attached to the nitrogen atom in the alpha-position. A very active metal deactivator, in particular copper deactivator, in this class of compounds is l,3-di(2'-pyridyl)- iminoisoindoline.
Especially suitable metal deactivators, which may be used in the fuel compositions according to the invention are compounds belonging to the class of the N,N'- disalicylidene-l ,Z-diaminoalkanes. Preferred in this class of compounds is N,N'-disalicylidene-1,2- diaminopropane.
The amount of metal deactivators which may be present in the fuel compositions according to the invention may vary within wide limits, between about 0.0001 and 0.01%w.
Anitoxidants, in particular alkylphenolic anitoxidants such as 2,6-di-tert-butyl-4-methylphenol and 2,4- dimethyl-o-tert-butylphenol may also be present in the 6 fuels according to the invention, preferably between about 0.005 and 0.05%w.
Conductivity improving agents, which decrease the tendency for self-inflammation during handling of fuels, in particular during pumping of aviation turbine fuels, may also be incorporated in the fuels. Suitable conductivity improving agents consist of a mixture of the calcium or barium salt of dialkyl (e.g., dioctyl) sodium sulfosuccinate, chromium salts of alkyl (e.g., C, --C, salicylic acids and a copolymer of alkyl methacrylates (e.g., lauryl and/or stearyl methacrylates) and a vinyl-pyridine (e.g., 2-methyl-5-vinylpyridino and/or 4 vinyl-pyridine).
The invention will be further characterized by the following examples.
EXAMPLE 1 Additive Synthesis Two additives consisting of N'-polyisobutenyl-N,N-
dimethylpropylene-l,3-diamine with different molecular weights were prepared. Additive 1: Polyisobutene with a molecular weight of 1280 was dissolved in isooctance. After addition of a crystal of iodine to this solution, chlorine was introduced at room temperature until the color of the solution faded. Subsequently, the solvent was vaporized. The residue contained 2.84%w chlorine, corresponding to a mono-chloro-product.
A mixture of 123.2 g of polyisobutenyl chloride prepared in this way, 60 ml toluene and 10 g pulverized potassium carbonate was heated to 130C in a nitrogen atmosphere, with stirring and subsequently, while the mixture was being stirred, 13.0 g N,N- dimethylpropylene-l,3-diamine was added dropwise over a period of 5 hours. Afterward, an additional amount of 4 g pulverized potassium carbonate was added and the reaction mixture while being stirred was kept at 130C for 15 hours. After cooling down, the reaction product was taken up in a 60/80 gasoline and washed with water until the washwater was free from chlorine. The reaction product was isolated by vaporizing the solvent;
The product obtained weighed 124.5 g and had a nitrogen content of 1.24%w. It contained both secondary and tertiary amino nitrogens and one carbon-to-carbon double bond. Additive 2: Polyisobutene with a molecular weight of 1635 was chlorinated, in the same way as described for additive 1, to a product with a chlorine content of 2.0%w.
A mixture of 140.6 g of this polyisobutenyl chloride, ml toluene and 10 g pulverized potassium carbonate was heated to C in a nitrogen atmosphere, with stirring and subsequently, while the mixture was being stirred, 10.5 g N,N-dimethylpropylene-1,3- diamine was added dropwise over a period of five hours. After that, an additional amount of 4 g pulverized potassium carbonate was added and the reaction mixture while being stirred was kept at 130C for 15 hours. The reaction mixture was finished in the same way as described for additive 1.
The product obtained weighed 141.5,g and had a nitrogen content of 0.93%w. Analysis established it as being N,N-dimethyl-N'-polyisobutenyl-propylene-1,3- diamine.
Additives A, B, C, and D(N-polyisobutenyltetraethylenepentamines) For comparison, four related compounds which, however, lie outside the scope of the present invention, were prepared, starting from tetraethylenepentamine and polyisobutenes with molecular weights of 950, 1280, i380 and 1635, respectively. The preparation of these additives was carried out in a way substantially the same as described for the additives l and 2.
Additive E and F: Also for comparison, two commercial gasoline dispersants were incorporated into the testing program.
Additive E is a reaction product of polyisobutenyl chloride, maleic anhydride and tetraethylenepentamine.
Additive F is a mixture of alkylarnine salts of alkylphosphoric acids.
EXAMPLE ii The additives 1, 2, A, D, E and F were tested as gasoline additives in a Sunbeam Talbot engine and in a Ford engine. The concentration of the additives in the gasoline was 0.01%w. For comparison, the two engine tests were also carried out with the same base gasoline containing no such additives. As base gasoline, a premium grade leaded gasoline was used.
Ford E 105 engine test: The extent of fouling of the carburetor was determined in a Ford E 105 engine equipped with a Solex B 30 lPSE carburetor. The carburetor was of the standard design except for the gas valve chamber having been bored and lined with a duralumin insert. After the test, the fouling of the carburetor was evaluated. in order to accelerate the formation of deposits, small, accurately metered amounts of blow-by gas from the engine and exhaust gas (representative of driving a car in heavy traffic) were returned to' the carburetor. The engine remained in operation for a total test period of 90 hours according to a scheme providing for operation in cycles consisting of running for 3.5 minutes at no load and running for 30 seconds with partly opened gas valve under conditions simulating driving on a road at normal load.
Sunbeam Talbot engine test: in this test, the inlet system fouling is determined on the basis of fouling of the inlet valves and the inlet valve rods. The test was carried out on a Sunbeam Talbot engine with a piston displacement of 2264 cm, a compression ratio of 6.45 1, and a maximum capacity of 70 bhp at 4000 rpm. Before the test was started, the engine, including the two carburetors, was cleaned whereupon the engine was kept in continuous operation for 32 hours, at a speed of 1500 rpm, a capacity of 15 bhp and a fuel consumption of 5.0 kg per hour. After the test had been finished, the fouling of the inlet valves and the inlet valve rods was evaluated.
The water-shedding properties of additive 1 and 2 and additives A-lF were determined in a test in which the fuel comprising 100 ppm (parts per million) additive is shaken with distilled water at ambient temperature under standard conditions. After adequate settling, the water content of a sample taken at a specified depth is determined by titration with Fischer reagent. The amount of free water is calculated from the total water content and basic solubility data.
The results of the engine tests and the water-shedding tests are given in Table l.
TABLE I Additive l 2 A Molecular weight of the olyisobutene use for the preparation of the additivel, 280 l, 835 950 Composition of the additive:
Number of nitrogen atoms 2 2 5 5 5 5 Number of hydroen atoms ound to nitro- Carburetor cleanliness effectiveness,
ercent: Sun eam Talbot enno test:
In at system cleanliness improvement over base fuel, percent Water-shedding properties, p.p.m. free water n is perfect.
The compositions according to the invention are thus shown to possess effective cleanliness properties and concomitantly excellent water-shedding characteristics.
EXAMPLE lIi Thermal Stability Test The thermal stability of aviation turbine fuels containing additive l was tested according to a modified version of the ASTM/CRC Fuel Coker Test, (ASTM D 1660). A test fuel reservoir and a preheater different from those prescribed in the ASTM method were used viz.:
1. As test fuel reservoir a stainless steel reservoir of 25 1 provided with a heating element was used wherein the fuel to be tested could be brought in one hour to 275F and kept at that temperature during the test in contact with the atmosphere.
2. The preheater contained an aluminium preheater tube, which was internally supported by a stainless steel tube. The outer tube of the preheater was surrounded by a 3 cm thick layer of insulating material.
Moreover, no in line micronic filter was present between the fuel reservoir and the preheater.
The aviation turbine fuel compositions were tested for five hours at a preheater fuel outlet temperature of 4351F and a filter temperature of 525F, maintaining a fuel temperature of 275F in the reservoir.
This modified version is considered to be a more severe test for the fuel than the ASTM D 1660 test proper, in view of the high preheater temperature and in view of the fact that the fuel to be tested is in contact with air at a high temperature.
The drop over the filter in inches mercury and the rating of the preheater tube deposits were determined as described in ASTM method D 1660.
An aviation turbine fuels there were used an acid treated kerosene and a hydrodesulfurized kerosene both with a Reid vapor pressure of 0.1 lb/sq inch at lF and a boiling range from l50250C.
on a gasoline fuel containing from 0.001 to percent by weight of N'-polyisobutenyl-N,N-dialkylpropylenel,3-diamine wherein the polyisobutenyl group has at least 50 and less than 200 carbon atoms and each alkyl ab e 2 ShOWS the results; tests 2 and 6 are for 5 group of said dialkyl is unbranched alkyl of one to three comparison, and not according to the invention. carbon atoms TABLE 2 Additives parts per million Results Additive 1 N,N-disali- 1,3-di(2- Conduc- Hydroaccording cylidenepyridyi)- tivity Press. drop Preheater treated to the 1,2-diam1n0- iminoisoimproving (inc tube kerosine invention propane indoline additive mercury) rating 50% solution of the calcium salt of dioctyl sodium suliosuccinate, chromium salts of alkylsaiicylic acids and a copolyrner of alkyl metheerylates and 2-rnethyl-5-viny1pyridinc.
"Time in minutes in which pressure drop amounted to inch mercury.
Thus, the inventive compositions showed markedly superior thermal stability. Further, the addition of N,N- '-disalicylidene-1,2-diamino propane to the inventive compositions apparently enhanced their effectiveness.
It is clear from the test results and preceding data that liquid hydrocarbon distillate fuel compositions containing polyamines according to the invention effectively counteract, nullify and/or inhibit fouling of vital parts of internal combustion engines.
We claim as our invention:
1. A method for reducing hydrocarbon exhaust gas emissions by operating an internal combustion engine 2. A method for reducing hydrocarbon exhaust gas emissions by operating an internal combustion engine on a gasoline fuel containing between 0.001 and 0.1 percent by weight of N-polyisobutenyl-N,N-
dimethylpropylene-l,3-diamine wherein the polyiso-.
weight.
Claims (3)
- 2. A method for reducing hydrocarbon exhaust gas emissions by operating an internal combustion engine on a gasoline fuel containing between 0.001 and 0.1 percent by weight of N''-polyisobutenyl-N,N-dimethylpropylene-1,3-diamine wherein the polyisobutenyl group has at least 50 and less than 200 carbon atoms.
- 3. The composition of claim 1 in which the alkyl groups are methyl.
- 4. The composition of cLaim 1 in which the amount of the diamine is between 0.001 and 0.1 percent by weight.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB3290669 | 1969-06-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3753670A true US3753670A (en) | 1973-08-21 |
Family
ID=10345781
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00051363A Expired - Lifetime US3753670A (en) | 1969-06-30 | 1970-06-30 | Hydrocarbon fuel compositions |
Country Status (4)
Country | Link |
---|---|
US (1) | US3753670A (en) |
CA (1) | CA917919A (en) |
GB (1) | GB1309907A (en) |
ZA (1) | ZA704424B (en) |
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4678479A (en) * | 1985-04-24 | 1987-07-07 | Holmes Robert T | Diesel fuel composition |
US5288393A (en) * | 1990-12-13 | 1994-02-22 | Union Oil Company Of California | Gasoline fuel |
USH1305H (en) | 1992-07-09 | 1994-05-03 | Townsend Daniel J | Reformulated gasolines and methods of producing reformulated gasolines |
US5340369A (en) * | 1991-05-13 | 1994-08-23 | The Lubrizol Corporation | Diesel fuels containing organometallic complexes |
US5344467A (en) * | 1991-05-13 | 1994-09-06 | The Lubrizol Corporation | Organometallic complex-antioxidant combinations, and concentrates and diesel fuels containing same |
US5350429A (en) * | 1992-03-19 | 1994-09-27 | Basf Aktiengesellschaft | Diaminoalkanes, their preparation and fuels and lubricants containing the diaminoalkanes |
US5352251A (en) * | 1993-03-30 | 1994-10-04 | Shell Oil Company | Fuel compositions |
US5360459A (en) * | 1991-05-13 | 1994-11-01 | The Lubrizol Corporation | Copper-containing organometallic complexes and concentrates and diesel fuels containing same |
US5376154A (en) * | 1991-05-13 | 1994-12-27 | The Lubrizol Corporation | Low-sulfur diesel fuels containing organometallic complexes |
US5458660A (en) * | 1994-09-19 | 1995-10-17 | Shell Oil Company | Fuel compositions |
US5458661A (en) * | 1994-09-19 | 1995-10-17 | Shell Oil Company | Fuel compositions |
US5489315A (en) * | 1994-09-19 | 1996-02-06 | Shell Oil Company | Fuel compositions comprising hydantoin-containing polyether alcohol additives |
US5507843A (en) * | 1994-09-19 | 1996-04-16 | Shell Oil Company | Fuel compositions |
US5518510A (en) * | 1991-05-13 | 1996-05-21 | The Lubrizol Corporation | Low-sulfur diesel fuels containing organo-metallic complexes |
US5559270A (en) * | 1994-12-15 | 1996-09-24 | Petrokleen, Ltd. | Method of synthesizing pure additives and the improved compositions thereby produced |
US5855630A (en) * | 1994-09-19 | 1999-01-05 | Shell Oil Company | Fuel compositions |
US5962738A (en) * | 1994-12-15 | 1999-10-05 | Petrokleen, Ltd. | Polymeric-amine fuel and lubricant additive |
US6210452B1 (en) | 2000-02-08 | 2001-04-03 | Hhntsman Petrochemical Corporation | Fuel additives |
US6261327B1 (en) | 1997-05-29 | 2001-07-17 | Shell Oil Company | Additive concentrates for rapidly reducing octane requirement |
US6312481B1 (en) | 1994-09-22 | 2001-11-06 | Shell Oil Company | Fuel compositions |
US20030173250A1 (en) * | 2002-03-13 | 2003-09-18 | Blackwood David Macdonald | Unleaded gasoline compositions |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB931436A (en) * | 1960-07-29 | 1963-07-17 | Shell Int Research | Hydrocarbon oil compositions having improved ageing stability |
US3419368A (en) * | 1967-01-23 | 1968-12-31 | Ashland Oil Inc | Thermally stabilized hydrocarbon liquid compositions |
US3438757A (en) * | 1965-08-23 | 1969-04-15 | Chevron Res | Hydrocarbyl amines for fuel detergents |
US3454555A (en) * | 1965-01-28 | 1969-07-08 | Shell Oil Co | Oil-soluble halogen-containing polyamines and polyethyleneimines |
-
1969
- 1969-06-30 GB GB3290669A patent/GB1309907A/en not_active Expired
-
1970
- 1970-06-29 CA CA086811A patent/CA917919A/en not_active Expired
- 1970-06-29 ZA ZA704424*A patent/ZA704424B/en unknown
- 1970-06-30 US US00051363A patent/US3753670A/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB931436A (en) * | 1960-07-29 | 1963-07-17 | Shell Int Research | Hydrocarbon oil compositions having improved ageing stability |
US3454555A (en) * | 1965-01-28 | 1969-07-08 | Shell Oil Co | Oil-soluble halogen-containing polyamines and polyethyleneimines |
US3438757A (en) * | 1965-08-23 | 1969-04-15 | Chevron Res | Hydrocarbyl amines for fuel detergents |
US3419368A (en) * | 1967-01-23 | 1968-12-31 | Ashland Oil Inc | Thermally stabilized hydrocarbon liquid compositions |
Cited By (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4678479A (en) * | 1985-04-24 | 1987-07-07 | Holmes Robert T | Diesel fuel composition |
US5288393A (en) * | 1990-12-13 | 1994-02-22 | Union Oil Company Of California | Gasoline fuel |
US6030521A (en) * | 1990-12-13 | 2000-02-29 | Union Oil Company Of California | Gasoline fuel |
US5837126A (en) * | 1990-12-13 | 1998-11-17 | Union Oil Company Of California | Gasoline fuel |
US5653866A (en) * | 1990-12-13 | 1997-08-05 | Union Oil Company Of California | Gasoline fuel |
US5593567A (en) * | 1990-12-13 | 1997-01-14 | Jessup; Peter J. | Gasoline fuel |
US5360459A (en) * | 1991-05-13 | 1994-11-01 | The Lubrizol Corporation | Copper-containing organometallic complexes and concentrates and diesel fuels containing same |
US5376154A (en) * | 1991-05-13 | 1994-12-27 | The Lubrizol Corporation | Low-sulfur diesel fuels containing organometallic complexes |
US5340369A (en) * | 1991-05-13 | 1994-08-23 | The Lubrizol Corporation | Diesel fuels containing organometallic complexes |
US5518510A (en) * | 1991-05-13 | 1996-05-21 | The Lubrizol Corporation | Low-sulfur diesel fuels containing organo-metallic complexes |
US5534039A (en) * | 1991-05-13 | 1996-07-09 | The Lubrizol Corporation | Organometallic complex-antioxidant combinations, and concentrates and diesel fuels containing same |
US5344467A (en) * | 1991-05-13 | 1994-09-06 | The Lubrizol Corporation | Organometallic complex-antioxidant combinations, and concentrates and diesel fuels containing same |
US5562742A (en) * | 1991-05-13 | 1996-10-08 | The Lubrizol Corporation | Copper-containing organometallic complexes and concentrates and diesel fuels containing same |
US5350429A (en) * | 1992-03-19 | 1994-09-27 | Basf Aktiengesellschaft | Diaminoalkanes, their preparation and fuels and lubricants containing the diaminoalkanes |
USH1305H (en) | 1992-07-09 | 1994-05-03 | Townsend Daniel J | Reformulated gasolines and methods of producing reformulated gasolines |
US5837867A (en) * | 1993-03-30 | 1998-11-17 | Shell Oil Company | Fuel compositions |
US5352251A (en) * | 1993-03-30 | 1994-10-04 | Shell Oil Company | Fuel compositions |
US5507843A (en) * | 1994-09-19 | 1996-04-16 | Shell Oil Company | Fuel compositions |
US5693107A (en) * | 1994-09-19 | 1997-12-02 | Shell Oil Company | Fuel compositions comprising hydantoin-containing polyether alcohol additives |
US5489315A (en) * | 1994-09-19 | 1996-02-06 | Shell Oil Company | Fuel compositions comprising hydantoin-containing polyether alcohol additives |
US5458661A (en) * | 1994-09-19 | 1995-10-17 | Shell Oil Company | Fuel compositions |
US5855630A (en) * | 1994-09-19 | 1999-01-05 | Shell Oil Company | Fuel compositions |
US5458660A (en) * | 1994-09-19 | 1995-10-17 | Shell Oil Company | Fuel compositions |
US6312481B1 (en) | 1994-09-22 | 2001-11-06 | Shell Oil Company | Fuel compositions |
US5559270A (en) * | 1994-12-15 | 1996-09-24 | Petrokleen, Ltd. | Method of synthesizing pure additives and the improved compositions thereby produced |
US5962738A (en) * | 1994-12-15 | 1999-10-05 | Petrokleen, Ltd. | Polymeric-amine fuel and lubricant additive |
US6261327B1 (en) | 1997-05-29 | 2001-07-17 | Shell Oil Company | Additive concentrates for rapidly reducing octane requirement |
US6210452B1 (en) | 2000-02-08 | 2001-04-03 | Hhntsman Petrochemical Corporation | Fuel additives |
US20030173250A1 (en) * | 2002-03-13 | 2003-09-18 | Blackwood David Macdonald | Unleaded gasoline compositions |
Also Published As
Publication number | Publication date |
---|---|
GB1309907A (en) | 1973-03-14 |
CA917919A (en) | 1973-01-02 |
ZA704424B (en) | 1971-03-31 |
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