Title of Invention

"A PROCESS FOR THE PREVENTION OF OXIDATIVE DEGRADATION AND GUM OR DEPOSIT FORMATION IN GASOLINE"

Abstract

A process for the prevention of oxidative degradation and gum or deposit formation in gasoline which comprises adding to gasoline subject to oxidative or thermal induced degradation an effective stabilizing amount of stabilizer system which is a nitroxide compound with the proviso that the nitroxide compound is not di-tert-butyl nitroxyl, l-oxyl-2,2,6,6- tetramethylpiperidine or a diaryl nitroxide, wherein the effective stabilizing amount of the nitroxide compound is from 0.05 to 10,000 ppm.

Full Text

The present invention relates to a process for the prevention of oxidative degradation and gum or deposit formation in gasoline. The instant invention pertains to the use of aliphatic nitroxides either alone or with synergistic coadditives as stabilizers for preventing the formation of gum deposits in gasoline. Gasoline, used extensively as a fuel for internal combustion engines, is a mixture of different hydrocarbons. Gasoline is prepared by a number of different processes. The actual composition of a gasoline is determined in part by the production methods used to formulate it and can also vary with the desired end-use to be made for the fuel. Among production methods are: fractional distillation of crude oil to prepare straight-run gasoline; cracking of high molecular weight hydrocarbons either thermally to prepare coker gasoline or catalytically in a FCC (fluidized catalytic cracker); coupling of low molecular weight propyl and butyl fractions to form dimate gasoline; reforming can catalytically produce high octane gasoline from lower octane feed stocks; and as a by-product of lower olefin (ethylene, propylene, etc.) production to form pyrolysis gasoline or "pygas". Quite independent of the method used to produce the gasoline, stability, especially by oxidative degradation, is a serious problem. Gasoline, as well as other hydrocarbon fuels, are known to form sticky deposits or gums both upon storage and under actual use conditions. These gummy residues can cause severe problems: for example, such deposits can cause valves to stick and such precipitates may cause tillers to clog. These problems can adversely effect both the handling and combustion performance of the fuel. Among the different types of gasolines, pygas and cracked gasoline (both coker and FCC) are the most prone to oxidation and deposit formation. Work in the area of gasoline stabilization has been performed over many years. One . common class of stabilizer for this purpose is the phenylenediamines (PDA) used alone or in admixture with other materials. United States Patent Nos. 3,322,520 and 3,556,748 teach that the phenylenediamine is usually N,N'-disubstituted with the substituents being either aliphatic or aromatic. United States Patent No. 5,509,944 teaches that mixtures of PDA, hindered phenols and dimethyl sulfoxide (DMSO) perform better than PDA alone. Pheny-lenediamines do not function well as stabilizers when the gasoline has a high acid number (>0.1 mg KOH/g gasoline). United States Patent No. 5,169,410 teaches that the use of a strongly basic organic amine can, by preferentially reacting with acid moieties, increase the stabilization efficacy of the phenylenediamine. United States Patent Nos. 2,305,676 and 2,333,294 demonstrate that the use of N-substituted p-aminophenol derivatives and certain polyamines are effective in stabilizing a variety of gasolines. United States Patent No. 4,648,885 discloses that a mixture of polyamines and N,N-diethylhydroxylamine is an effective stabilizer for distillate fuel oils. GB 1 316 342 suggests diaryl nitroxides as valuable compounds to prevent undesired oxidation of hydrocarbons such as gasoline, lubricating oils, mineral oils or waxes. However, despite these efforts to prevent oxidation of gasoline and the gummy deposits causing fouling during use of gasoline, there remains a need to stabilize gasoline more effectively. This need is greatest in the area of the less stable pyrolysis and coker gasolines due to their high level of unsaturation and in gasolines having a high level of acid impurities. Nitroxides have been known and used for a variety of applications for many years. They have been used as polymerization inhibitors for several vinyl monomers. United States Patent No. 5,254,760 teaches the use of a stable nitroxyl compound in conjunction with an aromatic nitro compound to inhibit the polymerization of styrene and other vinyl aromatic compounds. United States Patent No. 5,322,960 discloses mixtures of nitroxide, phenol and phenothiazines as an acrylate polymerization inhibitor. The use of nitroxides in stabilizing butadiene and other low molecular weight olefins during purification is recorded in United States Patent No. 4,670,131. Under specific conditions as taught in United States Patent No. 5,412,047, stable nitroxide radicals can act to control the molecular weight polydispersity and produce "living" polymers. Stable nitroxides have also been used as oxidation catalysts as seen in United States Patent Nos. 5,495,045 and 5,136,103. United States Patent No. 5,496,875 teaches the use of nitroxides as light and thermal stabilizers for polymers. None of the prior art teaches the use of aliphatic nitroxides as stabilizers for gasoline. Since aliphatic nitroxides are non-basic (or neutral), they do not react with any acidic components in the gasoline as described in United States Patent No. 5,169,401. Thus, the aliphatic nitroxides do not require the use of an amine coadditive as do the phenylenediamines. The object of this invention is to provide a method by which gasoline, particularly gasoline produced by cracking or as a by-product of olefin synthesis (pygas), can be stabilized against oxidative degradation and deposit formation. The present invention pertains to the use of aliphatic nitroxides as an additive for gasoline mixtures that will inhibit its oxidation and prevent the formation of gums or other deposits when gasoline is processed and stored. The gasoline mixture may contain, but is not limited to, one or more of the previously discussed straight-run, coker, FCC, dimate, reformed or pyrolysis gasolines. In particular, the very unstable pyrolysis and coker gasolines are effectively stabilized by the use of the aliphatic nitroxide stabilizers. The instant process for the prevention of oxidative degradation and gum or deposit formation comprises adding to gasoline subject to oxidative or thermal induced degradation an effective stabilizing amount of an aliphatic nitroxide compound. The effective stabilizing amount of the aliphatic nitroxide compound is from 0.05 to 10,000 ppm, preferably from 0.1 to 100 ppm, most preferably 0.5 to 25 ppm. Preferably the aliphatic nitroxide is a hindered amine aliphatic nitroxide. The aliphatic nitroxide can be of several different classes. Aliphatic (often hindered amine) aliphatic nitroxides are shown to be effective in the instant process. Especially preferred are the hindered amine nitroxyl radicals in general, i.e. compounds having at least one NO* group, where the * asterisk denotes an unpaired electron, and the nitrogen atom is further flanked by two carbon atoms, to neither of which hydrogen atoms are attached. These flanking carbon atoms may be further connected by various bridging groups to form cyclic structures such as for example six-membered piperidines, piperazines, five membered pyrrolidines and the like, as exemplified by, but not limited to the list below: di-tert-butyl nitroxyl, 1-oxyl-2,2,6,6-tetramethylpiperidine, l-oxyl-2,2,6,6-tetramethylpiperidin-4-ol, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl acetate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl2-ethylhexanoate, 1 -oxyl-2,2,6,6-tetramethylpiperidin-4-yl stearate, 1 -oxyl-2,2,6,6-tetramethylpiperidin-4-yl benzoate, 1 -oxyl-2,2,6,6-tetramethylpiperidin-4-yl 4-tert-butylbenzoate, bis(1 -oxyl-2,2,6,6-tetramethylpiperidin-4-yl) succinate, bis(1 -oxyl-2,2,6,6-tetramethylpiperidin-4-yl) adipate, bis(1 -oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(1 -oxyl-2,2,6,6-tetramethylpiperidin-4-yl) n-butylmalonate, bis(1 -oxyl-2,2,6,6-tetramethylpiperidin-4-yl) phthalate, bis(1 -oxyl-2,2,6,6-tetramethylpiperidin-4-yl) isophthalate, bis(1 -oxyl-2,2,6,6-tetramethylpiperidin-4-yl) terephthalate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) hexahydroterephthalate, N,N'-bis(1-Oxyl-2,2,6,6-tetramethylpiperidin-4-yl)adipamide, N-(1-Oxyl-2,2A6-tetramethylpiperidin-4-yl)caprolactam, N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)dodecylsuccinimide, 2,4,6-tris-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) cyanurate, 2,4,6-tris-[N-butyl-N-(1-oxyl-2>2,6,6-tetramethylpiperidin-4-yl]-s- triazine, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl3,5-di-tert-butyl-4-hydroxy hydrocinnamate or 4,4'-ethylenebis(1-oxyl-2,2,6,6-tetramethylpiperazin-3-one). Especially preferred is the hindered amine aliphatic nitroxide bis(1-oxyl-2,2,6,6-tetramethyl-piperidin-4-yl) sebacate, which shows excellent activity at 5 ppm concentration and shows activity even at concentrations of 1 ppm and lower. Also preferred is 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol. Another embodiment of the instant invention pertains to a process where the effective stabilizer system comprises a synergistic mixture of an aliphatic nitroxide compound and an aromatic amine, particularly a substituted phenylenediamine, or a phenolic antioxidant or mixture of aromatic amine and phenolic antioxidant. Examples and preferrences for the aliphatic nitroxide have been described above. Preferably the aromatic amine is a substituted phenylenediamine. Particularly preferred aromatic amines are : N.N'-di-isopropyl-p-phenylenediamine, N.N'-di-sec.-butyl-p-phenylenediamine, N.N'-di-sec.-butyl-o-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine, N.N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-di-(2-naphthyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-sec.-butyl-N'-phenyl-o-phenylenediamine, N-(1,3-dimethylbutyO-N'-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine; N,N'-di(1,4-dimethylpentyl)-o-phenylenediamine; diphenylamine, N-allyldiphenylamine, di-(4-isopropoxyphenyl)amine, N-phenyl-1 -naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, p,p'-di-tert-octyldiphenylamine, di-(4-methoxy-phenyl)amine, tert-octylated N-phenyl-1-naphthylamine, or a mixture of mono- and dialkylated tert-butyl-/tert-octyldiphenylamines. Especially preferred amines are N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, p.p'-di-tert-octyldiphenylamine, a mixture of mono- and dialkylated tert-butyl-/tert-octyldiphenylamines, or N,N'-di(1,4-dimethylpentyl)-p-phenylenediamine. Some phenolic antioxidants of interest are listed below: Alkylated Monophenols 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butylphenol, 2-tert-butyl-4,6-dimethyl-phenol, 2,6-di-tert-butyl-4-ethyl-phenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-i- butylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2-(|3-methylcyclohexyl)-4,6-dimethylphenol, 2,6-di-octa-decyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol, 2,6-di-tert-butyl-4- methoxymethylphenol, o-tert-butylphenol. Alkylidene-Bisphenols 2,2'-methylene-bis-(6-tert-butyl-4-methylphenol), 2,2'-methylene-bis-(6-tert-butyl-4-ethylphenol), 2,2'-methylene-bis-(4-methyl-6-(a-methyl-cyclohexyl)-phenol), 2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis-(6-nonyl-4-methylphenol), 2,2'-methylene-bis-(4,6-di-tert-butylphenol), 2,2'-ethylidene-bis-(4,6-di-tert-butylphenol), 2,2'-ethylidene-bis-(6-tert-butyl-4- or -5-isobutylphenol), 2,2'-methylene-bis-(6-(a-methylbenzyl-4-nonylphenol), 2,2I-methylene-bis-(6-(a,a-di-methylbenzyl)-4-nonylphenol), 4,4'-methylene-bis-(2,6-di-tert-butyl-phenol), 4,4'-methylene-bis-(6-tert-butyl-2-methylphenol), 1,1-bis-(5-tert-butyl-4-hydroxy-2-methyl-phenol)-butane, 2,6-di-(3-tert-butyl-5-methyl-2-hydroxy-benzyl)-4-methyl-phenol, 1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecy I)-mercaptobutane, ethyleneglycol-bis-[3,3-bis-(3'-tert-butyl-4'-hydroxyphenyl)- butyrate], bis-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene, bis-[2-(3'-tert-butyl-2'-hydroxy-5'-methyl-benzyl)-6-tert-but yl-4-methyl-phenyl]-terephthalate. The phenolic antioxidant of particular interest is selected from the group consisting of n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinammate), di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonate, thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 3,6-dioxaoctamethylene bis(3-methyl- 5-tert-butyl-4-hydroxyhydrocinnamate), 2,6-di-tert-butyl-p-cresol, 2,2'-ethylidene-bis(4,6-di-tert-butylphenol), 1,1,3,-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butaneI 3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexamethylene bis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamate), 1 -(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine, N,N'-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide), ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate], octyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate, bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide, N,N'-bis[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-ethyl]-oxamide, 2,6-di-tert-butylphenol, octyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate and methyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate. Preferred phenolic antioxidants are neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 1,3,5-tri-methyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 2,6-di-tert-butyl-p-cresol, 2,2'-ethylidene-bis(4,6-di-tert-butylphenol), methyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, octyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 2,6-di-tert-butylphenol or 3,6-dioxaocta-methylene bis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate). Especially preferred phenolic antioxidants are methyl 3,5-di-tert-butyl-4-hydroxyhydro-cinnamate, octyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate or 2,6-di-tert-butylphenol. When such a mixture of aliphatic nitroxide compound and aromatic amine, particularly a substituted phenylenediamine, or phenolic antioxidant is used, the effective stabilizing amount is from 0.05 to 5000 ppm of aliphatic nitroxide and 0.05 to 5000 ppm of aromatic amine, particularly substituted phenylenediamine, or phenolic antioxidant, preferably from 0.1 to 100 ppm of aliphatic nitroxide plus 0.1 to 100 ppm of aromatic amine, especially substituted phenylenediamine, or phenolic antioxidant or mixture of aromatic amine and phenolic antioxidant. It is also possible to combine the functionalities represented by the synergistic mixture described above in the same molecule. Such a molecule would be the compound described by LP. Nethsinghe and G. Scott, Rubber Chem. Technology, 57(5), 918 (1984) as 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl3,5-di-tert-butyl-4-hydroxyhydrocinnamate. Preferred embodiments of the instant invention comprise a process wherein the synergistic mixture is from 1 to 95% by weight of aliphatic nitroxide compound and 99 to 5% by weight of an aromatic amine, phenolic antioxidant or mixture thereof where the ratio of amine to phenolic antioxidant is 5:1 to 1:5. A more preferred embodiment comprises the mixture which is from 5 to 75% by weight of aliphatic nitroxide compound and 95 to 25% by weight of an aromatic amine, phenolic antioxidant or mixture thereof where the ratio of amine to phenolic antioxidant is 2:1 to 1:2. A still more preferred embodiment comprises the mixture which is from 10 to 50% by weight of aliphatic nitroxide compound and 90 to 50% by weight of an aromatic amine, phenolic antioxidant or mixture thereof where the ratio of amine to phenolic antioxidant is 1:1. A preferred embodiment is the synergistic mixture where the aliphatic nitroxide is bis(1-oxyl-2,2,6,6-tetramethy!piperidin-4-yl) sebacate, the aromatic amine is N,N'-di(1,4-dimethyl-pentyl)phenylenediamine, and the phenolic antioxidant is methyl 3,5-di-tert-butyl-4-hydroxy-hydrocinnamate. Still another embodiment of the instant invention pertains to a composition stabilized against oxidative degradation and against the formation of gum or undesirable deposits which comprises (a) gasoline, particularly unstable gasolines such as pyrolysis or coker gasoline, and (b) an effective stabilizing amount of an aliphatic nitroxide compound. Still another embodiment is a gasoline composition which is stabilized against oxidative degradation and against the formation of gum or undesirable deposits which comprises an effective synergistic mixture of a aliphatic nitroxide compound and an aromatic amine, particularly a substituted phenylenediamine, or a phenolic antioxidant or mixture of aromatic amine and phenolic antioxidant. Examples and preferences including preferred ratios and amounts for the individual components have been afore mentioned and apply also to the compositions. Preferably the gasoline is pyrolysis or coker gasoline. The composition can be produced by dissolving the aliphatic nitroxide, the aromatic amine or the phenolic antioxidant directly in the gasoline. It is however also possible to dissolve the components in a suitable solvent and to add the predisolved components to the gasoline. Suitable solvents are for example aliphatic hydrocarbons, aromatic hydrocarbons such as benzene toluene or xylene, ketones or ethers. Further embodiments of the present invention pertain to the use of an aliphatic nitroxide for the stabilization of gasoline against oxidative degradation and against the formation of gum or undesirable deposits and to the use of a synergistic mixture of an aliphatic nitroxide compound and an aromatic amine or a phenolic antioxidant or mixture of aromatic amine and phenolic antioxidant for the stabilization of gasoline against oxidative degradation and against the formation of gum or undesirable deposits. Accordingly there is provided a process for the prevention of oxidative degradation and gum or deposit formation in gasoline which comprises adding to gasoline subject tc oxidative or thermal induced degradation an effective stabilizing amount of stabilizer system which is a nitroxide compound with the proviso that the nitroxide compound is not di-tert- butyl nitroxyl, l-oxyl-2,2,6,6-tetramethylpiperidine or a diaryl nitroxide, wherein the effective stabilizing amount of the nitroxide compound is from 0.05 to 10,000 ppm. Accordingly there is also provided a composition stabilized against oxidative degradation and against the formation of gum or undesirable deposits which comprises (a) gasoline subject to oxidative degradation, and (b) an effective stabilizing amount of a stabilizer system which is a nitroxide compound, and with the proviso that the nitroxide is not di-tert-butyl nitroxyl, 1-oxyl- 2,2,6,6-tetramethylpiperidine or a diaryl nitroxide, wherein the effective stabilizing amount of the nitroxide compound is from 0.05 to 10,000 ppm. The following examples are meant for illustrative purposes only. Several standard accelerated test methods are known for the evaluation of the stability of fuels in general, and gasoline in particular. Two common ASTM methods for gasoline are (1) D 525 Test Method for Oxidation Stability of Gasoline (Induction Period Method); and (2) D 873 Standard Test Method for Oxidation Stability of Aviation Fuels (Potential Residue Method). Schrepfer and Stansky reported in Gasoline Stability Testing and inhibitor Application, Nation Fuels and Lubricants Meeting, (1981), that the latter method was much better in predicting the long term deposit formation in both stable and unstable gasolines. This method is used in order to evaluate the instant aliphatic nitroxide stabilizers. Example 1 The sample of gasoline used in the examples is collected from an olefin production unit (pygas). It is a 1:1 blend of inhibitor-free Cs and Cg+ streams. The samples are collected in oxygen-free containers cooled in an ice bath and stored in a refrigerator under nitrogen. In accordance with ASTM D 873-88, a 100 mL sample of pyrolysis gasoline in a bomb is heated in a boiling water bath under oxygen for four hours. The stabilized gasoline samples are prepared by adding 2 mL of a toluene solution of the stabilizer to 98 ml of pyrolysis gasoline producing a total volume of 100 ml. After heating, the aged gasoline is removed from the bomb and the total gum produced is determined. Table 1 below contains the results obtained when the known gasoline stabilizer N,N'-di(1 ,4-dimethylpentyl)phenylenediamine, either alone or with a hindered phenolic costabilizer is tested. These formulations are evaluated in order to act as benchmarks for comparing the effectiveness of the aliphatic nitroxide stabilizer systems. Table 1 Effect of Substituted Phenylenediamine Stabilizer Systems on Pygas Gum Formation in ASTM D 873 Potential Gum Test Concentration of Components in ppm (Table Removed) A is N,N'-di(1,4-dimethylpentyl)phenylenediamine. B is octyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate. C is methyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate. The combination of a substituted phenylenediamine (A) plus a phenolic antioxidant (B) each at a concentration of 12.5 ppm gives 2.2 mg/100 ml_ gum formation while compound (A) in combination with phenolic antioxidant (C) each at a concentration of 25 ppm reduces gum formation to a desirable low level (1.1 mg/100 mL). Table 2 below demonstrates the effectiveness of aliphatic nitroxide stabilizers when used alone. Even at a concentration of 1 ppm, an aliphatic nitroxide has approximately the equivalent performance of the substituted phenylenediamine stabilizer at 10 ppm. Table 2 Effect of Aliphatic nitroxide Stabilizer Systems on Pygas Gum Formation in ASTM D 873 Potential Gum Test Concentration of Components in ppm (Table Removed) D is bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate. G is 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol. Aliphatic nitroxides D and G at 10 ppm concentration are roughly 10 times more effective than phenylenediamine A at 10 ppm in preventing gum formation. Although the aliphatic nitroxides demonstrate superior stabilization performance over the current state of the art, this performance can be further improved by using synergistic mixtures of such aliphatic nitroxides with various costabilizers as can be seen in Table 3. Table 3 Effect of Aliphatic nitroxide Stabilizer Systems on Pygas Gum Formation in ASTM D 873 Potential Gum Test Concentration of Components in ppm (Table Removed) A is N,N'-di(1,4-dimethylpentyl)phenylenediamine. C is methyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate. D is bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate. F is di(4-tert-octylphenyl)amine. G is l-oxyl-2,2,6,6-tetramethylpiperidin-4-ol. From Table 3 it is clear that the combination of a hindered amine aliphatic nitroxide D or G with the substituted phenylenediamine A or phenolic antioxidant C gives synergistic stabilization. Even mixtures of aliphatic nitroxide D with diarylamine F, which is itself almost inactive alone, gives effective stabilization. CLAIM: 1. A process for the prevention of oxidative degradation and gum or deposit formation in gasoline which comprises adding to gasoline subject to oxidative or thermal induced degradation an effective stabilizing amount of stabilizer system which is a nitroxide compound with the proviso that the nitroxide compound is not di-tert- butyl nitroxyl, l-oxyl-2,2,6,6-tetramethylpiperidine or a diaryl nitroxide, wherein the effective stabilizing amount of the nitroxide compound is from 0.05 to 10,000 ppm. 2. A process as claimed in claim 2 wherein the effective stabilizing amount of nitroxide compound is from 0.1 to 100 ppm. 3. A process as claimed in claim 3 wherein the effective amount of nitroxide compound is from 0.5 to 25 ppm. 4. A process as claimed in claim 1 wherein the stabilizer system comprises an effective stabilizing amount of a synergistic mixture of the nitroxide compound and an aromatic amine or a phenolic antioxidant or mixture of aromatic amine and phenolic antioxidant. 5. A process as claimed in claim 1 wherein the nitroxide is a hindered amine nitroxide. 6. A process as claimed in claim 1 wherein the nitroxide is l-oxyl-2,2,6,6-tetramethylpiperidin-4-ol, l-oxyl-2,2,6,6-tetramethylpiperidin4-one, 1 -oxyl-2,2,6,6-tetramethylpiperidin4-ylacetate, l-oxyl-2,2,6,6-tetramethylpiperidin-4-yl2-ethylhexanoate, l-oxyl-2,2,6,6-tetramethylpiperidin-4-ylstearate, 1 -oxyl-2,2,6,6-tetramethylpiperidin-4-ylbenzoate, l-oxyl-2,2,6,6-tetramethylpiperidin-4-yl4-tert-butylbenzoate, bis( i -oxyl-2,2,6,6-tetramethylpiperidin-4-yl)succinate, bis(l-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)adipate, bis( 1 -oxyl-2,2,6,6-tetramethylpiperidin-4-yl)sebacate, bis( 1 -oxyl-2,2,6,6-tetramethylpiperidin-4-yl)n-butylmalonate, bis(l-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)phthalate, bis( 1 -oxyl-2,2,6,6-tetramethylpiperidin-4-yl)isophthalate, bis( 1 -oxyl-2,2,6,6-tetramethylpiperidin-4-yl)terephthalate, bis(l-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)hexahydroterephthalate, N,N'-bis(l-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)adipamide, N-(l-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)caprolactam, N-(l-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)dodecylsuccinimide, 2,4,6-tris-( 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)cyanurate, 2,4,6-tris->N-butyl-N-(l-oxyl-2,2,6,6-tetramethylpiperidin-4-yl!-s-triazine l-oxyl-2,2,6,6-tetramethylpiperidin-4-yl3,5-di-tert-butyl-4- hy droxyhydrocinnamate, or 4,4'-ethylenebis(l-oxyl-2,2,6,6-tetramethylpiperazin-3-one). 7. A process as claimed in claim 7 wherein the nitroxide is bis(l-oxyl- 2,2,6,6-tetramethylpiperidin-4-yl)sebacate. 8. A process as claimed in claim 8 wherein the nitroxide is 1-oxyl- 2,2,6,6-tetramethylpiperidin-4-ol. 9. A process as claimed in claim 5 wherein the aromatic amine is a substituted phenylenediamine. 10. A process as claimed in claim 5 wherein the effective stabilizing synergistic mixture comprises 0.05 to 5000 ppm of nitroxide compound and 0.05 to 5000 ppm of an aromatic amine, phenolic antioxidant or mixture of aromatic amine and phenolic antioxidant. 11. A process as claimed in claim 11 wherein the amount of nitroxide compound is 0.1 to 100 ppm and the amount of the aromatic amine, phenolic antioxidant or mixture of aromatic amine and phenolic antioxidant is 0.1 to 100 ppm. 12. A process as claimed in claim 5 wherein the aromatic amine is N,N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec.-butyl-p-phenylenediamine, N,N'-di-sec.-butyl-o-phenylenediamine, N,N'-bis( 1,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis( 1 -ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis( 1 -methylheptyl)-p-phenylenediamine, N, N' -dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-di-(2-naphthyl;-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-sec.-butyl-N'-phenyl-o-phenylenediamine, N-( 1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-(l-methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, N,N'-di( 1,4-dimethylpentyl)-o-phenylenediamine, diphenylamine, N-allyldiphenylamine, di-(4-isopropoxyphenyl)amine, N-phenyl-1 -naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, di-(4-methoxy-phenyl)amine, tert-octylated N-phenyl-1-naphthylamine, or a mixture of mono- and dialkylated tert-butyl-/tert-octyldiphenylamines. 13. A process as claimed in claim 13 wherein the aromatic amine is N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, a mixture of mono- and dialkylated tert-butyl-/tert- octyldiphenylamines, or N,N'-di(l,4-dimethylpentyl)-p- phenylenediamine. 14. A process as claimed in claim 5 wherein the phenolic antioxidant is neopentanetetrayl (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n- octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 1,3,5-trimethyl- 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 2,6-di-tert-butyl- p-cresol, 2,2'-ethylidene-bis(4,6-di-tert-butylphenol), methyl 3,5-di- tert-butyl-4-hydroxyhydrocinnamate, octyl 3,5-di-tert-butyl-4- hydroxyhydrocinnamate, 2,6-di-tert-butylphenol or 3,6- dioxaoctamethylene bis(3-methyl-5-tert-butyl-4- hydroxyhydrocinnamate). 15. A process as claimed in claim 15 wherein the phenolic antioxidant is methyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, octyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate or 2,6-di-tert- butylphenol. 16. A process as claimed in claim 5 wherein the synergistic mixture is from 1 to 95% by weight of nitroxide compound and 99 to 5% by weight of an aromatic amine, phenolic antioxidant or mixture thereof where the ratio of amine to phenolic antioxidant is 5:1 to 1:5. 17. A process as claimed in claim 17 wherein the mixture is from 5 to 75% by weight of nitroxide compound and 95 to 25% by weight of an aromatic amine, phenolic antioxidant or mixture thereof where the ratio of amine to phenolic antioxidant is 2:1 to 1:2. 18. A process as claimed in claim 18 wherein the mixture is from 10 to 50% by weight of nitroxide compound and 90 to 50% by weight of an aromatic amine, phenolic antioxidant or mixture thereof where the ratio of amine to phenolic antioxidant is 1:1. 19. A process as claimed in claim 17 wherein the nitroxide is bis(l- oxyl-2,2,6,6-tetramethylpiperidin-4-yl)sebacate, the aromatic amine is N,N'-di(l,4-dimethylpentyl)phenylenediamine, and the phenolic antioxidant is methyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate. 20. A composition stabilized against oxidative degradation and against the formation of gum or undesirable deposits which comprises (a) gasoline subject to oxidative degradation, and (b) an effective stabilizing amount of a stabilizer system which is a nitroxide compound, and with the proviso that the nitroxide is not di-tert-butyl nitroxyl, 1-oxyl- 2,2,6,6-tetramethylpiperidine or a diaryl nitroxide, wherein the effective stabilizing amount of the nitroxide compound is from 0.05 to 10,000 ppm. 21. A composition as claimed in claim 20 wherein the gasoline is pyrolysis or coker gasoline. 22. A composition as claimed in claim 23 wherein the effective stabilizing amount of nitroxide compound is from 0.1 to 100 ppm. 23. A composition as claimed in claim 22 wherein the effective amount of nitroxide compound is from 0.5 to 25 ppm. 24. A composition as claimed in claim 21 wherein the stabilizer system comprises an effective stabilizing amount of a synergistic mixture the nitroxide compound and an aromatic amine or a phenolic antioxidant or mixture of aromatic amine and phenolic antioxidant. 25. A composition as claimed in claim 21 wherein the nitroxide is a hindered amine nitroxide. 26. A composition as claimed in claim 21 wherein the nitroxide is l-oxyl-2,2,6,6-tetramethylpiperidin-4-ol, l-oxyl-2,2,6,6-tetramethylpiperidin-4-one, l-oxyl-2,2,6,6-tetramethylpiperidin-4-yl acetate, l-oxyl-2,2,6,6-tetramethylpiperidin-4-yl 2-ethylhexanoate, 1 -oxyl- 2,2,6,6- tetrame thylpiperidin4 -yl stearate, l-oxyl-2,2,6,6-tetramethylpiperidin-4-yl benzoate, l-oxyl-2,2,6,6-tetramethylpiperidin-4-yl 4-tert-burylbenzoate, bis(l-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)succinate, bis(l-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)adipate, bis(l-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)sebacate, bis( 1 -oxyl-2,2,6,6-tetramethylpiperidin-4-yl)n-butylmalonate, bis(l-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)phthalate, bis(l-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)isophthalate, bis(l-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)terephthalate, bis(l-oxyl-2,2,6,6-tetrarnethylpiperidin-4-yl)hexahydroterephthalate, N,N'-bis(l-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)adipamide, N-(l-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)caprolactam, N-(l-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)dodecylsuccinimide, 2. 4,6-tris-(l-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)cyanurate, 2,4,6-tris->N-butyl-N-(l-oxyl-2,2,6,6-tetramethylpiperidin-4-yl!-s-triazine l-oxyl-2,2,6,6-tetramethylpiperidin-4-yl 3,5-di-tert-butyl-4- hydroxyhydrocinnamate, or 4,4'-ethylenebis(l-oxyl-2,2,6,6-tetramethylpiperazin-3-one). 27. A composition as claimed in claim 26 wherein the nitroxide is bis(l-oxyl-2,2,6,6-tetramethylpiperidin4-yl)sebacate. 28. A composition as claimed in claim 26 wherein the nitroxide is 1- oxyl-2,2,6,6-tetramethylpiperidin-4-ol. 29. A composition as claimed in claim 24 wherein the aromatic amine is a substituted phenylenediamine. 30. A composition as claimed in claim 24 wherein the effective stabilizing synergistic mixture comprises 0.05 to 5000 ppm of nitroxide compound and 0.05 to 5000 ppm of an aromatic amine, phenolic antioxidant or mixture of aromatic amine and phenolic antioxidant. 31. A composition as claimed in claim 30 wherein the amount of nitroxide compound is 0.1 to 100 ppm and the amount of the aromatic amine, phenolic antioxidant or mixture of aromatic amine and phenolic antioxidant is 0.1 to 100 ppm. 32. A composition as claimed in claim 24 wherein the aromatic amine is N,N'-di-isopropyl-p-phenylenediamine, N, N' -di- sec. -butyl-p-phenylenediamine, N, N' -di- sec. -butyl-o-phenylenediamine, N,N'-bis( 1,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis( 1 -ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis( 1 -methylheptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N, N' -diphenyl- p-phenylenediamine, N, N1 -di- (2 -naphthyl) -p-phenylenediamine, N-sec.-buryl-N'-phenyl-o-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-( 1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-(l-methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, N,N'-di( 1,4-dimethylpentyl)-o-phenylenediamine, diphenylamine, N-allyldiphenylamine, di- (4 -isopropoxyphenyl) amine, N-phenyl-1 -naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, di-(4-methoxy-phenyl)amine, tert-octylated N-phenyl-1-naphthylamine, or a mixture of mono- and dialkylated tert-butyl-/tert-octyldiphenylamines. 33. A composition as claimed in claim 32 wherein the aromatic amine is N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, a mixture of mono- and dialkylated tert-butyl-/tert- octyldiphenylamines, or N,N'-di(l,4-dimethylpentyl)-p- phenylenediamine. 34. A composition as claimed in claim 24 wherein the phenolic antioxidant is neopentanetetrayl (3,5-di-tert-butyl-4- hydroxyhydrocinnamate), n-octadecyl 3,5-di-tert-butyl-4- hydroxyhydrocinnamate, l,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4- hydroxybenzyl) benzene, 2,6-di-tert-butyl-p-cresol, 2,2'-ethylidene- bis(4,6-di-tert-butylphenol), methyl 3,5-di-tert-butyl-4- hydroxyhydrocinnamate, octyl 3,5-di-tert-butyl-4- hydroxyhydrocinnamate, 2,6-di-tert-butylphenol or 3,6- dioxaoctamethylene bis(3-methyl-5-tert-butyl-4- hydroxyhydrocinnamate). 35. A composition as claimed in claim 34 wherein the phenolic antioxidant is methyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, octyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate or 2,6-di-tert- butylphenol. 36. A composition as claimed in claim 24 wherein the synergistic mixture is from 1 to 95% by weight of nitroxide compound and 99 to 5% by weight of an aromatic amine, phenolic antioxidant or mixture thereof where the ratio of amine to phenolic antioxidant is 5:1 to 1:5. 37. A composition as claimed in claim 36 wherein the mixture is from 5 to 75% by weight of nitroxide compound and 95 to 25% by weight of an aromatic amine, phenolic antioxidant or mixture thereof where the ratio of amine to phenolic antioxidant is 2:1 to 1:2. 38. A composition as claimed in claim 37 wherein the mixture is from 10 to 50% by weight of nitroxide compound and 90 to 50% by weight of an aromatic amine, phenolic antioxidant or mixture thereof where the ratio of amine to phenolic antioxidant is 1:1. 39. A composition as claimed in claim 36 wherein the nitroxide is bis( l-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)sebacate, the aromatic amine is N,N'-di(l,4-dimethylpentyl)phenylenediamine, and the phenolic antioxidant is methyl 3,5-tert-butyl-4- hydroxyhydrocinnamate. 40. A process substantially as hereinbefore described with reference to the foregoing examples. 41. A composition substantially as hereinbefore described with reference to the foregoing examples.

Documents:

1780-del-1997-abstract.pdf

1780-del-1997-claims.pdf

1780-del-1997-correspondence-others.pdf

1780-del-1997-correspondence-po.pdf

1780-del-1997-description (complete).pdf

1780-del-1997-form-1.pdf

1780-del-1997-form-13.pdf

1780-del-1997-form-19.pdf

1780-del-1997-form-2.pdf

1780-del-1997-form-3.pdf

1780-del-1997-form-4.pdf

1780-del-1997-gpa.pdf

1780-del-1997-petition-137.pdf

1780-del-1997-petition-138.pdf