US2165651A - Motor fuel - Google Patents

Description

latented July 11,1939 Q mm? STATES;

PATENT .orrics MOTOR ml.

nm v. and Johan c. n. oosterhout, Port Arthur; Ten, asslgnors to The Texas Company, V New York, N.-!', a corporation of Delaware No llrawlng. Application October 12, 1934, r

This invention relates to motor fuels and has to. do particularly with the treatment of antiknock motor fuelscontaining an anti-knock reegentjby the provision in the fuel of certain re- ;5 'agents which will prevent or. retard deterioration it that many gasolines containing tetraethyl lead anti-knock reagent are particularly unstable in sunlight and in a relatively short time become cloudy and even form white deposits in the cascline bowls or other dispensing or storing equip- ;3 ment.' Furthermore; many of the present day gasoiines of high anti-knock value contain cracked hydrocarbons in substantial proportions and the'presence of suclrwunsaturated hydrocarbons often causes the product to depreciate in, anti-knock value 'and tend to form colored.

and gummy bodies in sunlight and in storage.

gAlso, certain gasolines have a-relatively high sul-,

(on. 44 -9) v A further object of the invention. is to treat gasolinesof-relatively-high sulfur content and tending to be unstable in sunlight, particularly when contaig a lead anti-knock reagent, to

improve the normal stability of such products.

' In accordance with; the present invention the above and other objects are achieved by incorporating in the fuel certain stabilizing agents as will be fully described hereinafter.

.We have found that gasolines containing a lead tetraethyl anti-knock reagent and which tend to become cloudy and eventually to form a white deposit in sunlight may be successfully stabilized by incorporating in the gasoline a small proportion oi lecithin. v

The following results will show the efiect of lecithin. one, partially cracked gasoline contain-- inglead tetraethyl or ethyl fluid and known in the trade as Q gasoline and which is a grade -of gasoline containing not more than 1.5 cc. of

ethyl-fluid per gallon and having a, maximum octane rating of 70, The gasoline was copper, color due to the presence of a dye. The tests were made by exposing a control sample and samples containing various quantities of lecithin in glass containers to sunlight and notingthe change in cloudiness, color, gum formation and iur content" which often ail'ects adversely the anti-knock value." I c o it? ill. 7 '35 7 p v Control is l6 s 3 Copper... Red--. 6 10 7o c1 7 Control-+7.5 lbs. lecithin 1% 2 3 -.do ..do 6 :39 70 64 I qgiii aam i ttilsemm f2 3 a no "do-" 4 4m 1o 65: 4o 7 (in ing-1 22.5 lbs. lecithin a an :s as a 4 g at 70 o1 i Control-$37.5 lbs. numb an 4 a an an 4 55 7o \sc pcrlQOObbls.

stability of the gasoline in sunlight, particularly 4., in the presence or a; lead anti-knockreagent.

An important object-oi. the present invention is to manufacture a gasoline hydrocarbon motorfu'el containing an anti-knock reagent of the tetraethyl lead to stability, J q 1 Anotherobiect ofthe'inVention' is to prevent type which is of improved:

" or-retard deterioration in color, mum-orantiknockyalue of an anti-knock gasoline motor luel' containing a substantial proportion oi. un- 55 or. cracked It will be observed from the foregoing results that it ispossible to stabilize the sasolineso that.

no cloud tor-motion occurs for various periods of tim'e by the addition 01' the required quantity of lecithin. Thus, 15 lbs. per, 1000 barrels oi. lecithin stabilize the gasoline for about 2 hours whereas the untreated sample beco'mes cloudy in in the gasoline is of major consideration, the

lecithin is a valuable tool for stabilizing the gasoline. It has been found that, ingeneral, lecithin is more effective in inhibiting cloud formation in cracked gasoline than in straight run gasoline. It has also been found that samples of gasoline containing eflective amounts of lecithin remain stable in storage for at least three months and when thereafter exposed to slmlight, the samples are substantially as stable as before storage.

It is necessary in some cases, particularly in the treatment ofmore refractory products, such as those containing large amounts of straight cause a bleaching eifect when added to samples I which were of poor color. a

It has now been found that by combining both the strong inhibitor and phenols with lecithin to form a mixture of a strong inhibitor, phenols,

and lecithin, a very desirable combination is obtained which not only prevents cloud formation, but also retards the deterioration in color, gum and anti-knock properties. The following results show the effect of using a mixture of lecithin, a strong gum inhibitor and petroleum phenols or cresylic acid in two samples of unstable Q grades of gasoline.

Cloudand deposit ror- Gum formation Anti-knock mation, time in hours 0010' changes mg./l cc. value Ve Heavy Clear After After Alter clou y deposit Orig. Orig. Orlg. for 8MP 8 hrs. 8 hrs. 8 hrs.

Control No. l if; 4- 4 001313612.-. Salmon-.- 14 53 70 68- Control No. l+l lbs.lecithin+5 +8 o No change. 14 50 69 60 lbs. benzyl aminophenol+ gals. cresylic acid per 1.000 bbls. Control No. 2 3f; 1% 4 do- Salmon. 8 58 67 66 Control No. 2+l5lbs.lecithin+5 +8 do No change. 16 33 67 66 lbs. benzyl-aminophenol+l0 gals. crcsylic acid per 1,000 bbls. Control No. 2+15 lbs. lecit1|in+ +8 do do 10 30 66 7.5 lbs. benzyl-aminophenol g-bll'l gals. eresylie acid per 1,000

s. Control No. 2+l5 lbs. lecithin+ +8 do 11 24 66 66 7.5 lbs. pyrogallol+17 gals. cresylic acid per 1.000 bbls. Control No. 2+l5 lbs. lecithm+ +8 do ..do 14 34 67 66 6 lbs. benzyl-aminophenol+l0 gals. petroleum phenols per 1,000b ls. Control No. 2+l5 lbs. lec1thin+ +8 ...do....... do 16 32 66 66 5 lbs. pyrogallo1+10 gals. petroieum phenols per 1,000 bbls.

run gasoline, to use more effective stabilizing reagents than lecithin alone and in an effort to find such a material, it was found that acumbination of lecithin and a strong gum inhibitor, such as benzyl-aminophenol, pyrogallol, butyryl pyrogallol, alpha and beta naphthol, catechol, triamylamine, etc. would give much better results than lecithin alone. The following table shows the results obtained when adding lecithin in combination with certain inhibitors to a Q gasoline consisting largely of straight run gasoline and exposing the same to sunlight in glass containers.

Cloud and'deposit formation, time in hours Very Heavy g2 cloudy deposit eiteralter- Control 3% 2 5 Control+15 lbs. lecithin per 1000 bbls. 2% 4 5 Control+16 lbs. lecithin+7.5 lbs. butyrl pyrogallol r 1000 bbls 4% 6 Z Control+l5 l s. lecithin-Hi gals. petroleum phenols pe 1000 hbls 6% 0 24 Control-l- 15 lbs. lecithin-{4.5 lbs benzyleminophenol per 1000 bbls 24 While the present invention is directed chiefly to stabilizing gasolines containing ananti-knock reagent against discoloration and formation of a cloud or deposit in sunlight, nevertheless it. will be observed that some beneficial stabilizing effect on the gum and anti-knock properties may also be obtained. The particular gasolines. herein treated were particularly unstable with respect to cloud and deposit formation and relatively stable as to gum and anti-knock properties over periods of the extent of the present tests, but inv the case of gasolines which are more unstable as to gum and'anti-knock properties or over more extended periods of storage, the present inhibitors may show greater value in stabilizing the gum and anti-knock properties than the above results indicate, I

The present invention is advantageous for treating gasolines of high sulfur content such as those from South Texasand New Mexico crudes.

In the refining of such gasolines wherein the naphtha from which the gasoline is derived is acid treated and rerun it is often advantageous to sweeten before steam distillation'or both before and after. steam distillation; however, even after such treatments the sulfur content maybe about 0.075 to 0.10 per cent. Such gasolines con-' taining anti-knock reagents areoften quite unstable and the present invention provides a particularly valuable method of treating these products, although gasolines of lower sulfur content may be advantageously treated.

The combinations of lecithin, a strong gum inhibitor and cresylic acid have been found to be commercially valuable stabilizing reagents. Such a combination is very effective and each of the components appears to. have certain advantages.

of the anti-knock reagent and eliminate cloudi- Thus, the lecithin-tends torretard decomposition ness and formation of deposits. The gum inhibitor tends to augment the stabilizing effect of the lecithin and also to perform a valuable inhibiting action with-respect to color, gum and anti-knock deterioration. s The cresylic acid or petroleum phenols act as a mutual solvent and may replace acetone which is often used for this purpose. The cresylic acid also exerts considerable stabilizing effect on the color and facilitates the mixing of the inhibitor and gasoline to be treated. I

-, In practicing the. invention it is advantageous to dissolve the lecithin and gum inhibitor in the cresylic acid to form a stabilizer reagent and then add this reagent in the required amount to the gasoline to be treatedi The resulting mixture is ordinarily a liquid consisting of a solution of the lecithin and inhibitor dissolved in the cresylic acid. Such a mixture is easily handled and readily commingled'with the gasoline.

In case it .is desired to add the anti-knock'reagent and the stabilizer to the gasoline at the same time, we have found that a convenient and valuable reagent may be prepared by mixing the two reagents together. Accordingly, we may com bine the reagents described above, consisting of lecithin,'lecithin and 'a gum inhibitor, or lecithin,

a gum inhibitor and cresylic acid, Wlththe lead tetraethyl anti-knock reagent or ethyl fluid in the proportions desired ,to be added to thetgasoline. Such a reagent is not only convenient to handle but also the stabilizer reagent has a-beneficial effect on the anti-knock reagent whereby the latter is stabilized against decomposition. We have found that the anti-knock reagent so treated will keep for extended periods, of time without" decomposition or deposition of precipitates.

While we have obtained best results with petroleum phenols or phenols recovered from waste alkali liquors from treating cracked distillates, however, where petroleum phenols are not available, we may use other types of commercial mixtures of phenols, such as cresylic-acid, creosote oil, carbolic-oil', etc.

v The petroleum phenols referred to above are the phenolic bodies occurring in varying amounts in most cracked petroleum distillates. These phenols may be extracted from the distillate by a caustic alkali or carbonate solution from which the phenols may be recovered by partial or complete acidification and separationtherefromjof the resulting phenol layer. In the ordinary course of refinery operation,.these phenols are extracted from the cracked distillates by the refining reagents, such as caustic alkali wash or doctor reagents. The-phenols may be conveniently recovered from such refinery liquors by blowing with flue gas or other means of efl'ecting neutralization sufficient to liberate the phenols.

It is usually advantageous to redistill the phenols to separate high boiling bodiessuch as; tar and asphalt. It is also sometimes desirable to fractionatethe phenols and use only the more desirable fractions for the purposes of the present invention. I

we have. given examples o'f stabilizing agents which we have found useful but we do not wish to be limited to thespeciflc amounts of materials recited. One skilled in the art will obviously vary the amounts and proportions of the ingredients to give optimum results.

.We claim:

1. A stable antiknock motor fuel comprising gasoline and tetraethyl lead, said motor fuel normally tending to deteriorate in sunlight and containing small amounts of lecithin and an arcmatic ring compound substituted with one or more groups of the class of amino and hydroxy,

whereby such deterioration is substantially'retarded.

2. A composition according to claim 1 in which the aromatic ring compound is alpha-naphthol. 3. A composition according to claim 1 in which the aromatic ring compound is benzyl-aminm phenol. I e

4. A composition according to claim 1 in which the aromatic ring compound is pyrogallol.

5. A stable antiknock motor fuel comprising gasoline and tetraethyl lead, said motor fuel nor-- mally tending to deteriorate in sunlight, and containing small amounts of lecithin, cresylic acid and an aromatic compound substituted with one or more groups of the class of amino and hy-- droxy, whereby such deteriorationis substantially retarded.

6. The method of stabilizing, against deterioration in sunlight, an antiknock motor fuel com- .prising gasoline and tetraethyl lead, which comprises incorporating in the motor fuel small amounts of lecithin and an aromatic hydroxy compound substituted with one or more groups of the class of amino and'hydroxy. 7. The method of stabilizing, against deterioration insunlight, an antiknock motor .fuel comprising gasoline and tetraethyl lead, which com-' prises incorporating in the motor fuel smallamounts of lecithin, cresylic acid'and" an arc- "matic ring compound substituted with one or more groups ofthe class of amino and. hydroxy. 8. A stable anti-knock motor fuel comprising gasoline and lead tetraethyl, said motor fuel normally tending to deteriorate insunlight, stabilized 9. A stable anti-knock motor fuel comprising 10. A stable anti-knock motor fuel comprising I Y gasoline and lead tetraethyl, said motor fuel nor--- mally tending to deteriorate in sunlight, stabilized by containing small amounts of lecithin and benzyl .aminophenol. 11. The method of stabilizing, against deterioration in sunlight, anantiknock motor fuel comprising gasoline and tetraethyl lead, which compri'ses adding to the fuel small amounts of lecithin and alphanaphthol.

12. The method of stabilizing; against deterioration in sunlightfan antiknock motor fuel comprising gasoline and tetraethyl lead, whichcomprises adding to the fuel'small amounts of lecithin and benzyl aminophenol.

" HARRY V. REES.

JOI-IAN o. n. oos'raan'op'r.