Abstract:
A gasoline fuel composition comprising a major portion of gasoline and a minor portion of a diphenylamine, effective to increase the octane number of the gasoline composition, represented by the formula: ##STR1## where R and R&#39; are independently hydrogen or C 9  aliphatic hydrocarbons.

Description:
BACKGROUND OF THE INVENTION 1. Field of the Invention 
     The present invention relates to a gasoline with improved octane number. More specifically, the present invention relates to a non-metallic anti-knock fuel additive. 2. Description of Related Information 
     Spark initiated internal combustion gasoline engines require fuel of a minimum octane level which depends upon the design of the engine. If such an engine is operated on a gasoline which has an octane number lower than the minimum requirement for the engine, &#34;knocking&#34; will occur. Generally, &#34;knocking&#34; occurs when a fuel, especially gasoline, spontaneously and prematurely ignites or detonates in an engine prior to spark plug initiated ignition. It may be further characterized as a non-homogeneous production of free radicals that ultimately interfere with a flame wave front. Gasolines can be refined to have sufficiently high octane numbers to run today&#39;s high compression engines, but such refining is expensive and energy intensive. To increase the octane level at decreased cost, a number of metallic fuel additives have been developed which, when added to gasoline, increase its octane rating and therefore are effective in controlling engine knock. Although the exact mechanism is unknown, the-effectiveness of these metallic agents is believed to entail deactivation of free radical intermediates generated during combustion. The problem with metallic anti-knock gasoline fuel additives, however, is the high toxicity of their combustion products. For example, the thermal decomposition of polyalkyl plumbates, most notably tetramethyl- and tetraethyl lead, are lead and lead oxides. All of these metallic octane improvers have been banned nationwide, because their oxidation products produce metallic lead and a variety of lead oxide salts. Lead and lead oxides are potent neurotoxins and, in the gaseous form of an automotive exhaust, become highly neuro-active. 
     It would therefore be desirable to identify non-metallic anti-knock agents which would produce little toxic combustion products compared to metallic anti-knock agents, and which would provide a needed increase in octane ratings to eliminate &#34;knocking&#34;. 
     SUMMARY OF THE INVENTION 
     In accordance with certain of its aspects, the present invention provides a gasoline composition comprising a major portion of a mixture of hydrocarbons boiling in the gasoline boiling range and a minor portion, effective to increase the octane number of the gasoline composition, of a diphenylamine represented by the formula: ##STR2## where R and R&#39; independently comprise hydrogen or a C 9  aliphatic hydrocarbon. 
     In a second embodiment, the present invention provides a method of improving the octane number of a gasoline which comprises adding to a major portion of a mixture of hydrocarbons boiling in the gasoline boiling range, a minor, octane improving portion of the diphenylamine described above. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     We have found that the anti-knock gasoline fuel additive of the present invention provides significant increases in octane number for gasoline compositions. 
     The anti-knock gasoline fuel additive of the present invention comprises a diphenylamine represented by the formula: ##STR3## where R and R&#39; independently comprise hydrogen or a C 9  aliphatic hydrocarbon. Preferably, R and R&#39; are para- with respect to the nitrogen atom. 
     The synthesis of the nonyl substituted diphenylamine is routine. The following are illustrative: 
     1) condensing alkyl aniline using an iron catalyst according to the equation: ##STR4## 
     2) reduction of bis-acyl diphenyl amines according to the equation: ##STR5## 
     3) direct addition of R and R&#39; to diphenyl amine according to the equation: ##STR6## and the like, where at least one of R and R&#39; comprises a C 9  aliphatic hydrocarbon. 
     The anti-knock agent of the present invention is typically employed in a minor octane increasing amount. It may be added in an amount between 0.01 wt. % and 50 wt. %, preferably between 0.01 wt. % and 5 wt. % and more preferably between about 0.5 wt. % and about 2.0 wt. %. The additive can be blended into the gasoline by any method, because dialkyl diphenylamines show favorable solubility in hydrocarbon solvents. 
     The gasolines which can be treated by the process of this invention to raise their octane number boil in the range between about 50° F. and about 450° F., and may be straight run gasolines, but more preferably they will be blended gasolines which are available commercially. An example of a typical gasoline useful in the practice of the present invention is provided in Table I. 
     
                       TABLE I______________________________________Typical Gasoline______________________________________IBP             80.7° F. 5%            111.9° F.10%            124.5° F.20%            141.4° F.30%            159.4° F.40%            182.3° F.50%            207.6° F.60%            230.9° F.70%            251.2° F.80%            277.5° F.90%            320.3° F.95%            347.1° F.FBP            417.2° F.RECOVERY       99.2 vol. %LOSS            0.1 vol. %RESIDUE         0.7 vol. %______________________________________ 
    
     These commercial gasolines typically contain components derived from catalytic cracking, reforming, isomerization, etc. Although the octane number of any gasoline may be improved by the technique of this invention, it is preferred to treat charge gasolines of nominal octane number between 75-95. The gasolines may contain other common additives for the improvement of detergency, emissions, dispersancy, corrosion resistance, anti-haze, etc. 
     It is a feature of the gasoline compositions of the present invention that they exhibit increased motor octane number (MON) and research octane number (RON). The experimental engine parameters that distinguish MON from RON are summarized in Table II. 
     
                       TABLE II______________________________________RON v. MONExperimental Conditions        RON         MON        Light Duty; Heavy Duty;        Original CFR                    New CFR______________________________________Engine speed, rpm          600           900Intake air temperature, °F.          125           100Mixture temperature, °F.          not controlled                        300Spark advance  for maximum power                        automatic*          (later 13°)______________________________________ *Changes automatically with compression ratio; basic setting is 26.degree before top center at 5:1 compression ratio. 
    
     The additives of the present invention were tested for their ability to increase the RON and MON of a six component standard gasoline blend, shown in Table III. 
     
                       TABLE III______________________________________Experimental Gasoline BlendCompound       Amount (wt. %)______________________________________isopentane     30n-heptane      10i-octane       5n-dodecane     7toluene        25i-butylbenzene 10______________________________________ 
    
     EXAMPLE I 
     In Example I, 2.0 wt % of diphenylamine (R and R&#39;=hydrogen) was added to the experimental gasoline composition described above. Three samples of the base fuel and the base fuel plus additive were tested for research octane number response, using test method ASTM D2700. The results are presented in Table IV. Likewise, three samples of the base fuel and base fuel plus the additive were tested for motor octane number response, using test method ASTM D2699. The results are presented in Table V. 
     
                       TABLE IV______________________________________      Experimental                 Experimental Base FuelTest       Base Fuel  Plus DiphenylamineNumber     RON        Mixture RON______________________________________1          80.0       85.52          79.7       84.33          81.4       86.0Average    80.4       85.3______________________________________ 
    
     
                       TABLE V______________________________________                  Experimental Base FuelTest      Experimental Plus DiphenylamineNumber    Base Fuel MON                  Mixture MON______________________________________1         76.2         80.62         76.5         80.03         75.9         80.0Average   76.2         80.2______________________________________ 
    
     Thus, at a concentration of 2.0 wt %, diphenylamine provides a significant average RON increase of 4.9 units and a significant MON increase of 4.0 units. It provides this octane increase without recourse to metallic anti-knock additive agents. 
     EXAMPLE II 
     In Example II, 2.0 wt % of di-nonyl diphenylamine was added to the experimental gasoline composition described above. Five samples of the base fuel and the base fuel plus additive were tested for research octane number response, using test method ASTM D2700. The results are presented in Table VI. Likewise, five samples of the base fuel and base fuel plus the additive were tested for motor octane number response, using test method ASTM D2699. The results are presented in Table VII. 
     
                       TABLE VI______________________________________     Experimental                Experimental Base Fuel PlusTest      Base Fuel  di-nonyl diphenylamineNumber    RON        RON______________________________________1         81.5       83.22         81.8       83.73         81.6       83.74         81.8       83.55         82.0       83.1Average   81.7       83.4______________________________________ 
    
     
                       TABLE VII______________________________________     Experimental                Experimental Base Fuel PlusTest      Base Fuel  di-nonyl diphenylamineNumber    MON        MON______________________________________1         72.7       73.22         73.1       75.63         73.3       75.44         73.5       75.55         73.3       74.9Average   73.2       74.9______________________________________ 
    
     Thus, at a concentration of 2.0 wt %, the additive provides a significant average RON increase of 1.7 units and a significant MON increase of 1.7 units.