US2570377A - Fuel compositions - Google Patents

Description

Patented Oct, 9, 1951 FUEL COMPOSITIONS Anthony J. Revukas, Cranford, N. .L, assignor to Tide Water Associated OilCompanypBayonne, N. J., a corporation of Delaware v N Dr wing. p ion. Aug st 3!), 1.3 2;.

erial No. 115,253

15 Claims.- (Gl, 252 344),

The present invention relates to improved dis.- tlllate fuel compositions and particularly, to such compositions adaptable for use as fuels for operation of diesel engines.

As is known to those skilled in the art, the presence of water in petroleum distillate fuels often results in emulsion formation especially when such water-containing fuels are subjected to agitation or other conditions promoting emul sification. Unless such emulsion formation is retarded or emulsions that have been'formed are resolved so as to permit separation of water from the fuel, the water entering the system to be operated by the fuel deleteriously affects the performance of the system, particularly mechanisms therein of ferrous metals with which the Water.- containing fuel comes into contact. As an example, serious difficulties arise in marine operatlons when salt water, in amounts even as low as 0.01% by weight of a diesel fuel, enters diesel engines. The presence of water in the fuel enhances emulsification thereof and some of the emulsion normally passes through filtering mediums in the same manner as the fuel that has not been emulsified and, as a result, rapidengine failures often occur. Such failures are often due to corrosion of metal surfaces, as is manifested by surface pitting and formation of fatigue cracks on machined parts, to deleterious effects on fuel injectors resulting in broken or completely disintegrated check valve springs, to promotion of seizure of plungers in bushings and general corrosion of metal surfaces that are contacted by the water-containing fuel. Accordingly, the presence of water in petroleum distillate fuels, and particularly in diesel fuels, is highly undesirable and means are generally employed to separate the water, often in emulsified form, from the fuel. 'When the water present in the fuel is in emulsifled form, one method for treating the emulsion to prevent water from entering the system is to break the emulsion and separate water from the fuel. As manufactured, petroleum distillates suitable for use as fuels are normally water free or contain not more than a trace of water and, hence, such distillates per se present little, if any, difficulty from emulsification unless extraneous water becomes admixed therewith. In illustration of such fuels, reference is made to the Navy Department Specification 7.0 2e of May 15, 1945, entitled Oil, Fuel, Diesel, which, in listing the chemical and physical requirements for conform- 'ance therewith, sets forth that the diesel fuels must not contain more than a trace, as a maximum, of water and sediment. Nevertheless, and

in the handling o ffsuch fuels through pipe lines, storage thereof in tanks, and during transportation such as in seagoing tankers, extraneous water oftentimes becomes admixed with the fuel thereby providing difiiculties' inclusive of those aforesaid.

The present invention is based on a discovery that petroleum distillate fuels may be effectively inhibited against emulsification by dissolving in such fuels a small amount, sufiicient to substantially reduce the tendency of the fuel to emulsify, of an amine such as is defined more fully hereinafter, thereby providing improved distillate fuel compositions that obviate or substantially minimize the occurrence of difficulties as aforediscussed.

Broadly speaking, the amines embodied for use "by the present invention may be illustrated by the following structural Formula '1:

where n. R and B? are the same or d ferent aliphatic roups h vin a sum. of more than si carbon atoms, R standSiQl' a member from the group consisting of hydrogen, alkyl, aryl, alkaryl, and aralkyl radicals, and A is a phenol having at least one nuclear hydrogen atom replaced by a hydrocarbon group.

Amines suitable for practicing this invention -and falling within the aforedefined structural formula may be prepared by various means known to those skilled in the art and, hence, it is not believed necessary to set forth a detailed procedure for preparation thereof. However, and for purposes of il1ustration,'methods suitable for preparation of such amines are included in disclosures such as U. S. Patent -No. 2,363,134 (Mc- Cleary) and more specifically inaccordance with the-procedure in Example I, page 3, column 1 of that patent, as well as the procedure set forth in my copending application Serial No. 787,037 filed November 19,4947 (now U. S. Patent No. 2,489,672 issuedv November 29, 1949). As is ap- 'parent from the disclosure in the aforesaid patent and copendingapplication, a suitable method for preparation of amines as .contemplated for use 'hereiri involves the reaction between a suitable phenol, an aldehyde and a secondary amine.

In a specific and preferred aspect, the invention embodies use of amines such as may be prepared by reaotion'nf a secondary alkylamine with formaldehyde and a suitable phenol to form amines of the following structural Formula 2:

wherein R and R are alkyl radicals containing a sum of more than six carbon atoms, and A is a phenol having at least one nuclear hydrogen atom replaced by a hydrocarbon group. Secondary alkylamines (containing a sum of more than six carbon atoms) suitable for preparing the compounds of the aforesaid structural formula include dibutylamine, di-Z-ethylhexylamine, dilaurylamine, and the like, and suitable phenols include cardanol, para-tert. amyl phenol, pentadecyl phenol and the like. More specific illustrations of amines falling withinthe aforesaid structural formulaand suitable for practicing this invention include diamylaminomethyl para tert.-amyl phenol, diamylaminomethyl, 2,4-diamylphenol, dlbutylaminomethylcardanol, diamylaminomethylcardanol, diamylami n o in ct h y l pentadecylphenol, di-2 ethylhexylaminomethylcardanol, dilaurylaminomethylcardanol, and the like. a I

Althou h compounds of the aforesaid Formula 2 are particularly preferred, other amines that may be employed include compounds of the 'aforedeflned structural Formula 1 wherein R may be an alkyl, aryl, alkaryl or aralkyl radical.

As compared to the aforedefined structural Formula 2 wherein by use of formaldehyde in the reaction the nitrogen atom is linked t the phenol group by a methylene group, the use of higher aliphatic aldehydes during the reaction provides amines of structural Formula 1 wherein R is an alkyl group. Thus, by use of acetaldehyde, the group links the nitrogen atom to the phenol grouping;

and when an aldehyde such as propionaldehyde is used, the linking group is Similarly, when still higher aliphatic aldehydes such as butylaldehyde, octylaldehyde, etc. are

employed, R represents an alkyl group containing a correspondingly higher number of carbon atoms, and when R is represented by radicals "such as aryl, alkaryl, and aralkyl, the amines of effective demulsifying properties imparted to petroleum distillate fuels by use of tertiary amines as embodied for use herein. In the examples set forth herein, the test compositions were prepared by dissolving the tertiary amine in the fuel, mixing the thus prepared solution with either distilled or synthetic sea water, and

subjecting the resulting compositions to the de- "fined test procedures to determine demulsifyin characteristics.

EXAMPLE I A diesel fuel of specification 7-0-2e grade and having an A. P. I. gravity of 36.1 and a viscosity of 35.7 SUS at F. was subjected to the following Procedure A and, under the conditions thereof, 35 minutes was required for demulsification. However, by use of the same fuel oil under the same test conditions except that 0.1% of diamylaminomethylcardanol had been added to the fuel oil, the emulsion was completely resolved within 20 minutes.

Test Procedure A The apparatus consists of a \motor-driven mixer and a seamless copper tubing vessel 12 inches in height having an inside diameter of 2.5 inches. A pet cock is situated in the vessel so that the center line of the pet cock is at the 100 milliliter level of the copper vessel. milliliters of the fuel oil under test and 10 milliliters of synthetic sea water are poured into the mixing vessel and warmed to 100 F. The composition in the vessel is then stirred at 7000B. P. M. for 5 minutes and 100 milliliters of the emulsion drained oiI by means of the pet cock into a centrifuge tube while stirring is maintained. The emulsified sample in the, 100 milliliter centrifuge tube is whirled at 2600 revolutions per minute for 5 minutes and then about 6 milliliters are poured into a 10 milliliter comparator tube having two flat sides. This sample is compared with the original test composition for clarity. If both compositions are equivalent in clarity, the result is recorded as 5 minute demulsification time. If the two samples are dissimilar in clarity, the

centrifuged sample is returned to the centrifuge tube and again whirled at 2600 revolutions per minute for 5 minutes, followed by another comparison for'clarity. The procedure is continued until an equivalent in clarity is obtained, and

:the total time recorded as demulsification time.

In the handling of petroleum distillate fuels,

contamination thereof often results due to the with bunker fuel oils and the like. The presence of such contaminants in petroleum distillate fuels may be highly undesirable in that when water becomes admixed with the fuel, the bunker fuel oils may also tend to promote emulsification, thus making it even more difficult to separate the water from the fuel composition. However,

by practicing the present invention, petroleurn distillate fuels contaminated with such contaminants having a tendency t enhance emulsification may also be effectively imparted with emulsion-inhibiting properties to thereby, facilitate removal of water from the fuels as is illustrated by the following Example II:

EXAMPLE II A diesel fuel containing about 50% by volume of synthetic sea water emulsified badly when contaminated with about 0.5% by weight of 'a straight run parafiinic bunker fuel. When tested under the conditions of the following Procedure B, such a contaminated fuel oil composition possessed l0 milliliters in emulsified form after readings.

60 minutes. However, by practice of the present invention, and adding 0 .2% by weight of diam-yiaminomethylca-rdanol to the contaminated diesel fuel, highly improved demulsification occurred in that only 2 milliliters of emulsion were present at the 60 minute reading. 7

Test Procedure B The apparatus employed comprises. a-motordriven mixer, a 100 milliliter graduate, and. a con-,

stant temperature bath.

Eighty ml. of the test composition consisting of 40 ml. of test oil and 40 ml. of distilled water been completely separated into a layer of water and a layer of oil, or whether an oil-water emulsion is still present. If the emulsion has not been completely broken, the amount that is present is recorded as milliliters of cuff by direct reading on, the graduate at 30 minute and 60 minute When emulsion is present, the test composition comprises a bottom layer of water, a top layer of oil and an intermediate layer of emulsion.

EXAMPLE III As another example, a light hydrocarbon diesel fuel of Navy Specification 70'-2e grade was subjected to test in accordance with the aforesaid Procedure B using a temperature of 77 F.

When either synthetic sea water or distilled water was employed, 2 to 4 milliliters of emulsion existed at the 30 minute reading under the conditions of the test procedure. However, by use of the same fuel oil containing 0.1% of diamylami- *nomethylcardanol and, irrespective of Whether of specific demulsifying agents and concentrations thereof employed, use thereof has been made for illustrative and not limitative purposes as the invention embodies use of demulsifying agents falling within the generic structural formula as aforedefined. As to the concentration of demulsifying agent employed, the concentration thereof may be varied depending upon various factors as, for example, the susceptibility of the petroleum distillate fuel to emulsify and the degree of demulsification desired. For most purposes, suitable results are obtained by use of the demulsifying agent in amounts ranging from about 0.02 to about 0.1% based on the weight of the fuel. However, it is within the scope of the invention to employ the demulsifying agent in amounts other than the aforesaid range as, for example, from about 0 .005 to about 1.0% and even higher, e. g., 2%, as for particular fuel oils the lower concentrations show suitable improvement in demulsifying characteristics whereas with certain more readily emulsifiable fuels, the higher concentration may be more desirably employed.

In practicing my invention, the contemplated amine demulsifiers may be added in desired amounts to the fuel oils that have emulsified as 'aresult of water having become admixed therewith or may added to. the fuel oil to suppress emulsi'flcation thereof when such oils" are subsequently exposed to conditions promoting emulsification by admixture: of water therewith. For such purposes, the clemulsifiers of the present invention may be employed per se, in mixtures thereof, or' incombination with a suitable vehiclee. g., a petroleum fraction, to form a concentrated solution or dispersion for addition to. the fuels to be treated. For example, when it is desired to add the demulsifying agent in the form of a concentrated solution or dispersion, it is preferable that such a solution or dispersion be prepared by employing a vehicle that is compatible with and. does not deleteriously'affect the performanceof the petroleum distillate fuel to be treated. Hence, particularly suitable vehicles for preparing concentrated solutions or dispersions of. ,the demulsifying agents include petroleum fractions similar to or identical to the petroleum distillate fuel. to be treated in. accordance with this invention. In illustration, such concentrates may comprise a petroleum distillate or other suitable liquid hydrocarbon in admixture withe demulsifier as embodied herein and wherein the demulsifier is present in an amount of about 10 to 75% based on the weight of the concentrate.

Asspecific illustrations, such concentrates may comprise a suitable hydrocarbon vehicle, e. g., diesel fuels, kerosenes, and other mineral oil fracti0ns,'in which there is dissolvedor dispersed a demulsifier such as diamylaminomethyl cardanol in amounts varying from about 10 to 75% by weight of the concentrate, and, in still more specific illustration, 'a suitable concentrate comprising about 50% by weight of diamylaminomethyl cardanol in admixture with a petroleum hydrocarbon of diesel fuel grade.

The term synthetic sea water, as used herein,

intended to include a composition prepared by dissolving the following compounds and concentrations thereof. in a sufiicient amount of distilled water to make up one liter of solution:

Grams Magnesium chloride (MgClaGHzOL 11f Calcium chloride (CaC12) anhydrous 1.2 "Sodium sulfate (Na2SO4) 4.0 Sodium chloride (NaCl) 25.0

The present application is a continuation-inpart of my copending application Serial No. 718,599, filed December 26, 1946 (now abandoned).

Although the present invention has been described in conjunction with certain preferred embodiments thereof, those skilled in the art will readily recognize that variations and modifications can be made. Such variations and modifications are to be considered to be within the purview of the specification and the scope of the appended claims.

I claim:

1. As a new composition, a petroleum distillate fuel having dissolved therein a small amount, suflicient to suppress the tendency of said fuel to emulsify, of a compound having the formula:

H /R1 nil-N wherein R and R. are aliphatic groups having a sum of more than six carbon atoms, R is a member from the group consisting of hydrogen, alkyl, aryl, aralkyl and alkaryl radicals, and A is a phenol having at least one nuclear hydrogen atom replaced by a hydrocarbon group.

. 2. A composition, as defined in claim 1, wherein the defined compound is employed in an amount of about 0.005 to about 2% based on the weight of the fuel.

3. As a new composition, a petroleum distillate fuel having dissolved therein a small amount, suificient to substantially suppress the tendency of said fuel to emulsify, of a compound of the formula:

wherein R and R are alkyl radicals containing a sum of more than six carbon atoms, and A is 'a phenol having at least one nuclear hydrogen atom replaced by an aliphatic group.

4. A composition, as defined in claim 3, wherein the defined compound is dissolved in the fuel in an amount of about 0.005 to 2% based on the weight of said fuel.

5. A composition, as defined in claim 3, wherein the petroleum distillate fuel is a diesel fuel.

6. A composition, as defined in claim 3, where- V in the defined compound is a dialkylaminomethylcardanol.

7. A composition, as defined in claim 3, wherein the defined compound is diamylaminomethylcardanol.

8. A method for resolving an emulsion formed by a petroleum distillate fuel with water which comprises adding to said emulsion a small "amount, sufficient to resolve said emulsion, of a compound having the following formula:

la R1 'wherein R and R are aliphatic groups having a sum of more than six carbon atoms, R is a -member from the group consisting of hydrogen,

alkyl, aryl, aralkyl and alkaryl radicals, and A is a phenol having at least one nuclear hydrogen atom replaced by a hydrocarbon group.

9. As a concentrate, adaptable for use as an emulsification-inhibiting additive for liquid hydrocarbons, an oil-soluble amine of the following formula in admixture with a petroleum dis- 8 tillate fuel, said amine being present in an: amount of about 10 to about 75% based on the weight of the concentrate and having the following formula:

wherein R and R are aliphatic groups having a sum of more than six carbon atoms, R is a member from the group consisting of hydrogen, alkyl, aryl, aralkyl and alkaryl radicals, and A is a phenol having at least one nuclear hydrogen atom replaced by a hydrocarbon group.

10. A method, as defined in claim 8, wherein R, is hydrogen.

11. A method, as defined in claim 8, wherein A is a phenol having at least one nuclear hydrogen atom replaced by an aliphatic group.

12. A method, as defined in claim 8, wherein R is hydrogen and A is a phenol having at least REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,340,036 Zimmer et a1 Jan. 25, 1944 2,353,192 Sargent et al July 11, 1944 2,360,323 Herlocker et al Oct. 17, 1944 2,360,324 Herlocker et al.. Oct. 17, 1944 2,363,134 McCleary Nov. 21, 1944 2,410,911 Wasson et a1 Nov. 12, 1946 2,414,729 Fleming et a1 Jan. 21, 1947 2,453,850 Mikeska et a1 Nov. 16, 1948 2,457,634 Bond et al Dec. 28, 1948

Claims (1)

1. 8. A METHOD OF RESOLVING AN EMULSION FORMED BY A PETROLEUM DISTILLATE FUEL WITH WATER WHICH COMPRISES ADDING TO SAID EMULSION A SMALL AMOUT, SUFFICIENT TO RESOLVE SAID EMULSION, OF A COMPOUND HAVING THE FOLLOWING FORMULA: