US2918361A - Stabilization of hydrocarbons - Google Patents
Stabilization of hydrocarbons Download PDFInfo
- Publication number
- US2918361A US2918361A US617210A US61721056A US2918361A US 2918361 A US2918361 A US 2918361A US 617210 A US617210 A US 617210A US 61721056 A US61721056 A US 61721056A US 2918361 A US2918361 A US 2918361A
- Authority
- US
- United States
- Prior art keywords
- ketone
- phenylene diamine
- inhibitor
- diamine
- gasoline
- 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
- 229930195733 hydrocarbon Natural products 0.000 title description 20
- 150000002430 hydrocarbons Chemical class 0.000 title description 20
- 230000006641 stabilisation Effects 0.000 title description 4
- 238000011105 stabilization Methods 0.000 title description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 35
- 239000003502 gasoline Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 10
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 7
- 150000004985 diamines Chemical class 0.000 claims description 7
- 230000006866 deterioration Effects 0.000 claims description 5
- 230000000087 stabilizing effect Effects 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 description 30
- 239000004215 Carbon black (E152) Substances 0.000 description 14
- 125000001931 aliphatic group Chemical group 0.000 description 8
- -1 for example Chemical class 0.000 description 7
- 150000002576 ketones Chemical class 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000012169 petroleum derived wax Substances 0.000 description 4
- 235000019381 petroleum wax Nutrition 0.000 description 4
- 238000005932 reductive alkylation reaction Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 230000000979 retarding effect Effects 0.000 description 3
- LSKONYYRONEBKA-UHFFFAOYSA-N 2-Dodecanone Chemical compound CCCCCCCCCCC(C)=O LSKONYYRONEBKA-UHFFFAOYSA-N 0.000 description 2
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VUVUIDMZOWHIIJ-UHFFFAOYSA-N Methyl-n-nonadecyl-keton Natural products CCCCCCCCCCCCCCCCCCCC(C)=O VUVUIDMZOWHIIJ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- IYTXKIXETAELAV-UHFFFAOYSA-N Nonan-3-one Chemical compound CCCCCCC(=O)CC IYTXKIXETAELAV-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- ZAJNGDIORYACQU-UHFFFAOYSA-N decan-2-one Chemical compound CCCCCCCCC(C)=O ZAJNGDIORYACQU-UHFFFAOYSA-N 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- VKCYHJWLYTUGCC-UHFFFAOYSA-N nonan-2-one Chemical compound CCCCCCCC(C)=O VKCYHJWLYTUGCC-UHFFFAOYSA-N 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- MRMOZBOQVYRSEM-UHFFFAOYSA-N tetraethyllead Chemical compound CC[Pb](CC)(CC)CC MRMOZBOQVYRSEM-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- VKZGZMNKJFNRAV-UHFFFAOYSA-N 1-Hexadecen-3-one Chemical compound CCCCCCCCCCCCCC(=O)C=C VKZGZMNKJFNRAV-UHFFFAOYSA-N 0.000 description 1
- KLTVSWGXIAYTHO-UHFFFAOYSA-N 1-Octen-3-one Chemical compound CCCCCC(=O)C=C KLTVSWGXIAYTHO-UHFFFAOYSA-N 0.000 description 1
- MNIGRDBXCHCIHR-UHFFFAOYSA-N 1-Tetradecen-3-one Chemical compound CCCCCCCCCCCC(=O)C=C MNIGRDBXCHCIHR-UHFFFAOYSA-N 0.000 description 1
- IEDKVDCIEARIIU-UHFFFAOYSA-N 2-Nonadecanone Chemical compound CCCCCCCCCCCCCCCCCC(C)=O IEDKVDCIEARIIU-UHFFFAOYSA-N 0.000 description 1
- CJPNOLIZCWDHJK-UHFFFAOYSA-N 2-Pentadecanone Chemical compound CCCCCCCCCCCCCC(C)=O CJPNOLIZCWDHJK-UHFFFAOYSA-N 0.000 description 1
- POQLVOYRGNFGRM-UHFFFAOYSA-N 2-Tetradecanone Chemical compound CCCCCCCCCCCCC(C)=O POQLVOYRGNFGRM-UHFFFAOYSA-N 0.000 description 1
- RHLVCLIPMVJYKS-UHFFFAOYSA-N 3-octanone Chemical compound CCCCCC(=O)CC RHLVCLIPMVJYKS-UHFFFAOYSA-N 0.000 description 1
- DPLGXGDPPMLJHN-UHFFFAOYSA-N 6-Methylheptan-2-one Chemical compound CC(C)CCCC(C)=O DPLGXGDPPMLJHN-UHFFFAOYSA-N 0.000 description 1
- ZPQAKYPOZRXKFA-UHFFFAOYSA-N 6-Undecanone Chemical compound CCCCCC(=O)CCCCC ZPQAKYPOZRXKFA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- TVTCXPXLRKTHAU-UHFFFAOYSA-N Heptadecan-2-one Chemical compound CCCCCCCCCCCCCCCC(C)=O TVTCXPXLRKTHAU-UHFFFAOYSA-N 0.000 description 1
- XCXKZBWAKKPFCJ-UHFFFAOYSA-N Hexadecan-2-one Chemical compound CCCCCCCCCCCCCCC(C)=O XCXKZBWAKKPFCJ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004264 Petrolatum Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000010730 cutting oil Substances 0.000 description 1
- XTDXBZMKUMZNMH-UHFFFAOYSA-N dec-1-en-3-one Chemical compound CCCCCCCC(=O)C=C XTDXBZMKUMZNMH-UHFFFAOYSA-N 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- HFIPGXZCEJXIAM-UHFFFAOYSA-N dodec-1-en-3-one Chemical compound CCCCCCCCCC(=O)C=C HFIPGXZCEJXIAM-UHFFFAOYSA-N 0.000 description 1
- ZAQZICGOYPRHCK-UHFFFAOYSA-N dodecan-6-one Chemical compound CCCCCCC(=O)CCCCC ZAQZICGOYPRHCK-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FHDDEBHJGWQEQF-UHFFFAOYSA-N heptadec-1-en-3-one Chemical compound CCCCCCCCCCCCCCC(=O)C=C FHDDEBHJGWQEQF-UHFFFAOYSA-N 0.000 description 1
- NFRKSAMCQGIGRC-UHFFFAOYSA-N heptadecan-7-one Chemical compound CCCCCCCCCCC(=O)CCCCCC NFRKSAMCQGIGRC-UHFFFAOYSA-N 0.000 description 1
- KCNOEZOXGYXXQU-UHFFFAOYSA-N heptatriacontan-19-one Chemical compound CCCCCCCCCCCCCCCCCCC(=O)CCCCCCCCCCCCCCCCCC KCNOEZOXGYXXQU-UHFFFAOYSA-N 0.000 description 1
- CIAHHJXQZXLMPN-UHFFFAOYSA-N hexadecan-6-one Chemical compound CCCCCCCCCCC(=O)CCCCC CIAHHJXQZXLMPN-UHFFFAOYSA-N 0.000 description 1
- XMIMKDVDMTZIIW-UHFFFAOYSA-N hexadecan-7-one Chemical compound CCCCCCCCCC(=O)CCCCCC XMIMKDVDMTZIIW-UHFFFAOYSA-N 0.000 description 1
- 239000010720 hydraulic oil Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- BGEHHAVMRVXCGR-UHFFFAOYSA-N methylundecylketone Natural products CCCCCCCCCCCCC=O BGEHHAVMRVXCGR-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- FSWDLYNGJBGFJH-UHFFFAOYSA-N n,n'-di-2-butyl-1,4-phenylenediamine Chemical compound CCC(C)NC1=CC=C(NC(C)CC)C=C1 FSWDLYNGJBGFJH-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- HILCQVNWWOARMT-UHFFFAOYSA-N non-1-en-3-one Chemical compound CCCCCCC(=O)C=C HILCQVNWWOARMT-UHFFFAOYSA-N 0.000 description 1
- YUPOCHDBBHTUBJ-UHFFFAOYSA-N nonadecan-10-one Chemical compound CCCCCCCCCC(=O)CCCCCCCCC YUPOCHDBBHTUBJ-UHFFFAOYSA-N 0.000 description 1
- XQSSCNRELFJEBR-UHFFFAOYSA-N octadec-1-en-3-one Chemical compound CCCCCCCCCCCCCCCC(=O)C=C XQSSCNRELFJEBR-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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- YFURFLWAOAZPGU-UHFFFAOYSA-N pentadec-1-en-3-one Chemical compound CCCCCCCCCCCCC(=O)C=C YFURFLWAOAZPGU-UHFFFAOYSA-N 0.000 description 1
- YSHXMTRDMDYAEC-UHFFFAOYSA-N pentadecan-6-one Chemical compound CCCCCCCCCC(=O)CCCCC YSHXMTRDMDYAEC-UHFFFAOYSA-N 0.000 description 1
- VUXXXYMMZBAUSE-UHFFFAOYSA-N pentadecan-7-one Chemical compound CCCCCCCCC(=O)CCCCCC VUXXXYMMZBAUSE-UHFFFAOYSA-N 0.000 description 1
- 229940066842 petrolatum Drugs 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- MTZWHHIREPJPTG-UHFFFAOYSA-N phorone Chemical compound CC(C)=CC(=O)C=C(C)C MTZWHHIREPJPTG-UHFFFAOYSA-N 0.000 description 1
- 229930193351 phorone Natural products 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000010731 rolling oil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010736 steam turbine oil Substances 0.000 description 1
- OAFHCOXSIJKFEV-UHFFFAOYSA-N tetradecan-6-one Chemical compound CCCCCCCCC(=O)CCCCC OAFHCOXSIJKFEV-UHFFFAOYSA-N 0.000 description 1
- ZEKPOTWCBTUBEB-UHFFFAOYSA-N tetradecan-7-one Chemical compound CCCCCCCC(=O)CCCCCC ZEKPOTWCBTUBEB-UHFFFAOYSA-N 0.000 description 1
- CNJBRDUPIHYDFA-UHFFFAOYSA-N tridec-1-en-3-one Chemical compound CCCCCCCCCCC(=O)C=C CNJBRDUPIHYDFA-UHFFFAOYSA-N 0.000 description 1
- CYIFVRUOHKNECG-UHFFFAOYSA-N tridecan-2-one Chemical compound CCCCCCCCCCCC(C)=O CYIFVRUOHKNECG-UHFFFAOYSA-N 0.000 description 1
- KPVFRXPKBAAIIE-UHFFFAOYSA-N tridecan-6-one Chemical compound CCCCCCCC(=O)CCCCC KPVFRXPKBAAIIE-UHFFFAOYSA-N 0.000 description 1
- ULIAPOFMBCCSPE-UHFFFAOYSA-N tridecan-7-one Chemical compound CCCCCCC(=O)CCCCCC ULIAPOFMBCCSPE-UHFFFAOYSA-N 0.000 description 1
- ODRZDGZUYNRFMX-UHFFFAOYSA-N tritriacontan-17-one Chemical compound CCCCCCCCCCCCCCCCC(=O)CCCCCCCCCCCCCCCC ODRZDGZUYNRFMX-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/223—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom
Definitions
- novel features of the present invention are particularly useful in the stabilization of gasoline, they also have particular utility in the stabilization of higher boiling hydrocarbons including, for example, naphthas, kerosene, mineral oil, lubricating oil, cutting oil, rolling oil, electrical oil, insulating oil, hydraulic oil, transmission oil, transformer oil, steam turbine oil, diesel oil, burner oil, fuel oil, petroleum greases, petroleum waxes, petrolatum, etc.
- the inhibitors of the present invention are comparatively nonvolatile and readily soluble in hydrocarbons. Therefore, these inhibitors also are especially suitable for use in heavier hydrocarbonaceous materials.
- the present invention relates to a method of stabilizing a hydrocarbon which comprises incorporating therein a stabilizing amount of an N,N'-disec-aliphatic-p-phenylene diamine inhibitor in which both aliphatic groups contain at least 8 carbon atoms each.
- the present invention relates to a method of stabilizing gasoline which comprises incorporating therein from about 0.001% to about 1% by weight of N,N-di-3-(5-methylheptyl) p phenylene diamine.
- the present invention relates to a method of stabilizing petroleum Wax which comprises incorporating therein from about 0.0001% to about 5% by weight of N,N'-di-4-(2,6-dimethylheptyl)- p-phenylene diamine.
- the present invention relates to a hydrocarbon stabilized with an N,N'-di-sec-aliphaticp-phenylene diamine in which both aliphatic groups contain at least 8 carbon atoms each.
- the inhibitor of the present invention comprises a specific type of N,N'-di-aliphatic-pphenylene diamine. Both aliphatic groups must contain at least 8 carbon atoms each and preferably from 8 to about 20 carbon atoms each. Furthermore, the aliphatic group must be attached to the nitrogen atom at an intermediate carbon atom of the aliphatic group, and this is designated by identifying the aliphatic groups as secaliphatic. Inhibitors having this composition and configuration appear to be of higher potency and to offer other advantages over the use of substituted phenylene diamine compounds of shorter chain alkyl groups and those in which the alkyl groups are attached at terminal carbon'atoms to the nitrogen atoms. 1
- the inhibitor compounds of the present invention reduce the intake manifold deposits in an automobile. .engineto approximately one-half of that obtained whenusing compounds, containing shorter alkyl groups.
- the inhibitors of the present invention are of improved potency in retarding deteriora- I tion of hydrocarbons, particularly deterioration caused by oxidation. These inhibitors are comparatively nonvolatile and thereby are retained satisfactorily in the hydrocarbonaceous material. tially non-toxic and therefore may be handled safely dur-' ing preparation and use. Also, the inhibitors may be used safely in petroleum Waxes which subsequently are' utilized for coating material for containers or wrappers of food products. Still further, these inhibitors are substantially Water insoluble and, therefore, will not be lost in the event that the hydrocarbonaceous material contacts Water.
- the inhibitors of the present invention may be pre-' pared in any suitable manner.
- these inhibitors are prepared by the reductive alkylation of p-phenylene diamine or p-nitroaniline with a suitable ketone.
- a suitable ketone for effecting the reductive alkylation, it will be noted that the resultant aliphatic group will be attached at an intermediate carbon atom to the nitrogen atom.
- Representative ketones suitable for use in the reductive alkylation include methyl isohexyl ketone, methyl heptyl ketone, methyl octyl ketone, meth-.
- methyl tetradecyl ketone methyl pentadecyl ketone, meth yl hexadecyl ketone, methyl heptadecyl ketone, methyl" octadecyl ketone, methyl nonadecyl ketone, methyl eicos-.
- ethyl heptyl ketone ethyl octyl ketone, ethyl nonyl ketone, ethyl decyl ketone, ethyl undecyl ketone, ethyl dodecyl ketone, etc.
- propyl butyl ketone propyl amyl ketone, propyl hexyl ketone, propyl heptyl ketone, propyl octyl ketone, propyl nonyl ketone, propyl decyl ketone,
- propyl undecyl ketone, etc. dibutyl ketone, butyl amyl ketone, butyl hexyl ketone, butyl heptyl ketone, butyl octyl ketone, butyl nonyl ketone, butyl decyl ketone, etc.,
- amyl octyl ketone amyl nonyl ketone, amyl decyl ketone,
- dihexyl ketone dihexyl ketone, hexyl heptyl ketone, hexyl octyl ketone, hexyl nonyl ketone, hexyl decyl ketone, etc.
- the reductive alkylation may be effected in any suitable manner.
- a suitable catalyst for effecting the reaction comprises a mixture of the oxides of chromium, copper and barium, although other suitable catalysts may be employed. Other catalysts include those containing cobalt, nickel, platinum, palladium, molybdenum, etc.
- the reaction is effected at an elevated tempera-" ture of from about to about 250 C. and a hydrogen pressure of from about 5 to about 200 atmospheres.
- the inhibitors are substan 3 p-phenylene diamine, N,N'-di-2-(4,8-di-methyldecyl)-pphenylene diamine, N,N-di-Z-undecyl-p-phenylene diamine, N,N'-di-2-(5,10-di-methylundecyl)-pphenylene diamine, N,Nf-di-2-dodecyl-p-phenylene diamine, N,N'-di-2- (l-methyldodecyl)-p-phenylene diamine, N,N-di-2-(4,9- di-methyldodecyl)-p-phenylene diamine, N,N'-di-2-(4,7, l'Q-trimethyldodecyl)-p-phenylene diamine, etc., N,Ndi 3- octyl-p-phenylene diamine, N,N-di-3-(5
- the inhibitor may be prepared by the reaction of p-phenylene diamine or p-nitroaniline with a suitable unsaturated ketone including, for example, vinyl amyl ketone, phorone, vinyl hexyl ketone, vinyl heptyl ketone, vinyl ojctyl ketone, vinyl nonyl ketone, vinyl decyl ketone, vinyl undecyl ketone, vinyl dodecyl ketone, vinyl tridecyl ketone, vinyl tetradecyl ketone, vinyl pentadecyl ketone, etc.
- a suitable unsaturated ketone including, for example, vinyl amyl ketone, phorone, vinyl hexyl ketone, vinyl heptyl ketone, vinyl ojctyl ketone, vinyl nonyl ketone, vinyl decyl ketone, vinyl undecyl ketone, vinyl dodecyl ketone, vinyl tride
- inhibitors in this class r N,N'-di-3-(I-QctenyU-p-phenylene diamine, N,N-di- 4 ;(2,6-di-methyl-2,5-heptadienyl)-p-phenylene diamine, etc.
- This reaction is effected in substantially the same manner as hereinbefore set forth and, depending upon the extent, of hydrogenation, the product may comprise N,N'-di-alkenyl-p-phenylene diamine or a mixture of an N,N'-di-alkenyl-p-phenylene diamine and N,N'-di-alkylp-phenylene diamine.
- the inhibitor of the present invention may be incorporated in the hydrocarbon in any suitable manner.
- the hydrocarbon is a liquid
- the inhibitor compound may be readily dissolved therein and preferably is followed by suitable mixing in order to obtain complete mixing of the inhibitor with the hydrocarbon.
- the hydrocarbon is a solid
- the inhibitor may be dissolved therein by suitable mixing and, when desired, mild heating of the hydrocarbon followed by suitable mixing.
- the inhibitor compound is a solid, it may be dissolvedin the hydrocarbon as such or it may be dissolved in a suitable solvent including hydrocarbon, ketone, ether, etc., or the inhibitor compound may be heated to liquefy it and then utilized as a liquid.
- the inhibitor will be used in an amount of from about 0.0001% to about 5% by weight of the hydrocarbon, although in some cases lower or higher concentrations may be employed.
- concentration to be used will depend upon the particular hydrocarbon fraction being treated. In most cases, concentrations of from about 0.0001% to about 1% and more particularly from about 0.001% to about 1% by weight generally will be employed.
- the inhibitor of the present invention may be used along with other additives incorporated in the. hydrocarbon fraction.
- the other additives will depend upon the particular hydrocarbon fraction being treated.
- a metal deactivator, tetraethyl lead, dye, etc. may be incorporated in the gasoline.
- various supplementary nontoxic inhibitors, synergists, etc. are employed.
- it. is .understood thatother antioxidants maybe 4 used along with the inhibitor of the present invention and, when desired, the inhibitor and other additives may be prepared as a mixture with one or more of these additives and incorporated in this manner in the hydrocarbon fraction.
- Example I N,N'-di-3-(5-methylheptyl)-p-phenylene diamine is used in a concentration of 0.01% by weight to stabilize a Pennsylvania cracked gasoline having an uninhibited induction period of 100 minutes. Upon the addition of the inhibitor as hereinbefore set forth, the induction period of the gasoline is increased sutficiently for satisfactory use of the gasoline.
- Example II 0.05% by weight of N,N'-di-4-(2,6-di-rnethylheptyl)-pphenylene diamine is incorporated in petroleum wax. This serves to retard oxidative deterioration of th e wax.
- Example III As hereinbefore set fo'rth, a particular advantageto the use of the inhibitor compounds of the present invention is the reduction in intake manifold deposits. This illustrated in comparative tests conducted with a gasoline comprising a blend of catalytic reformed, straight run and thermally cracked gasolines, the blend having an ASTM gum content of 6 mg. These runs were made in a Chevrolet engine operated at the following conditions:
- Gasoline comprising a substantial proportionof cracked gasoline normally subject to oxidative-deterioration and containing a stabilizing-amount of a compound selected from the group consisting of N,N'.-di-3-(5-mth.
Description
STABILIZATION OF HY DROCARBONS Joseph A. Chenicek, Prairie View, and Robert H. Rosenwald, Western Springs, Ill., assignors, by mesne assignments, to Universal i] Products Company, Des Plaines, Ill. a corporation of Delaware j No Drawing. Application October 22, 1956 Serial No. 617,210
'5 Claims. (Cl. 44-74) This application is a continuation-in-part of copending application Serial No. 425,755, filed April 26, 1954, now abandoned, and relates more particularly to a novel method of preventing and/or retarding deterioration of hydrocarbons.
While the novel features of the present invention are particularly useful in the stabilization of gasoline, they also have particular utility in the stabilization of higher boiling hydrocarbons including, for example, naphthas, kerosene, mineral oil, lubricating oil, cutting oil, rolling oil, electrical oil, insulating oil, hydraulic oil, transmission oil, transformer oil, steam turbine oil, diesel oil, burner oil, fuel oil, petroleum greases, petroleum waxes, petrolatum, etc. As will be hereinafter set forth, the inhibitors of the present invention are comparatively nonvolatile and readily soluble in hydrocarbons. Therefore, these inhibitors also are especially suitable for use in heavier hydrocarbonaceous materials.-
In one embodiment the present invention relates to a method of stabilizing a hydrocarbon which comprises incorporating therein a stabilizing amount of an N,N'-disec-aliphatic-p-phenylene diamine inhibitor in which both aliphatic groups contain at least 8 carbon atoms each.
' Ina specific embodiment the present invention relates to a method of stabilizing gasoline which comprises incorporating therein from about 0.001% to about 1% by weight of N,N-di-3-(5-methylheptyl) p phenylene diamine.
In another specific embodiment the present invention relates to a method of stabilizing petroleum Wax which comprises incorporating therein from about 0.0001% to about 5% by weight of N,N'-di-4-(2,6-dimethylheptyl)- p-phenylene diamine.
In another embodiment the present invention relates to a hydrocarbon stabilized with an N,N'-di-sec-aliphaticp-phenylene diamine in which both aliphatic groups contain at least 8 carbon atoms each.
It will be noted that the inhibitor of the present invention comprises a specific type of N,N'-di-aliphatic-pphenylene diamine. Both aliphatic groups must contain at least 8 carbon atoms each and preferably from 8 to about 20 carbon atoms each. Furthermore, the aliphatic group must be attached to the nitrogen atom at an intermediate carbon atom of the aliphatic group, and this is designated by identifying the aliphatic groups as secaliphatic. Inhibitors having this composition and configuration appear to be of higher potency and to offer other advantages over the use of substituted phenylene diamine compounds of shorter chain alkyl groups and those in which the alkyl groups are attached at terminal carbon'atoms to the nitrogen atoms. 1
As an illustration of a particular advantage offered by the inhibitor compounds of the present invention as compared to similar compounds containing shorter chain alkyl groups, the inhibitor compounds of the present invention reduce the intake manifold deposits in an automobile. .engineto approximately one-half of that obtained whenusing compounds, containing shorter alkyl groups.
This will be illustrated in Example III of the presentapplication. The reduction of intake manifold deposits obviously is of importance because it permits long time operation of the engine and will not result in plugging of the manifold and accordingly failure of the engine ina.
shorter period of time.
As hereinbefore set forth, the inhibitors of the present invention are of improved potency in retarding deteriora- I tion of hydrocarbons, particularly deterioration caused by oxidation. These inhibitors are comparatively nonvolatile and thereby are retained satisfactorily in the hydrocarbonaceous material. tially non-toxic and therefore may be handled safely dur-' ing preparation and use. Also, the inhibitors may be used safely in petroleum Waxes which subsequently are' utilized for coating material for containers or wrappers of food products. Still further, these inhibitors are substantially Water insoluble and, therefore, will not be lost in the event that the hydrocarbonaceous material contacts Water.
The inhibitors of the present invention may be pre-' pared in any suitable manner. In a preferred method, these inhibitors are prepared by the reductive alkylation of p-phenylene diamine or p-nitroaniline with a suitable ketone. When using a ketone for effecting the reductive alkylation, it will be noted that the resultant aliphatic group will be attached at an intermediate carbon atom to the nitrogen atom. Representative ketones suitable for use in the reductive alkylation include methyl isohexyl ketone, methyl heptyl ketone, methyl octyl ketone, meth-.
yl nonyl ketone, methyl decyl ketone, methyl undecyl ketone, methyl dodecyl ketone, methyl tridecyl ketone,
methyl tetradecyl ketone, methyl pentadecyl ketone, meth yl hexadecyl ketone, methyl heptadecyl ketone, methyl" octadecyl ketone, methyl nonadecyl ketone, methyl eicos-.
yl ketone, etc., ethyl amyl ketone, ethyl hexyl ketone,
ethyl heptyl ketone, ethyl octyl ketone, ethyl nonyl ketone, ethyl decyl ketone, ethyl undecyl ketone, ethyl dodecyl ketone, etc., propyl butyl ketone, propyl amyl ketone, propyl hexyl ketone, propyl heptyl ketone, propyl octyl ketone, propyl nonyl ketone, propyl decyl ketone,
propyl undecyl ketone, etc., dibutyl ketone, butyl amyl ketone, butyl hexyl ketone, butyl heptyl ketone, butyl octyl ketone, butyl nonyl ketone, butyl decyl ketone, etc.,
diamyl ketone, amyl hexyl ketone, amyl heptyl ketone,
amyl octyl ketone, amyl nonyl ketone, amyl decyl ketone,
etc., dihexyl ketone, hexyl heptyl ketone, hexyl octyl ketone, hexyl nonyl ketone, hexyl decyl ketone, etc.
The reductive alkylation may be effected in any suitable manner. A suitable catalyst for effecting the reaction comprises a mixture of the oxides of chromium, copper and barium, although other suitable catalysts may be employed. Other catalysts include those containing cobalt, nickel, platinum, palladium, molybdenum, etc. In. general, the reaction is effected at an elevated tempera-" ture of from about to about 250 C. and a hydrogen pressure of from about 5 to about 200 atmospheres.
octyl)-p-phenylene diamine, N,N'-di-2-nonyl-p-phenylene diamine, N,N'-di-2-(7-methylnonyl)-p-phenylene diamine, N,N-di-2-decyl-p-phenylene diamine, N,N'-di-2-(4-rneth-- yldecyl) -p-phenylene diamine, N,N'-di-2-(S-methyddecyl) Ice Patented Dec. 22,1950
The inhibitors are substan 3 p-phenylene diamine, N,N'-di-2-(4,8-di-methyldecyl)-pphenylene diamine, N,N-di-Z-undecyl-p-phenylene diamine, N,N'-di-2-(5,10-di-methylundecyl)-pphenylene diamine, N,Nf-di-2-dodecyl-p-phenylene diamine, N,N'-di-2- (l-methyldodecyl)-p-phenylene diamine, N,N-di-2-(4,9- di-methyldodecyl)-p-phenylene diamine, N,N'-di-2-(4,7, l'Q-trimethyldodecyl)-p-phenylene diamine, etc., N,Ndi 3- octyl-p-phenylene diamine, N,N-di-3-(5-methyloctyl)- p-phenylene diamine, N,N-di-3-(5,7-dimethyloctyl)-pphenylene diamine, N,N-di-3-nonyl-p-phenylene diamine, N,N-di-3-(7-methylnonyl)-p-phenylene diamine, N,N'- di-B-decyl-p-phenylene diamine, N,N-di-3-(5,9-dimethyldecyl)-p-phenylene diamine, N,N'-di-3-(6-ethyldecyl)-pphenylene diamine, N,N'-di-3-undecyl-p-phenylene diarfiine, N,N '-di-3-(9-methylundecyl)-p-phenylene diamine, N,Nf di 3 (6,9 di ethylundecyl) p phenylene diamine, N,N'-di-3-dodecyl-p-phenylene diamine, N,N- di-3-(6-methyldodecyl)-p-phenylene diamine, N,N.'-di-3- (IO-ethyldodecyl)-p-phenylene diamine, N,N'-di-3-(5- ethyl-1l-methyldodecyl)-p-phenylene diamine, etc.
When the aliphatic groups comprise alkenyl groups, the inhibitor may be prepared by the reaction of p-phenylene diamine or p-nitroaniline with a suitable unsaturated ketone including, for example, vinyl amyl ketone, phorone, vinyl hexyl ketone, vinyl heptyl ketone, vinyl ojctyl ketone, vinyl nonyl ketone, vinyl decyl ketone, vinyl undecyl ketone, vinyl dodecyl ketone, vinyl tridecyl ketone, vinyl tetradecyl ketone, vinyl pentadecyl ketone, etc. Representative examples of inhibitors in this class r N,N'-di-3-(I-QctenyU-p-phenylene diamine, N,N-di- 4 ;(2,6-di-methyl-2,5-heptadienyl)-p-phenylene diamine, etc. This reaction is effected in substantially the same manner as hereinbefore set forth and, depending upon the extent, of hydrogenation, the product may comprise N,N'-di-alkenyl-p-phenylene diamine or a mixture of an N,N'-di-alkenyl-p-phenylene diamine and N,N'-di-alkylp-phenylene diamine.
It is understood that the various inhibitors which may be prepared and used in accordance with the present invention are not necessarily equivalent in the same or different hydrocarbons but all of them will be efiective in retarding oxidative deterioration thereof.
The inhibitor of the present invention may be incorporated in the hydrocarbon in any suitable manner. When the hydrocarbon is a liquid, the inhibitor compound may be readily dissolved therein and preferably is followed by suitable mixing in order to obtain complete mixing of the inhibitor with the hydrocarbon. Similarly, when the hydrocarbon is a solid, the inhibitor may be dissolved therein by suitable mixing and, when desired, mild heating of the hydrocarbon followed by suitable mixing. When the inhibitor compound is a solid, it may be dissolvedin the hydrocarbon as such or it may be dissolved in a suitable solvent including hydrocarbon, ketone, ether, etc., or the inhibitor compound may be heated to liquefy it and then utilized as a liquid.
In general, the inhibitor will be used in an amount of from about 0.0001% to about 5% by weight of the hydrocarbon, although in some cases lower or higher concentrations may be employed. The exact concentration to be used will depend upon the particular hydrocarbon fraction being treated. In most cases, concentrations of from about 0.0001% to about 1% and more particularly from about 0.001% to about 1% by weight generally will be employed.
. When desired, the inhibitor of the present invention may be used along with other additives incorporated in the. hydrocarbon fraction. The other additives will depend upon the particular hydrocarbon fraction being treated. For example, in gasoline a metal deactivator, tetraethyl lead, dye, etc., may be incorporated in the gasoline. When incorporated in wax for subsequent use in. contact food products, various supplementary nontoxic inhibitors, synergists, etc. are employed. In any event, it. is .understood thatother antioxidants maybe 4 used along with the inhibitor of the present invention and, when desired, the inhibitor and other additives may be prepared as a mixture with one or more of these additives and incorporated in this manner in the hydrocarbon fraction.
The following examples are introduced to illustrate further the novelty and utility of the present invention but not with the intention of unduly limiting the same.
Example I N,N'-di-3-(5-methylheptyl)-p-phenylene diamine is used in a concentration of 0.01% by weight to stabilize a Pennsylvania cracked gasoline having an uninhibited induction period of 100 minutes. Upon the addition of the inhibitor as hereinbefore set forth, the induction period of the gasoline is increased sutficiently for satisfactory use of the gasoline.
Example II 0.05% by weight of N,N'-di-4-(2,6-di-rnethylheptyl)-pphenylene diamine is incorporated in petroleum wax. This serves to retard oxidative deterioration of th e wax.
Example III As hereinbefore set fo'rth, a particular advantageto the use of the inhibitor compounds of the present invention is the reduction in intake manifold deposits. This illustrated in comparative tests conducted with a gasoline comprising a blend of catalytic reformed, straight run and thermally cracked gasolines, the blend having an ASTM gum content of 6 mg. These runs were made in a Chevrolet engine operated at the following conditions:
Speed r.p.m 2500 Load B.H.P 30 Jacket temp. F Oil temp -Q F... 65 Air-fuel ratio F..- 14.5 Duration hours 60 deposits were measured. These results are reported below:
Additive: Deposit, grams None 24.9 N,N-di-sec-butyl-p-phenylene diamine 12.4 N,N di 3 (5 methylheptyl) p phenylene diamine 6.2
From the above data, it will be noted that the intake manifold deposits were reduced approximately one-half by the addition of N,N'-di-sec-butyl-p-phenylene diamine. While this is an important reduction in the intake manifold deposits, it will be noted that N,N'-di-3-(5-methylheptyl)-p-phenylene diamine reduced the intake manifold deposits to approximately one-quarter of that obtained with the control sample of gasoline and to approximately one-half of that obtained with the gasoline containing N,N'-di'sec-butyl-p-phenylene diamine. As hereinbefore set forth, this reductio'n in intake manifold deposits is of importance and serves to prolong the satisfactory operation of the engine.
a We claim as our invention:
1. Gasoline comprising a substantial proportionof cracked gasoline normally subject to oxidative-deterioration and containing a stabilizing-amount of a compound selected from the group consisting of N,N'.-di-3-(5-mth.
References Cited in the file of this patent UNITED STATES PATENTS Dryer June 14, 1938 Woods et a1. June 13, 1944 Thompson Feb. 28, 1950 Thompson Sept. 5, 1950 Thompson June 22, 1954 Bell ct a1 Oct. 19, 1954 Moriarty Nov. 9, 1954 De Pree Jan. 3, 1956 Biswell Feb. 14, 1956 McCoy Apr. 17, 1956
Claims (1)
1. GASOLINE COMPRISING A SUBSTANTIAL PROPORTION OF CRACKED GASOLINE NORMALLY SUBJECT TO OXIDATIVE DETERIORATION AND CONTAINING A STABILIZING AMOUNT OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF N,N''-DI-3-(5-METHYLHEPTYL) P-PHENYLENE DIAMINE AND N,N''-DI-2-OCTYL-PPHENYLENE DIAMINE.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BE592769D BE592769A (en) | 1956-10-22 | ||
US617210A US2918361A (en) | 1956-10-22 | 1956-10-22 | Stabilization of hydrocarbons |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US617210A US2918361A (en) | 1956-10-22 | 1956-10-22 | Stabilization of hydrocarbons |
Publications (1)
Publication Number | Publication Date |
---|---|
US2918361A true US2918361A (en) | 1959-12-22 |
Family
ID=24472713
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US617210A Expired - Lifetime US2918361A (en) | 1956-10-22 | 1956-10-22 | Stabilization of hydrocarbons |
Country Status (2)
Country | Link |
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US (1) | US2918361A (en) |
BE (1) | BE592769A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US3404087A (en) * | 1965-01-04 | 1968-10-01 | Eastman Kodak Co | Stabilizing and sweetening additive for hydrocarbons |
US5509944A (en) * | 1994-08-09 | 1996-04-23 | Exxon Chemical Patents Inc. | Stabilization of gasoline and gasoline mixtures |
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US2120244A (en) * | 1935-08-31 | 1938-06-14 | Universal Oil Prod Co | Treatment of motor fuel |
US2351384A (en) * | 1942-11-18 | 1944-06-13 | Shell Dev | Lithium soap grease |
US2498630A (en) * | 1945-10-27 | 1950-02-28 | Universal Oil Prod Co | Stabilization of organic compounds |
US2521425A (en) * | 1948-02-13 | 1950-09-05 | Universal Oil Prod Co | Stabilization of phenylene diamines and aminophenols with amine-sulfur dioxide reaction products |
US2681935A (en) * | 1951-09-28 | 1954-06-22 | Universal Oil Prod Co | Stabilization of aryl amino compounds |
US2692288A (en) * | 1951-03-29 | 1954-10-19 | Eastman Kodak Co | Production of n-tertiary alkylated aromatic secondary diamines |
US2694034A (en) * | 1950-06-30 | 1954-11-09 | Universal Oil Prod Co | Treatment of saturated distillates |
US2729691A (en) * | 1951-10-27 | 1956-01-03 | Ethyl Corp | Synergistic stabilizing compositions for organic materials comprising a mixture of an arylamine and an alkylenediamine |
US2734808A (en) * | 1956-02-14 | P-phenylenediamine gasoline stabilizers | ||
US2742349A (en) * | 1952-02-25 | 1956-04-17 | Ethyl Corp | Synergistic stabilizing compositions |
-
0
- BE BE592769D patent/BE592769A/xx unknown
-
1956
- 1956-10-22 US US617210A patent/US2918361A/en not_active Expired - Lifetime
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2734808A (en) * | 1956-02-14 | P-phenylenediamine gasoline stabilizers | ||
US2120244A (en) * | 1935-08-31 | 1938-06-14 | Universal Oil Prod Co | Treatment of motor fuel |
US2351384A (en) * | 1942-11-18 | 1944-06-13 | Shell Dev | Lithium soap grease |
US2498630A (en) * | 1945-10-27 | 1950-02-28 | Universal Oil Prod Co | Stabilization of organic compounds |
US2521425A (en) * | 1948-02-13 | 1950-09-05 | Universal Oil Prod Co | Stabilization of phenylene diamines and aminophenols with amine-sulfur dioxide reaction products |
US2694034A (en) * | 1950-06-30 | 1954-11-09 | Universal Oil Prod Co | Treatment of saturated distillates |
US2692288A (en) * | 1951-03-29 | 1954-10-19 | Eastman Kodak Co | Production of n-tertiary alkylated aromatic secondary diamines |
US2681935A (en) * | 1951-09-28 | 1954-06-22 | Universal Oil Prod Co | Stabilization of aryl amino compounds |
US2729691A (en) * | 1951-10-27 | 1956-01-03 | Ethyl Corp | Synergistic stabilizing compositions for organic materials comprising a mixture of an arylamine and an alkylenediamine |
US2742349A (en) * | 1952-02-25 | 1956-04-17 | Ethyl Corp | Synergistic stabilizing compositions |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US3404087A (en) * | 1965-01-04 | 1968-10-01 | Eastman Kodak Co | Stabilizing and sweetening additive for hydrocarbons |
US5509944A (en) * | 1994-08-09 | 1996-04-23 | Exxon Chemical Patents Inc. | Stabilization of gasoline and gasoline mixtures |
Also Published As
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