US2352760A - Antiknock compound and motor fuel containing same - Google Patents

Description

Patented July 4, 1944 UNITED STATES 7 2.35am V aN'nKNocx comrounn AND Moron FUEL con'mmmo seam Richmond 'r. Bell, peel-nerd, m, aesignor to The Pure Oil Company, Chicago, 111., a corporation of Ohio 'No Drawing. Application October 15, 1941 SerialNo. 415,066

18 Claims. (01. 44-88) This invention relates to high octane motor I fuel, to a method of preparing the s ame, and to a new composition of matter having the ability to increase octane number of hydrocarbon motor fuel.

Although it is known that various metal carbonyls and carbonyl compounds such as iron pentacarbonyl, iron tetracarbonyl, nitrosyl carbonyls of various metals and metal tricarbonyl mercaptides will impart improved antiknock properties to hydrocarbon motor. fuels, these compounds all have a serious drawback in that.

they are relatively unstable in the presence of light and/or air at ordinary atmospheric tembility under normal storage conditions, in a series of storage tests run on motor fuel samples the octane of which had been improved by the addition of iron tricarbonyl mercaptides, it was found that after 56 days in storage in the presence of light and air at room temperature, not only was a large amount of fiocculent precipitate formed, but from 50% to 100% of the octane increase caused by the addition of the iron com,- pound had been lost.

The object of this invention is to provide a carbonyl compound which has a high degree of stability in the presence of light and/or air.

Another object of this invention is to provide rating of the motor fuel and the motor fuel will remain stable over long periods of time without formation of precipitatesand without deterioration in octane rating.

In order to prepare the novel compositions in accordance with my invention, the polymeric metal carbonyl-for example, iron tetracarbonyl-is added to an oxygen-free solution of lecithin or other phosphatide iii a hydrocarbon solvent such as naphtha, or other inert solvent, and the mixture agitated or stirred at a temperature of approximately 170-180" F. in the absence of oxygen for a period of thirty to sixty minutes. A complete color change takes place from dark green to dark yellow or deep red, depending upon the concentration of the solution, indicating that a reaction takes place.

In preparing the reaction product between the carbonyl and the phosphatide the ratio of carbonyl to phosphatide may vary within rather wide limits. I have found that a mole ratio of polymeric metal carbonyl to phosphatide ranging from 1 to 1, to a ratio of 10 to 1 to be satisfactory.

A series of blends of rrotor fuel were made up from straight run naphtha and various amounts of iron pentacarbonyl, iron tetracarbonyl and the reaction product of iron tetracarbonyl and lecithin, the reaction product being designated in the following table as Fe X, and the increased octane obtained in each case was determined. The results are tabulated in Table I:

Table I Oct. No. increase calcu- Oct Octane lated in di- Semple Naphtba N Compound present Iron Lecithin No.inrect procrease portion for l g. iron per gel.

1 Blend "A" 2 Blend .B

as lecithin and cephalin are reacted with polymeric metal carbonyls such as' iron tetracarbonyl, iron nonacarbonyl, cobalt tetracarbonyl and cobalt tricarbonyl, a reaction product is formed which is highly stable to light and/or air and which when added to hydrocarbon motor fuel in relatively small amounts increases the octane so In the case of the naphthas containing the 50 iron pentacarbonyl andthe iron tetracarbonyl,

the solutions were made by dissolving these two iron compoundsin naphtha containing lecithin in the amount indicated in the table. In the case of the Fe X reaction product, it was dis- 55 solved in naphtha which did not contain lecithin,

but the table indicates the amount of lecithin present in the naphtha in the form of the reaction product. As shown by the table, the ability of Fe Xto increase octane is better than iron tetracarbonyl but not as good as iron pentacarbonyl. However, the reaction product has the advantage being fairly stable in the presence of light and air; whereas iron pentacarbonyl rapidly deteriorates unless lecithin is present, and even in the case of lecithin it is not as stable It has previously been pointed out that the reaction takes place only between polymeric metal carbonyls and phosphatides. An attempt to react iron pentacarbonyl, a monomeric carbonyl, with lecithin produced no color change in as the Fe X reaction product. the solutipn when heated and stirred under the The novel knock inhibitor composition in acconditions hereinbefore set forth for the reaccordance with my invention may be prepared in tion between lecithin and iron tetracarbonyl. concentrated solution in a solvent such as The color of the reaction product between naphtha or toluene and the concentrated solum lecithin and iron tetracarbonyl varies from dark tion used as the knock inhibitor additive or-the yellow through brown to dark red, depending phosphatide and carbonyl may be added in the upon the concentration of the solution in which desired amounts to thegasoline whose knock it is prepared. The -more dilute solutions are r t g it is desired to improve and the mixture yellow and the most concentrated solutions are he d to the desired temperature. e y. red. It a small amount of a concentrated solu- 1 1'70-180 F., to form the reaction pro u in tion of the reaction product is added to motor situ. In preparing the desired reaction product fuel or naphtha the color of the naphtha at the temperature should be sufliciently high to first tum red but upon standing from 24 to 72 caufse g; rgpld fi gz ggg i s ig g g gf hours the color changes to dark yellow or brown, to 6 0mm on p depending on the amount of concentrate. ucts. At temperatures below F.- reaction In order to dete the stabmt of various takes place very slowly, whereas at temperatures 1 t1 1 m minim d t y 1 above 240 F. decomposition products form with u ms 0 e react on Pro uc a number 0 appreciable amounts of precipitate. At atmossamples were Prepared with varying of pheric temperatures of E no visible 25 iron tetracarbonyl to lecithin and the samples action appears to take place. At temperatures were Permitted to stand in glass bottles in ilo1 -l80 F. reaction is completed in from 15 li ht at atmospheric temperatures w all to 20 minutes without any noticeable decompoin the top 01! the bottles. The results oi. the sition. storage tests are given in Table II:

Table II Extent 0:! preci ltate forma- Fewo) Solvent or fuel Color after ays sample Mol. phosphstide on used 10 days Trace Slight Appreclsblo alteraiter-- aiter (Heat. 1 0.28 Petroleum naph- Yellow 3i 1 the. 2 L4 0.76 do Deepyellow 31 1 3 E 1.25 .do Amber.- 15 31 1 4 3.00 do Darkbrown 10 31 l 1 b tl i ll 1 l6#l,000bbls. A be s1 2 3322312 iiiflbtil 5333133812381 Ewhow 1.1.1.3.. D ap mben 15 31 c-1 11.4 do Darkbrown 1 2 21 1 C 1 1 0.76 Gasoline .1 21

1 09.9 Pettgolsum naph- Deep red 36 l 21 B. C 2 .1 0.5 Gasoline Yellow I14 1 z 2 E9 1.0 .do Darkyellow 1 C 2. 3 2.0 .do Amber 6 l4 1 c .g Z1) 4.0 .do Brown 2 14 1 z 5 0.5 Ethyl gasollne Lightred 14 1 c. 3 L13 67.2 Toluene Deepreduu 14 1 C 3 1 E 0.5 Gasoline Yellow I14 1 C32 1.0 .(10 Darkyellow 14 1 g 2.0 -do Amber e 14 1 0-34.-- 1-2 4.0 .do Brown 2 14 i 1 0-3-5... 5* 0.5 -.---do .r Lightred 14 1 (3-4 fl 113.6 Toluene Deep red 11 1 C44 4.0 Gasoline Brown 10 1 C5 113.6 Toluene Deepred 2 5 10 1 0-5-4- 4.0 Gasoline Brown 1 10 In the foregoing table samples 1-8 were pre-' pared by forming the reaction product in situ in"the naphtha. Samples C-l, 2, 0-3, 0-4 {and C4 represent concentrated solutions of the reaction product which were prepared and the remaining samples were prepared by blending these concentrated solutions of the reaction product with motor fuel. It is apparent from the results in the table that the most stable solutions are prepared by forming the reaction products in situ in motor fuel in proportions in which it is desired to use them and that the smaller the amount of reaction product in solution, the. more stable is the resulting solution. It is further apparent that the most stable concentrate' that was prepared was the concentrate prepared using toluene as the solvent. Aromatic hydrocarbon solvents are therefore preferred because of their stabilizing effect on the reaction product. The addition of isobutyl p-aminophenol had no effect on the stability of the solutions but did affect the color thereof, causing them to become considerably darker.

The reaction products formed by the reaction of the polymeric metal carbonyls and the phosphatides can be reduced to'the solid form by evaporating concentrates thereof either at room temperature or by gentle heating. The solid product is clear, dark brown in color, is nonsticky and non-brittle, is stable in air indefinitely andresembles a soft resin or plastic. This product can be redissolved in gasoline or aromatic solvents to give the required motor fuel blend or concentrate.

The stabilization of motor fuel containing metal carbonyls by addition of phosphatides to the fuel is claimed in my co-pending application Serial No. 415,065.

I' claim:

1. Amotor fuel comprising a major portion of hydrocarbons boiling within gasoline boiling range and a minor portion of the reaction product obtained by reacting a phosphatide with a polymeric metal carbonyl within the temperature range of approximately 150-240 F. in the absence of oxygen.

2. A motor fuel in accordance with claim 1 in which the phosphatide is lecithin. a

3. A motor fuel in accordance with claim 1 in which the phosphatide is cephalin.

4. A motor fuel in accordance with claim 1 in which the polymeric metal carbonyl is iron tetracarbonyl.

5. A motor fuel in accordance with claim 1 in which the polymeric metal carbonyl is cobalt tetracarbonyl. v

6. A motor fuel in accordance with claim 1 in which the polymeric metal carbonyl is cobalt tricarbonyl.

7. A motor fuel comprising a major portion of hydrocarbons boiling within gasoline boiling range and a minor portion of the reaction product obtained by reacting between approximately 1 to 10 moles of polymeric metal carbonyl with approximately 1 mol of a phosphatide at a temperature between approximately 150-240 F. in the absence of oxygen.

8. A composition of matter useful as amadditive for motor fuels comprising the reaction product of a polymeric metal carbonyl and a phosphatide at a temperature between approximately 150 and 240 F. in the absence of oxygen.

9. A composition in, accordance with claim 8 12. Method of preparing a motor fuel additive 0 comprising reacting a polymeric metal carbonyl with a phosphatide at a temperature between approximately 150 and 240 F. in the absence of oxygen.

13. Method in accordance with claim 12 in which the proportion in moles of polymeric metal carbonyl to phosphatide ranges from approximately 10 to 1 of the former to 1 part of the latter.

14. Method in accordance with claim 12 in which the phosphatide is lecithin.

15. Method in accordance with claim 12 in which-the metal carbonyl is a polymeric iron being present in the form of anoxygen-free solution in an inert solvent.

18. A motor fuel additive comprising the reaction product obtained by heating a polymeric iron carbonyl and a solution of a phosphatide in an inert aromatic solvent to a temperature of approximately -180" F. in the absence of oxygen until the reaction is completed, the molar ratio of'carbonyl to phosphatide being from 1 to 0 10 of the former to 1 of the latter- RICHMIOND T. BEIL.