US3377148A - Gasoline fuel composition - Google Patents

Description

United States Patent Ofitice F EL CGMPOSITIGN South Euclid, and John 8. Mann, Warrensville Heigh Ohio, assignors to The Standard Oil'Com'pany, Cleveland, Ohio, ,a corporation of Ohio I No Drawing. Filed Mar. 15, 1965, vSer.- No. 439,993

' 7 Claims. (Cl. 44-63) GASOLINE Richard J. DeGray,

The present invention relates 'to an improved gasoline and to the method of its manufacture and more particularly pertains to a high octane gasoline containing tetraalkyl lead and a reaction product of an amide and a monocarboxylic acid or its anhydride or acid halide as lead appreciator and to the process for manufacture thereof. The present invention deals with a novel class of gasoline additives which increase the octane number of leaded motor fuels. These additives, or tetra-alkyl lead extenders asthey are sometimes referred to, consist of gasoline soluble reaction products of a monocarboxylic acid or its anhydride with an amide having the grouping The additivesmost useful in the the following:

present invention include O RPNJLMLW ing from 1 to 12 carbon .atoms. More preferred in the. Q

present invention are compounds of the foregoing types wherein R is an alkyl group having'from 1 to 18 carbon atoms, R and R are each independently hydrogen or an alkylgroup containing from l to 4 carbon atoms, R is an alkyl or .alkenyl group having from -1 to 6 carbon atoms, R is an alkyl or alkenyl group containing from 1 to 18 carbon atoms, R is an 'al-kylene group havingfrom 1 to 6 carbon atoms, R is an alkyl .group having from 1 to 12 carbon atoms and R- is an alkylene group having from 1 to 12 carbon atoms. Specific compounds of the foregoing types which are particularly preferred in the present invention include:

" 'fuel, with 3,377,148 Patented Apr. v9.,

CH: CH:

In the foregoing compounds the exact structure of the acid adducts with the various amides is unknown, The acid adducts are prepared by mixing the carboxylic acid and the amide. The acetylated amides are prepared by reacting the amide which contains at least one hydrogen bonded to the amide nitrogen with the carboxylic acid anhydride or acyl halide. I V v V The effective concentration of the additives of this invention in leaded motor fuel range from about (X05 to about 3% by Weight based on the weight of the motor maximum benefits being derived in therange of from about 0.5 to 1.5% by Weight of the additive.

3 The increase in octane number obtained with the additives of this invention in a given gasoline varies'with' the con: centration of the additive, the concentration of tetraethyl lead in the gasoline as well as the type of fuel employed. Maximum response to the additives is obtained in an aromatic fuel. The additives also are generally more effective with increased concentration of the tetraalkyl lead in the gasoline. The amount of tetraalkyl lead in the gasolines useful in the present invention can vary from 1 to 6 ml. of tetraalkyl lead per gallon of gasoline.

The acid adduct additives of this invention may be prepared at moderate temperatures, i.e., at room temperature or slightly above, by simply mixing the amide with the acid. The reactants are generally miscible and normally a solvent is not necessary for carrying out the reaction. If desired, the reaction may be carried out in the presence of a solvent such as toluene or a catalytically reformed hydrocarbon, particularly in instances in which one of the reactants is a solid. Generally the formation of the carboxylic acid-amide adduct is exothermic.

As was indicated earlier, the exact nature of the carboxylic acid-amide .adducts is not known but they are probably combined by primary or secondary chemical bonding or by a combination of these two types of bonds.

The reaction product of amides containing at least one hydrogen on the amide nitrogen with carboxylic acid or acyl halides are believed to be acylated amides.

This invention is further illustrated in the following example.

EXAMPLE The additives used were prepared as follows: (A) N-dodecyl trimethylene urea-acetic acid adduct,

glacial acetic acid. Upon shaking the mixture there was a definite evolution of heat. Similar results were obtained when the foregoing reaction was carried out in the abr sence of toluene.

(B) Pyrrolidone-acetic acid adduct was prepared by mixing 17.02 g. of pyrrolidone and 12.01 g. of glacial acetic acid at a temperature slightly above 25 C. (the melting point of pyrrolidone). The heat of reaction increased the temperature of the mixture and the resulting solution was a homogeneous liquid.

(C) Pyrrolidone-acetic acid adduct was prepared as in B except that 18.72 g. of pyrrolidone were reacted with 12.01 g. of acetic acid.

(D) N-methyl pyrrolidone-acetic acid adduct was prepared by mixing 19.82 'g. of N-methyl pyrrolidone and 12.01 g. of glacial acetic acid with stirring at about room temperature. Heat was evolved from the reaction and the final solution was a homogeneous product.

=(E) 'N-methyl pyrrolidone-acetic acid adduct was prepared as in ,D except that 20.80 g. of N-methyl pyrrolidone were reacted with 12.01 g. of glacial acetic acid.

(F) N-oleyl trimethylene urea-acetic acid adduct was prepared by a procedure similar to that given in A using 80.4 g. of oleyl amine and 12.01 g. of urea. To this reaction mixture were added 12.01 g. of acetic acid.

(G) Acetylated pyrrolidone was prepared by mixing 34.04 g. of pyrrolidone and 20.42 g. of acetic anhydride in a 250 ml. flask. The mixture was heated to 110 C. and this was accompanied by a gradual change in color of the reaction mixture to a dark brown color. At 160 C. the reaction appeared to be complete. The product was homogeneous and soluble in gasoline.

(H) Pyrrolidone-acrylic acid adduct was prepared by mixing 85.10 g. of pyrrolidone and 72.06 g. of acrylic acid with stirring. A considerable amount of heat was evolved. The product was a homogeneous liquid at room temperature.

The properties of the fuels (1-3) used are as follows:

ASTM D86 (Distillation Test) Properties 01 Fuel 2 Percent F.

Percent. saturates, 70 10 141 Percent Olefins, 8 30 202 Percent Aromatics, 23 238 Reid Vapor Pressure, p.s i 9 70 272 Gravity at R, 0.7388..... 90 344 Tetraethyl Lead, ce./gal., 2.58 394 ASTM D-86 Properties of Fuel 3 Percent F.

Percent Saturates, 40- 10 168 Percent Olefins, 17.... 30 218 Percent Aromatics, 43 40 258 Reid Vapor Pressure, p.s.i., 4.39 300 Gravity at 60 R, 0.7872 90 366 Tetraethyl Lead, cc.lgal., 3.05 430 1 End Point.

Engine data illustrating the lead appreciator response obtained using the standard F-l and F-2 octane test procedures are shown in Tables I, II, III and IV. The additive compositions, additive concentrations and tetraethyl lead concentrations were varied and the results were compared with tertiary butyl acetate at its most effective concentration.

TABLE I.'.F1 OCTANE RESPONSE Lead Level, ccJgal 0 Additive B H G B H G B H G Coneenration:

Blank. 93. 1 97. 1 98. 7 98. 9 98. 7 0.25%. +1. 0 +0. 7 +1. 5 0.50% +1. 5 +1. 1. +1. 0 0.75% +0. 1 +0. 1 +0. 1 +0. 7 +0. 6 +1. 1 +2.4 +1. 5 +1. 4 1.00%. +2. 0 +1. 4 +1. 7 1.25, 0... +0. 2 +0. 3 +0. 3 0 -0. 2 +0. 7 +1. 4 +1. 0 +2. 0 1.50%- +1. 3 +0. 8 +2. 2 1.75% +0. 6 +0. 4 +0. 6 0. 3 0. 7 +0. 5 +0. 8 +0. 4 +1. 7 0.75% t-Butyl Acetate +0. 1 +0. 5 +0.8 +0. 6 +0. 9

Fuel: No. 3.

3,377,148 6 U v r TABLE irl-r-z OCTANE RESPONSE Lead Level, eta/gal 0 1.5 3.0 Additive B H G B H o B n 0 Concentration:

Blank 81. 1 86.8 87.3 7.8 87.5 0.25 +1.0 +0.7 +1.0 0.50 +1. 0 +1.2 +0.8 0.75 0 +0. 1 +0. 1 +0. 2 0 +0. 0 +1. 0 +1.7 +1.8 1.00 l +1.7 +1.8 +1.7 1.25 +0.5 +0.4 +0.2 --0.2 0.0 +0.4 +1.8 +1.2 +1.8 1.50 +1.1 +0.8 +1. 7 1.75% +0.5 +0.5 +0.0 0.3 -0.0 0.1 +1.0 +0.0 +1.8 0.75%i-nut lAeem ;.-;;QL; +0.2 +0.1 +1.3 +1.-0 +1.2

Fuel: No. 3.

At the 3 cc. lead level, the additives of this invention exhibit their most favorable response, which in some cases is double the increase alforded by tertiary butyl acetate.

The optimum concentration for the reaction products pf pyrrolidone with acetic acid and acrylic acid was found in'the regionof from 0.5 to 1.5- weight percent. -With the -acetyl pyrrolidone, however, a peak in the response curve appeared at about 0.25% concentration at the 3 cc. tetraethyl lead level. i

The effect on octane number of reaction products of acetic acid with acetamide and the product 0 R-i'k-N-RLCHgOOOH I 1 wherein R is an alkyl group having from-8m 10 carbon atoms, and R and R are methyl groups are shown in Ta-bIeIIII." These "data'i'ndicate that considerable increase in octane number in both the F-1 and F-2 ratings is obtained'with'these additives.

TABLE III Fu el: No. 1 plus 3.5'cc. tetramethyl lead per gal.

The gasoline samples listed in Table V were stored for ten days in the presence of 1% Water before octanes were evaluated. (Continuously. during this. storage period the bottles containing the samples were agitated in a manner l'which insured intimate contact between water and gaso- Table VI summarizes the road octane performance of pyrrolidone-acetic acid, pyrrolidone-acrylic acid and ter tiary butyl acetate as tetraethyl lead appreciatorsRatings were made in an all-weather chassis dynamometer room at 60 F. and relative humidity. Each fuel was rated three times in each ofjthree cars. Cars used were the i961 Pontiac, 1961 Oldsmobile and 1962 Chrysler. At the 3 cc; tetraethyl lead level, the pyrrolidone acetate and acrylate were again demonstrated to be superior to tertiary butyl acetate. An increase of 0.1 octane was obtained with tertiary butyl acetate compared with 0.4 and 0.6 increase for pyrrolidone-acetic acid and pyrrolidorie-acrylic acid, re- Pt Y-.

TABLE VL-ROAD OCTANE PERFORMANCE OF LEAD APPRECIATORS F-l F-2 Octane Octane [F Fuel N0 2] I 4 Number Number Vol. Percent Add Tetraethyl Lead Level, Blank (Fuel No. a plus 3 cc. tetraethyl lead)- 98. Y 87. 2 i t 0.75% Dimethyl Acetamide-Aeetic Acid 100.3 V 89.8 I

100.5 0 CH: 100 8 C H11ClII-CHiCOOH 90.0 88.8 0

100. 5 101.1 The octane response of the reaction products of N-oleyl 45 and N-dodecyl derivatives of trimethylene urea with 100 8 acetic acid are shown in Table IV.

TABLE IV.-OCTANE RESULTS F-i F-2 Fuel Treatments Octane A Octane Octane A Octane Number Number Number Number Blank (Fuel No. 1 plus 3.5 cc. Tetraethyl Lead per gal.) 101. l 92. 5 1.00% Additive A 101.7 +0.6 92. 4 -0. 1 Blank (Fuel No. 1 plus 3.2 cc. Tetraethyl Lead per gal.) 101. 4 9 7 0.5% Additive 101.8 +0. 4 92.8 +0. 1 1.0% Additive F 102.0 +0. 6 93. 1 +0. 4

The eflect of N-methyl pyrrolidone-acetic acid adduct We claim:

and related compounds are disclosed in Table V. It is interesting to note that pyrrolidone itself at 1% by weight concentration shows a significant increase of 0.4 octane, but the effect is not as great as that shown by the acetic acid reaction product with pyrrolidone. The addition of excess pyrrolidone to the acetic acid reaction product of pyrrolidone results in no additional increase in octane 65 number.

TABLE V.OCIANE DATA F-i Fuel Treatments Octane A Octane Number Number Blank 100. 8 1.0% Additive B-. 101.5 +0.7 1.0% Additive 0-.-. 101.5 +0.7 1.0 yrrolidone. 101. 2 +0. 4 1.0% 'tive 1)-- 101.4 +0.6 1.0% Additive E 101. 3 +0. 5

1. A gasoline containing from 1 to 6 ml. of tetraalkyl lead per gallon and from 0.05 to 3% by weight of a lead appreciator selected from the group consisting of:

.1 "iL niLw is a hydrocarbon group is a hydrocarbon 5 grouphaving from 1 to 18 carbon atoms, R is a hydrocarbondiradical having from 1- to 12-carbons,- R is a- I member from the group consistingtof hydrogen and a hydrocarbon group having from 1 to 12 carbon atoms andR'l is a hydrocarbon diradical'having from 1 to 12 carbon atoms. 1

2. The gasoline of claim 1 wherein the lead appreciator V. I CnHu-N NH-CH'QCOOH CH1 CH2 C 1 3. The gasoline of claim 1 wherein the lead appreciator is Ca N-H-CHaC O OH HF- H1 4. The gasoline of claim 1 wherein the lead appreciator is 0 II o 7 C 1 NfCB 'QBfl Hr- H:

'5. The gasoline of claim wherein the lead appreciator V G CHa(CH2)vCH=CH(CHa)1-N N-H-CHaC00H CID H H:

i i 6. The gasolineof claim l wherein the leadappreciator is V V W i I v 7. The gasoline of claim 1 wherein the lead appreciator 1S 1 References Cited DANIEL EIWYMAN, Primary Examiner.

Y. H. SMITH, Assistant Examiner.

Claims (1)

1. A GASOLINE CONTAINING FROM 1 TO 6 ML. OF TETRAALKYL LEAD PER GALLON AND FROM 0.05 TO 3% BY WEIGHT OF A LEAD APPRECIATOR SELECTED FROM THE GROUP CONSISTING OF