EP0279090B1 - Gasoline compositions containing hexavalent molybdenum - Google Patents
Gasoline compositions containing hexavalent molybdenum Download PDFInfo
- Publication number
- EP0279090B1 EP0279090B1 EP87301344A EP87301344A EP0279090B1 EP 0279090 B1 EP0279090 B1 EP 0279090B1 EP 87301344 A EP87301344 A EP 87301344A EP 87301344 A EP87301344 A EP 87301344A EP 0279090 B1 EP0279090 B1 EP 0279090B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- molybdenum
- gasoline
- fuel composition
- compound
- octane requirement
- 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
Links
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims description 99
- 239000000203 mixture Substances 0.000 title claims description 80
- 229910052750 molybdenum Inorganic materials 0.000 title claims description 49
- 239000011733 molybdenum Substances 0.000 title claims description 48
- -1 molybdenum(VI) compound Chemical class 0.000 claims abstract description 101
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 95
- 238000002485 combustion reaction Methods 0.000 claims abstract description 56
- 239000000446 fuel Substances 0.000 claims description 93
- 229930195733 hydrocarbon Natural products 0.000 claims description 51
- 150000002430 hydrocarbons Chemical class 0.000 claims description 51
- 239000004215 Carbon black (E152) Substances 0.000 claims description 47
- 239000007788 liquid Substances 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 238000009835 boiling Methods 0.000 claims description 11
- 150000002739 metals Chemical class 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 125000005608 naphthenic acid group Chemical class 0.000 claims description 6
- 150000004985 diamines Chemical class 0.000 claims description 5
- 239000003446 ligand Substances 0.000 claims description 5
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 description 22
- 239000005078 molybdenum compound Substances 0.000 description 22
- 150000002752 molybdenum compounds Chemical class 0.000 description 22
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 15
- 239000006079 antiknock agent Substances 0.000 description 13
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical class O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000000654 additive Substances 0.000 description 10
- 239000010687 lubricating oil Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 238000010348 incorporation Methods 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 125000001183 hydrocarbyl group Chemical group 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 235000019198 oils Nutrition 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- 150000002989 phenols Chemical class 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 6
- 150000002611 lead compounds Chemical class 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 6
- 230000001629 suppression Effects 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 150000002751 molybdenum Chemical class 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- YRAJNWYBUCUFBD-UHFFFAOYSA-N 2,2,6,6-tetramethylheptane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(C)(C)C YRAJNWYBUCUFBD-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 239000013522 chelant Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 150000003460 sulfonic acids Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 229920002367 Polyisobutene Polymers 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 230000029936 alkylation Effects 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000002199 base oil Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002826 coolant Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000003254 gasoline additive Substances 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 150000002697 manganese compounds Chemical class 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 125000005474 octanoate group Chemical group 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical class CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- DDHUNHGZUHZNKB-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diamine Chemical compound NCC(C)(C)CN DDHUNHGZUHZNKB-UHFFFAOYSA-N 0.000 description 1
- JKTAIYGNOFSMCE-UHFFFAOYSA-N 2,3-di(nonyl)phenol Chemical class CCCCCCCCCC1=CC=CC(O)=C1CCCCCCCCC JKTAIYGNOFSMCE-UHFFFAOYSA-N 0.000 description 1
- BPRYUXCVCCNUFE-UHFFFAOYSA-N 2,4,6-trimethylphenol Chemical compound CC1=CC(C)=C(O)C(C)=C1 BPRYUXCVCCNUFE-UHFFFAOYSA-N 0.000 description 1
- SBMPIZWDWDNTJU-UHFFFAOYSA-N 2,4-didodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=C(O)C(CCCCCCCCCCCC)=C1 SBMPIZWDWDNTJU-UHFFFAOYSA-N 0.000 description 1
- CEGGECULKVTYMM-UHFFFAOYSA-N 2,6-dimethylheptane-3,5-dione Chemical compound CC(C)C(=O)CC(=O)C(C)C CEGGECULKVTYMM-UHFFFAOYSA-N 0.000 description 1
- GJMUCDMIIVSROW-UHFFFAOYSA-N 2,8-dimethylnonane-4,6-dione Chemical compound CC(C)CC(=O)CC(=O)CC(C)C GJMUCDMIIVSROW-UHFFFAOYSA-N 0.000 description 1
- JUBNMICNBGWPRR-UHFFFAOYSA-J 2-(3-methylcyclopentyl)acetate molybdenum(4+) Chemical compound CC1CC(CC1)CC(=O)[O-].[Mo+4].CC1CC(CC1)CC(=O)[O-].CC1CC(CC1)CC(=O)[O-].CC1CC(CC1)CC(=O)[O-] JUBNMICNBGWPRR-UHFFFAOYSA-J 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- KZELEKCSKLUYAS-UHFFFAOYSA-J 2-cyclopentylacetate molybdenum(4+) Chemical compound C1(CCCC1)CC(=O)[O-].[Mo+4].C1(CCCC1)CC(=O)[O-].C1(CCCC1)CC(=O)[O-].C1(CCCC1)CC(=O)[O-] KZELEKCSKLUYAS-UHFFFAOYSA-J 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- YKJSOAKPHMIDLP-UHFFFAOYSA-J 2-ethylhexanoate;molybdenum(4+) Chemical compound [Mo+4].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O YKJSOAKPHMIDLP-UHFFFAOYSA-J 0.000 description 1
- BDXGMDGYOIWKIF-UHFFFAOYSA-N 2-methylpropane-1,3-diamine Chemical compound NCC(C)CN BDXGMDGYOIWKIF-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- JZBVVNOPMZSANQ-UHFFFAOYSA-N 3,3-dimethylbutan-2-one Chemical compound CC(=O)C(C)(C)C.CC(=O)C(C)(C)C JZBVVNOPMZSANQ-UHFFFAOYSA-N 0.000 description 1
- UUMLGOUCUSYIAU-UHFFFAOYSA-N 3-dodecyl-6-hydroxycyclohexa-2,4-dien-1-one Chemical compound O=C1C(C=CC(=C1)CCCCCCCCCCCC)O UUMLGOUCUSYIAU-UHFFFAOYSA-N 0.000 description 1
- VTEUOJYHOLBKID-UHFFFAOYSA-J 3-dodecylcyclohexane-1-carboxylate molybdenum(4+) Chemical compound C(CCCCCCCCCCC)C1CC(CCC1)C(=O)[O-].[Mo+4].C(CCCCCCCCCCC)C1CC(CCC1)C(=O)[O-].C(CCCCCCCCCCC)C1CC(CCC1)C(=O)[O-].C(CCCCCCCCCCC)C1CC(CCC1)C(=O)[O-] VTEUOJYHOLBKID-UHFFFAOYSA-J 0.000 description 1
- GSOHKPVFCOWKPU-UHFFFAOYSA-N 3-methylpentane-2,4-dione Chemical compound CC(=O)C(C)C(C)=O GSOHKPVFCOWKPU-UHFFFAOYSA-N 0.000 description 1
- BPIHCIRSGQKCLT-UHFFFAOYSA-N 3-propan-2-ylpentane-2,4-dione Chemical compound CC(C)C(C(C)=O)C(C)=O BPIHCIRSGQKCLT-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical class C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- OKUMHINSMZOUIZ-UHFFFAOYSA-N 4-(2-ethylhexyl)phenol Chemical compound CCCCC(CC)CC1=CC=C(O)C=C1 OKUMHINSMZOUIZ-UHFFFAOYSA-N 0.000 description 1
- KJWMCPYEODZESQ-UHFFFAOYSA-N 4-Dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=C(O)C=C1 KJWMCPYEODZESQ-UHFFFAOYSA-N 0.000 description 1
- FIJLPSJMPXGRJL-UHFFFAOYSA-N 4-Methylheptane-3,5-dione Chemical compound CCC(=O)C(C)C(=O)CC FIJLPSJMPXGRJL-UHFFFAOYSA-N 0.000 description 1
- NKXZDXDSOFEDSF-KTKRTIGZSA-N 4-[(z)-octadec-9-enyl]phenol Chemical compound CCCCCCCC\C=C/CCCCCCCCC1=CC=C(O)C=C1 NKXZDXDSOFEDSF-KTKRTIGZSA-N 0.000 description 1
- QIZUBPHXHVWGHD-UHFFFAOYSA-N 4-octadecylphenol Chemical compound CCCCCCCCCCCCCCCCCCC1=CC=C(O)C=C1 QIZUBPHXHVWGHD-UHFFFAOYSA-N 0.000 description 1
- KHZGUWAFFHXZLC-UHFFFAOYSA-N 5-methylhexane-2,4-dione Chemical compound CC(C)C(=O)CC(C)=O KHZGUWAFFHXZLC-UHFFFAOYSA-N 0.000 description 1
- IGMOYJSFRIASIE-UHFFFAOYSA-N 6-Methylheptan-2,4-dione Chemical compound CC(C)CC(=O)CC(C)=O IGMOYJSFRIASIE-UHFFFAOYSA-N 0.000 description 1
- PKAVSIHPPVFDHU-UHFFFAOYSA-N 7-methyloctane-3,5-dione Chemical compound CCC(=O)CC(=O)CC(C)C PKAVSIHPPVFDHU-UHFFFAOYSA-N 0.000 description 1
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BLVIWFXPWAYTAB-UHFFFAOYSA-J C(CCCC)(=O)[O-].[Mo+4].C(CCCC)(=O)[O-].C(CCCC)(=O)[O-].C(CCCC)(=O)[O-] Chemical compound C(CCCC)(=O)[O-].[Mo+4].C(CCCC)(=O)[O-].C(CCCC)(=O)[O-].C(CCCC)(=O)[O-] BLVIWFXPWAYTAB-UHFFFAOYSA-J 0.000 description 1
- PYJBHIKDWKTOGU-UHFFFAOYSA-J C(CCCCCCCCCCC)(=O)[O-].[Mo+4].C(CCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCC)(=O)[O-] Chemical compound C(CCCCCCCCCCC)(=O)[O-].[Mo+4].C(CCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCC)(=O)[O-] PYJBHIKDWKTOGU-UHFFFAOYSA-J 0.000 description 1
- RURHXWFFEQJVTM-UHFFFAOYSA-J C(CCCCCCCCCCC)C1=CC=C(C(=O)[O-])C=C1.[Mo+4].C(CCCCCCCCCCC)C1=CC=C(C(=O)[O-])C=C1.C(CCCCCCCCCCC)C1=CC=C(C(=O)[O-])C=C1.C(CCCCCCCCCCC)C1=CC=C(C(=O)[O-])C=C1 Chemical compound C(CCCCCCCCCCC)C1=CC=C(C(=O)[O-])C=C1.[Mo+4].C(CCCCCCCCCCC)C1=CC=C(C(=O)[O-])C=C1.C(CCCCCCCCCCC)C1=CC=C(C(=O)[O-])C=C1.C(CCCCCCCCCCC)C1=CC=C(C(=O)[O-])C=C1 RURHXWFFEQJVTM-UHFFFAOYSA-J 0.000 description 1
- CLLMBHCKCCOJQC-UHFFFAOYSA-J C(CCCCCCCCCCCCC)(=O)[O-].[Mo+4].C(CCCCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCCCC)(=O)[O-] Chemical compound C(CCCCCCCCCCCCC)(=O)[O-].[Mo+4].C(CCCCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCCCC)(=O)[O-] CLLMBHCKCCOJQC-UHFFFAOYSA-J 0.000 description 1
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Classifications
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- 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
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/10—Use of additives to fuels or fires for particular purposes for improving the octane number
-
- 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
- C10L1/18—Organic compounds containing oxygen
- C10L1/1814—Chelates
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- 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
- C10L1/18—Organic compounds containing oxygen
- C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
- C10L1/1828—Salts thereof
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- 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
- C10L1/18—Organic compounds containing oxygen
- C10L1/188—Carboxylic acids; metal salts thereof
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- 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
- C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
- C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
- C10L1/2437—Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters
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- 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
- C10L1/26—Organic compounds containing phosphorus
- C10L1/2633—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
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- 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
- C10L1/30—Organic compounds compounds not mentioned before (complexes)
- C10L1/305—Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond)
Definitions
- One aspect of the invention is an unleaded gasoline, used in "clean,” new engines, containing a low concentration of a hydrocarbon soluble molybdenum (VI) compound comprising a major portion of gasoline and about 0.1 to about 20 parts of the molybdenum (VI) compound per one million parts of gasoline.
- a molybdenum (VI) compound can be used in an amount which is sufficient to provide from about 0.01 to about 10 parts of molybdenum, calculated as the metal, per million parts of gasoline.
- a further aspect of the invention is a concentrate of a hydrocarbon soluble molybdenum (VI) compound containing about 0.1 to about 50 wt% of the compound in a suitable diluent which can be dissolved in proper proportion in gasoline or lubricating oil to provide about 0.1 to about 10,000 parts of molybdenum (VI) compound per one million parts of gasoline or about 0.001 to about 5 wt% of molybdenbum (VI) compound in a lubricating oil.
- a hydrocarbon soluble molybdenum (VI) compound containing about 0.1 to about 50 wt% of the compound in a suitable diluent which can be dissolved in proper proportion in gasoline or lubricating oil to provide about 0.1 to about 10,000 parts of molybdenum (VI) compound per one million parts of gasoline or about 0.001 to about 5 wt% of molybdenbum (VI) compound in a lubricating oil.
- any hydrocarbon soluble molybdenum(VI) compound which is stable in hydrocarbon or petroleum storage or distribution facilities can be used in gasoline in accordance with this invention.
- the molybdenum(VI) or compound is selected from the group consisting of molybdenum(VI) sulfonates, molybdenum(VI) diamine complexes, amine salts of molybdic acid and isopoly molybdic acid, and molybdenum(VI) compounds which are free of nitrogen, sulfur and phosphorus.
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Abstract
Description
- This invention relates to improved unleaded gasoline compositions. More particularly, the invention relates to the incorporation of molybdenum(VI) compounds into an unleaded gasoline for the purpose of reducing elevated steady state octane requirement and suppressing octane requirement increase in spark ignition internal combustion engines.
- A great number of gasoline additives, including antiknock agents, deposit reducing agents, demulsifiers, etc., have been developed in recent years. A commercially important antiknock agent, tetraalkyl lead, has, until recently, been universally used to prevent engine knock by increasing the octane number of gasoline. However, with increased sensitivity to lead in the environment and with the use of catalytic converters that can be poisoned by lead, broad restrictions have been placed on the use of lead in gasoline. In the absence of lead, greater amounts of expensive, high octane blending stock must be used to produce gasoline having sufficient octane for current production automobiles.
- Along with the increased cost of production of unleaded gasoline, a particularly harmful problem has arisen. Engines operating on unleaded gasoline commonly experience increasing incidence and severity of knock as they age. A new or "clean" engine can operate efficiently and without knock using a gasoline having a research octane number of about 85. The same engine with about 8,000-12,000 accumulated miles can often require a gasoline having an octane number about 95-100 or higher. This increase in the octane number required to prevent knock is called octane requirement increase (ORI).
- ORI is believed to be one result of thermally insulating combustion chamber deposits formed from gasoline contaminants and from the incomplete combustion of gasoline and lubricating oil. Initially the rate of deposit formation is substantially greater than the rate of disintegration, and the deposits rapidly build. As the deposits thicken, the rate of disintegration approaches and eventually equals the rate of formation. At this point, the deposits reach a steady state thickness. Knock in the engine appears to increase in incidence and severity as the deposit builds and reaches a constant or steady state elevated rate of incidence and severity corresponding to the steady state thickness of the deposit. At this point the engine commonly has an elevated steady state octane requirement which can be 2 to 15 research octane numbers greater than the octane requirement when new.
- While we do not wish to be limited to a theory of ORI, we believe that the combustion chamber deposits have the substantial ability to prevent transfer of thermal energy from the combustion chamber into engine coolant, causing accumulation of thermal energy in the deposits and in the combustion chamber. When a spark ignites the air/fuel mixture in the combustion chamber, a flame front is initiated and combustion rapidly and smoothly progresses from the spark plug to the "end-gas region" opposite to the spark plug. The high pressure flame front rapidly compresses the unburned air/fuel mixture which is at a relatively lower pressure in the end-gas region as the front progresses through the chamber. Commonly, the combustion progresses through the combustion chamber, and knock is not heard. However, if the temperature of the combustion chamber and the air/fuel mixture has been substantially increased by the insulating properties of the deposits, the rapid compression of the air/fuel mixture in the end-gas region causes an immediate autodetonation which is different than normal progressive combustion. This autodetonation causes the "knocking" or "pinging" sound, can reduce operating efficiency and can cause engine damage. See J. D. Benson, "Some Factors Which Affect Octane Requirement Increase," SAE Paper 750933, Detroit, Michigan, October 1975, for a detailed treatment of ORI.
- ORI can readily be remedied with leaded gasoline by increasing the lead concentration. In unleaded fuels, a greater amount of high octane blending stock must be used to increase the octane. However, high octane blending stock commonly contains aromatic constituents that are more likely to leave thermally insulating deposits and increase ORI.
- With the suppression of ORI, more gasoline with a lower octane number could be produced per barrel of crude oil at lower cost. Since the production of high octane gasoline consumes more energy than the production of lower octane gasoline, refining operations would become more energy efficient. Further, in the absence of ORI, engine manufacturers could build more fuel efficient engines by increasing compression and adjusting spark timing. Such engines would perform satisfactorily with a fuel having the same or lower octane as is currently available.
- In this application, octane requirement increase shall mean the gradual increase in octane requirement observed as an engine ages. Elevated steady state octane requirement shall mean the octane requirement of an engine with combustion chamber deposits that have reached a steady state both in thickness and in resistance to thermal energy flow.
- The incorporation of certain specific molybdenum compounds into gasoline has been suggested for the purpose of providing a composition having improved lubricating and antiwear properties. U.S. Patent Nos. 4,164,473; 4,176,073; and 4,176,074 disclose the use of molybdenum complexes of hydroxy amines, molybdenum complexes of lactone oxazoline dispersants, and molybdenum complexes of oxazoline dispersants respectively for this purpose. Similarly, U.S. Patent Nos. 4,192,757 and 4,201,683 disclose, for this purpose, the use of molybdenum complexes which are obtained by reaction of a hydrocarbyl substituted thio-bis-phenol with a molybdenum compound in the presence of an amine in an alkyl substituted phenol or alkanol solvent, respectively. In addition, U.S. Patent No. 3,994,697 teaches that a solid pellet comprising various metals in combination with molybdenum disulfide can be placed in the fuel reservoir of an internal combustion engine where it slowly disintegrates to produce extremely minute particles which are dispersed in the fuel and are delivered to the fuel-contacting parts of the engine to deposit a lubricant film thereon.
- U.S. Patent Nos. 3,615,293 and 3,755,195 disclose the incorporation of various organic molybdenum compounds into a gasoline fuel which contains an organomanganese antiknock agent. These patents teach that the molybdenum compounds are effective in reducing spark plug fouling by gasoline fuels which contain organomanganese antiknock agents. It is further disclosed that suitable organic molybdenum compounds include molybdenum salts and chelates. However, these references fail to suggest the incorporation of a molybdenum compound into gasoline for any purpose in the absence of an organomanganese antiknock agent.
- U.S. Patent No. 3,317,571 discloses the preparation of organomolybdenum compounds wherein one or more molecules containing an amide or thioamide linkage are bonded to the molybdenum atom through a sulfur or oxygen linkage and which is stabilized by additional covalent bonding to a plurality of carbonyl groups. This patent discloses that such compounds can be used in gasoline, either alone or in combination with lead alkyls, as antiknock agents. It fails, however, to either teach or suggest the use of a molybdenum(VI) compound for any purpose.
- U.S. Patent No. 3,272,606 discloses that small amounts of a covalent molybdenum polycarbonyl compound can be used in gasoline in combination with an organolead antiknock agent to enhance the antiknock properties of the organolead antiknock agent. However, this reference fails to suggest the incorporation of a molybdenum compound into gasoline for any purpose in the absence of an organolead antiknock agent.
- U.S. Patent No. 2,086,775 is directed to the incorporation of various organometallic compounds into a liquid fuel for an internal combustion engine. Suitable organometallic compounds are those of cobalt, nickel, manganese, iron, copper, uranium, molybdenum, vanadium, zirconium, beryllium, platinum, palladium, thorium, chromium, aluminum, and the rare earth metals. In addition, the liquid fuel may also contain an organolead antiknock agent. It is disclosed that use in an internal combustion engine of a fuel containing small amounts of these organometallic compounds results in the formation of a catalytic deposit within the combustion chambers of the engine which is effective for the elimination of knock and the improvement of combustion within the engine. However, this patent offers no guidance for selecting a molybdenum(VI) compound for use in a gasoline composition which is substantially free of other metals for the purpose of suppressing octane requirement increase and reducing elevated steady state octane requirement in spark ignition internal combustion engines.
- U.S. Patent No. 3,155,620 is directed to the use of cycloheptatriene transition metal coordination compounds of the Group VIB metals as additives for liquid hydrocarbon compositions. This patent teaches that such additives can be used to increase the octane of liquid fuels and to provide improved lubricating properties when incorporated into lubricating oil compositions. It is further disclosed that these coordination compounds can be used in combination with antiknock agents such as organolead compounds. However, this patent fails to either teach or suggest the use of a molybdenum(VI) compound for any purpose.
- U.S. Patent No. 3,440,028 is directed to the incorporation of a metal halide hydrocarbyl orthophosphate additive into leaded gasoline compositions for the purpose of suppressing the tendency of the lead to increase undesirable surface ignition within the combustion chambers of an engine. The metal of the additive can be selected from the group consisting of manganese and metals of Groups IB, IIA, IIB, IVA, VIB and VIII of the Periodic Table. Similarly, U.S. Patent No. 3,240,576 discloses that the addition to leaded gasoline of a gasoline soluble organomolybdenum compound will provide a substantial reduction of surface ignition in the combustion chambers of a spark ignition internal combustion engine. These patents do not, however, suggest the addition of a molybdenum compound to unleaded gasoline for any purpose.
- U.S. Patent No. 3,401,184 is directed to a method for the preparation of metal organo orthophosphates wherein the metal can be selected from Groups II, IV, VI and VIII of the Periodic Table. It is disclosed that these compounds have utility as gasoline additives and that when so used they impart rust inhibition, surface ignition suppression, carburetor detergency, carburetor icing alleviation and reduction in octane requirement increase to the gasoline composition. In addition, U.S. Patent No. 3,282,838 discloses the use of amine salts of chromic or molybdic acid as corrosion inhibitors in petroleum hydrocarbons such as gasoline. These amine salts contain either a chromic or molybdic ion of +6 valence and are used at a concentration level between about 0.005 and 5 weight percent.
- Finally, U.S. Patent No. 3,003,859 discloses the incorporation into a liquid hydrocarbon, such as gasoline, of about 0.005 to about 5 percent by weight of a metal-organic material which is obtained by heating a normally-solid metallic chelate compound formed from a beta-keto ester to a temperature above its melting point. It is further disclosed that these metal chelates can be formed from metallic elements of the Periodic Table comprising the Groups IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIB, VIIB and VIII including the lanthanide and actinide series of rare earth elements. This patent, however, fails to offer any guidance for selecting a molybdenum(VI) compound for the purpose of suppressing octane requirement increase and reducing elevated steady state octane requirement in spark ignition internal combustion engines.
- The present invention is directed to the discovery that the incorporation of small amounts of a gasoline soluble molybdenum(VI) compound into unleaded gasoline affords a fuel composition which is effective in reducing elevated steady state octane requirement and suppressing octane requirement increase in spark ignition internal combustion engines.
- According to one aspect of the present invention there is provided a gasoline fuel composition comprising a major proportion of a liquid hydrocarbon fuel of gasoline boiling range in combination with a molybdenum (VI) compound which is soluble in said hydrocarbon fuel, wherein the amount of said molybdenum (VI) compound is sufficient to provide from 0.01 to 1000 parts of molybdenum per one million parts of hydrocarbon fuel, said fuel composition is substantially free of metals other than molybdenum, and said molybdenum (VI) compound is selected from molybdenum (VI) sulfonates, molybdenum (VI) diamine complexes wherein the diamine ligand is of the formula R⁴R⁵N-(CR⁴R⁵)n-NR⁴R⁵ where n is an integer from 1 to 20 and each R⁴ and R⁵ is independently selected from hydrogen and alkyl of 1 to 20 carbon atoms, and molybdenum (VI) compounds which are free of nitrogen, sulfur, and phosphorus.
- The invention further provides a method for reducing elevated steady start octane requirements and/or suppressing octane requirement increase in spark internal combustion engines which comprises operating the engine with a gasoline fuel composition as defined above.
- One embodiment of the invention is a gasoline fuel composition comprising a major proportion of a liquid hydrocarbon fuel of gasoline boiling range in combination with a molybdenum(VI) compound which is soluble in said hydrocarbon fuel, wherein the amount of said molybdenum (VI) compound is from about 0.1 to about 20.0 parts per one million parts of hydrocarbon fuel, said fuel composition is substantially free of metals other than molybdenum, and said molybdenum(VI) compound is selected from the group consisting of molybdenum (VI) sulfonates, molybdenum (VI) diamine complexes, amine salts of molybdic acid and isopolymolybdic acid, and molybdenum(VI) compounds which are free of nitrogen, sulfur and phosphorus.
- Another embodiment of the invention is a gasoline fuel composition comprising a major proportion of a liquid hydrocarbon fuel of gasoline boiling range in combination with a molybdenum(VI) compound which is soluble in said liquid hydrocarbon fuel, wherein the amount of said molybdenum(VI) compound is effective to suppress octane requirement increase in a spark ignition internal combustion engine, said fuel composition is substantially free of metals other than molybdenum, and said molybdenum(VI) compound is selected from the group consisting of molybdenum(VI) sulfonates, molybdenum(VI) diamine complexes, amine salts of isopoly molybdic acid, and molybdenum(VI) compounds which are free of nitrogen, sulfur and phosphorus.
- Another embodiment of the invention is a gasoline fuel composition comprising a major proportion of a liquid hydrocarbon fuel of gasoline boiling range in combination with a molybdenum(VI) compound which is soluble in said liquid hydrocarbon fuel, wherein the amount of said molybdenum (VI) compound is effective to reduce elevated steady state octane requirement in a spark ignition internal combustion engine, said fuel composition is substantially free of metals other than molybdenum, and said molybdenum(VI) compound is selected from the group consisting of molybdenum(VI) sulfonates, molybdenum(VI) diamine complexes, amine salts of isopoly molybdic acid, and molybdenum(VI) compounds which are free of nitrogen, sulfur and phosphorus.
- A further embodiment of the invention is a method for reducing elevated steady state octane requirement in a spark ignition internal combustion engine and maintaining the resulting reduced steady state octane requirement which comprises operating said engine on a first gasoline fuel composition until a reduced steady state octane requirement is achieved and maintaining said reduced steady state octane requirement by operating the engine on a second gasoline fuel composition, wherein said first fuel comprises a major proportion of a liquid hydrocarbon fuel of gasoline boiling range in combination with an amount of a soluble molybdenum(VI) compound which is sufficient to provide from about 10 to about 1000 parts of molybdenum per million parts of liquid hydrocarbon fuel, wherein said second fuel comprises a major proportion of a liquid hydrocarbon fuel of gasoline boiling range in combination with an amount of a soluble molybdenum(VI) compound which is sufficient to provide from about 0.01 to about 10 parts of molybdenum per million parts of liquid hydrocarbon fuel, and wherein both of said first and second fuels are substantially free of lead.
- A further embodiment of the invention is a method for reducing elevated steady state octane requirement and/or suppressing octane requirement increase in a spark ignition internal combustion engine which comprises operating said engine with a gasoline fuel composition comprising a major proportion of a liquid hydrocarbon fuel of gasoline boiling range in combination with a molybdenum(VI) compound which is soluble in said liquid hydrocarbon fuel, wherein the amount of said molybdenum (VI) compound is effective to reduce elevated steady state octane requirement and/or suppress octane requirement increase in said engine, said fuel composition is substantially free of metals other than molybdenum, and said molybdenum (VI) compound is selected from the group consisting of molybdenum (VI) sulfonates, molybdenum (VI) diamine complexes, amine salts of molybdic acid and isopoly molybdic acid, and molybdenum (VI) compounds which are free of nitrogen, sulfur and phosphorus.
- A still further embodiment of the invention is a method for reducing elevated steady state octane requirement in a spark ignition internal combustion engine having an increased octane requirement of about 2 to about 7 units after operation with gasoline substantially free of lead and molybdenum which comprises operating said engine with a gasoline fuel composition comprising a major proportion of a liquid hydrocarbon fuel of gasoline boiling range in combination with a molybdenum (VI) compound which is soluble in said hydrocarbon fuel, wherein the amount of said molybdenum (VI) compound is sufficient to provide from about 10 to about 1000 parts of molybdenum per million parts of said hydrocarbon fuel, and the amount of said gasoline fuel composition is effective to reduce said elevated steady state octane requirement by at least about 20%.
- The general object of this invention is to sup-press ORI and reduce elevated steady state octane requirement arising in internal combustion engines using unleaded fuels. Another object is to modify the thermal conductivity of combustion chamber deposits to increase heat conduction and thereby reducing elevated steady state octane requirement and suppressing ORI. Still another object of the invention is to promote the formation of thermally conductive deposits in internal combustion engines. A further object of the invention is to provide low octane gasoline that can be used in an engine without harmful knock arising as the engine ages. A still further object of the invention is to increase the efficiency of gasoline production by producing more low octane gasoline from crude oil.
- We have discovered that the octane requirement increase and the elevated steady state octane requirement caused by combustion chamber deposits in internal combustion engines can be prevented or reduced by operation of an internal combustion engine wherein the combustion processes in the combustion chamber are performed in the presence of a hexavalent molybdenum, molybdenum(VI) or molybdenum +6 compound. The hexavalent molybdenum compound can be provided to the combustion chamber by a gasoline substantially free of lead compounds containing a gasoline soluble hexavalent molybdenum compound, or by a lubricating oil containing the molybdenum compound which is transported into the combustion chamber during the operation of the engine. We have further discovered certain preferred hydrocarbon soluble compounds containing molybdenum in the +6 oxidation state that are effective in preventing octane requirement increase and are effective in reducing elevated steady state octane requirement.
- The generic use of molybdenum compounds of any oxidation state to prevent octane requirement increase and reduce elevated steady state octane requirement has been investigated by us previously. However, now we have found that only molybdenum(VI) compounds serve to efficiently afford these results. Apparently, only molybdenum(VI) compounds efficiently alter the thermal energy transfer characteristics of combustion chamber deposits so that heat can be rapidly conducted from combustion chamber to engine coolant. Since the modified deposits no longer impede efficient removal of heat from the combustion chamber, the gasoline is ignited solely by the spark and the fuel is burned uniformly in the combustion chamber, efficiently transmitting combustion energy to the road in the absence of knock, ping, loss in efficiency or mechanical damage.
- Although the subject invention is not to be so limited, it is believed that a greater thermal conductivity per unit mass of combustion chamber deposit results from higher levels of organic oxygen and that such highly oxidized deposits are generated efficiently in the presence of molybdenum only when the molybdenum is in the +6 oxidation state. In principle, molybdenum of lower oxidation state could be oxidized to the +6 oxidation state within an engine during the combustion of fuel. However, the conditions under which gasoline is combusted in a spark ignition internal combustion engine appear to be unsuitable to render such a process of significance. Among other possible factors, it is believed that the fuel combustion cycles are too short to effect such a modification of molybdenum oxidation state.
- Briefly, the improved gasoline compositions of this invention can be prepared by combining with a major portion of gasoline substantially free of lead compounds an effective octane requirement increase suppressing or an effective steady state octane requirement reducing amount of a gasoline soluble compound containing molybdenum(VI), hexavalent molybdenum, or molybdenum +6. The improved lubricants of the invention can be prepared by combining with a lubricant an effective amount of a hydrocarbon soluble molybdenum(VI) compound.
- One aspect of the invention is an unleaded gasoline, used in "clean," new engines, containing a low concentration of a hydrocarbon soluble molybdenum (VI) compound comprising a major portion of gasoline and about 0.1 to about 20 parts of the molybdenum (VI) compound per one million parts of gasoline. Alternatively, such a molybdenum (VI) compound can be used in an amount which is sufficient to provide from about 0.01 to about 10 parts of molybdenum, calculated as the metal, per million parts of gasoline.
- Another aspect of the invention is a gasoline, for use in "dirty" engines that have reached an elevated steady state octane requirement caused by deposits in the combustion chamber, to substantially reduce the elevated steady state octane requirement. This composition, which modifies the existing deposits and reduces the elevated steady state octane requirement, comprises a major portion of gasoline and about 20 to about 10,000 parts of a hydrocarbon soluble molybdenum (VI) compound per one million parts of gasoline. Alternatively, such a molybdenum (VI) compound can be used in an amount which is sufficient to provide from about 10 to about 1000 parts of molybdenum, calculated as the metal, per million parts of gasoline.
- A further aspect of the invention is a concentrate of a hydrocarbon soluble molybdenum (VI) compound containing about 0.1 to about 50 wt% of the compound in a suitable diluent which can be dissolved in proper proportion in gasoline or lubricating oil to provide about 0.1 to about 10,000 parts of molybdenum (VI) compound per one million parts of gasoline or about 0.001 to about 5 wt% of molybdenbum (VI) compound in a lubricating oil.
- A still further aspect of the invention is a lubricating oil containing a hydrocarbon soluble molybdenum compound which when used to lubricate an engine provides to the combustion chamber a substantial amount of molybdenum(VI), by oxidation of a molybdenum compound or by other means, that can suppress ORI or reduce elevated steady state octane requirement. Commonly, lubricating oils contain about 0.001 to about 5 wt%; preferably about 0.01 to about 2 wt%; and most preferably, to reduce molybdenum consumption and provide maximum benefit, about 0.01 to about 1 wt% of molybdenum(VI) compound.
- Significant amounts of lead and manganese compounds have been widely used in gasoline as antiknock agents. Lead compounds, particularly tetraalkyl lead compounds, have been most extensively used, whereas manganese compounds have been primarily used to enhance the antiknock properties of lead compounds. However, the molybdenum(VI) containing gasoline compositions of this invention are preferably substantially free of lead, more preferably substantially free of both lead and manganese, and most preferably substantially free of metals other than molybdenum.
- Any hydrocarbon soluble molybdenum(VI) compound which is stable in hydrocarbon or petroleum storage or distribution facilities can be used in gasoline in accordance with this invention. Preferably, the molybdenum(VI) or compound is selected from the group consisting of molybdenum(VI) sulfonates, molybdenum(VI) diamine complexes, amine salts of molybdic acid and isopoly molybdic acid, and molybdenum(VI) compounds which are free of nitrogen, sulfur and phosphorus. More preferably, the molybdenum(VI) compound is selected from the group consisting of molybdenum(VI) sulfonates, molybdenum(VI) diamine complexes, amine salts of isopoly molybdic acid, molybdenum(VI) carboxylates, molybdenum(VI) salts of naphthenic acids, molybdenum(VI) phenates, molybdenum(VI) alkoxides, molybdenum(VI) aryloxides, and molybdenum(VI) beta-diketone complexes.
- Although phosphorus containing compounds of molybdenum(VI) can be used in the practice of this invention, they are ordinarily not preferred. This is a consequence of the fact that phosphorus is considered to be harmful to the catalytic converters which are currently employed to control the emission of hydrocarbons, carbon monoxide and nitrogen oxides from automotive engines.
- Molybdenum compounds useful to suppress ORI or reduce elevated steady state octane requirement include a broad variety of molybdenum(VI) compositions.
- A useful class of molybdenum(VI) compositions can be formed by the reaction of molybdenum in a variety of forms with a ligand. Examples of these ligands are acetylacetone, N-nitrosophenylhydroxylamine, dimethylglyoxime, ethylenediamine, ethylenediaminetetraacetic acid, nitrilotriacetic acid, 8-hydroxyquinoline, benzoylacetone, 2,4-pentanediene, beta-diketones, oxygen, halogens, Mannich products, phosphates, phosphine oxides, alkanol amines, sulfoxides formamides and other similar well known chelating agents.
- Another useful class of hydrocarbon soluble molybdenum compositions includes molybdenum(VI) beta-diketonates wherein the beta-diketone can be represented by the formula:
At least one proton on the carbon atom between the carbonyl groups is necessary for the formation of the molybdenum complex. The removal of this proton generates a beta-diketone anion which can chelate the metal ion present. R¹ and R² are hydrocarbyl groups of 1 to 50 carbon atoms and include primary, secondary and tertiary alkyl, alkenyl and aromatic groups. Preferred alkyl groups are methyl, ethyl, isopropyl, t-butyl, sec-amyl, 2-ethylhexyl, eicosyl, pentacontyl, having both normal chains and branched chains. R³ can be hydrogen or a hydrocarbyl group of 1 to 50 carbon atoms. Preferably, R³ is hydrogen or an alkyl group, for example methyl, ethyl, isopropyl, t-butyl, amyl, n-hexyl, pentacontyl, etc., having both normal and branched chain. Beta-diketones are well known in the art, some are available commercially, and all are readily prepared by methods well known in the art. - The commonly used compounds are prepared from beta-diketones wherein R¹ and R² represent alkyl groups of 1 to 20 carbon atoms and R³ represents hydrogen. More specifically, the preferred beta-diketones are 2,4-pentanedione, 3-methyl-2,4-pentanedione, 3-isopropyl-2,4-pentanedione, 2,4-hexanedione, 2-methyl-3,5-hexanedione, 4-methyl-3,5-heptanedione, 3,5-heptanedione, 2,6-dimethyl-3,5-heptanedione, 2-methyl-4,6-heptanedione, 2-methyl-4,6-octanedione, 2,8-dimethyl-4,6-nonanedione, and 2,2,6,6-tetramethyl-3,5-heptanedione. Other beta-diketone complexes are discussed by Morgan and Castell, J. Chem. Soc., 3252 (1928).
- Another useful class of hydrocarbon soluble molybdenum(VI) complexes that can be used in the practice of this invention is composed of molybdenum (VI) diamine complexes wherein the diamine ligand is represented by:
R⁴R⁵N-(CR⁴R⁵)n-NR⁴R⁵
wherein n is an integer from 1 to 20, preferably for reasons of stability of the molybdenum-amine product, n is 2 to 4. The R⁴ and R⁵ substituents can be independently hydrogen or alkyl of 1 to 20 carbon atoms and the amino groups can be independently primary, secondary or tertiary groups. Representative diamines include ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 2-methyl-1,3-diaminopropane, 2,2-dimethyl-1,3-diaminopropane, ortho-phenylenediamine and the corresponding 1 to 20 carbon alkyl-substituted diamines. - Another useful class of molybdenum(VI) compositions includes the neutralization products of molybdic acid including iso and heteropoly molybdic acid with an oil soluble base and the neutralization of an acid with a molybdenum base.
- Still another class of hydrocarbon soluble molybdenum(VI) compounds which can be used in accordance with this invention comprises molybdenum(VI) carboxylates such as those disclosed by Cavitt in U.S. Patent No. 3,595,891 and Hnizda in U.S. Patent No. 3,755,195 which are expressly incorporated by reference herein.
- Examples of suitable molybdenum(VI) carboxylates of this type are molybdenum pentanoate, molybdenum octanoate, molybdenum oleate, molybdenum linoleate, molybdenum adipate, molybdenum 2-ethylhexanoate, molybdenum benzoate, molybdenum tetradecanoate, molybdenum orthophthalate, molybdenum 4-dodecylbenzoate, molybdenum stearate, molybdenum laurate and the like. Molybdenum(VI) salts of mixtures of fatty acids obtained from natural products such as olive oil, tall oil, cottonseed oil, tallow, coconut oil and the like are also useful. Other molybdenum(VI) compounds of this type are the salts of alicyclic carboxylic acids. Specific examples of useful molybdenum(VI) salts of alicyclic carboxylic acids are molybdenum cyclopentanecarboxylate, molybdenum cyclopentylacetate, molybdenum 3-methylcyclopentylacetate, molybdenum camphoate, molybdenum cyclohexanecarboxylate, molybdenum 3-dodecylcyclohexanecarboxylate, molybdenum 2,6-dicyclohexylcyclohexanecarboxylate, molybdenum 2-cyclohexyl-4,6-dipentyl-4-methylcyclohexanecarboxylate, molybdenum 4-methylcyclohexanecarboxylate, molybdenum 2,2,6-trimethylcyclohexanecarboxylate and the like.
- Another class of hydrocarbon soluble molybdenum(VI) compositions which is useful in the practice of this invention are salts of the so-called naphthenic acids. The term "naphthenic acids" is applied to a mixture of carboxylic acids obtained from the alkali washes of petroleum. These acids are complex mixtures of normal and branched aliphatic acids, alkyl derivatives of cyclopentane- and cyclohexane-carboxylic acids and cyclopentyl and cyclohexyl derivates of aliphatic acids. The alicyclic carboxylic acids appear to be the major constituents of these mixtures. The composition of these naphthenic acids will vary depending on factors such as the source of petroleum, the refining procedure, etc. A more detailed discussion of these naphthenic acids is presented in "Chemical Technology of Petroleum," William A. Gruse and Donald R. Stevens, 3rd edition, pp. 65-67, 1960, McGraw-Hill Publishing Company, which is incorporated by reference.
- Molybdenum(VI) sulfonates wherein the sulfonate moiety has the general formula:
ArSO
can also be used in the practice of this invention. Sulfonic acid compounds useful to prepare molybdenum(VI) sulfonates can have the following general formula:
XSO₃-(Ar)n-Am
wherein A is hydrogen, an alkyl, or other hydrocarbyl group with hydroxy-, chloro-, or bromo-substituents; Ar is an aryl unit including benzene, naphthalene, etc.; m is an integer of 1 to 5; n is an integer of 0 to 5; and X is a halogen or hydrogen. A can be any substantially hydrocarbyl or substituted hydrocarbyl group which results in a hydrocarbon benzene sulfonic acid. A can be a hydrogen or a substantially aliphatic group with about 1 to 15 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, nonyl, decyl, dodecyl, pentadecyl and the like, with a molecular weight of about 120 and greater; an intermediate molecular weight alkyl group such as polyisobutylene or polypropylene polymers with 15 to 1,000 carbon atoms with a molecular weight of about 200 to 14,000; a high molecular weight hydrocarbyl such as polyolefin having a number average molecular weight in excess of 14,000; and others. A can be substituted with groups such as chlorine, bromine, or hydroxy groups. Also, Ar can have more than one substituent, for example, alkyl, hydroxyalkyl, or haloalkyl. - Other suitable oil soluble benzenesulfonic acids are the oil soluble, so-called petroleum sulfonic acids which are also commonly referred to as mahogany acids, having a molecular weight from about 350 to 750, aryl sulfonic acids, and alkaryl sulfonic acids. Examples of other suitable sulfonic acids are diparaffin wax-substituted phenolsulfonic acid, cetylchlorobenzenesulfonic acid, cetylphenoldisulfidesulfonic acid, cetylphenolmonosulfidesulfonic acid, etc. Other suitable oil-soluble sulfonic acids are well described in the art such as U.S. Patent Nos. 2,616,604; 2,626,207; 2,767,209; and others. The inexpensive, low molecular weight polypropylbenzenesulfonic acids having a molecular weight of about 200 to 1,200 are preferred.
- Another class of useful compounds is comprised of molybdenum(VI) phenates which are the reaction product of a molybdenum compound and a phenol compound. Examples of useful phenol compounds include:
4-methylphenol,
4-octadecylphenol,
4-oleylphenol,
4-(2-ethyl-n-hexyl)phenol,
2,6-dimethylphenol,
2,4,6-trimethylphenol,
o-chlorophenol,
2-dodecylphenol,
2,4-didodecylphenol,
p-nonylphenol,
2-tert-butylphenol,
4-dodecylphenol,
4-polyisobutylene substituted phenol,
and the like. - An especially useful type of a molybdenum(VI) phenate is that derived from a commercial mixture of alkylated phenols. Commercial alkylation of phenols generally is accomplished by treating the phenol with an olefin, or polyolefin or mixtures thereof in the presence of an alkylating agent. This commercial alkylation ordinarily produces a mixture of various alkyl phenols. For example, if a phenol is alkylated with a C₉ olefin, the product will contain monononylphenols, dinonylphenols, and trinonylphenols. Likewise, if a mixture of C₉, C₁₀, and C₁₈ olefins is used in the alkylation, a mixture of various C₉, C₁₀, and C₁₈ alkylated phenols is obtained.
- Still another class of hydrocarbon soluble molybdenum(VI) compounds includes alkoxides and aryloxides that can be prepared by reacting a molybdenum halide compound with an alcohol or a phenol, for example:
MoO₂Cl₂ + 2ROH = MoO₂(OR)₂ + 2HCl
- Preferred hydrocarbon soluble molybdenum(VI) compounds, for reasons of solubility in gasoline and lubricating oil and the substantial reduction of octane requirement increase and equilibrium octane requirement, include cis-dioxobis(dipivaloylmethanato)molybdenum(VI), MoO₂(THD)₂ and trans-dioxobis (dipivalolylmethanato)molybdenum(VI), molybdenum(VI) octoate and naphthanate, methylenebis(2-oxo-4-dodecylphenol)molybdenum(VI), dioxo-N,N'-(2-oxo-4-nonylbenzyl)ethylenediaminemolybdenum(VI) and molybdenum(VI) sulfonate.
- The foregoing compounds are intended to be exemplary of hydrocarbon soluble molybdenum(VI) compounds known and preferred at this time, and should not be used to unduly limit the scope of the invention.
- In somewhat greater detail, the improved gasolines and lubricants of this invention having the ability to prevent substantial octane requirement increase and to reduce high equilibrium octane requirement are produced by combining a gasoline or a lubricating oil with an amount of a hydrocarbon soluble hexavalent molybdenum compound which is effective to reduce elevated steady state octane requirement and/or suppress octane requirement increase.
- Varying threshold concentrations exist for each of many molybdenum(VI) compounds for reduction of the octane requirement increase. The threshold for each compound lies between about 0.01 and 3.0 parts of molybdenum per one million parts of gasoline. The threshold concentration varies due to the effect on the molybdenum of the radicals or groups attached. In new engines, the concentration of the molybdenum can range from 0.01 to about 10 parts of molybdenum per million parts of gasoline to prevent substantial increase in octane requirement. In "dirty" engines, i.e., engines that have been operated on unleaded gasoline not containing molybdenum compounds, which have reached a high steady state octane requirement, a gasoline containing about 10 to about 1000 parts of molybdenum per million parts of gasoline can be used until the steady state octane requirement has been reduced to near the "clean" octane requirement level. At that point, the concentration of the molybdenum in the gasoline can be reduced to about 0.01 to about 10.0 parts per million parts of gasoline.
- The hydrocarbon fuels to which the molybdenum(VI) compounds can be added comprise hydrocarbons boiling in the gasoline range which range is normally about 20°C-225°C. The base fuel can comprise straight-chain or branched-chain paraffins, cycloparaffins, olefins, and aromatic compounds or any mixture of such hydrocarbons obtainable from straight-run naphtha, polymeric gasoline, natural gasoline, thermally or catalytically cracked hydrocarbon stocks, alkylate gasoline and catalytically reformed stocks. The fuels can have a research octane number of about 60 to about 100 or preferably about 85 to about 95 for reason of fuel economy and engine performance. The gasoline may also contain conventional gasoline additives such as nonmetallic antiknock compounds, dyes, antioxidants, anti-icing agents, rust inhibitors, detergents, antipreignition agents, stabilizers, intake valve deposit control additives and the like. Commonly, gasolines contain a carrier fluid which remains stable and fluid in the induction system and can promote induction system cleanliness by dissolving hydrocarbon soluble deposits. A preferred embodiment of the invention involves the use of a minor amount of methyl t-butyl ether as an antiknock agent.
- The molybdenum(VI) compounds are effective in lubricant compositions when used in amounts providing about 0.001 to about 5 wt%, preferably about 0.01 to about 2 wt% and more preferably about 0.01 to about 1 wt% of molybdenum(VI) compound based on the oil. Suitable lubricating base oils are mineral oils, petroleum oils, synthetic lubricating oils, and natural lubricating oils of animal or vegetable origin. Concentrates of the additive in appropriate base oils containing about 10 to about 90 weight percent of the additive based on the oil are convenient for producing finished lubricants by dilution with additional base oil. A variety of other additives can be used beneficially with the additives of this invention, including antioxidants, dispersants, corrosion inhibitors, wear inhibitors, friction modifiers, detergents, antibacterial agents, antifoam agents, etc.
- The gasoline soluble molybdenum compounds are tested for ORI suppression and elevated steady state octane requirement reduction using the CRC E-15 technique with primary reference fuels and full boiling range reference fuels on an engine dynomometer. A GM 3.7 liter (231 cubic inch) V-6, and a Ford 2.3 liter (140 cubic inch) 4-cylinder in-line engine were connected to a load dynomometer. The fuel line is connected via a valve to a test fuel containing various concentrations of molybdenum compound and other containers containing standard fuel having known octane numbers. The conditions of the test are as follows: the temperature of the coolant and oil is maintained at 93°C (200°F) ± 6°C (10°F), the temperature of the inlet air was 40°C-49°C (110°F-120°F), and the temperature of the transmission was maintained at 82°C (180°F) ± 6°C (10°F). The air/fuel ratio was held at about stoichiometric, ignition timing and exhaust gas recirculation was maintained at the stock value. The engine was operated on fuel with and without gasoline soluble molybdenum compound for up to 30,000 equivalent miles (48000km). At intervals of 4,000 equivalent miles (6500km) the standard test fuels were burned in the engine to determine the octane requirement of the engine. After the octane requirement was determined the engines were returned to the test fuel.
- The following are examples of the preparation of gasoline soluble additive compounds used in gasoline and tables of test results displaying the octane requirement activity of molybdenum compounds in the engine. The examples and tables of data are illustrative of the invention. Since many embodiments of the invention can be made, the examples and data should not be used to limit the scope of the invention.
- Into a 3-liter, three-neck flask equipped with a mechanical stirrer, thermometer, temperature control assembly, and an addition funnel and condenser on a side arm adapter was charged 2 liters of anhydrous dioxane, a slurry of 180 grams (1.55 moles) of anhydrous methyl trimethyl acetate, and 144 grams (3.0 moles) of a 50 percent oil dispersion of sodium hydride. The mixture was stirred and heated to reflux and 160 grams (1.60 moles) of dry pinacolone (3,3-dimethyl-2-butanone) and 200 milliliters of anhydrous dioxane were added dropwise to the stirred and heated mixture over a period of 2 hours. After the addition of the pinacolone was complete, the mixture was held at reflux for 5.5 hours. From the mixture hydrogen gas was evolved. The reaction mixture was chilled in an ice bath and 360 milliliters of concentrated hydrochloric acid were cautiously added to the cold mixture. The resulting acidified mixture was poured into a 6-liter separatory funnel containing 1 liter of water and was extracted with 700 milliliters of pentane. The pentane phase was repeatedly washed with water, dried over magnesium sulfate, and distilled to 93°C to remove pentane. Crude 2,2,6,6-tetramethylheptane-3,5-dione (THDH) (260.7 grams) in oil was recovered. This procedure was repeated three times and the preparations were combined and fractionally distilled to recover 531.6 grams of THDH.
- Into a 250 milliliter Erlenmeyer flask attached to a reflux condenser was charged a slurry of 50.0 grams (0.29 moles) of 2,2,6,6-tetramethyl-3,5-heptanedione (THDH) and 9.8 grams (0.09 moles) of molybdenum trioxide (MoO₃). The mixture was stirred magnetically and was heated to reflux for 20 hours. The amber colored solution was filtered and upon standing changed to a blue-green solution. The mixture contained 11.5 wt. % molybdenum. Crystals of cis-dioxobis(dipivaloylmethanato)molybdenum(VI) or MoO₂(THD)₂ were recovered upon slow evaporation of the excess ketone.
- Into a 500 milliliter Erlenmeyer flask equipped with a distillation trap and condenser was charged a slurry of 138 grams (0.75 moles) of 2,2,6,6-tetramethyl-3,5-heptanedione (THDH) and 27.0 grams (0.188 moles) of MoO₃. The mixture was stirred and was heated on a hot plate to reflux. The mixture was allowed to react for a period of 25.5 hours while 5.0 milliliters of water were azeotropically removed from the reaction mixture (1.48 moles of water per mole of molybdenum trioxide). The dark red brown solution was filtered hot. The filtrate solidified to a dark brown mass upon standing. The recovered substance was identified as trioxotetra(dipivaloylmethanato)dimolybdenum(V,VI) by IR and NMR spectra and also by ESCA spectra of the product from a similar preparation.
- Into a 500 milliliter Erlenmeyer flask equipped with a distillation trap and condenser assembly was charged a slurry of 36.4 grams (0.25 moles) of MoO₃ and 196.1 grams (1.06 moles) of THDH. The mixture was stirred magnetically and heated to reflux temperature. After 18.5 hours, 6.0 milliliters of water were azeotropically removed (1.32 moles of water per mole of molybdenum trioxide). The reaction mixture was centrifuged and the centrifugate solidified upon standing. The reaction product contained both molybdenum(VI) and molybdenum(V) chelate as shown by a singlet M-O absorbance and a doublet O-Mo-O absorbance in the IR spectrum.
- Into a 500 milliliter Erlenmeyer flask equipped with a condenser assembly and distillation trap was charged a slurry of 9.8 grams (0.7 moles) of molybdenum trioxide and 50 grams (0.27 moles) of THDH. The mixture was stirred mechanically and was heated to reflux for 14.5 hours. 1.6 milliliters of water were azeotropically removed (1.31 moles of water per mole of molybdenum trioxide). The THDH in the distillation trap was returned to the reaction mixture, and the mixture was then stripped in vacuum of excess THDH. The resulting product was recrystallized from ethanol. Trans-dioxo(dipivaloylmethanato)molybdenum(VI) chelate (3.2 grams) was recovered as a first crop from the more soluble cis isomer.
- To a 500 milliliter Erlenmeyer flask equipped with a magnetic stirrer and heater was charged 54 grams of molybdic oxide (MoO₃), 106 grams of water and 22.5 grams of 28 percent aqueous ammonia. The mixture was stirred and heated until dissolution. The ammonium and molybdate product was charged to a 3-liter 3-neck flask equipped with a reflux condenser, water trap, dropping funnel and gas inlet tube containing 500 milliliters of normal heptane and 100 grams of a Mannich product comprising the reaction product of a polyisobutylene substituted phenol having a molecular weight of about 950, paraformaldehyde and diethylenetriamine and oleic acid. The mixture was stirred and heated at reflux for 4.25 hours. Water of reaction was removed by azeotropic distillation, and the mixture was centrifuged. The product was filtered and stripped of heptane by heating to 138°C with a nitrogen stream. The product contained 2.2 wt% molybdenum, 1.31 wt% nitrogen, and had a 40°C viscosity of 2516 SSU.
- An examination of Tables I and II shows that only molybdenum(VI) compounds provide measurable suppression of ORI or reduction of elevated steady state octane requirement.
- In the initially clean engines (Table I) only the Mo(VI)THD, the Mo(VI)Mannich and the Mo(VI)octoate provided measurable octane requirement increase suppression. The mixed Mo(V-VI)THD at 3 ppm and 6 ppm failed to give any measurable suppression.
- In initially dirty engines (Table II) only the Mo(VI)octoate provided reduction of elevated steady state octane requirement. The Mo(V-VI)THD provided no measurable benefit.
Claims (10)
- A gasoline fuel composition comprising a major proportion of a liquid hydrocarbon fuel of gasoline boiling range in combination with a molybdenum (VI) compound which is soluble in said hydrocarbon fuel, wherein the amount of said molybdenum (VI) compound is sufficient to provide from 0.01 to 1000 parts of molybdenum per one million parts of hydrocarbon fuel, said fuel composition is substantially free of metals other than molybdenum, and said molybdenum (VI) compound is selected from molybdenum (VI) sulfonates, molybdenum (VI) diamine complexes wherein the diamine ligand is of the formula R⁴R⁵N-(CR⁴R⁵)n-NR⁴R⁵ where n
is an integer from 1 to 20 and each R⁴ and R⁵ is independently selected from hydrogen and alkyl of 1 to 20 carbon atoms, and molybdenum (VI) compounds which are free of nitrogen, sulfur, and phosphorus. - A gasoline fuel composition according to Claim 1 wherein said molybdenum (VI) compound is selected from molybdenum (VI) carboxylates, molybdenum (VI) salts of naphthenic acids, molybdenum (VI) phenates, molybdenum (VI) alkoxides, molybdenum (VI) aryloxides and molybdenum (VI) beta-diketone compounds.
- A gasoline fuel composition as according to Claim 1 wherein said molybdenum (VI) compound is a molybdenum (VI) beta-diketone complex.
- A gasoline fuel composition as claimed in any preceding claim which additionally comprises a minor amount of methyl t-butyl ether which is effective to reduce knock in a spark ignition internal combustion engine.
- A gasoline fuel composition according to any of Claims 1 to 4 wherein the amount of said molybdenum (VI) compound is 0.1 to 20.0 parts per one million parts of hydrocarbon fuel.
- A gasoline fuel composition according to any of Claims 1 to 4 wherein the amount of said molybdenum (VI) compound is sufficient to provide from 0.01 to 10 parts of molybdenum per million parts of said hydrocarbon fuel.
- A gasoline fuel composition according to any of Claims 1 to 4 wherein said molybdenum (VI) compound is sufficient to provide from 10 to 1,000 parts of molybdenum per million parts of said hydrocarbon fuel.
- A method of reducing elevated steady state octane requirement and/or suppressing octane requirement increase in a spark ignition internal combustion engine which method comprises operating said engine with the gasoline fuel composition set forth in any of Claims 1 to 7.
- A method according to Claim 8 for reducing elevated steady state octane requirement in a spark ignition internal combustion engine and maintaining the resulting reduced steady state octane requirement which comprises operating said engine on a first gasoline fuel composition until a reduced steady state octane requirement is achieved and maintaining said reduced steady state octane requirement by operating the engine on a second gasoline fuel composition, wherein said first fuel composition comprises a gasoline fuel composition according to Claim 7 and wherein said second fuel composition comprises a gasoline fuel composition according to Claim 6.
- A method according to Claim 8 for reducing elevated steady state octane requirement in a spark ignition internal combustion engine having an increased octane requirement of about 2 to about 7 units after operation with gasoline substantially free of lead and molybdenum, which comprises operating said engine with a gasoline fuel composition according to Claim 7 and the amount of said gasoline fuel composition is effective to reduce said elevated steady state octane requirement by at least about 20%.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/833,225 US4647293A (en) | 1980-09-25 | 1986-02-24 | Gasoline compositions containing hexavalent molybdenum |
AT87301344T ATE69835T1 (en) | 1987-02-17 | 1987-02-17 | GASOLINE COMPOSITIONS CONTAINING HEXAVAL MOLYBDENUM. |
DE8787301344T DE3774868D1 (en) | 1987-02-17 | 1987-02-17 | HEALTHY MOLYBDAIC GASOLINE COMPOSITIONS. |
EP87301344A EP0279090B1 (en) | 1987-02-17 | 1987-02-17 | Gasoline compositions containing hexavalent molybdenum |
Applications Claiming Priority (1)
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EP87301344A EP0279090B1 (en) | 1987-02-17 | 1987-02-17 | Gasoline compositions containing hexavalent molybdenum |
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EP0279090A1 EP0279090A1 (en) | 1988-08-24 |
EP0279090B1 true EP0279090B1 (en) | 1991-11-27 |
Family
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EP87301344A Expired EP0279090B1 (en) | 1980-09-25 | 1987-02-17 | Gasoline compositions containing hexavalent molybdenum |
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EP (1) | EP0279090B1 (en) |
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US3124600A (en) * | 1964-03-10 | Organometallic compounds | ||
US2086775A (en) * | 1936-07-13 | 1937-07-13 | Leo Corp | Method of operating an internal combustion engine |
GB770278A (en) * | 1954-04-30 | 1957-03-20 | Exxon Research Engineering Co | Fuel composition |
US2881062A (en) * | 1955-08-17 | 1959-04-07 | Tide Water Associated Oil Comp | Hydrocarbon fuel |
GB894852A (en) * | 1958-12-08 | 1962-04-26 | Geoffrey Wilkinson | Cycloheptatrienyl metallocarbonyl compounds |
US3168368A (en) * | 1960-04-27 | 1965-02-02 | Air Prod & Chem | Method of treating exhaust gases of internal combustion engines |
US3282838A (en) * | 1960-05-10 | 1966-11-01 | Texaco Inc | Petroleum liquids containing amine salts of molybdic acid |
US3093671A (en) * | 1960-11-14 | 1963-06-11 | Ethyl Corp | Cyclic diene group vi-beta metal carbonyls |
BE612084A (en) * | 1960-12-30 | |||
US3755195A (en) * | 1968-12-20 | 1973-08-28 | Ethyl Corp | Spark plug anti-foulant |
AU5525773A (en) * | 1972-06-14 | 1974-11-07 | Continental Oil Co | Stable oil-soluble metal sulfonate compositions stable oil-soluble metal sulfonate compositions |
US4266945A (en) * | 1979-11-23 | 1981-05-12 | The Lubrizol Corporation | Molybdenum-containing compositions and lubricants and fuels containing them |
US4647293A (en) * | 1980-09-25 | 1987-03-03 | William H. Magidson | Gasoline compositions containing hexavalent molybdenum |
US4357149A (en) * | 1980-09-25 | 1982-11-02 | Standard Oil Company (Indiana) | Hydrocarbon-soluble oxidized, sulfurized polyamine-molbdenum compositions and gasoline containing same |
GB2089431B (en) * | 1980-12-06 | 1984-06-06 | Weir Pumps Ltd | Preventing surge in pumps |
-
1987
- 1987-02-17 AT AT87301344T patent/ATE69835T1/en not_active IP Right Cessation
- 1987-02-17 EP EP87301344A patent/EP0279090B1/en not_active Expired
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