US2441172A - Modified fuels and lubricants - Google Patents
Modified fuels and lubricants Download PDFInfo
- Publication number
- US2441172A US2441172A US429131A US42913142A US2441172A US 2441172 A US2441172 A US 2441172A US 429131 A US429131 A US 429131A US 42913142 A US42913142 A US 42913142A US 2441172 A US2441172 A US 2441172A
- Authority
- US
- United States
- Prior art keywords
- derivatives
- produced
- compounds
- fuel
- motor
- 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
- 239000000446 fuel Substances 0.000 title description 127
- 239000000314 lubricant Substances 0.000 title description 10
- 238000000034 method Methods 0.000 description 48
- 238000006243 chemical reaction Methods 0.000 description 40
- 150000001875 compounds Chemical class 0.000 description 38
- 238000011282 treatment Methods 0.000 description 33
- 239000000975 dye Substances 0.000 description 28
- 229930195733 hydrocarbon Natural products 0.000 description 27
- 150000002430 hydrocarbons Chemical class 0.000 description 27
- 239000004215 Carbon black (E152) Substances 0.000 description 26
- 238000004519 manufacturing process Methods 0.000 description 24
- 150000008049 diazo compounds Chemical class 0.000 description 23
- 239000000470 constituent Substances 0.000 description 21
- 239000000463 material Substances 0.000 description 21
- 150000001412 amines Chemical class 0.000 description 20
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 20
- -1 dimethylanili-ne Chemical compound 0.000 description 19
- 239000003502 gasoline Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 150000004795 grignard reagents Chemical class 0.000 description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 10
- 238000004821 distillation Methods 0.000 description 10
- 239000004615 ingredient Substances 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 9
- 238000011065 in-situ storage Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 150000002989 phenols Chemical class 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 7
- 239000010687 lubricating oil Substances 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 150000002429 hydrazines Chemical class 0.000 description 6
- RSAZYXZUJROYKR-UHFFFAOYSA-N indophenol Chemical compound C1=CC(O)=CC=C1N=C1C=CC(=O)C=C1 RSAZYXZUJROYKR-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 5
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 5
- 239000000987 azo dye Substances 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 230000000875 corresponding effect Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 239000003209 petroleum derivative Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000001117 sulphuric acid Substances 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 3
- 238000003747 Grignard reaction Methods 0.000 description 3
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 150000004982 aromatic amines Chemical class 0.000 description 3
- 229950011260 betanaphthol Drugs 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- QZHXKQKKEBXYRG-UHFFFAOYSA-N 4-n-(4-aminophenyl)benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1NC1=CC=C(N)C=C1 QZHXKQKKEBXYRG-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001540 azides Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- CLRSZXHOSMKUIB-UHFFFAOYSA-M benzenediazonium chloride Chemical compound [Cl-].N#[N+]C1=CC=CC=C1 CLRSZXHOSMKUIB-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000006193 diazotization reaction Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical class [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229940046892 lead acetate Drugs 0.000 description 2
- 150000002611 lead compounds Chemical class 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- LGDPTPLJZGPOJL-UHFFFAOYSA-N n,n-dimethyl-2-nitrosoaniline Chemical compound CN(C)C1=CC=CC=C1N=O LGDPTPLJZGPOJL-UHFFFAOYSA-N 0.000 description 2
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 2
- VPCDQGACGWYTMC-UHFFFAOYSA-N nitrosyl chloride Chemical compound ClN=O VPCDQGACGWYTMC-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- GZSUIHUAFPHZSU-UHFFFAOYSA-N 9-ethyl-2,3-dihydro-1h-carbazol-4-one Chemical compound C12=CC=CC=C2N(CC)C2=C1C(=O)CCC2 GZSUIHUAFPHZSU-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- 239000005749 Copper compound Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical group O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 1
- 239000004157 Nitrosyl chloride Substances 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000000297 Sandmeyer reaction Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- WBLCSWMHSXNOPF-UHFFFAOYSA-N [Na].[Pb] Chemical compound [Na].[Pb] WBLCSWMHSXNOPF-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229960003116 amyl nitrite Drugs 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- CIZVQWNPBGYCGK-UHFFFAOYSA-N benzenediazonium Chemical compound N#[N+]C1=CC=CC=C1 CIZVQWNPBGYCGK-UHFFFAOYSA-N 0.000 description 1
- RRRODXJHANJPEB-UHFFFAOYSA-L benzenediazonium;sulfate Chemical compound [O-]S([O-])(=O)=O.N#[N+]C1=CC=CC=C1.N#[N+]C1=CC=CC=C1 RRRODXJHANJPEB-UHFFFAOYSA-L 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 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
- 238000004040 coloring Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- IUOALNGUUSBIEJ-UHFFFAOYSA-N diazomethanamine Chemical compound NC=[N+]=[N-] IUOALNGUUSBIEJ-UHFFFAOYSA-N 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- LZDSILRDTDCIQT-UHFFFAOYSA-N dinitrogen trioxide Chemical compound [O-][N+](=O)N=O LZDSILRDTDCIQT-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- WHRIKZCFRVTHJH-UHFFFAOYSA-N ethylhydrazine Chemical compound CCNN WHRIKZCFRVTHJH-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000000727 fraction Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 239000008241 heterogeneous mixture Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 150000002680 magnesium Chemical class 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- CSDTZUBPSYWZDX-UHFFFAOYSA-N n-pentyl nitrite Chemical compound CCCCCON=O CSDTZUBPSYWZDX-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IQZPDFORWZTSKT-UHFFFAOYSA-N nitrosulphonic acid Chemical compound OS(=O)(=O)[N+]([O-])=O IQZPDFORWZTSKT-UHFFFAOYSA-N 0.000 description 1
- BMNDJWSIKZECMH-UHFFFAOYSA-N nitrosyl bromide Chemical compound BrN=O BMNDJWSIKZECMH-UHFFFAOYSA-N 0.000 description 1
- 235000019392 nitrosyl chloride Nutrition 0.000 description 1
- 239000012457 nonaqueous media Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 239000003027 oil sand Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- 150000004031 phenylhydrazines Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- KAQHZJVQFBJKCK-UHFFFAOYSA-L potassium pyrosulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OS([O-])(=O)=O KAQHZJVQFBJKCK-UHFFFAOYSA-L 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000001044 red dye Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- UOCLRXFKRLRMKV-UHFFFAOYSA-N trolnitrate phosphate Chemical compound OP(O)(O)=O.OP(O)(O)=O.[O-][N+](=O)OCCN(CCO[N+]([O-])=O)CCO[N+]([O-])=O UOCLRXFKRLRMKV-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/003—Marking, e.g. coloration by addition of pigments
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/226—Organic compounds containing nitrogen containing at least one nitrogen-to-nitrogen bond, e.g. azo compounds, azides, hydrazines
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
- C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
- C10M171/007—Coloured or dyes-containing lubricant compositions
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
-
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/18—Containing nitrogen-to-nitrogen bonds, e.g. hydrazine
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/18—Containing nitrogen-to-nitrogen bonds, e.g. hydrazine
- C10M2215/182—Azo compounds
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/221—Six-membered rings containing nitrogen and carbon only
-
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
- C10M2215/226—Morpholines
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/30—Heterocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/02—Groups 1 or 11
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/06—Groups 3 or 13
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/08—Groups 4 or 14
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/10—Groups 5 or 15
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/12—Groups 6 or 16
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/14—Group 7
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/16—Groups 8, 9, or 10
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2070/00—Specific manufacturing methods for lubricant compositions
- C10N2070/02—Concentrating of additives
Definitions
- This invention relates to hydrocarbon distillates including such distillates lighter than kerosene, particularly in the range of motor fuels and lubricants, which distillates contain constituents to modify their characteristics desirably, for fuel or lubricant purposes including such fuel or lubricant modifying components which serve such purposes as antioxidants, anti-knock components, anti-gum agents, dyes, etc.
- Particular objects of the present invention include the production of such modified distillates containing modifying components which dye or color the mixture, and more particularly when produced in situ in the distillates, desirably from components at least one of which is present or formed in the distillate, whether fuel or lubricant, from constituents present in such fuel or lubricant as formed by normal processes under which such distillates are produced.
- the present application is concerned with the preparation of metallo-organic and other derivatives directly in the fuel or analogous material, and preferably from constituents of the fuel or analogous material itself without the addition of extraneous hydrocarbon sources is particularly emphasized, the oil-s of hydrocarbon character or their derivatives or fractions or distillates being converted into compounds in part, or to a limited extent, which upon further treatment are readily converted into the metallo-organo and other derivatives.
- extraneous substances either for the purpose of forming the metalloorganic substances within the fuel, or as a partial source for such metallo-organic and other substances, some of the latter also being derived from the fuel or analogous material, may also be added to the gasoline or other material treated.
- the hydrocarbon materials treated may be the hydrocarbon oils, their fractions and distillates including the gasolines, produced by various processes and other hydrocarbon products that have fuel value.
- gasolines for example, may be those from straight distillation processes, from cracking processes either in the presence or .absence of air, from natural gas, etc., etc;
- the metallo-organo derivatives are to be produced of the alkyl type, it is desirable to have present in the gasolines or other hydrocarbon product, lower members of the paraffin series, and consequently gasolines containing such lower paraflins, such as ethane, propane and butane are particularly desirable, but the gasolines containing aromatics also are readily converted into the desired metallo-organic compounds.
- Gasolines and related materials produced during cracking or analogous heat and pressure treatment in the presence of air are highly advantageous, and more particularly when in such processes the gasolines produced contain even a small amount of Oxygen-containing substances, such as the ethers, since such oxygencontaining substances often actcatalytically in the processes of converting some of the described intermediate substances into metallo-organic compounds.
- Oxygen-containing substances such as the ethers
- the presence of such oxygen-containing compounds as the aldehydes, ketones, etc., are desirable for other purposes set forth below. Diesel fuels are, of course, included.
- lead tin
- silicon antimony
- arsenic phosphorus
- mercury thallium
- Lead compounds are particularly used for illustrative purposes therein in view of the wide use of lead compounds.
- other metals such as copper, chromium, zinc, etc., may be utilized.
- the metallo organic compounds do not have to be separately handled.
- the production of such metallo organic compounds in the fuel and from fuel constituents may be carried outso that the fuel is present in a more limited quantity whereby a concentrated metallo-organic containing product'is obtained which may be secured by distilling ofi the hydrocarbon products present, or which subsequently be diluted with more fuel or gasoline or related substance to the concentration desired, or the metallo organic substance or substances may be prepared in the gasoline or analogous material in a very dilute condition, so that further dilution is unnecessary, and the special fuel is directly produced Without more.
- the preparation of the desired ingredients in very dilute condition is particularly desirable where some of the constituents thus produced are not very soluble in the motor fuels, although the very small quantities of such mate. rials present needed for anti-knock, antioxidant,
- catalysts particularly ,reterred t as Grig-nard catalysts are particularly referred to, including for example, primary, secondary, tertiar amines, and their .alkyl addition productssuch amines being aliphatic, aromatic or heterocycl-ic derivatives.
- primary, secondary, tertiar amines, and their .alkyl addition products such amines being aliphatic, aromatic or heterocycl-ic derivatives.
- amines being aliphatic, aromatic or heterocycl-ic derivatives.
- Other desirable catalysts or agents that. may be present include ether, ethers in general, ammonia and itsderivatives, esters.
- These compounds may exist in the gasoline or other material undergoing treatment, so the addition of such catalysts is not specifically necessary. And this is particularly .trueain connection with the g-asolines produced by oxida- .tion processes, including both those of the vapor and liquidphase oxidation reactions.
- Other compounds,.like the amines, etc., etc., referred to above may be present in the gasoline byvarious methods, as indicated'below, wherein they ma be produced from constituents; of the gasolines themselves, or may be. introduced from external sources.
- the catalyst added may be selected from the named substances or other derivatives, particularly with regard to their value in fuel compositions, for example, the simpler others, and the amines. particularly the aromatic series thus being indicated.
- the metallo-organo derivatives may be produced in various ways, for example, by methods set forth in Patents Nos. 2.012356, 2134.625, and. application Seria No. 323 840. .filed March 13, 1940. now Patent No. 2,272 134. dated Feb. 3. 1942, of which the instant specification is a continuation-in-part.
- Grignards are well known as excellent intermediates for the synthesis of a number of organic compounds. So that they may be used as set forth. in the prior description to form a large .number of organic compounds that have value in distillates. For example, by appropriate treatments, they may be converted into alcohols, phenols, aldehydes, ketones, etc. And these reactions may be utilized so that a portion of the G-rignard reagents are converted into the metallo derivatives and a portion into other organic conipounds.
- many of the products may be made in the fuel from the halides by taking crude hydrocarbon materials that must be subjected to distillation or other treatment, or treatments, in order to obtain motor fuels from them, by adding the requisite materials to them to form the metallo compounds, or converting a portion of .such crude materials into compounds that will .form metallo derivatives, and then carrying out the distillation or other treatments, so that a gasoline or analogous material or fuel is obtained containing the metallo-organic compounds that have been formed during the distillation or other treatment, which may or may not have been carried out under pressure.
- halogenated fractions as for example, halogenated motor fuel fractions which may accordingly be treated as set forth above.
- introduction of halogen followed by contact of the halogenated product with the sodium lead alloy, for example, before distillation, or at various stages thereof, will result in fractions such as motor fuels produced with the metallo derivatives in the fuel during the distillation.
- the Grignard reagents as indicated above, are .utillzable. however in many other directions for the production of both metallo derivatives other than those of the alkyl and aryl types strictly, and also for the production of many valuable ingredients in motor fuels and lubricants which do not necessarily contain any metallo component.
- the metallo-aryl Grignard reagents may also be desirably employed in the production of are compounds, for example, benzene magnesium iodide yielding with benzene diazonium chloride, azo benzene in accordance with the following re action.
- Such azo compounds are desirable components inmntor fuels, and these types of reactions of whichthat illustrated is merely exemplary may be utilized in the production of azo dyes in the motor fuels from constituents thereof, as more fully explained below.
- the Grignard reagents are easily produced in the motor fuel from constituents thereof as set forth above,and the diazo compounds may also be produced herein both by methods explained above and by subsequent methods, and such constituents produced in the motor fuel then permitted to react to produce the azo compounds.
- Substituted azo compounds of the true dye type may thus be produced in the motor fuel, and in view of their production in complex mixtures in such motor fuel from derivatives thereof, dyes can be produced in the motor fuel that remain in solution therein, which is dinicult in the production of many types of dyes by extraneous reactions, followed by their incorporation into motor fuels. Entirely new varieties of dyes in complex mixtures are thus producible in the motor fuel from constituents in this way.
- the Grignard reagents may be produced from the motor fuels themselves, and reacted with diazo salts produced outside of the motor fuels, or as noted above, the diazo salts may also be produced in the motor fuels, or a portion thereof for reaction with the Grignard reagents. Or, as explained below, the diazo compounds may be produced from the motor fuel constituents themselves and reacted with Grignard reagents from external sources.
- the amines have been produced in the motor fuel, or are present therein, and they may, of course, be added from extraneous sources for this purpose, but desirably they are produced in complex mixture in the motor fuels themselves by any of the methods set forth above, they lend them selves to a wide variety of treatments for the production of various types of derivatives of great importance in the motor fuels, since they may be readily converted into anti-gum components, dyes, etc.
- diazonium derivatives and alcohols by the utilization of hi trous acid, its salts and esters are, of course, available. While diazotization is usually carried out at low temperatures in aqueous solution, it is not necessary that aqueous solutions be employed, although they can be applied in manners analogous to that set forth above for other reactions involving the use of aqueous solutions.
- the motor fuel containing the aminized derivatives may be agitated with the nitrous acid solution, whether produced from the salts or from the esters, so that the aqueous phase is in continuous contact with the hydrocarbon phase. And conversion of the amino derivatives is accordingly accomplished.
- the reactions are desirably carried out in nonaqueous media.
- the presence of the alcohols formed by the action Of the nitrous acid on the aliphatic amines is important in such reactions, since such alcohols act as a satisfactory medium in which the diazotization may be carried out.
- absolute alcohol may be saturated with nitrous fumes, and the saturated alcohol then added to the aminized motor fuel with the resulting production of diazo compounds.
- Other methods include the addition of absolute alcohol or ether, if desired, but they are not essential to the aminized motor fuel, and then passing dry hydrogen chloride into such solution, heating to 40 or 50 until the last traces of acid are removed.
- the theoretical quantity of amylnitrite is then added, and this can even be done at ordinary temperatures, although lower temperatures are usually preferable in the production of diazo compounds, particularly where wide varieties of such diazo compounds are formed as is true in the treatment of aminized motor fuels, some of the diazo compounds only being stable at lower temperatures, as around 0.
- the diazo compounds are thus formed in the motor fuel fraction from components thereof.
- Nitrosyl bromide and nitrosyl chloride, as well as nitro sulphonic acid may also be employed for the production of the diazo compounds.
- the aminized motor fuel either with or without alcohols present, or introduced for that purpose, has added thereto an alcoholic solution of hydrogen chloride containing 2.5-3.0 mols of acid as compared with the amines present.
- the composition is cooled in ice, and a solution of nitroso chloride, for example, in toluene added.
- the diazo salt is thus produced.
- the diazo salts may also be produced from the nitroso aryl hydrazine referred to above by passing nitrous fumes into the solution of the nitroso aryl hydrazine. in the motor fuel by methods of production that will follow from reactions given above, or introduced into the motor fuel for that particular purpose may be treated with nitrogen trioXide, preferably in ethereal solution to yield corresponding diaso salts. Also by the action of chlorine or bromine on the phenyl hydrazine derivatives produced in any of the methods set forth above will result in the production of diazo salts.
- the hydrazines may also be utilizedfor producing diazo paraflins:
- the importance of the diazo compounds is readily recognized because of their various reactivities to produce diiferent types of derivatives of great importance in'the modified motor fuels.
- Their reduction to produce hydrazines has already been indicated above, and such hydrazines are readily methylated -or alkylated as by the treatment with methyl iodide to produce'alkyl hydrazine.
- the reduction of the diazonium salts to the hydrazines may, for example, be carried out by treatment with stannous chloride-and hydrochloric acid, the aqueous phase being agitated with the hydrocarbon phase containing the diazo salts until the desired reduction is produced.
- aldehydes may be readily produced in the motor fuel. If the motor fuel containing the diazo compounds are warmed and agitated. with an aqueous solution, they. yield phenols. Similarly warmed with halogen acids, halogen derivatives are obtained. Phenyl diazonium sulphate thus warmed with hydriodic acid yields iodobenzene, nitrogen and acids. various cuprous salts may be utilized in accordance with the Sandmeyer reaction to produce cor-. responding derivatives. Thus cuprous cyanide yields phenyl nitrile caHaCN, and the. nitriles,.of
- aryl hydrazines when treated with nitrousacid yield nitrosyl derlva-- 10a tives, and the-latter upon agitation with water are convertedinto azide derivatives.
- azides may be derived through thediazoniumv compounds, and the hydrazines, as wellas through the Grignard reagents, asstated I earlier.
- anti-gumming derivatives such as anthraquinone
- anthraquinone are readily produced in the motor fuels containing aromatics by the addition of phthalic anhydride and aluminum chloride,
- the diazoniui'n compounds present in the motor fuel by reactions as setforth above will be complex mixtures of such derivatives, and the result will be a heterogeneous mixture of derivatives; but the fiuxing action of such derivatives with each other enables a homogeneous composition to be produced since only small portions of the dye need be necessarily present in any event to give the gasoline the desired color.
- Such derivatives may be produced by preparing the diazo compounds in the motor fuels themselves from constituents thereof, and adding the amines to react therewith from extraneous sources, or the aromatic amines may be produced in the motor fuel, and the diazo salts produced extraneously thereof, or both sets of compounds may be produced directly in the motor fuel from components thereof, and the dye developed in situ in the motor fuel.
- the Grignard reagents may be utilized for the production of diazo compounds, both of the aliphatic and aromatic series, and such diazo derivatives are important components in the motor fuels, whether or not they contain metallic derivatives, both varieties of which will be illustrated below, namely those containing metallo components, and those free from them.
- Diazo components are valuable in the motor fuels from two standpoints. Both because they have properties as anti-gum derivatives, and also because they increase the power obtained from motor fuels.
- the contents of such diazo compounds in motor fuel may be very low, not running more than 1% in any event, and substantially smaller proportions, as low as .1% in the motor fuels giving markedly increased and valuable properties thereto.
- derivatives of the diazo amino paramns are readily prepared, for which purpose the alkyl Grignard reagents may be reacted with the alkyl azides, of which the following reaction is exemplary:
- diazo aryl derivatives may be produced in an analogous way, and particularly diazo amino paraffins, and diazo amino aryls.
- the diazo compounds may be coupled with phenols, amino phenols, etc., amino sulphonic acids and other derivatives usually coupled with such derivatives to produce amino azo compounds. or their derivatives.
- amino-azo derivatives may be further diazotized in the motor fuel, and coupled with further components to produce disazo dyes.
- a motor fuel fraction containing alpha-naphthylamine is coupled with diazotized para-anisidine using approximately a fraction of the motor fuel containing 30 parts of alpha-napnthylamine with approximately 25 parts of the diazotized compound.
- the resulting amino-azo derivative in the motor fuel is further diazotized by agitation with an aqueous medium containing 11 parts of hydrochloric acid and 15 parts of sodium nitrite for 1 hour at 10 C.
- the aqueous phase is separated, and approximately 30 parts of betanaphthol are added to the motor fuel fraction containing the diazo compounds, and coupling takes place. If desired, however, to accelerate the coupling, the fraction containing the betanaphthol and the diazo derivative may be agitated with an aqueous medium containing approximately 9 parts of caustic soda, and approximately 20 parts of sodium carbonate in water,
- a bluish red dye is thus produced in solution in the gasoline fraction, directly therein, at least in part produced from components of the motor fuel itself.
- the naphthylamine may be produced with the motor fuel itself, the betanaphthol may be produced in another portion of the motor fuel by reactions indicated above, and even the para-anisidine may be produced from a fraction of treated motor fuel by processes indicated above.
- Various derivatives of this type may be produced, so that a wide variety of disazo Dyes of the indophenol and indamine type may be readily produced in the motor fuel from components therein. The production of various amines and phenol derivatives from components of the motor fuels has been given above.
- the aromatic amines are present in the motor fuel, it may be subjected to oxidation to produce the indamines therein, or phenols may first be added to produce the indophenol derivatives on oxidation, or where phenols are present, amines may be added from an extraneous source, or different'fractions of the motor fuels may be treated to produce amines in one fraction and phenols in the other, and such fractions then mixed and subjected to oxidation to produce the desired indophenol or indamine, as the case may be.
- the phthalein dyes may be prepared, forz-exa'mple, zfrom motor .fuel ifractions montaining phenol Jdesirably produced from: constituents of l the motor fuel insitu by. methods setforthabove, bycondensation with lphthalic anhydride, phenol itself thus yielding phenol vcphthalein.
- Other -phthalein derivatives may :be prepared inan analogous manner.
- Ihe anthraquinoneltypes of dyes are particu- -la'rly important in the motor. fuels, and. may be Elie acrldine dyestuffs may similarly be produced in the motor -fuel in situ irom' components of-the motor -fuel itself.
- the aryl amines produced in the motor iuel may be condensed with benzaldehyde from an extraneous source; or the benzaldehyde "may be produced in-the motor fuel from constituents thereof; and thearyl amines introduced for the condensation reaction, followed by treatment 'withhydrochloric acid-to split off ammonia; thepxidation to produce-thedye base.
- the dyes utilized suchhydrocarbonfractions or distillates and whether-produced in situ particularly from components -ofthe hydrocarbon fractions themselves, or produced externally of the-hydrocarbonfraction-andaddedthereto;may desirably be metallized' and" thus converted into metal containing compounds which' serve a 'dual function.
- the metal employe'disanantiknock metal as hereinabove set “forth and "the metallized dyeis present- ⁇ in 'a'motor fuel the dye will serve both to color the" fuel and" to provideanti-knockproperties.
- the metals may include the alkaline earths and generally themetals of. groups II, III, IV, V and VI of theperiodic system as well as iron, cobalt and nickel; but alkali metal compoundsare not excluded.
- mixed metal-derivatives may be .produced in, for example;-mtorfuels and lubricating oils to exhibitcombinedadiuvant properties.
- the metal derivatives such aslead,-mercury or tin compoundsmay be formed"byagitating the motor fuel withan aqueous'solutionof the cor-responding metal salt such asleadacetate'or mercury chloride ortin chloride, desirablyin the presence of anacid such as hydrochloric or acetic acid and moderately heating; as for example,
- metal derivatives of-the other-types of dyes set forth above containing armetalliza'ble "group may be produced" by analogous methods.
- an ind'ophenol may be produced-in situ'in the lubricating oil, for-example, bymetho'ds set forth above.
- the indophenol produced from m'troso dimethylaniline and phenol may-be present in the" lubricating oil produced in situ therein by methods set forth above to form the nitroso dimethylaniline and the phenol which upon oxidation areconverted to the indophenot of-the iollowing formula in its reduced state:
- the indophenol may be"producedexternany *of the fraction and incorporated therein.
- the correspondingmetal -compound is obtained by agitating-thefraction with, for example, a lead acetate solution containing acetic acid in the proportions ofl-part of dye to 1 parts of lead acetate.
- the treatment may be carried "out with warming as seltfo'rth abovepand agitation overa period of *sev'eral'hours. 'The hydrocarbon Tractionis' then. separated, "washed and'dried.
- .dye compounds * may be produced'which includes metal having additional adjuvant propertiesisoi'thatia single type of compound'maythus exhibit amfiltiplicity of properties, asfor example, coloring andanti knockpropertiesj etc.
- the motor fuel fraction may be aminized by the various methods referred to above, and then halogenated to produce chloramino derivatives in the motor fuel of both alkyl and aryl character, and such chloramino derivatives may thereupon be utilized for any of the reactions set forth above, including conversion into metallo-organic derivatives having amino compounds bound in the molecule containing the metallo ingredient, or the Grignard reagents may be produced from the halogen-amino derivatives, for example, and such Grignard reagents reacted in accordance with the methods set forth above. So that various combinations of the several processes set forth herein may be utilized.
- one portion of the motor fuel may be subjected to one type of treatment for the production of a particular class of derivatives, while another portion is subjected to a different treatment, and the two fractions then time that the hydrogenation treatment is utilized for producing the hydrogenated motor fuels.
- the ingredients necessary to produce the desired classes of compounds upon reduction may be present in the hydrocarbon material before the hydrogenation treatment applied to the motor fuel, so that upon completion of the hydrogenation treatment, thereduction of the compounds present may be simultaneously carried out, the hydrogenated motor fuel derivatives being produced at the same time that the classes of compounds for anti-gum or other purposes are being produced in the motor fuel.
- the ingredients necessary to produce the desired derivatives upon treatment of sulphuric acid may be introduced into the hydrocarbon materials before combined to have present both types of derivatives, or successive operations of these methods plary reactions are given, they are merely exemplary of the type of compounds being produced, since a number of derivatives in that class or type of compound will be produced by these reactions when carried out in situ, but complex combinations will take place between various ingredients of the motor fuels themselves, where different organic derivatives are present.
- a number of reactions as set forth above utilize reduction processes.
- the reduction reactions may take place at the same the application of the sulphuric acid treatment, for example, so that the refining with sulphuric acid is carried out simultaneously with the treatment with acid necessary to produce anti-gum or other types of derivatives.
- While the invention has been particularly illustrated with motor fuel fractions such as gasoline, other hydrocarbon fractions and distillates may be similarly treated.
- components, fractions or distillates of the character known as lubricating oilsand generally any of the hydrocarbon fractions and distillates produced from petroleum derivatives having boiling points substantially higher than the motor fuel ranges may be treated by any of the methods set forth above so that such modified lubricating oils or other hydrocarbon fractions or distillates may be modifled in accordance with the various methods set forth above to produce new types of products containing the desired derivatives either produced outside of such lubricating oil or other hydrocarbon fraction or distillate and subsequently added thereto, or more desirably produced in situ by the methods set forth above in such lubricating oils or other hydrocarbon frac tions or distillates.
- the term indigenous is used herein to refer to components present in the distillate whether fuel or lubricant which are constituents of such distillate as normally manufactured, and to distinguish from components added to the distillate from extraneous sources for special purposes.
- a liquid petroleum distillate containing a metallized amino azo dye 1.
- distillate is selected from the group consisting of hydrocarbon motor fuels and lubrioants.
- a liquid petroleum distillate containing a heavy metal derivative of an amino azo dye having a metallizable OH group 3.
Description
Patented May 11, 1948 ,rrtrzz UNITED STATES PATENT OFFICE MODIFlED FUELS AND LUBRICANTS Sol Shapp'irio, Washington, No Drawing. Application January 31, 1942,
Serial No. 429,131
'7 Claims. (01. 252-423) This invention relates to hydrocarbon distillates including such distillates lighter than kerosene, particularly in the range of motor fuels and lubricants, which distillates contain constituents to modify their characteristics desirably, for fuel or lubricant purposes including such fuel or lubricant modifying components which serve such purposes as antioxidants, anti-knock components, anti-gum agents, dyes, etc.
Particular objects of the present invention include the production of such modified distillates containing modifying components which dye or color the mixture, and more particularly when produced in situ in the distillates, desirably from components at least one of which is present or formed in the distillate, whether fuel or lubricant, from constituents present in such fuel or lubricant as formed by normal processes under which such distillates are produced.
Other objects and advantages will appear from the more particular description given below, it being understood, however, that this more particular description is given by way of illustration and explanation only, and not by way of limitation, since modifications thereof may be made by those skilled in the art without departing from the scope and spirit of the present invention.
The present application is concerned with the preparation of metallo-organic and other derivatives directly in the fuel or analogous material, and preferably from constituents of the fuel or analogous material itself without the addition of extraneous hydrocarbon sources is particularly emphasized, the oil-s of hydrocarbon character or their derivatives or fractions or distillates being converted into compounds in part, or to a limited extent, which upon further treatment are readily converted into the metallo-organo and other derivatives. In addition, extraneous substances, either for the purpose of forming the metalloorganic substances within the fuel, or as a partial source for such metallo-organic and other substances, some of the latter also being derived from the fuel or analogous material, may also be added to the gasoline or other material treated.
The hydrocarbon materials treated may be the hydrocarbon oils, their fractions and distillates including the gasolines, produced by various processes and other hydrocarbon products that have fuel value. Such gasolines, for example, may be those from straight distillation processes, from cracking processes either in the presence or .absence of air, from natural gas, etc., etc; As pointed out, where the metallo-organo derivatives are to be produced of the alkyl type, it is desirable to have present in the gasolines or other hydrocarbon product, lower members of the paraffin series, and consequently gasolines containing such lower paraflins, such as ethane, propane and butane are particularly desirable, but the gasolines containing aromatics also are readily converted into the desired metallo-organic compounds. Gasolines and related materials produced during cracking or analogous heat and pressure treatment in the presence of air are highly advantageous, and more particularly when in such processes the gasolines produced contain even a small amount of Oxygen-containing substances, such as the ethers, since such oxygencontaining substances often actcatalytically in the processes of converting some of the described intermediate substances into metallo-organic compounds. The presence of such oxygen-containing compounds as the aldehydes, ketones, etc., are desirable for other purposes set forth below. Diesel fuels are, of course, included.
If certain desired lower members of the paraffin series are not already present in the gasoline or other material to be treated, they may be added to the same; and, of course, the same applies to other constituents that may be desired in the final products. Instead of converting the constituents of the gasoline or analogous material directly into the intermediate that is to be converted into the metallo compounds, there may be added to the gasoline or similar material, a substance which will be converted into the metallo compound desired, the gasoline remaining substantially as it was before the conversion and the metallo compounds being derived solely from the added substances, or any combination of these steps may be utilized.
Among the metals and non-metals that maybe introduced into gasoline by the processes there set forth, there may be mentioned lead, tin, silicon, antimony, arsenic, phosphorus, mercury, thallium, etc. Lead compounds are particularly used for illustrative purposes therein in view of the wide use of lead compounds. For certain purposes such as metallized dyes, other metals such as copper, chromium, zinc, etc., may be utilized.
In the preparation of the metallo organic compounds in the fuel or analogous material, the metallo organic compounds do not have to be separately handled. The production of such metallo organic compounds in the fuel and from fuel constituents may be carried outso that the fuel is present in a more limited quantity whereby a concentrated metallo-organic containing product'is obtained which may be secured by distilling ofi the hydrocarbon products present, or which subsequently be diluted with more fuel or gasoline or related substance to the concentration desired, or the metallo organic substance or substances may be prepared in the gasoline or analogous material in a very dilute condition, so that further dilution is unnecessary, and the special fuel is directly produced Without more. The preparation of the desired ingredients in very dilute condition is particularly desirable where some of the constituents thus produced are not very soluble in the motor fuels, although the very small quantities of such mate. rials present needed for anti-knock, antioxidant,
anti-gum, or dye purposes, etc., do not "require.
absolute solution, although in. such dilutions in which they are used, they are readily obtainable in solution form, or if necessary blending agents may be utilized to produce the requisite solubility.
In many of the reactions of making metalloorganic derivatives, the presence of catalysts have been found to be highly desirable, such catalysts particularly ,reterred t as Grig-nard catalysts are particularly referred to, including for example, primary, secondary, tertiar amines, and their .alkyl addition productssuch amines being aliphatic, aromatic or heterocycl-ic derivatives. Examples Fare aniline, dimethylanili-ne, carbazol, phenyl hydrazine, quinoline; etc. Other desirable catalysts or agents that. may be present include ether, ethers in general, ammonia and itsderivatives, esters. These compounds may exist in the gasoline or other material undergoing treatment, so the addition of such catalysts is not specifically necessary. And this is particularly .trueain connection with the g-asolines produced by oxida- .tion processes, including both those of the vapor and liquidphase oxidation reactions. Other compounds,.like the amines, etc., etc., referred to above may be present in the gasoline byvarious methods, as indicated'below, wherein they ma be produced from constituents; of the gasolines themselves, or may be. introduced from external sources. The catalyst added may be selected from the named substances or other derivatives, particularly with regard to their value in fuel compositions, for example, the simpler others, and the amines. particularly the aromatic series thus being indicated.
The metallo-organo derivatives may be produced in various ways, for example, by methods set forth in Patents Nos. 2.012356, 2134.625, and. application Seria No. 323 840. .filed March 13, 1940. now Patent No. 2,272 134. dated Feb. 3. 1942, of which the instant specification is a continuation-in-part.
While in the production of Grignard reagents mono-halogen derivatives are particularly emphasized, where the halogen derivatives areconverted into amines or other derivatives, higher halogen derlvatives are desirable leading'to .the
=are-desirable ingredients as anti-gum agents, etc.
While a number of metal derivatives may thus be introduced into the distillate by being direcly therein, if desired after the production of one metallo-organic compound, it may be converted partially or wholly into other metallo compounds. An'd furthermore, if desired, instead of the Grignard intermediates produced as set forth above, or added to the distillateicr example, the Grignard reagents might be prepared in the usual manner and then added .to the gasoline or other distillate-the latter may be converted into other derivatives than the metallo derivatives. The
"Grignards are well known as excellent intermediates for the synthesis of a number of organic compounds. So that they may be used as set forth. in the prior description to form a large .number of organic compounds that have value in distillates. For example, by appropriate treatments, they may be converted into alcohols, phenols, aldehydes, ketones, etc. And these reactions may be utilized so that a portion of the G-rignard reagents are converted into the metallo derivatives and a portion into other organic conipounds.
.And further, many of the products may be made in the fuel from the halides by taking crude hydrocarbon materials that must be subjected to distillation or other treatment, or treatments, in order to obtain motor fuels from them, by adding the requisite materials to them to form the metallo compounds, or converting a portion of .such crude materials into compounds that will .form metallo derivatives, and then carrying out the distillation or other treatments, so that a gasoline or analogous material or fuel is obtained containing the metallo-organic compounds that have been formed during the distillation or other treatment, which may or may not have been carried out under pressure.
Thus the introduction of the halogen to the material undergoing distillation will yield halogenated fractions, as for example, halogenated motor fuel fractions which may accordingly be treated as set forth above. Or the introduction of halogen followed by contact of the halogenated product with the sodium lead alloy, for example, before distillation, or at various stages thereof, will result in fractions such as motor fuels produced with the metallo derivatives in the fuel during the distillation.
The Grignard reagents, as indicated above, are .utillzable. however in many other directions for the production of both metallo derivatives other than those of the alkyl and aryl types strictly, and also for the production of many valuable ingredients in motor fuels and lubricants which do not necessarily contain any metallo component.
The metallo-aryl Grignard reagents may also be desirably employed in the production of are compounds, for example, benzene magnesium iodide yielding with benzene diazonium chloride, azo benzene in accordance with the following re action.
Such azo compounds are desirable components inmntor fuels, and these types of reactions of whichthat illustrated is merely exemplary may be utilized in the production of azo dyes in the motor fuels from constituents thereof, as more fully explained below. In this connection it may be pointed out that the Grignard reagents are easily produced in the motor fuel from constituents thereof as set forth above,and the diazo compounds may also be produced herein both by methods explained above and by subsequent methods, and such constituents produced in the motor fuel then permitted to react to produce the azo compounds. Substituted azo compounds of the true dye type may thus be produced in the motor fuel, and in view of their production in complex mixtures in such motor fuel from derivatives thereof, dyes can be produced in the motor fuel that remain in solution therein, which is dinicult in the production of many types of dyes by extraneous reactions, followed by their incorporation into motor fuels. Entirely new varieties of dyes in complex mixtures are thus producible in the motor fuel from constituents in this way. The Grignard reagents may be produced from the motor fuels themselves, and reacted with diazo salts produced outside of the motor fuels, or as noted above, the diazo salts may also be produced in the motor fuels, or a portion thereof for reaction with the Grignard reagents. Or, as explained below, the diazo compounds may be produced from the motor fuel constituents themselves and reacted with Grignard reagents from external sources.
The production of various amines and their derivatives, such as the hydroxyl amines have been given above derivable from the Grignard types of reagents. Various other methods for producing the amines and their derivatives in the motor fuels from constituents thereof may be utilized, as set forth in application Serial No. 323,840.
Once the amines have been produced in the motor fuel, or are present therein, and they may, of course, be added from extraneous sources for this purpose, but desirably they are produced in complex mixture in the motor fuels themselves by any of the methods set forth above, they lend them selves to a wide variety of treatments for the production of various types of derivatives of great importance in the motor fuels, since they may be readily converted into anti-gum components, dyes, etc.
One of the most important methods for deriving desirable components therefrom is by treatment with nitrous acid or its salts and esters. Under such treatments the aliphatic amines in the fuel are converted into alcohols, which are, of themselves, important components of the motor fuel mixtures for various purposes, while the aromatic and cyclic amines are converted into diazo derivatives, which lend themselves to various treatments, such as reduction, coupling, etc.
Various methods for producing such diazonium derivatives and alcohols by the utilization of hi trous acid, its salts and esters are, of course, available. While diazotization is usually carried out at low temperatures in aqueous solution, it is not necessary that aqueous solutions be employed, although they can be applied in manners analogous to that set forth above for other reactions involving the use of aqueous solutions. For example, the motor fuel containing the aminized derivatives may be agitated with the nitrous acid solution, whether produced from the salts or from the esters, so that the aqueous phase is in continuous contact with the hydrocarbon phase. And conversion of the amino derivatives is accordingly accomplished. In order to avoid loss of desirable products into the water phase, however, the reactions are desirably carried out in nonaqueous media. The presence of the alcohols formed by the action Of the nitrous acid on the aliphatic amines is important in such reactions, since such alcohols act as a satisfactory medium in which the diazotization may be carried out.
Thus absolute alcohol may be saturated with nitrous fumes, and the saturated alcohol then added to the aminized motor fuel with the resulting production of diazo compounds. Other methods include the addition of absolute alcohol or ether, if desired, but they are not essential to the aminized motor fuel, and then passing dry hydrogen chloride into such solution, heating to 40 or 50 until the last traces of acid are removed. The theoretical quantity of amylnitrite is then added, and this can even be done at ordinary temperatures, although lower temperatures are usually preferable in the production of diazo compounds, particularly where wide varieties of such diazo compounds are formed as is true in the treatment of aminized motor fuels, some of the diazo compounds only being stable at lower temperatures, as around 0. The diazo compounds are thus formed in the motor fuel fraction from components thereof.
t should be kept in mind, as pointed out above in connection with other types of compounds and methods, that'it is not necessary to treat the entire fraction of gasoline in this manner, but only a portion thereof may be subjected to such reactions, and after the production of the diazo compounds, such fractions added to the remaining portion of the motor fuel. Or the diazo compounds may be produced in concentrated condi tion, and then diluted with the motor fuel constituents to produce the final fuel. The diazo compounds, while sometimes insoluble, will usually be found to be present in solution because of the complex derivatives obtained from the treatment of the motor fuels themselves, in which thevarious ingredients fiux each other, and produce a homogeneous composition. But where minor quantities of the diazo compounds in high dilution are utilized, the suspension of such diazo compounds in the motor fuel components also produce compositions that may be utilized directly.
Nitrosyl bromide and nitrosyl chloride, as well as nitro sulphonic acid may also be employed for the production of the diazo compounds. Thus the aminized motor fuel, either with or without alcohols present, or introduced for that purpose, has added thereto an alcoholic solution of hydrogen chloride containing 2.5-3.0 mols of acid as compared with the amines present. The composition is cooled in ice, and a solution of nitroso chloride, for example, in toluene added. The diazo salt is thus produced.
The diazo salts may also be produced from the nitroso aryl hydrazine referred to above by passing nitrous fumes into the solution of the nitroso aryl hydrazine. in the motor fuel by methods of production that will follow from reactions given above, or introduced into the motor fuel for that particular purpose may be treated with nitrogen trioXide, preferably in ethereal solution to yield corresponding diaso salts. Also by the action of chlorine or bromine on the phenyl hydrazine derivatives produced in any of the methods set forth above will result in the production of diazo salts.
The reactions referred to above have particu- Quinone oxime present larly enrphasized: therproductiorrof .the :diazo salts andccompoun ds :of.:.the aromatic :andrcyclic. type whereas :examples :of producing the .diazo .parafe fiRSShaVCIaISWDGGD given at an earlier portioniof';
thisispecification; The hydrazines may also be utilizedfor producing diazo paraflins: Thusalkyl hydrazines produced in the motor-fuel aby anyof' the-methods set forth above'on treatment with potassium pyrosulphate, followedby oxidation ofthe resulting compound with mercuric. oxide yields diazo compounds. treated with potassium hydrosulphate gives potassium ethyl hydrazine sulphonate,
which on treatment with-the mercuricoxideis converted into potassium diazo ethyl sulphonate C2H5N=N.SO3K.
The importance of the diazo compounds is readily recognized because of their various reactivities to produce diiferent types of derivatives of great importance in'the modified motor fuels. Their reduction to produce hydrazines has already been indicated above, and such hydrazines are readily methylated -or alkylated as by the treatment with methyl iodide to produce'alkyl hydrazine. The reduction of the diazonium salts to the hydrazines may, for example, be carried out by treatment with stannous chloride-and hydrochloric acid, the aqueous phase being agitated with the hydrocarbon phase containing the diazo salts until the desired reduction is produced.
To briefly indicate some of the-other important reactions of the diazo compounds, the following may be noted. If a motor iuel containing the diazo compounds is heated with absolute alcohol, they yield hydrocarbons and aldehydes.
Thus phenyl diazonium chloride heated with ab 40 solute alcohol yields benzene on the one hand, and acetaldehyde on the other in accordance with the following equation:
And by such reactions aldehydes may be readily produced in the motor fuel. If the motor fuel containing the diazo compounds are warmed and agitated. with an aqueous solution, they. yield phenols. Similarly warmed with halogen acids, halogen derivatives are obtained. Phenyl diazonium sulphate thus warmed with hydriodic acid yields iodobenzene, nitrogen and acids. various cuprous salts may be utilized in accordance with the Sandmeyer reaction to produce cor-. responding derivatives. Thus cuprous cyanide yields phenyl nitrile caHaCN, and the. nitriles,.of
course, upon reduction may be readily converted into amines. It is not intended by these reactions to indicate that specific individual compounds.
are being treated, but these reactions exemplify the complex derivatives that are produciblein.
" 5 amines and their derivatives, phenyl diazonium themotor fuels by these various treatments of the diazo compounds, complex mixturesof such derivatives, of' course, being obtained by these treatments, since the motor fuels contain .variousv diazoderivatives of complex character.
Thediazo compounds treated with hydr'oxyl'.7
amine result in. amines. Thusdiazo benzeneohloeride yields aniline... And when. treated .withsulphur. dioxide .sulphazides .are producedoLwhich. the following formulation is sumciently exam: PI y;
Thus ethyl hydrazine The 65 CsHa.NH.NHSO2.C6H5+N2+2H2SO4-I-2HC1 Such reactions may be carried out by agitating:
theahydrocarbon fractions containing the diazo compoundswithaqueous solutions of sulphur ,di
oxide; the water-removing the acids present;
It may be noted that the aryl hydrazines when treated with nitrousacid yield nitrosyl derlva-- 10a tives, and the-latter upon agitation with water are convertedinto azide derivatives. Suchreactions may becarried out by agitating the 'hy-' drocarbon fraction containing the phenylhy-= drazinewiththe aqueous medium containing the nitrous acid, the process proceeding in'accordance wit-h the following reaction:
I /NH9 cunsnnnm HO.NO=C5H5N H2O=CtH N 21110 Thus the azides may be derived through thediazoniumv compounds, and the hydrazines, as wellas through the Grignard reagents, asstated I earlier.
Other types of anti-gumming derivatives, such as anthraquinone, are readily produced in the motor fuels containing aromatics by the addition of phthalic anhydride and aluminum chloride,
7 the phthalic anhydride reacting with the benzol, for .example, to give anthraquinone, while higher derivatives are produced from other homologues.
The various processes outlined above may be carried out'by utilizing the reacting ingredients in theirtheoretical molecular equivalent proportions in accordance with the equations for the reactions illustrated. Such molecular equivalent proportions beingbased on the content of the ingredient of the motor fuel which is tobe utilized. Thus where chlorhydrocarbons are being reacted, the reactions may be based on the use of the fraction containing the chlorhydrocarbons, utilizing an amount of such fraction which will yield the molecularly equivalent amount of chlorine. Similar considerations will apply to other reactions involving the amines, etc, etc.
The presence of various derivatives of the diazo'and amino types produced in the motorchloride yielding, for example, with 'dimethylaniline, dimethylaniline azobenzeue in accordance with the following formulation:
Thisis exemplary oia wide variety of aminoe azo...compounds thatcan thus-be produced.di.-. rectly in the .motorfuelj. .Of course, individual.
75.. compounds areth'us not generally produced, since;
the diazoniui'n compounds present in the motor fuel by reactions as setforth above will be complex mixtures of such derivatives, and the result will be a heterogeneous mixture of derivatives; but the fiuxing action of such derivatives with each other enables a homogeneous composition to be produced since only small portions of the dye need be necessarily present in any event to give the gasoline the desired color. Such derivatives may be produced by preparing the diazo compounds in the motor fuels themselves from constituents thereof, and adding the amines to react therewith from extraneous sources, or the aromatic amines may be produced in the motor fuel, and the diazo salts produced extraneously thereof, or both sets of compounds may be produced directly in the motor fuel from components thereof, and the dye developed in situ in the motor fuel.
Thus, the Grignard reagents may be utilized for the production of diazo compounds, both of the aliphatic and aromatic series, and such diazo derivatives are important components in the motor fuels, whether or not they contain metallic derivatives, both varieties of which will be illustrated below, namely those containing metallo components, and those free from them. Diazo components are valuable in the motor fuels from two standpoints. Both because they have properties as anti-gum derivatives, and also because they increase the power obtained from motor fuels. The contents of such diazo compounds in motor fuel may be very low, not running more than 1% in any event, and substantially smaller proportions, as low as .1% in the motor fuels giving markedly increased and valuable properties thereto. For example, derivatives of the diazo amino paramns are readily prepared, for which purpose the alkyl Grignard reagents may be reacted with the alkyl azides, of which the following reaction is exemplary:
N OHaN\ CHaMgI=CHaN(MgI)N:NCHs
And as a result of which reaction there is produced compounds corresponding with the magnesium salt of diazo amino methane. In the application of such reactions herein, there will usually be produced complex derivatives of such components. The magnesium derivative produced in accordance with the preceding method, may be permitted to remain in the motor fuel itself, or may be treated as a Grignard for other reactions, such as those to which the Grignards are capable, particularly as emphasized above. Thus various metallo derivatives may be produced, such as the copper compound:
or other metallic derivatives, such as those of lead, etc. may similarly be produced and utilized in the motor fuel, both because of the lead component, and also because of the diazo grouping present. While the alkyl derivatives have been particularly referred to, diazo aryl derivatives may be produced in an analogous way, and particularly diazo amino paraffins, and diazo amino aryls.
In a strictly analogous manner, the diazo compoundsmay be coupled with phenols, amino phenols, etc., amino sulphonic acids and other derivatives usually coupled with such derivatives to produce amino azo compounds. or their derivatives. I
Of course, such amino-azo derivatives may be further diazotized in the motor fuel, and coupled with further components to produce disazo dyes. As exemplary thereof, the following may be noted. A motor fuel fraction containing alpha-naphthylamine is coupled with diazotized para-anisidine using approximately a fraction of the motor fuel containing 30 parts of alpha-napnthylamine with approximately 25 parts of the diazotized compound. The resulting amino-azo derivative in the motor fuel is further diazotized by agitation with an aqueous medium containing 11 parts of hydrochloric acid and 15 parts of sodium nitrite for 1 hour at 10 C. The aqueous phase is separated, and approximately 30 parts of betanaphthol are added to the motor fuel fraction containing the diazo compounds, and coupling takes place. If desired, however, to accelerate the coupling, the fraction containing the betanaphthol and the diazo derivative may be agitated with an aqueous medium containing approximately 9 parts of caustic soda, and approximately 20 parts of sodium carbonate in water,
the temperature being maintained at about 5 C. A bluish red dye is thus produced in solution in the gasoline fraction, directly therein, at least in part produced from components of the motor fuel itself. Since the naphthylamine may be produced with the motor fuel itself, the betanaphthol may be produced in another portion of the motor fuel by reactions indicated above, and even the para-anisidine may be produced from a fraction of treated motor fuel by processes indicated above. Various derivatives of this type may be produced, so that a wide variety of disazo Dyes of the indophenol and indamine type may be readily produced in the motor fuel from components therein. The production of various amines and phenol derivatives from components of the motor fuels has been given above. Where the aromatic amines are present in the motor fuel, it may be subjected to oxidation to produce the indamines therein, or phenols may first be added to produce the indophenol derivatives on oxidation, or where phenols are present, amines may be added from an extraneous source, or different'fractions of the motor fuels may be treated to produce amines in one fraction and phenols in the other, and such fractions then mixed and subjected to oxidation to produce the desired indophenol or indamine, as the case may be. Thus for motor fuel fractions containing para-amido-dimethyl aniline and alpha-naphthol, or nitrosodimethylaniline and alpha-naphtrol upon oxidation an indophenol is obtained. The reactions may proceed at room temperatures but elevated temperatures may be employed, as for example, above F, in which event the reactions are desirably carried out under pressure in order to avoid loss of desirable lighter constituents from the motor fuel. And this observation, of course, applies to the various reactions hereinabove setforth where,,the elevated temperatures are employed, and wherein pres-,- sures are desirably maintained in order to avoid loss of desirable-constituentsiinithe motor fuel.
The phthalein dyes may be prepared, forz-exa'mple, zfrom motor .fuel ifractions montaining phenol Jdesirably produced from: constituents of l the motor fuel insitu by. methods setforthabove, bycondensation with lphthalic anhydride, phenol itself thus yielding phenol vcphthalein. Other -phthalein derivatives may :be prepared inan analogous manner.
. Ihe anthraquinoneltypes of dyes=are particu- -la'rly important in the motor. fuels, and. may be Elie acrldine dyestuffs may similarly be produced in the motor -fuel in situ irom' components of-the motor -fuel itself. For=-example,--the aryl amines produced in the motor iuel may be condensed with benzaldehyde from an extraneous source; or the benzaldehyde "may be produced in-the motor fuel from constituents thereof; and thearyl amines introduced for the condensation reaction, followed by treatment 'withhydrochloric acid-to split off ammonia; thepxidation to produce-thedye base.
--Various other types *of "dyes may, of course; be
produced by analogousreactions. *Itshouldalso be kept in mind'that --many "of the dyes, and particularly the complex amino 1 and phenolic compounds are in "themselves "anti gumming agents, so'that they "have -double propertiesdn the--motor fuel -in--producing'-not- 'only--a*colored motor fuel, but also tend -toprevent the formation of gums.
The dyes utilized suchhydrocarbonfractions or distillates and whether-produced in situ particularly from components -ofthe hydrocarbon fractions themselves, or produced externally of the-hydrocarbonfraction-andaddedthereto;may desirably =be metallized' and" thus converted into metal containing compounds which' serve a 'dual function. Thus-if the metal employe'disanantiknock metal as hereinabove set "forth and "the metallized dyeis present-{in 'a'motor fuel, the dye will serve both to color the" fuel and" to provideanti-knockproperties. The same is true in connection with such metallized dyes used'irflu- 'bricating oil fractions-"but herethemetarmaybe other heavy metals which form "derivatives with the dye compound and exhibit their adjuvant properties in such lubricating oils. For the latter' purpose the metals may include the alkaline earths and generally themetals of. groups II, III, IV, V and VI of theperiodic system as well as iron, cobalt and nickel; but alkali metal compoundsare not excluded. Where severalmetallizing groups are present, mixed metal-derivatives may be .produced in, for example;-mtorfuels and lubricating oils to exhibitcombinedadiuvant properties.
7 :A metallizable group should =be'-pr'esent-' in the dye compound, such groups including OH; C'GOI-I, SOsI-L'eta, and thepre'sence'of hydroxyand carboxy groups in the moleculeworthouto theaazo group in azovdyes,lisrparticularly:important.
'While the dye: compounds need mot-necessarily -be soluble the hydrocarbon fraction, they generally will besoluble at least whenyproduce'd in situ because of their mixedcharacter. Solubilizing groups may beiintroducediorl thisi-purpose including long alkyl: chains of both straight chain: and branching chairi type.
The following examplesvwill i-llustratessometof these features. Assumingia motorfuelzcontaining an azo dye of the following formula:
produced insitu by methods "setfOfth"flbOVe' 'or added to the mot-or fuel from "an -extraneous source, the metal derivatives such aslead,-mercury or tin compoundsmay be formed"byagitating the motor fuel withan aqueous'solutionof the cor-responding metal salt such asleadacetate'or mercury chloride ortin chloride, desirablyin the presence of anacid such as hydrochloric or acetic acid and moderately heating; as for example,
to or 0 pressure being-usedto prevent undue loss of"the-vblatile-constituents "Assuming a dye of the str'ubtureset forth abovefllOO parts of the motor fuel-containingl' 'partof such dyemay be treated with 1- /2'partsof-lead'acetate or-1 parts of mercury chloride or 1 part of'tin chloride :in acid A solution with agitation topro- 'duce the l corresponding derivatives. Theflayers I are permitted a to strtttifyarid the hydrocarbon layer carrying the -metalllzed dyederivative"is withdrawn, washed necessary an'd driecl.
Similarly, metal derivatives of-the other-types of dyes set forth above containing armetalliza'ble "group may be produced" by analogous methods. Thus an ind'ophenol may be produced-in situ'in the lubricating oil, for-example, bymetho'ds set forth above. As a specific example, the indophenol produced from m'troso dimethylaniline and phenol may-be present in the" lubricating oil produced in situ therein by methods set forth above to form the nitroso dimethylaniline and the phenol which upon oxidation areconverted to the indophenot of-the iollowing formula in its reduced state:
a loss) on Or the indophenol may be"producedexternany *of the fraction and incorporated therein. In
this as in other cases where solubility of the dye in "the hydrocarbon fraction is not sufii'cient blencling agents or -so1ubi-lizing *groups may be present. The correspondingmetal -compound is obtained by agitating-thefraction with, for example, a lead acetate solution containing acetic acid in the proportions ofl-part of dye to 1 parts of lead acetate. The treatment may be carried "out with warming as seltfo'rth abovepand agitation overa period of *sev'eral'hours. 'The hydrocarbon Tractionis' then. separated, "washed and'dried.
By the methods -s'et -fo'rth "above, .dye compounds *may be produced'which includes metal having additional adjuvant propertiesisoi'thatia single type of compound'maythus exhibit amfiltiplicity of properties, asfor example, coloring andanti knockpropertiesj etc.
While various individual"processesand'm'ethoils of producing particular "'typesiofcompouiids have been set-"forth- "abova combinatlons"of'tliose various methods may be employed to produce double substitutions and various'derivatives of organic character. For example, instead of chlorinating or halogenating the motor fuel fraction, the motor fuel fraction may be aminized by the various methods referred to above, and then halogenated to produce chloramino derivatives in the motor fuel of both alkyl and aryl character, and such chloramino derivatives may thereupon be utilized for any of the reactions set forth above, including conversion into metallo-organic derivatives having amino compounds bound in the molecule containing the metallo ingredient, or the Grignard reagents may be produced from the halogen-amino derivatives, for example, and such Grignard reagents reacted in accordance with the methods set forth above. So that various combinations of the several processes set forth herein may be utilized. And as indicated in connection with several individual methods set forth above, one portion of the motor fuel may be subjected to one type of treatment for the production of a particular class of derivatives, while another portion is subjected to a different treatment, and the two fractions then time that the hydrogenation treatment is utilized for producing the hydrogenated motor fuels. For example, the ingredients necessary to produce the desired classes of compounds upon reduction may be present in the hydrocarbon material before the hydrogenation treatment applied to the motor fuel, so that upon completion of the hydrogenation treatment, thereduction of the compounds present may be simultaneously carried out, the hydrogenated motor fuel derivatives being produced at the same time that the classes of compounds for anti-gum or other purposes are being produced in the motor fuel. Similarly, where refining treatments are employed, involving treatments with caustic soda or sulphuric acid or successive treatments of that character, and where, for example, an acid treatment is necessary in connection with the production of particular types of compounds in accordance with the methods set forth above, the ingredients necessary to produce the desired derivatives upon treatment of sulphuric acid may be introduced into the hydrocarbon materials before combined to have present both types of derivatives, or successive operations of these methods plary reactions are given, they are merely exemplary of the type of compounds being produced, since a number of derivatives in that class or type of compound will be produced by these reactions when carried out in situ, but complex combinations will take place between various ingredients of the motor fuels themselves, where different organic derivatives are present.
Furthermore, while the methods set forth above have been particularly illustrated in connection with their application to motor fuel fractions, those methods may be applied to petroleum oils or distillates or fractions therefrom, whether cracked or uncra-cked, before the distillation or preparation of the motor fuel fractions themselves, so that advantage may be taken of the subsequent steps utilized in the production of the motor fuels themselves to complete the processes of producing particular classes of compounds, as set forth herein. This may be illustrated in a number of ways. A number of the methods set forth above require the application of heat to complete the reactions. Such compounds as require heat to complete the reactions, particularly where elevated temperatures are employed, and the hydrocarbon materials undergoing treatment are, therefore, desirably treated under pressure, these methods may be carried out by taking the hydrocarbon materials before distillation or other heat treatment to produce the motor fuel fractions, and incorporating the necessary react-ants to produce the classes of compounds desired, so that upon the distillation or heat treatment to produce the motor fuel itself, the methods are carried out for producing simultaneously the classes of compounds resulting from the reactions set forth. Similarly, a number of reactions as set forth above utilize reduction processes. In view of the wide use of hydrogenation methods in the production of motor fuels today, as well as lubricants, etc., the reduction reactions may take place at the same the application of the sulphuric acid treatment, for example, so that the refining with sulphuric acid is carried out simultaneously with the treatment with acid necessary to produce anti-gum or other types of derivatives. These several examples will illustrate the application of ordinary refining methods as they are carried out at the present time in the plant, and their utilization in producing particular types of derivatives in the modified motor fuels in accordance with the present methods, so that a single reaction of that character is sufficient to accomplish both ends.
While the invention has been particularly illustrated with motor fuel fractions such as gasoline, other hydrocarbon fractions and distillates may be similarly treated. For example, components, fractions or distillates of the character known as lubricating oilsand generally any of the hydrocarbon fractions and distillates produced from petroleum derivatives having boiling points substantially higher than the motor fuel ranges, may be treated by any of the methods set forth above so that such modified lubricating oils or other hydrocarbon fractions or distillates may be modifled in accordance with the various methods set forth above to produce new types of products containing the desired derivatives either produced outside of such lubricating oil or other hydrocarbon fraction or distillate and subsequently added thereto, or more desirably produced in situ by the methods set forth above in such lubricating oils or other hydrocarbon frac tions or distillates.
The term indigenous is used herein to refer to components present in the distillate whether fuel or lubricant which are constituents of such distillate as normally manufactured, and to distinguish from components added to the distillate from extraneous sources for special purposes.
Having thus set forth my invention, I claim:
1. A liquid petroleum distillate containing a metallized amino azo dye.
2. A composition as set forth in claim 1 in which the distillate is selected from the group consisting of hydrocarbon motor fuels and lubrioants.
3. A liquid petroleum distillate containing a heavy metal derivative of an amino azo dye having a metallizable OH group.
4. A liquid petroleum distillate containing a metallized amino azo dye, the metal being se-
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US429131A US2441172A (en) | 1942-01-31 | 1942-01-31 | Modified fuels and lubricants |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US429131A US2441172A (en) | 1942-01-31 | 1942-01-31 | Modified fuels and lubricants |
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US2441172A true US2441172A (en) | 1948-05-11 |
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US429131A Expired - Lifetime US2441172A (en) | 1942-01-31 | 1942-01-31 | Modified fuels and lubricants |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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EP1580254A2 (en) * | 2004-03-25 | 2005-09-28 | HM Customs & Excise | Hydrocarbon markers |
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US1996391A (en) * | 1931-05-09 | 1935-04-02 | Strans Joseph | Oil soluble dyestuffs |
US2023142A (en) * | 1931-09-22 | 1935-12-03 | Shell Dev | Motor fuel of high antiknock value |
US2052193A (en) * | 1933-12-30 | 1936-08-25 | Standard Oil Dev Co | Stabilizing dyed hydrocarbon liquids |
US2087597A (en) * | 1930-11-21 | 1937-07-20 | Standard Oil Dev Co | Method for inhibiting gum formation in low boiling hydrocarbon oils and products obtained thereby |
US2136455A (en) * | 1936-08-11 | 1938-11-15 | Socony Vacuum Oil Co Inc | Diesel fuel |
US2147713A (en) * | 1932-08-17 | 1939-02-21 | John W Orelup | Process of treating oil |
US2205408A (en) * | 1938-08-09 | 1940-06-25 | Gen Aniline & Film Corp | Fluorescent hydrocarbon oil |
US2235466A (en) * | 1937-06-15 | 1941-03-18 | Shell Dev | Antiknock motor fuel |
US2238553A (en) * | 1938-03-14 | 1941-04-15 | Standard Oil Co California | Diesel engine fuel |
US2272134A (en) * | 1940-03-13 | 1942-02-03 | Shappirio Sol | Modified motor fuel and process of making same |
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US1722074A (en) * | 1927-05-05 | 1929-07-23 | Chapleau Walter | Combined chair, receptacle, and dustpan |
US1779061A (en) * | 1927-09-26 | 1930-10-21 | Standard Oil Co California | High-compression-motor fuel |
US1953438A (en) * | 1930-11-03 | 1934-04-03 | Gen Aniline Works Inc | Process for coloring organic products |
US2087597A (en) * | 1930-11-21 | 1937-07-20 | Standard Oil Dev Co | Method for inhibiting gum formation in low boiling hydrocarbon oils and products obtained thereby |
US1996391A (en) * | 1931-05-09 | 1935-04-02 | Strans Joseph | Oil soluble dyestuffs |
US2023142A (en) * | 1931-09-22 | 1935-12-03 | Shell Dev | Motor fuel of high antiknock value |
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Publication number | Priority date | Publication date | Assignee | Title |
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EP1580254A2 (en) * | 2004-03-25 | 2005-09-28 | HM Customs & Excise | Hydrocarbon markers |
EP1580254A3 (en) * | 2004-03-25 | 2005-11-23 | HM Customs & Excise | Hydrocarbon markers |
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