US3608232A - Gasoline composition containing vanadium salts of phosphorus compounds - Google Patents
Gasoline composition containing vanadium salts of phosphorus compounds Download PDFInfo
- Publication number
- US3608232A US3608232A US723580A US3608232DA US3608232A US 3608232 A US3608232 A US 3608232A US 723580 A US723580 A US 723580A US 3608232D A US3608232D A US 3608232DA US 3608232 A US3608232 A US 3608232A
- Authority
- US
- United States
- Prior art keywords
- gasoline
- salt
- composition
- chromium
- metal
- 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
Links
- 239000000203 mixture Substances 0.000 title abstract description 52
- 150000003681 vanadium Chemical class 0.000 title description 21
- 150000003018 phosphorus compounds Chemical class 0.000 title description 8
- -1 PHOSPHORUS COMPOUND Chemical class 0.000 abstract description 41
- 229910052751 metal Inorganic materials 0.000 abstract description 32
- 239000002184 metal Substances 0.000 abstract description 32
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 29
- 239000011574 phosphorus Substances 0.000 abstract description 29
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 23
- 229930195733 hydrocarbon Natural products 0.000 abstract description 23
- 150000003839 salts Chemical class 0.000 abstract description 18
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical class [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 17
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 12
- 239000001257 hydrogen Substances 0.000 abstract description 12
- 229910052720 vanadium Inorganic materials 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 150000002611 lead compounds Chemical class 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract 1
- 125000004432 carbon atom Chemical group C* 0.000 description 24
- MRMOZBOQVYRSEM-UHFFFAOYSA-N tetraethyllead Chemical compound CC[Pb](CC)(CC)CC MRMOZBOQVYRSEM-UHFFFAOYSA-N 0.000 description 19
- 229910052804 chromium Inorganic materials 0.000 description 16
- 239000011651 chromium Substances 0.000 description 16
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 150000002148 esters Chemical class 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 239000000654 additive Substances 0.000 description 12
- 125000004429 atom Chemical group 0.000 description 12
- 150000001844 chromium Chemical class 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 9
- 230000006835 compression Effects 0.000 description 9
- 238000007906 compression Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000000446 fuel Substances 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 7
- 125000005037 alkyl phenyl group Chemical group 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- 150000002815 nickel Chemical class 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 6
- 229940045605 vanadium Drugs 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 150000001868 cobalt Chemical class 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 150000003014 phosphoric acid esters Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 3
- 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
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000005690 diesters Chemical class 0.000 description 3
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical class OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 239000006079 antiknock agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 2
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- 150000005691 triesters Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 150000003739 xylenols Chemical class 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- NSENZNPLAVRFMJ-UHFFFAOYSA-N 2,3-dibutylphenol Chemical compound CCCCC1=CC=CC(O)=C1CCCC NSENZNPLAVRFMJ-UHFFFAOYSA-N 0.000 description 1
- PTMRDOLOEDPHLB-UHFFFAOYSA-N 2,3-dipentylphenol Chemical compound CCCCCC1=CC=CC(O)=C1CCCCC PTMRDOLOEDPHLB-UHFFFAOYSA-N 0.000 description 1
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 1
- FDIPWBUDOCPIMH-UHFFFAOYSA-N 2-decylphenol Chemical compound CCCCCCCCCCC1=CC=CC=C1O FDIPWBUDOCPIMH-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- HMWIHOZPGQRZLR-UHFFFAOYSA-N 2-hexadecylphenol Chemical compound CCCCCCCCCCCCCCCCC1=CC=CC=C1O HMWIHOZPGQRZLR-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- WCRKLZYTQVZTMM-UHFFFAOYSA-N 2-octadecylphenol Chemical compound CCCCCCCCCCCCCCCCCCC1=CC=CC=C1O WCRKLZYTQVZTMM-UHFFFAOYSA-N 0.000 description 1
- LCHYEKKJCUJAKN-UHFFFAOYSA-N 2-propylphenol Chemical compound CCCC1=CC=CC=C1O LCHYEKKJCUJAKN-UHFFFAOYSA-N 0.000 description 1
- JOONSONEBWTBLT-UHFFFAOYSA-N 2-tetradecylphenol Chemical compound CCCCCCCCCCCCCCC1=CC=CC=C1O JOONSONEBWTBLT-UHFFFAOYSA-N 0.000 description 1
- ZVNPWFOVUDMGRP-UHFFFAOYSA-N 4-methylaminophenol sulfate Chemical compound OS(O)(=O)=O.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ZVNPWFOVUDMGRP-UHFFFAOYSA-N 0.000 description 1
- ZNPSUQQXTRRSBM-UHFFFAOYSA-N 4-n-Pentylphenol Chemical compound CCCCCC1=CC=C(O)C=C1 ZNPSUQQXTRRSBM-UHFFFAOYSA-N 0.000 description 1
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- GLMOMDXKLRBTDY-UHFFFAOYSA-A [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GLMOMDXKLRBTDY-UHFFFAOYSA-A 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- UWQIEDGNGUIPKS-UHFFFAOYSA-N benzene 2,2,4-trimethylpentane Chemical compound C1=CC=CC=C1.CC(C)CC(C)(C)C UWQIEDGNGUIPKS-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical class [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910000156 lead(II) phosphate Inorganic materials 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical class CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 125000003884 phenylalkyl group Chemical group 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000012002 vanadium phosphate Substances 0.000 description 1
- 239000008096 xylene Substances 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
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
-
- 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
-
- 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
- C10L1/26—Organic compounds containing phosphorus
- C10L1/2633—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
- C10L1/2641—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond) oxygen bonds only
-
- 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)
- C10L1/265—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond) oxygen and/or sulfur bonds
-
- 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)
- C10L1/306—Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond) organo Pb compounds
Definitions
- a gasoline composition consisting essentially of a hydrocarbon gasoline, an anti-knock quantity of a tetralower-alkyl lead compound, and a gasoline-soluble vanadium or chromium salt of a phosphorus compound having the formula RO OH RO ⁇ /SH RO/ ⁇ O RO ⁇ S wherein R is a hydrocarbon radical of up to 30 carbon atoms, R is selected from the group consisting of hydrogen and R, S is sulfur and O is oxygen.
- the amount of metal salt added is sufiicient to provide about 0.002 to 0.8 milligram atoms, preferably about 0.025 to 0.3 milligram atoms, of the selected metal per gallon of gasoline.
- a gasoline soluble non-metallic auxiliary phosphorus compound can be added to the composition to provide additional beneficial effects.
- the present invention relates to distillate hydrocarbon fuel compositions which when employed in spark ignition engines lead to improvements especially with respect to rumble.
- the compositions also exhibit other desirable characteristics such as increased anti-corrosive, anti-preignition and anti-stalling properties.
- Some compositions of the invention improve octane requirement increase when used in spark ignition engines.
- rumble is one of the major factors restricting compression ratios at the current levels.
- the rumble phenomenon is the result of deposit induced ignition which creates abnormal pressure rises in the combustion chambers, thereby causing flexing of the crankshaft.
- the flexing crankshaft manifests itself by loud unnatural or shuddering engine noises.
- phosphate compounds such as tricresyl phosphate, cresyl diphenyl phosphate, etc.
- phosphate compounds such as tricresyl phosphate, cresyl diphenyl phosphate, etc.
- the gasoline includes a partial ester salt of a metal having an atomic number from 23 to 24 and a partial ester salt of a metal having an atomic number from 27 to 28, especially a combination of such chromium and nickel salts.
- compositions of the invention also exhibit anti-rusting vanti-preignition and anti-stalling or carburetor deicing properties.
- the nickel and chromium salts are further advantageous in that they are especially resistant towards deposit formation when gasoline containing them is stored over water.
- the present invention is directed to the use of the phosphorus compounds in gasolines compositions which contain a lead anti-knock compound to reduce rumble and/or other adverse effects created by the addition of the lead compound
- the additives can also be advantageously employed in metal octane-improving additivefree, e.g. non-leaded gasolines to, for example aid in rust preventing, reducing preignition and anti-stalling or carburetor deicing.
- R is a hydrocarbon radical of up to about 30 or more carbon atoms on the average, often at least about 5 and preferably about 8 to 18 carbon atoms, S is sulfur, R is hydrogen or R, and O is oxygen.
- R can be an aliphatic, aromatic or mixed aliphatic-aromatic radical and is preferably non-olefinic and non-acetylenic, i.e. having adjacent carbon atoms no closer than 1.40 angstroms.
- the total number of carbon atoms in a molecule of the phosphorus compound is preferably up to about 30 or even up to about 40 and the chromium or vanadium salt of the phosphorus compound is soluble in gasoline at least to the extent employed in this invention.
- the phosphorus compounds from which the metal salts of the invention are made can be obtained by methods known to the art as, for instance, by reacting aliphatic alcohols, including cycloaliphatic alcohols, or aromatic hydroxy compounds With P 0 to form the phosphoric acid esters (I) and with P 8 to form the dithiophosphoric acid esters (II).
- the preferred alcohols are alkanols which can be straight or branch chained and alkyl-substituted phenols Whose alkyl substituents contain a total of up to 18 carbon atoms, and preferably are lower alkyl, especially methyl.
- the aromatic hydroxy compounds and aliphatic alcohols may be substituted with non-deleterious groups.
- Suitable alcohols are pentanol, butanol, octanol, isooctanol, Z-ethyl-heptanol, dodecanol, oleyl alcohol, octadecyl alcohol, tetradecyl alcohol, alcohols prepared by the x0 process, phenol and alkylated phenols such as cresol, xylenol, propyl phenol, butyl phenol, dibutyl phenol, monoamylphenol, diamyl phenol, decyl phenol, dodecyl phenol, tetradecyl phenol, hexadecyl phenol and octadecyl phenol.
- phenol and alkylated phenols such as cresol, xylenol, propyl phenol, butyl phenol, dibutyl phenol, monoamylphenol, diamyl phenol, decyl phenol
- the reaction of the alcohol and P 0 or P 5 to prepare the partial esters can be conducted by heating the reactants at temperatures of from about 75 C. to about 125 C. for a period of time sufiicient to effect substantially complete reaction, usually about 1 to 15 hours.
- An inert solvent such as toluene, xylene or the like may be used to facilitate the reaction.
- Suitable molar ratios of alcohol to P 05 and P S may be about 3:1, and 4:1 respectively.
- the ester products of phosphoric acid (I) thus produced can be, for instance, monoalkyl, dialkyl, mono aryl or diaryl esters or any combination thereof.
- the mixed esters are often present, for instance, in a mole ratio of at least about 25% of each, say about 60 to 40% monoester: 40 to 60% diester.
- the metal salts of the esters can be prepared by directly reacting the esters with the metal carbonate or acetate. Either the metal or the acidic component of the salts may be used in excess and either the monoor dipartial ester salts may be employed but they are conveniently prepared and made available as the mixed ester salts. Mixed chromium and vanadium phosphate may also be employed.
- the diester products of dithiophosphoric acid (II) thus produced can be, for instance, dialkyl or diary] esters or any combination thereof.
- the metal salts of the esters can be prepared by directly reacting the esters with the metal carbonate or acetate and either the metal or the acidic component of the salts may be used in excess.
- gasoline-soluble phosphorus compound having the formula:
- R has the value described above with respect to the phosphorus compounds from which the chromium and vanadium salts of the invention are made;
- R is hydrogen or R and n is an integer of 0 or 1.
- R is preferably an aromatic, e.g. phenyl, hydrocarbon radical of 6 to 12 carbon atoms and can be substituted, for instance, With lower alkyl groups say of l to 4 carbon atoms.
- the phosphorus compound can be a mono-, di-, or triester, or a mixture of such and is preferably a triester. It is also preferred to employ a phenyl, alkyl phenyl or a mixed phenyl-alkyl phenyl ester of phosphorus.
- one or more of the ester groups is preferably an alkyl phenyl radical, often of about 7 to 15 carbon atoms. See U.S. Pat. No. 2,889,212 for a further list of the useful phosphates and phosphites.
- auxiliary phosphate and phosphite additives can be prepared by reacting the appropriate alcohol or aromatic hydroxy compound with phosphoric acid to make the phosphate or with phosphorus trichloride to form the phosphite.
- suitable alcohols and aromatic hydroxy compounds are those mentioned above in the description of the phosphorous esters used to form the metal salts of the invention.
- suitable alkyl phenols are crtho, m a and para a eso g and xylenol; 2,4-dimethyl-6-tertiary butylphenol; octyl and nonyl phenols, etc.
- leaded gasoline to which the additives of the present invention are incorporated is meant hydrocarbon fractions boiling primarily in the gasoline range, usually about 100 to 425 F., having added thereto a small amount, generally between about 1 to 6 cc. per gallon, of a tetra-loWer-alkyl lead compound as an antiknock agent.
- the gasolines are usually composed of a major amount of a blend of hydrocarbon mineral oil fractions boiling primarily in the aforementioned range and will contain varying proportions of parafiins, olefins, naphthenes and aromatics derived by distillation, cracking and other refining and chemical conversion processes practiced upon crude oil fractions.
- Straight run gasolines gasolines derived from cracking gas oil, gasolines or reformate from reforming straight run naphtha over a platinum-alumina catalyst in the presence of hydrogen, etc., are components frequently used in making up a gasoline composition.
- a typical premium gasoline besides containing a small amount of a te-tra-loWer-alkyl lead compound as an anti-knock agent may also contain small amounts of other non-hydrocarbon constituents used to impart various properties to the gasoline in its use in internal combustion engines, e.g. halohydrocarbon scavengers, oxidation inhibitors, etc.
- Such gasolines frequently have a Research Method octane number of about 90 to 105, and a Motor Method octane number of about to 98.
- the ester salts of chromium and vanadium are incorporated in the leaded gasoline in minor amounts sulficient to provide a composition exhibiting improved rumble characteristics while the nickel and cobalt salts are used in minor amounts sufiicient to afford a decrease in octane number requirement increase.
- the actual amount of each additive employed will vary depending upon the particular gasoline employed, its lead contents, etc.
- the metal salt is employed to supply 0.002 to 0.4 or even 0.8, preferably 0.025 to 0.3 millimole or milligram atoms of the metal chromium and/ or vanadium per gallon of gasoline.
- the additive will usually provide the gasoline with 0.00004 to 0.008, preferably 0.0005 to 0.006 gram of metal per gram of lead.
- the cobalt or nickel salt when used is also generally present in an amount of about 0.002 to 0.8 millimole of metal per gallon of gasoline.
- a combination of the chromium or vanadium salts and the cobalt or nickel salt is advantageously in the range of about 0.002 to 0.8 milligram atoms or millimoles per gallon of gasoline.
- auxiliary phosphate or phosphite additive When used, about 0.05 to 0:6 theory, preferably about 0.15 to 0.5 theory, of the auxiliary phosphate or phosphite additive, based on the lead content of the gasoline, are employed.
- theory as applied to the amount of the second phosphorus additive means the amount required to react stoiehiometrically with the lead so that all of the lead atoms and all of the phosphorus atoms form Pb3(PO4)2.
- the corresponding vanadium salt was made in a similar manner using vanadium pentoxide. Analysis pentox ide. Analysis of the product showed 1.55% vanadium and 6.41 phosphorus.
- EXAMPLE H Two moles of mixed, approximately 50% mono and approximately 50% di, C -x0 alcohol esters of phosphoric acid were reacted with slightly more than two moles of cobaltous carbonate in a hexane solvent. The reaction was carried out at 75 C. for one hour, and the product was then filtered. The hydrocarbon solubles were water-washed several times, refiltered and the resulting cobalt salt of mixed monoand di-C oxo esters of phosphoric acid was dried to constant weight, cobalt 4.53% and phosphorus 4.50%.
- the corresponding nickel salt was made in a similar manner using nickel carbonate, with the reaction being conducted at 80 to 90 C. Analysis of the product showed 6.52% nickel and 6.35% phosphorus.
- EXAMPLE III A sample of a base gasoline was obtained which was composed of 25 volume percent straight run gasoline, 25 volume percent butane-butylene alkylate and 25 volume percent reformed naphtha.
- the base gasoline analyzed 6% olefins and 20% aromatics and contained 3 cc. per gallon of TEL as Motor Mix (TEL Motor Mix contains 59.2% tetraethyl lead, 13.0% ethylene dibromide, 23.9% ethylene dichloride and 3.9% hydrocarbon diluent, dyes, etc.).
- the base gasoline containing the tetra-ethyl lead had an API gravity of 61.2, an octane number of 100 by the Research Method and an octane number of 92 by the Motor Method.
- the ASTM distillation of the gasoline was as follows:
- IBP 93 Into the separate portions of the leaded gasoline are added either the chromium salt of Example -I in a concentration that provides 25 lbs. of the ester salt per 1000 barrels of the leaded gasoline or the vanadium salt of Example I in a concentration that provides 25 lbs. of the ester salt per 1000 barrels of the leaded gasoline.
- the gasoline also contained 0.2 theory of cresyl diphenyl phosphate, about 2.5 pounds of phenylenediamine, an oxidation inhibitor, per 1000 barrels of gasoline and a commercial amine salt of a phosphoric acid ester corrosion inhibitor.
- LIB number is a measure of the rumble tendency of an engine after a given time of use. The number represents the percent isooctane [containing 3 cc./ gal. TEL] required in a blend with benzene [containing 3 cc./gal. TEL] after a given period of engine operation using the fuel under test, to avoid rumble at a given r.p.m., e.g. 2000 rpm.
- the test procedure comprises stopping the gasoline to the engine at any given period of engine operation and employing as a fuel to the engine containing a certain percent of isooctane in an isooctane-benzene blend (containing 3 cc. T-EL/gal.), manually opening the throttle at a given rate and recording the rpm. at which rumble occurs, if any in fact occurs.
- the faster you are able to run the engine with the lowest percent of isooctane in the blend the better the rumble resistance of the engine.
- the lower the LIB number the better the rumble characteristics of the engine.
- EXAMPLE IV The chromium and vanadium salts of Example I were added, in the amount of 2 pounds per 1000 barrels, to a gasoline containing 37 volume percent light straight run gasoline, 23 volume percent light catalytically cracked gasoline, 13 volume percent heavy catalytically reformed gasoline and 27 volume percent heavy catalytically cracked gasoline.
- a 4-hour accelerated rust test the base gasoline gave a poor or E rating but after addition of the chromium salt a rust rating of B+ was obtained and after addition of the vanadium salt to the base gasoline a rating of B was obtained. In testing these salts the gasoline also contained 3 cos.
- TEL/gaL 0.2 theory of cresyl diphenyl phosphate, 0.15 volume percent methanol and a metal deactivator, 1 lb./1000 barrels.
- the corrosion test involved placing a steel specimen in contact with agitated gasoline and water at 100 F. for about four hours and the specimen is inspected to ascertain the extent of rust according to ratings A to E, see US. Pat. No. 2,966,458.
- EXAMPLE V A composition of superior rumble and octane requirement increase characteristics is the final chromium saltcontaining gasoline of Example III also having in addition 20 lbs. per 1000 barrels of the nickel salt of Example II.
- EXAMPLE VI Also included in the gasoline were phenylene diamine oxidation inhibitor and 3.0 cc. of tetraethyl lead admixed with an ethylene dichloride scavenger.
- Chromium salt N0./1,000 bbls. gasoline GDP, theories 0 These data establish the elficiency of the chromium salt in combating surface ignition in the presence or absence of cresyl diphenyl phosphate.
- EXAMPLE VII One mole of dithiodiisodecyl phosphoric acid ester is reacted with slightly more than one mole of chromium acetate in a hexane solvent. The reaction is carried out at C., for one hour, and the product is then filtered. The hydrocarbon solubles are water-washed several times,
- the salt contains a calculated metal content of 6.4% by weight chromium.
- EXAMPLE VIII Two moles fo dithiodiisodecylphosphoric acid ester are reacted with slightly more than two moles of cobaltous carbonate in a hexane solvent. The reaction is carried out at 75 C., for one hour, and the product is then filtered. The hydrocarbon solubles are water-washed several times, refiltered and the resulting cobalt salt of the dithiodiisodecylphosphoric acid ester is dried. The calculated cobalt content of the product is 6.7% by weight.
- the corresponding nickel salt calculated at 6.6% by Weight nickel, is made in a similar manner using nickel carbonate, with the reaction being conducted at 80 to 90 C.
- a sample of a base gasoline is obtained which is composed of 25 volume percent straight run gasoline, 25 volume percent light catalytically cracked gasoline, 25 volume percent butane-butylene alkylate and 25 volume percent reformed naphtha.
- the base gasoline analyzes 6% olefins and 20% aromatics and contains 3 cc., per gallon of TEL as Motor Mix (TEL Motor Mix contains 59.2% tetraethyl lead, 13.0% ethylene dibromide, 23.9% ethylene dichloride and 3.9% hydrocarbon diluent, dyes etc.)
- the base gasoline containing the tetraethyl lead has an API gravity of 61.2, an octane number of 100 by the Research Method and an octane number of 92 by the Motor Method.
- the ASTM distillation of the gasoline is as follows:
- EXAMPLE X The chromium and vanadium salts of Example VII when added, in the amount of 2 pounds per 1000 barrels to a leaded (3 cc. TEL as Motor Mix) gasoline composed of 37 volume percent light straight run gasoline, 23 volume percent light catalytically cracked gasoline, 13 volume percent heavy catalytically reformed gasoline and 27 volume percent heavy catalytically cracked gasoline, provides a composition of enhanced rust resistance.
- EXAMPLE XI Compositions of superior rumble and octane requirement increase characteristics are the final chromium saltcontaining gasolines of Example IX also having in addition 20 lbs. per 1000 barrels of the nickel salt of Example VIII.
- EXAMPLE XII A leaded (3 cc. TEL as Motor Mix gasoline composed of 14 volume percent straight run gasoline, 32.7 volume O ⁇ /SH RO ⁇ S RO wherein R is a hydrocarbon radical of up to 30 carbon atoms, and R is selected from the group consisting of hydrogen and R and the amount of said vanadium salt being 0.002 to 0.8 milligram atoms of metal per gallon of gasoline.
- composition of claim 1 in which there is also included about 0.05 to 0.6 theory of a gasoline-soluble phosphorous compound having the formula and wherein R is a hydrocarbon radical of up to about 30 carbon atoms on the average, R is selected from the group consisting of hydrogen and R, and n is an integer having a value of 0 or 1.
- composition of claim 2 wherein at least one R in the structure of claim 2 is an alkyl phenyl radical of 7 to 15 carbon atoms.
- composition of claim 3 wherein the amount of phosphorus compound is abuot 0.15 to 0.5 theory.
- vanadium salt is a salt of a phosphorus compound having the formula RO ⁇ /OH R'O 0 wherein R is a hydrocarbon radical of from about 8 to 18 carbon atoms, and R is selected from the group consisting of hydrogen and R, the amount of said vanadium salt being 0.025 to 0.3 milligram atoms of vanadium per gallon of gasoline.
- composition of claim 5 in which there is also included about 0.05 to 0.6 theory of a gasoline-soluble phosphorus compound having the formula RO ⁇ /OR RO o wherein R is a lower alkyl phenyl radical of 7 to 15 carbon atoms and R is selected from the group consisting of phenyl and R.
- composition of claim 6 wherein the non-metallic phosphorus compound is cresyl diphenyl phosphate.
- composition of claim 1 in which there is included about 0.002 to 0.8 milligram atoms per gallon of said gasoline of a gasoline-soluble metal salt of a phosphorus compound having the formula R'O ⁇ OH 2: R'O o wherein R is a hydrocarbon radical of up to 30 carbon atoms and R is selected from the group consisting of hydrogen and R said metal having an atomic number of from 27 to 28.
- composition of claim 8 in which there is also included about 0.05 to 0.6 theory of a gasoline-soluble phosphorus compound having the formula wherein R is a hydrocarbon radical of up to about 30 carbon atoms on the average, R' is selected from the group consisting of hydrogen and R, and n is an integer having a value of or 1.
- composition of claim 9 wherein at least one R in the structure of claim 9 is an alkyl phenyl radical of 7 to 15 carbon atoms.
- composition of claim 10 wherein the amount of prosphorus compound is about 0.15 to 0.5 theory.
- vanadium salt is a salt of a phosphorus compound having the formula:
- R is an alkyl radical of 8 to 18 carbon atoms on the average, the amount of said vanadium salt being sufficient to provide 0.025 to 0.3 milligram atoms of vanadium per gallon of gasoline.
- composition of claim 13 in which there is also included about 0.05 to 0.6 theory of a gasolinesoluble phosphorus compound having the formula:
- RO ⁇ /OR RO o wherein R is a lower alkyl phenyl radical of 7 to carbon atoms on the average, and R is selected from the group consisting of phenyl and R.
- composition of claim 14 wherein the nonmetallic phosphorus compound is cresyl diphenyl phosphate.
- composition of claim 1 in which there is included about 0.002 to 0.8 milligram atoms of a gasolinesoluble metal salt of a phosphorus compound having the formula:
- R is a hydrocarbon radical of up to 30 carbon atoms on the average, said metal having an atomic number of from 27 to 28.
- composition of claim 15 in which there is also included about 16 to 195 pounds per thousand barrels of a gasoline-soluble phosphorus compound having the formula:
- composition of claim 17 wherein at least one R in the structure of claim 23 is an alkyl phenyl radical of 7 to 15 carbon atoms.
- composition of claim 18 wherein the amount of phosphorus compound is about 48 to pounds per thousand barrels of gasoline.
- composition of claim 1 wherein there is included about 0.025 to 0.3 milligram atoms per gallon of gasoline of a gasoline-soluble metal salt of a phosphorus compound having the formula:
- RO ⁇ /SH I R0 s wherein R is an alkyl group of 8 to 18 carbon atoms on the average, said metal having an atomic number of from 27 to 28.
- composition of claim 1 wherein there is included about 0.025 to 0.3 milligram atoms per gallon of gasoline of a gasoline-soluble metal salt of a phosphorus compound having the formula:
- R is an alkyl group of 8 to 18 carbon atoms on the average and R is selected from the group consisting of hydrogen and R, said metal having an atomic number of from 27 to 28.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
A GASOLINE COMPOSITION CONSISTING ESSENTIALLY OF A HYDROCARBON GASOLINE, AN ANTI-KNOCK QUANTITY OF A TETRALOWER-ALKYL LEAD COMPOUND, AND A GASOLINE-SOLUBLE VANADIUM OR CHROMIUM SALT OF A PHOSPHORUS COMPOUND HAVING THE FORMULA
R-O-P(=O)(-O-R'')-OH OR R''-O-P(=S)(-O-R)-SH
WHEREIN R IS A HYDROCARBON RADICAL OF UP TO 30 CARBON ATOMS, R'' IS SELECTED FROM THE GROUP CONSISTILNG OF HYDROGEN AND R, S IS SULFUR AND O IS OXYGEN. THE AMOUNT OF METAL SALT ADDED IS SUFFICIENT TO PROVIDE ABOUT 0.002 TO 0.8 MILLIGRAM ATOMS, PREFERABLY ABOUT 0.025 TO 0.3 MILLIGRAM ATOMS, OF THE SELECTED METAL PER GALLON OF GASOLINE. A GASOLINE SOLUBLE NON-METALLIC AUXILIARY PHOSPHORUS COMPOUND CAN BE ADDED TO THE COMPOSITION TO PROVIDE ADDITIONAL BENEFICIAL EFFECTS.
R-O-P(=O)(-O-R'')-OH OR R''-O-P(=S)(-O-R)-SH
WHEREIN R IS A HYDROCARBON RADICAL OF UP TO 30 CARBON ATOMS, R'' IS SELECTED FROM THE GROUP CONSISTILNG OF HYDROGEN AND R, S IS SULFUR AND O IS OXYGEN. THE AMOUNT OF METAL SALT ADDED IS SUFFICIENT TO PROVIDE ABOUT 0.002 TO 0.8 MILLIGRAM ATOMS, PREFERABLY ABOUT 0.025 TO 0.3 MILLIGRAM ATOMS, OF THE SELECTED METAL PER GALLON OF GASOLINE. A GASOLINE SOLUBLE NON-METALLIC AUXILIARY PHOSPHORUS COMPOUND CAN BE ADDED TO THE COMPOSITION TO PROVIDE ADDITIONAL BENEFICIAL EFFECTS.
Description
United States Paten 3,608,232 GASOLINE COMPOSITION CONTAINING VANA- DIUM SALTS F PHOSPHORUS COMPOUNDS Frederick L. Voelz, Orland Park, and Walter F. Schoen, South Holland, Ill., assignors to Atlantic Richfield Company, New York, N.Y.
N0 Drawing. Continuation-impart of applications Ser. No. 427,078, Jan. 21, 1965, and Ser. Nos. 470,598 and 470,628, both July 8, 1965, said application Ser. No. 427,078 being a continuation-in-part of application Ser. No. 306,273, Sept. 3, 1963. This application Apr. 23, 1968, Ser. No. 723,580 Int. Cl. C011 1/26 US. C]. 44-69 22 Claims ABSTRACT OF THE DISCLOSURE A gasoline composition consisting essentially of a hydrocarbon gasoline, an anti-knock quantity of a tetralower-alkyl lead compound, and a gasoline-soluble vanadium or chromium salt of a phosphorus compound having the formula RO OH RO\ /SH RO/ \O RO \S wherein R is a hydrocarbon radical of up to 30 carbon atoms, R is selected from the group consisting of hydrogen and R, S is sulfur and O is oxygen. The amount of metal salt added is sufiicient to provide about 0.002 to 0.8 milligram atoms, preferably about 0.025 to 0.3 milligram atoms, of the selected metal per gallon of gasoline. A gasoline soluble non-metallic auxiliary phosphorus compound can be added to the composition to provide additional beneficial effects.
This application is a continuation-in-part of applications Ser. No. 427,078, filed Jan. 21, 1965, now abandoned, Ser. No. 470,598, filed July 8, 1665 now abandoned, and Ser. No. 470,628, filed July 8, 1965 now abandoned. Application Ser. No. 427,078 is a continuation-in-part of application Ser. No. 306,273, filed Sept. 3, 1963, now abandoned.
The present invention relates to distillate hydrocarbon fuel compositions which when employed in spark ignition engines lead to improvements especially with respect to rumble. The compositions also exhibit other desirable characteristics such as increased anti-corrosive, anti-preignition and anti-stalling properties. Some compositions of the invention improve octane requirement increase when used in spark ignition engines.
In order to improve the efficiency and increase the horsepower ratings of gasoline engines, engine manufacturers have significantly increased compression ratios during the past decade. In 1952, for example, no major US. automobile manufacturer made a stock engine having a compression ratio as high as 8.0/1. Today engines having compression ratios greater than 10.0/ 1 are common. These high compression ratio engines have revealed a relatively new type of abnormal combustion called rumble. In fact, rumble is one of the major factors restricting compression ratios at the current levels. The rumble phenomenon is the result of deposit induced ignition which creates abnormal pressure rises in the combustion chambers, thereby causing flexing of the crankshaft. The flexing crankshaft manifests itself by loud unnatural or shuddering engine noises.
Another disadvantage attending the use of known additives to lessen abnormal combustion of gasoline in, for instance, automobile engines, is that they adversely affect the nature and increase the amount of deposits within the combustion space. These effects take on greater importance in the case of the higher compression ratio engines. A fuel having an octane number appropriate to the designed engine compression ratio is therefore unable to give the same anti-knock performance after the formation of such extensive deposits. To obtain the intended autiknock performance requires a fuel of higher octane number; and this effect has become known as the octane requirement increase" or Ori of the engine.
Various commonly employed gasoline additives as, for example, phosphate compounds such as tricresyl phosphate, cresyl diphenyl phosphate, etc., although known to improve engine operation with respect to preignition, rumble, wild ping, autoignition and spark plug fouling, have no decreasing effect on octane number requirement increase and many even have an adverse effect. Also to combat rumble effectively, relatively large amounts of the additives may be needed.
It has now been found that leaded gasolines having added thereto a small amount of a gasoline-soluble chromium or vanadium salt of certain phosphorus and thiophosphorus compounds provides a composition which improves rumble. Further improvements in terms of octane requirement increase and in some cases rumble are afforded by also including in the gasoline composition a nickel or cobalt salt of the phosphorus compounds of the invention. Thus in a preferred form the gasoline includes a partial ester salt of a metal having an atomic number from 23 to 24 and a partial ester salt of a metal having an atomic number from 27 to 28, especially a combination of such chromium and nickel salts. The compositions of the invention also exhibit anti-rusting vanti-preignition and anti-stalling or carburetor deicing properties. The nickel and chromium salts are further advantageous in that they are especially resistant towards deposit formation when gasoline containing them is stored over water.
While the present invention is directed to the use of the phosphorus compounds in gasolines compositions which contain a lead anti-knock compound to reduce rumble and/or other adverse effects created by the addition of the lead compound the additives can also be advantageously employed in metal octane-improving additivefree, e.g. non-leaded gasolines to, for example aid in rust preventing, reducing preignition and anti-stalling or carburetor deicing.
The phosphorus compounds, from which metal salts of the invention are made, have the following formulae:
wherein R is a hydrocarbon radical of up to about 30 or more carbon atoms on the average, often at least about 5 and preferably about 8 to 18 carbon atoms, S is sulfur, R is hydrogen or R, and O is oxygen. R can be an aliphatic, aromatic or mixed aliphatic-aromatic radical and is preferably non-olefinic and non-acetylenic, i.e. having adjacent carbon atoms no closer than 1.40 angstroms. The total number of carbon atoms in a molecule of the phosphorus compound is preferably up to about 30 or even up to about 40 and the chromium or vanadium salt of the phosphorus compound is soluble in gasoline at least to the extent employed in this invention.
The phosphorus compounds from which the metal salts of the invention are made can be obtained by methods known to the art as, for instance, by reacting aliphatic alcohols, including cycloaliphatic alcohols, or aromatic hydroxy compounds With P 0 to form the phosphoric acid esters (I) and with P 8 to form the dithiophosphoric acid esters (II). The preferred alcohols are alkanols which can be straight or branch chained and alkyl-substituted phenols Whose alkyl substituents contain a total of up to 18 carbon atoms, and preferably are lower alkyl, especially methyl. The aromatic hydroxy compounds and aliphatic alcohols may be substituted with non-deleterious groups. Illustrative of suitable alcohols are pentanol, butanol, octanol, isooctanol, Z-ethyl-heptanol, dodecanol, oleyl alcohol, octadecyl alcohol, tetradecyl alcohol, alcohols prepared by the x0 process, phenol and alkylated phenols such as cresol, xylenol, propyl phenol, butyl phenol, dibutyl phenol, monoamylphenol, diamyl phenol, decyl phenol, dodecyl phenol, tetradecyl phenol, hexadecyl phenol and octadecyl phenol.
The reaction of the alcohol and P 0 or P 5 to prepare the partial esters can be conducted by heating the reactants at temperatures of from about 75 C. to about 125 C. for a period of time sufiicient to effect substantially complete reaction, usually about 1 to 15 hours. An inert solvent such as toluene, xylene or the like may be used to facilitate the reaction. Suitable molar ratios of alcohol to P 05 and P S may be about 3:1, and 4:1 respectively.
The ester products of phosphoric acid (I) thus produced, can be, for instance, monoalkyl, dialkyl, mono aryl or diaryl esters or any combination thereof. The mixed esters are often present, for instance, in a mole ratio of at least about 25% of each, say about 60 to 40% monoester: 40 to 60% diester. The metal salts of the esters can be prepared by directly reacting the esters with the metal carbonate or acetate. Either the metal or the acidic component of the salts may be used in excess and either the monoor dipartial ester salts may be employed but they are conveniently prepared and made available as the mixed ester salts. Mixed chromium and vanadium phosphate may also be employed.
The diester products of dithiophosphoric acid (II) thus produced can be, for instance, dialkyl or diary] esters or any combination thereof. The metal salts of the esters can be prepared by directly reacting the esters with the metal carbonate or acetate and either the metal or the acidic component of the salts may be used in excess.
In order to provide leaded gasolines of further enhanced characteristics, for instance, as to preignition, spark plug fouling and even, in at least some cases, rumble, there can be included in the gasoline composition of the invention a gasoline-soluble phosphorus compound having the formula:
RO OR wherein R has the value described above with respect to the phosphorus compounds from which the chromium and vanadium salts of the invention are made; R is hydrogen or R and n is an integer of 0 or 1. R is preferably an aromatic, e.g. phenyl, hydrocarbon radical of 6 to 12 carbon atoms and can be substituted, for instance, With lower alkyl groups say of l to 4 carbon atoms. Thus, the phosphorus compound can be a mono-, di-, or triester, or a mixture of such and is preferably a triester. It is also preferred to employ a phenyl, alkyl phenyl or a mixed phenyl-alkyl phenyl ester of phosphorus. Thus, one or more of the ester groups is preferably an alkyl phenyl radical, often of about 7 to 15 carbon atoms. See U.S. Pat. No. 2,889,212 for a further list of the useful phosphates and phosphites.
These auxiliary phosphate and phosphite additives can be prepared by reacting the appropriate alcohol or aromatic hydroxy compound with phosphoric acid to make the phosphate or with phosphorus trichloride to form the phosphite. Illustrative of suitable alcohols and aromatic hydroxy compounds are those mentioned above in the description of the phosphorous esters used to form the metal salts of the invention. Examples of suitable alkyl phenols are crtho, m a and para a eso g and xylenol; 2,4-dimethyl-6-tertiary butylphenol; octyl and nonyl phenols, etc.
By the term leaded gasoline to which the additives of the present invention are incorporated is meant hydrocarbon fractions boiling primarily in the gasoline range, usually about 100 to 425 F., having added thereto a small amount, generally between about 1 to 6 cc. per gallon, of a tetra-loWer-alkyl lead compound as an antiknock agent. The gasolines are usually composed of a major amount of a blend of hydrocarbon mineral oil fractions boiling primarily in the aforementioned range and will contain varying proportions of parafiins, olefins, naphthenes and aromatics derived by distillation, cracking and other refining and chemical conversion processes practiced upon crude oil fractions. Straight run gasolines, gasolines derived from cracking gas oil, gasolines or reformate from reforming straight run naphtha over a platinum-alumina catalyst in the presence of hydrogen, etc., are components frequently used in making up a gasoline composition. A typical premium gasoline, besides containing a small amount of a te-tra-loWer-alkyl lead compound as an anti-knock agent may also contain small amounts of other non-hydrocarbon constituents used to impart various properties to the gasoline in its use in internal combustion engines, e.g. halohydrocarbon scavengers, oxidation inhibitors, etc. Such gasolines frequently have a Research Method octane number of about 90 to 105, and a Motor Method octane number of about to 98.
The ester salts of chromium and vanadium are incorporated in the leaded gasoline in minor amounts sulficient to provide a composition exhibiting improved rumble characteristics while the nickel and cobalt salts are used in minor amounts sufiicient to afford a decrease in octane number requirement increase. The actual amount of each additive employed will vary depending upon the particular gasoline employed, its lead contents, etc. In any event the metal salt is employed to supply 0.002 to 0.4 or even 0.8, preferably 0.025 to 0.3 millimole or milligram atoms of the metal chromium and/ or vanadium per gallon of gasoline. The additive will usually provide the gasoline with 0.00004 to 0.008, preferably 0.0005 to 0.006 gram of metal per gram of lead. This often means that about 0.5 to 15 or 20 more of the chromium or vanadium salts to the metal salt ester, preferably about 4 to 10 pounds, per 1000 barrels of gasoline is added. The cobalt or nickel salt when used is also generally present in an amount of about 0.002 to 0.8 millimole of metal per gallon of gasoline. A combination of the chromium or vanadium salts and the cobalt or nickel salt is advantageously in the range of about 0.002 to 0.8 milligram atoms or millimoles per gallon of gasoline.
When used, about 0.05 to 0:6 theory, preferably about 0.15 to 0.5 theory, of the auxiliary phosphate or phosphite additive, based on the lead content of the gasoline, are employed. The term theory as applied to the amount of the second phosphorus additive means the amount required to react stoiehiometrically with the lead so that all of the lead atoms and all of the phosphorus atoms form Pb3(PO4)2.
The following examples are given to illustrate the advantages provided leaded gasolines by the additives of the present invention.
EXAMPLE I One mole of mixed, approximately 50% monoand approximately 5 0% di-, C -0x0 alcohol esters of phosphoric acid was reacted with slightly more than one mole of chromium acetate in a hexane solvent. The reaction was carried out at C. for one hour, and the product was then filtered. The hydrocarbon solubles were Water- Washed several times, refiltered and the resulting chromium salt of mixed monoand di-C oxo esters of phosphoric acid was dried to constant weight, analyzing L827? chromium and 6.86 phosphorus.
The corresponding vanadium salt was made in a similar manner using vanadium pentoxide. Analysis pentox ide. Analysis of the product showed 1.55% vanadium and 6.41 phosphorus.
EXAMPLE H Two moles of mixed, approximately 50% mono and approximately 50% di, C -x0 alcohol esters of phosphoric acid were reacted with slightly more than two moles of cobaltous carbonate in a hexane solvent. The reaction was carried out at 75 C. for one hour, and the product was then filtered. The hydrocarbon solubles were water-washed several times, refiltered and the resulting cobalt salt of mixed monoand di-C oxo esters of phosphoric acid was dried to constant weight, cobalt 4.53% and phosphorus 4.50%.
The corresponding nickel salt was made in a similar manner using nickel carbonate, with the reaction being conducted at 80 to 90 C. Analysis of the product showed 6.52% nickel and 6.35% phosphorus.
EXAMPLE III A sample of a base gasoline was obtained which was composed of 25 volume percent straight run gasoline, 25 volume percent butane-butylene alkylate and 25 volume percent reformed naphtha. The base gasoline analyzed 6% olefins and 20% aromatics and contained 3 cc. per gallon of TEL as Motor Mix (TEL Motor Mix contains 59.2% tetraethyl lead, 13.0% ethylene dibromide, 23.9% ethylene dichloride and 3.9% hydrocarbon diluent, dyes, etc.). The base gasoline containing the tetra-ethyl lead had an API gravity of 61.2, an octane number of 100 by the Research Method and an octane number of 92 by the Motor Method. The ASTM distillation of the gasoline was as follows:
IBP 93 Into the separate portions of the leaded gasoline are added either the chromium salt of Example -I in a concentration that provides 25 lbs. of the ester salt per 1000 barrels of the leaded gasoline or the vanadium salt of Example I in a concentration that provides 25 lbs. of the ester salt per 1000 barrels of the leaded gasoline. The gasoline also contained 0.2 theory of cresyl diphenyl phosphate, about 2.5 pounds of phenylenediamine, an oxidation inhibitor, per 1000 barrels of gasoline and a commercial amine salt of a phosphoric acid ester corrosion inhibitor.
The above gasoline with the metal phosphate ester additives is evaluated in a 1962 Chevrolet V-8, 327 cubic inch, 10.2:1 compression ratio engine to obtain the equilibrium rumble requirement (LIB). LIB number is a measure of the rumble tendency of an engine after a given time of use. The number represents the percent isooctane [containing 3 cc./ gal. TEL] required in a blend with benzene [containing 3 cc./gal. TEL] after a given period of engine operation using the fuel under test, to avoid rumble at a given r.p.m., e.g. 2000 rpm. The test procedure comprises stopping the gasoline to the engine at any given period of engine operation and employing as a fuel to the engine containing a certain percent of isooctane in an isooctane-benzene blend (containing 3 cc. T-EL/gal.), manually opening the throttle at a given rate and recording the rpm. at which rumble occurs, if any in fact occurs. The faster you are able to run the engine with the lowest percent of isooctane in the blend the better the rumble resistance of the engine. Thus, the lower the LIB number the better the rumble characteristics of the engine.
The above fuel without the chromium or vanadium salt, gave in this engine an equilibrium rumble requirement of 70 LIB. After the engine was cleaned, the same fuel without the amine phosphate corrosion inhibitor but containing 25 pounds of the chromium salt of Example I per 1000 barrels, when used in the engine gave an LIB number of only 10. In a similar test with the same fuel but containing 25 pounds of the vanadium salt of Example I per 1000 barrels instead of the chromium salt, the LIB rating is also significantly reduced.
EXAMPLE IV The chromium and vanadium salts of Example I were added, in the amount of 2 pounds per 1000 barrels, to a gasoline containing 37 volume percent light straight run gasoline, 23 volume percent light catalytically cracked gasoline, 13 volume percent heavy catalytically reformed gasoline and 27 volume percent heavy catalytically cracked gasoline. In a 4-hour accelerated rust test the base gasoline gave a poor or E rating but after addition of the chromium salt a rust rating of B+ was obtained and after addition of the vanadium salt to the base gasoline a rating of B was obtained. In testing these salts the gasoline also contained 3 cos. TEL/gaL, 0.2 theory of cresyl diphenyl phosphate, 0.15 volume percent methanol and a metal deactivator, 1 lb./1000 barrels. The corrosion test involved placing a steel specimen in contact with agitated gasoline and water at 100 F. for about four hours and the specimen is inspected to ascertain the extent of rust according to ratings A to E, see US. Pat. No. 2,966,458.
EXAMPLE V A composition of superior rumble and octane requirement increase characteristics is the final chromium saltcontaining gasoline of Example III also having in addition 20 lbs. per 1000 barrels of the nickel salt of Example II.
EXAMPLE VI Also included in the gasoline were phenylene diamine oxidation inhibitor and 3.0 cc. of tetraethyl lead admixed with an ethylene dichloride scavenger.
The table below reports data as wild ping counts per hour obtained in preignition tests using the above gasoline containing the chromium salt additive of Example I and from 0 to 0.3 theory of cresyl diphenyl phosphate (CDP).
Chromium salt, N0./1,000 bbls. gasoline GDP, theories 0 These data establish the elficiency of the chromium salt in combating surface ignition in the presence or absence of cresyl diphenyl phosphate.
EXAMPLE VII One mole of dithiodiisodecyl phosphoric acid ester is reacted with slightly more than one mole of chromium acetate in a hexane solvent. The reaction is carried out at C., for one hour, and the product is then filtered. The hydrocarbon solubles are water-washed several times,
refiltered and the resulting chromium salt of the dithiodiisodecylphosphoric acid ester is dried to constant weight. The salt contains a calculated metal content of 6.4% by weight chromium.
The corresponding vanadium salt calculated at 4.0% by weight V, is made in a similar manner using vanadium pentoxide.
EXAMPLE VIII Two moles fo dithiodiisodecylphosphoric acid ester are reacted with slightly more than two moles of cobaltous carbonate in a hexane solvent. The reaction is carried out at 75 C., for one hour, and the product is then filtered. The hydrocarbon solubles are water-washed several times, refiltered and the resulting cobalt salt of the dithiodiisodecylphosphoric acid ester is dried. The calculated cobalt content of the product is 6.7% by weight.
The corresponding nickel salt, calculated at 6.6% by Weight nickel, is made in a similar manner using nickel carbonate, with the reaction being conducted at 80 to 90 C.
EXAMPLE IX A sample of a base gasoline is obtained which is composed of 25 volume percent straight run gasoline, 25 volume percent light catalytically cracked gasoline, 25 volume percent butane-butylene alkylate and 25 volume percent reformed naphtha. The base gasoline analyzes 6% olefins and 20% aromatics and contains 3 cc., per gallon of TEL as Motor Mix (TEL Motor Mix contains 59.2% tetraethyl lead, 13.0% ethylene dibromide, 23.9% ethylene dichloride and 3.9% hydrocarbon diluent, dyes etc.) The base gasoline containing the tetraethyl lead has an API gravity of 61.2, an octane number of 100 by the Research Method and an octane number of 92 by the Motor Method. The ASTM distillation of the gasoline is as follows:
F. IBP 93 122 50% 201 90% 338 Into separate portions of the leaded gasoline are added either the chromium salt of Example VII in a concentration that provides 25 lbs., of the ester salt per 1000 barrels of the leaded gasoline or the vanadium salt of Example VII in a concentration that provides 25 lbs., of the leaded gasoline. The gasoline also contains 0.2 theory of cresyl diphenyl phosphate, about 2.5 pounds of phenylenediamine, an oxidation inhibitor, per 1000 barrels of gasoline and a commercial amine salt of a phosphoric acid ester corrosion inhibitor.
The above gasoline compositions when evaluated in a 1962. Chevrolet V-8, 327 cubic inch, 10.2:1 compression ratio engine exhibited an improved equilibrium rumble requirement (LIB).
EXAMPLE X The chromium and vanadium salts of Example VII when added, in the amount of 2 pounds per 1000 barrels to a leaded (3 cc. TEL as Motor Mix) gasoline composed of 37 volume percent light straight run gasoline, 23 volume percent light catalytically cracked gasoline, 13 volume percent heavy catalytically reformed gasoline and 27 volume percent heavy catalytically cracked gasoline, provides a composition of enhanced rust resistance.
EXAMPLE XI Compositions of superior rumble and octane requirement increase characteristics are the final chromium saltcontaining gasolines of Example IX also having in addition 20 lbs. per 1000 barrels of the nickel salt of Example VIII.
EXAMPLE XII A leaded (3 cc. TEL as Motor Mix gasoline composed of 14 volume percent straight run gasoline, 32.7 volume O\ /SH RO \S RO wherein R is a hydrocarbon radical of up to 30 carbon atoms, and R is selected from the group consisting of hydrogen and R and the amount of said vanadium salt being 0.002 to 0.8 milligram atoms of metal per gallon of gasoline.
2. The composition of claim 1 in which there is also included about 0.05 to 0.6 theory of a gasoline-soluble phosphorous compound having the formula and wherein R is a hydrocarbon radical of up to about 30 carbon atoms on the average, R is selected from the group consisting of hydrogen and R, and n is an integer having a value of 0 or 1.
3. The composition of claim 2 wherein at least one R in the structure of claim 2 is an alkyl phenyl radical of 7 to 15 carbon atoms.
4. The composition of claim 3 wherein the amount of phosphorus compound is abuot 0.15 to 0.5 theory.
5. The composition of claim 1 wherein the vanadium salt is a salt of a phosphorus compound having the formula RO\ /OH R'O 0 wherein R is a hydrocarbon radical of from about 8 to 18 carbon atoms, and R is selected from the group consisting of hydrogen and R, the amount of said vanadium salt being 0.025 to 0.3 milligram atoms of vanadium per gallon of gasoline.
6. The composition of claim 5 in which there is also included about 0.05 to 0.6 theory of a gasoline-soluble phosphorus compound having the formula RO\ /OR RO o wherein R is a lower alkyl phenyl radical of 7 to 15 carbon atoms and R is selected from the group consisting of phenyl and R.
7. The composition of claim 6 wherein the non-metallic phosphorus compound is cresyl diphenyl phosphate.
8. The composition of claim 1 in which there is included about 0.002 to 0.8 milligram atoms per gallon of said gasoline of a gasoline-soluble metal salt of a phosphorus compound having the formula R'O\ OH 2: R'O o wherein R is a hydrocarbon radical of up to 30 carbon atoms and R is selected from the group consisting of hydrogen and R said metal having an atomic number of from 27 to 28.
9. The composition of claim 8 in which there is also included about 0.05 to 0.6 theory of a gasoline-soluble phosphorus compound having the formula wherein R is a hydrocarbon radical of up to about 30 carbon atoms on the average, R' is selected from the group consisting of hydrogen and R, and n is an integer having a value of or 1.
10. The composition of claim 9 wherein at least one R in the structure of claim 9 is an alkyl phenyl radical of 7 to 15 carbon atoms.
11. The composition of claim 10 wherein the amount of prosphorus compound is about 0.15 to 0.5 theory.
12. The composition of claim 8 wherein the metal of atomic number 27 to 28 is nickel.
13. The composition of claim 1 wherein the vanadium salt is a salt of a phosphorus compound having the formula:
wherein R is an alkyl radical of 8 to 18 carbon atoms on the average, the amount of said vanadium salt being sufficient to provide 0.025 to 0.3 milligram atoms of vanadium per gallon of gasoline.
14. The composition of claim 13 in which there is also included about 0.05 to 0.6 theory of a gasolinesoluble phosphorus compound having the formula:
RO\ /OR RO o wherein R is a lower alkyl phenyl radical of 7 to carbon atoms on the average, and R is selected from the group consisting of phenyl and R.
15. The composition of claim 14 wherein the nonmetallic phosphorus compound is cresyl diphenyl phosphate.
16. The composition of claim 1 in which there is included about 0.002 to 0.8 milligram atoms of a gasolinesoluble metal salt of a phosphorus compound having the formula:
wherein R is a hydrocarbon radical of up to 30 carbon atoms on the average, said metal having an atomic number of from 27 to 28.
17. The composition of claim 15 in which there is also included about 16 to 195 pounds per thousand barrels of a gasoline-soluble phosphorus compound having the formula:
R 0 OR RO/ 011 wherein R is a hydrocarbon radical of up to about 30 carbon atoms on the average, R is selected from the group consisting of hydrogen and R, and n is an integer having a value of 0 to 1.
18. The composition of claim 17 wherein at least one R in the structure of claim 23 is an alkyl phenyl radical of 7 to 15 carbon atoms.
19. The composition of claim 18 wherein the amount of phosphorus compound is about 48 to pounds per thousand barrels of gasoline.
20. The composition of claim 16 wherein the metal of atomic number 27 to 28 is nickel.
21. The composition of claim 1 wherein there is included about 0.025 to 0.3 milligram atoms per gallon of gasoline of a gasoline-soluble metal salt of a phosphorus compound having the formula:
RO\ /SH I R0 s wherein R is an alkyl group of 8 to 18 carbon atoms on the average, said metal having an atomic number of from 27 to 28.
22. The composition of claim 1 wherein there is included about 0.025 to 0.3 milligram atoms per gallon of gasoline of a gasoline-soluble metal salt of a phosphorus compound having the formula:
wherein R is an alkyl group of 8 to 18 carbon atoms on the average and R is selected from the group consisting of hydrogen and R, said metal having an atomic number of from 27 to 28.
References Cited UNITED STATES PATENTS 2,889,212 6/1959 Yust et al. 44--69 3,445,206 5/1969 Revukas 44-69 DANIEL E. WYMAN, Primary Examiner Y. H. SMITH, Assistant Examiner US. Cl. X.R.
44--68, 78, Dig. 3, Dig. 4
UNITED STATES PATENT eFFroE CERTIFICATE OF CORRECTIGN Patent o, 3, 3 Dated September 28, 1971 Inventor(5) Walter F. SChOen and Frederick L. VO1Z It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column 1, line MO: "1665" should be -l965--.
Column 5, lines 2 and 3: Delete "Analysis pentoxide."
Column 7, line 9: "f0" should be --of--.
Column 8, Line 38: "abuot" should be -about-.
Column 10, line 1 "23" should be --17--.
Signed and sealed this 23rd day of May 1972.
(SEAL) Attest:
ROBERT GOTTSCI-ZALK EDWARD MFLETCHR, JR.
Commissioner of Patents Attesting Officer 'ORM PC4050 H0-691 USCOMM-DC bOL-U'G-Pfl r: us, sovznnmam PFHNTING OFFiCE lsus 0-356-334
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US72358068A | 1968-04-23 | 1968-04-23 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3608232A true US3608232A (en) | 1971-09-28 |
Family
ID=24906849
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US723580A Expired - Lifetime US3608232A (en) | 1968-04-23 | 1968-04-23 | Gasoline composition containing vanadium salts of phosphorus compounds |
Country Status (1)
Country | Link |
---|---|
US (1) | US3608232A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2421946A1 (en) * | 2009-04-22 | 2012-02-29 | Green Earth Naturally, LLC | Fuel additive |
-
1968
- 1968-04-23 US US723580A patent/US3608232A/en not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2421946A1 (en) * | 2009-04-22 | 2012-02-29 | Green Earth Naturally, LLC | Fuel additive |
EP2421946A4 (en) * | 2009-04-22 | 2012-11-21 | Green Earth Naturally Llc | Fuel additive |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US2892691A (en) | Motor fuels and motor fuel additives | |
GB753223A (en) | Improvements in and relating to motor fuels | |
CA1122800A (en) | Polyether amine-maleic anhydride in gasoline | |
US3228758A (en) | Fuels containing amine salts of alkyl acid phosphates | |
US3307928A (en) | Gasoline additives for enhancing engine cleanliness | |
US2860958A (en) | Antiknock compositions | |
EP0804524A1 (en) | Organophosphorus additives for improved fuel lubricity | |
US3231347A (en) | Gasolene composition containing organometallic orthophosphates | |
US3608232A (en) | Gasoline composition containing vanadium salts of phosphorus compounds | |
US3502452A (en) | Gasoline composition | |
US3506416A (en) | Gasoline composition | |
US3303007A (en) | Motor fuel composition | |
US2948600A (en) | Antiknock compositions | |
US2819953A (en) | Fuel composition | |
US4602919A (en) | Gasoline compositions containing malonates | |
US3481717A (en) | Gasoline composition | |
US3275668A (en) | Organometallic orthophosphates | |
US3481719A (en) | Gasoline composition | |
US3751235A (en) | Gasoline composition | |
US3282662A (en) | Organic co-antiknock agents | |
US3305330A (en) | Amine-phosphorus-containing adducts and motor fuel containing same | |
US3511623A (en) | Gasoline composition containing a metal salt of an azole compound | |
US3481718A (en) | Gasoline fuel composition | |
US2980520A (en) | Gasoline motor fuel | |
US2979523A (en) | Addition products of dialkyl acid orthophosphate and olefin oxides |