US3198613A

US3198613A - Fuel oil composition

Info

Publication number: US3198613A
Application number: US218116A
Authority: US
Inventors: John H Udelhofen
Original assignee: Standard Oil Co
Current assignee: Standard Oil Co
Priority date: 1962-08-20
Filing date: 1962-08-20
Publication date: 1965-08-03
Anticipated expiration: 1982-08-03

Description

3,198,613 FUEL GIL CGMPGEiITIUN John H. Udelhofen, Glenwood, 111., assignor to Standard Gil Company, Chicago, 11]., a corporation of Indiana No Drawing. Filed Aug. 20, 1962, Ser. No. 21%,116 11 Ciaims. (Cl. 4-4-71) This application is a continuation-in-part of Serial No. 26,944, filed May 5, 1960, now abandoned.

This invention relates to distillate heating oil compositions containing stabilizers. More particularly, this invention relates to distillate furnace or heater oil composition containing addition agents capable of imparting oxidation stability to the distillate furnace or heater oil.

Heating oil compositions are those used for heating purposes such as home and industrial heating by furnaces, burner heaters and the like. In storage of distillate heating oil compositions there arises a serious problem of inhibiting oxidative deterioration of the oil under storage conditions. The deterioration of distillate heating oils through oxidation under conditions of storage manifest itself in the appearance of darker colors, sediment, etc. in the oil. Sediment formation is often the most troublesome problem with which formulators of heating oil blends are concerned because sediment formation normaliy may result in clogging of furnace system equipment such as filters, screens, nozzles, burners, etc., with sludge formed from sediment. The deterioration of heating oils is much more prevalent Where the oil contains cracked materials and because of recent tendencies to blend heating oils by mixing virgin oil fractions with cracked components, oxidative deterioration has become a problem associated with many commercial blends. The oxidative deterioration problem has, therefore, attracted much study and many addition agents have been proposed for stabilizing heating oils.

1 have now discovered new addition agents having exceptionally good utility in low concentrations in distillate heating oil compositions as stabilizers. The addition agent of this invention is an oil-soluble betaine or a quaternary ammonium salt and corresponds to the structural formula:

H X to C O- linkage. Where R has more than one carbon atom, any other carbon atoms of the R group are connected to the one carbon atom as side chains with respect to the chain. Such linkage is definitive of all alkylidene groups hereinafter which are directly linked to both a quaternary ammonium nitrogen atom and a 3,198,033 Patented Aug, 3, 1965 The distillate heating oil composition of this invention comprises a distillate heating oil containing from about 0.000l to about 5 Weight percent, and more advantageously between 0.0001 and 0.1 weight percent, of the betaines defined herein. The preferred distillate heater oil composition of this invention contains the betaine in an amount of from about 0.001 to about 0.05 weight percent. The betaines may also be formulated in addition agent concentrates in a suitable organic solvent as is more particularly described below.

if the betaine used has low solubility in the distillate oil, solvents such as aromatic hydrocarbons and alcohols may be used in sufiicient amounts to solubilize the betaine.

In addition to functioning as stabilizers, the betaines used herein may also function in distillate heating oil media as rust inhibitors, anti-static agents, dispersants and corrosion inhibitors.

The betaine intended herein may also be called an alkylidene-carboxy betaine of an aliphatic tertiary amine, which betaine contains at least one substituent group selected from the class consisting of amino and metal carboxylate, wherein the alkylidene group contains from 1 to 7 carbon atoms.

The metals of the metal carboxylate group herein are the metals selected from the class consisting of alkali metals and alkaline earth metals. Examples are sodium, potassium, lithium, barium, calcium and strontium.

referred are sodium, potassium, barium and calcium because of their availability.

With reference again to the above formula, the betaines of this invention, more particularly, may advantageously contain from about 20 to about 55 carbon atoms. The alkylidene group (R) may more advantageously contain from 1 to about 4 carbon atoms and preferably is a methylene group.

It is understood that his compounds of the herein described betaines, such as those bis compounds wherein the quaternary ammonium nitrogen atoms are linked through an alkylene group, are also intended.

The aliphatic tertiary amine component group of the above structure contains the quaternary ammonium nitrogen atom (which contributes the illustrated positive charge) as the tertiary nitrogen atoms of the amine and this nitrogen atom is linked directly through an alkylidene group (R) to the carboxy group (illustrated as having the negative charge). The tertiary amine component roup may be derived from the corresponding tertiary amine.

The tertiary amine component group may be any acyclic hydrocarbon tertiary amine group having at least one amino and/or metal carboxylate substituent and/ or constituent, i.e., containing an amino and/or metal carboxylate group.

Usually the betaines may be prepared by reaction of the corresponding tertiary amine with a suitable salt or ester of an wmonohalogenated aliphatic carboxylic acid. The reaction may be carried out in the presence of a sol vent such as benzene, ethanol, n-butanol, isopropanol, etc., and in the presence of a promoter such as an inorganic iodide, e.g., potassium iodide. The reaction may conveniently be carried out at the reflux temperature of the solvent and may take from two to fifty hours for substantial completion. An acceptable temperature for the reaction may be in the range of from about 50 F. to about 200 F. although higher or lower temperatures a 3 may be used. The reaction proceeds to form a betaine product wherein the portion of the betaine is derived from the ester or salt of the a-monohalogenated aliphatic carboxylic acid. Thus, the size and configuration of the R (alkylidene) group is determined by the aliphatic group of the monohalogenated aliphatic carboxylic acid salt or ester and may be pre-selected by any chemist of ordinary skill by selection of the appropriate acid salt or ester.

Variations in the above preparation may be useful, desirable or even necessary in some cases. For example, in the preparation of a betaine having a metal carboxylate constituent in the tertiary amine component group, it would be impractical to attempt to first prepare the exact corresponding tertiary amine first because it may readily be prepared in situ during formation of the betaine by reacting a secondary amine with twice as much of the corresponding metal salt of the monohalogenated aliphatic carboxylic acid as would normally be used for the equimolar addition. added and one remains in the form of the metal salt, i.e., as a metal carboxylate group attached to the nitrogen of the secondary amine to provide the tertiary amine component. Other variations in preparation will be evident to those skilled in the art, e.g. well known preparation technique for obtaining bis compounds. The reactions involved, e.g., acylation, are well known and do not form a part of this invention except for obtaining the useful product defined herein.

Two carboxy groups are thereby Examples of salts or esters of the u-monohalogenated aliphatic carboxylic acids which may be used in the above exemplified procedure of preparation of the betaines of this invention are: sodium chloroacetate, sodium bromoacetate, methyl chloroacetate, butyl bromoacetate, sodium a-chlorobutyrate, sodium a-chlorovalerate, methyl a-tbromovalerate, sodium a-chlorocaproate, sodium a-bromocaprylate, isopropyl monobromo butyrate, sodium a-chloroethylhexanoate, sodium Ot-ChlOYO-dimethyl-valerate, etc. Of course, the corresponding calcium, magnesium, potassium or other salts may also be used in lieu of the sodium salts but may be less available or more expensive.

The substituted aliphatic acyclic tertiary amine betaines useful in accordance herewith may more particularly be defined by the following structural formula:

wherein R is as defined above, at least one of the R groups is an alkyl group having from 1 to 12, and preferably 1 to 6, carbon atoms and containing a snbstituent group selected from the class consisting of an amino group and an alkali or alkaline earth metal carboxylate group, and the remainder of the R groups are alkyl groups having from 1 to 22 carbon atoms and preferably from about 10 to 22 carbon atoms.

Thus, the betaines useable hereinarea class of betaines consisting of N-(carboxyalkylidene) amino acyclic tertiary amine betaines, and alkali and alkaline earth metal carboxylate acyclic tertiary amine betaines.

In the nomenclature herein, certain alkyl groups are referred to as coco, soybean and tallow. Such terms indicate the source of fatty acids from which the alkyl group has been derived, i.e., coconut fatty acids, soybean fatty acids and tallow fatty acids. These groups generally are derived from mixed'C to C fatty acids. The coco groups are derived from coconut fatty acids and average about C to C The soybean groups are derived from soybean fatty acids and average about C The tallow groups used herein are hydrogenated tallow groups derived from tallow fatty acids and average about C and tallow and hydrogenated tallow are used interchangeably to describe such groups.

THE N- CARBOXYALKYLIDENE AMINO ACYCLIC TERTIARY AMINE BETAINES The N-(carboxyalkylidene) amino acyclic tertiary amine betaines useable herein advantageously have the following structural formula: V t

wherein R is an alkylidene group having from 1 to 7 and preferably from 1 to 4 carbon atoms, R is an alkyl group having from 1 to 22 and preferably 10 to 22 carbon atoms, and R is an amino alkyl group having from 1 to about 12 and preferably 1 to 6 carbon atoms.

Bis compounds of the above are also intended and may advantageously have the following structural formula:

wherein R and R are defined as above, R is R R and R are each selected from R and R and R is an alkylene group having from 2 to 12 and preferably 2 to 6 carbon atoms.

The betaines of Formula 1 above may be preparedby reacting the corresponding N,N-dialkyl alkylene diamine, or N,N-dialkyl polyalkylene, triamine, tetramine or pentamine with the salt or ester of mono-halogenated aliphatic carboxylic acid in about equimolar amounts. The betaines of Formula 2 are bis-compounds and may be prepared in the same manner except that the salt or ester of monohalogenated carboxylic acid is used in an amount 'suflicient to provide two moles per mole of amine and the amine used is a polyalkylene polyamine, e.g., a polyamino acyclic tertiary amine betaines are: N-(carboxy methylene) N-aminopropyl N,N-di(hydrogenated tallow) amine betaine, N-(carboxy 2-butylidene) N-aminoheptyl N,N-dicoco amine betaine, N-(carboxy 2-propylidene) N-aminopropyl N,N-dioleyl amine betaine, N-(carboxy 3-hexylidene) N-aminohexyl N,N-dihexecosyl amine betaine, N-(carboxymethylene) N-aminomethyl N,N-di-' soybean amine betaine, N-(carboxymethylene) N-aminododecyl N,N-dihexyl amine betaine, N-(carboxymethylene) N-aminododecyl N,N-dimethyl amine betaine, N- (carboxymethylene) N-aminoisooctyl N,N-diisoocty1 amine betaine, N-(carboxymethylene) N-aminopropyl N,N-di(hydrogenated tallow) amine betaine, N-(carboxy-methylene) N-aminopropyl N,N-dicoco amine be- More examples, with reference to Formula 2 above, i.e., bis compounds, are as defined below with respect to component groups of the Formula 2 defined above:

6 ance herewith, is prepared by reacting 6.5 grams of N,N- ditallow tetraethylene pentamine with 1.0 gram of sodium chloroacetate in the presence of one crystal of K1 Example R1 R R3; Rab R30 R4 a Methylene Eicosyl 3-aminopropyl 3-aminopropy1. 3-aminopropyl Propylene. b l-butylidene Tallow TaLow Tallow .a o Do. 0. 1-hexylidene I-lexaclecyl- 2-aminoethyl Hexadecyl. Ethylene. cl. l-propylidene Octadecyl 0 Octadecyl o. e. 2-heptylidene Dodeeyl Aminododecyl Dodeeyl Dodecylene. f- Methylene do Methyl Do.

Aminohexyl Octyl. Hexylene. Aminodecyk. "do Decylene. Zarninoethyl. Zaminoeth Ethylene. do Stearyl o. Do.

3-aminopropyl Coco 3-aminopropyl Propylene. r do Z-aminoothyk- 2-aminoethyl Ethylene.

do Hexadecyl 3-aminopropyl Propylene. do "lallo Do.

do. Ethylene. .do- Propylene. .do I D 0. .do Do. 2-nminoethyl. Ethylene. .do D0.

Example of Preparation (I) The N-(carboxymethylene) N-(3-aminopropyl) N,N- ditallow amine betaine, useable in accordance herewith, is prepared by reacting 5.94 grams of N,N-ditallow 1,3- propylene diamine (marketed as Duom en ZHT) With 1.2 grams of sodium chloroacetate in the presence of one crystal of potassium iodide (catalyst) in 30 ml. of nbutanol solvent for 24 hours at the reflux temperature of the solvent. The mixture is then filtered to remove solids and the final product is separated from the filtrate as a semi-solid by vacuum distilling to remove solvent. The yield of product is 6 grams.

Example of Preparation (11) The N-(carboxy l-butylidene) N-ethylaminoethyl N- ethyl N-decyl amine betaine, useable in accordance herewith, is prepared by reacting 5.1 grams of N-decyl triethylene diamine with 3.1 grams of methyl a-chlorovalerate in the presence of one crystal of potassium iodide (catalyst) in 50 ml. of n-butanol solvent for 16 hours at the reflux temperature of the solvent. The mixture is then filtered to remove solids and the final product is separated from the filtrate as a semi-solid by vacuum distilling to remove solvent.

Example 0 Preparation (III) The N',N,N"-tristearyl N"-ethylaminoethyl N',N"-di- (carboxymethylene) ethylene diamine betaine, useable in accordance herewith, is prepared by reacting 4.5 grams of N',N,N"-tristearyl triethylene triamine (may be derived from stearic acid and triethylene triamine) with 1.2 grams of sodium chloroacetate in the presence of one crystal of K1 (catalyst) in 100 ml. of n-butanol solvent for 20 hours at the refiux temperature of the solvent. The mixture is then filtered to remove solids and the final product is separated from the filtrate as a semi-solid by vacuum distilling to remove solvent.

xample of Preparation (IV) The N-(carboxymethylene) N-tallow N-methyl N- aminopropyl amine betaine, useable in accordance here With, is prepared by reacting 5.2 grams of N-tallow N- methyl 1,3-propylene diamine with 1.5 grams of sodium chloroacetate in the presence of one crystal of K1 (catalyst) in 50 ml. of n-butanol solvent for 24 hours at the reflux temperature of the solvent. The mixture is then filtered to remove solids and the final product is separated from the filtrate as a semi-solid by vacuum distilling to remove solvent.

Example of Preparation (V) The N-(carboxymethyl) N,N-ditallow N-aminoethylaminoethylaminoethyl amine betaine, useable in accord- (catalyst) in ml. of isopropanol solvent for 30 hours at the reflux temperature of the solvent. The mixture is then filtered to remove solids and the final product is separated from the filtrate as a semi-solid by vacuum distilling to remove solvent.

THE N-(CARBOXYALKYLIDENE) ALKALI AND ALKALINE EARTH METAL CARBOXYLATE ACYCLIC TERTIARY AMINE BETAINES The N-(carboxyalkylidene) alkali and alkaline earth metal carboxylate acyclic tertiary amine betaines useable herein advantageously have the following structural formula:

wherein R is an alkylidene group having from 1 to 7 and preferably from 1 to 4 carbon atoms, R is an alkyl group having from 1 to 22 and preferably 10 to 22 carbon atoms, M is a metal selected from the class consisting of alkali and alkaline earth metals and n is an integer of from I to 2 inclusive and corresponds with the valence of said metal.

The betaines of Formula 3 above may be prepared by reacting the corresponding dialkyl amine with the salt or ester or monohalogenated aliphatic carboxylic acid in amounts providing at least about two moles of the salt or ester per mole of dialkyl amine in the reaction mixture and neutralizing the resulting product with a molar excess of basic a hall or alkaline earth metal compound. Neutralization is carried out during the reaction of the amine and salt or ester by adding the basic alkali or alkaline earth metal compound to the reaction mixture. Examples of suitable alkali and alkaline earth metal compounds are: NaHCO KHCO Na CO BaO, NaOH, KOH, CuO, BaS, SrO, LrOF-l, etc.

Specific examples of useable N-(carboxyalkylidene) alkali and alkaline earth metal carboxylate acyclic tertiary amine betaines are:

N- carb oxymethylene) N,l l-ditallow N- (sodium carboxyrnethylene) amine betaine,

N-(carboxy l-hexylene) N,Ndidodecyl N-(potassium carboxymethylene) amine betaine,

N-(carboxymethylene) N,N-dihexadecyl N-(lithium carboxypropylene) amine betaine,

barium di-{5-[N,N-ditallow 'N-(carboxy 2-butylidene) amino] valerate}betaine,

calcium di-{Z-[NN-didecyl N-(carboxymethylene) amino] acetate}betaine,

strontium di-{2-[N,Ndistearyl N-carboxymethylene) example, a heavy industrial residual fuel (e.g., Bunker C), a furnace oil, a heater oil fraction, kerosene, a gas oil, or any other like light oil intended for furnace or heater fuel use. Of course, any mixtures of oils are also intended. The distillate heating oil may be virgin or cracked petroleum distillate oil. Thedistillate heating f'oiI may advantage boil in the range of frbm about N-(carboxymethylene) N-(sodium carboxymethylene) N,N-dioctyl amine betaine, N-(carboxymethylene) N-(sodium carboxymethylene) N,N-diheptadecyl amine betaine f N-(carhoxymethylene) N-(sodium carboxymethylene) N,N-dieicosyl amine betaine, N-(carboxymethylene) N-(sodium carboxymethylene) N,N-dicoco amine betaine, 7 V N -(carboxymethylene) N-(sodium carboxymethylene) N,N-disoybeanamine betaine, and the like.

Example of Preparation (VI) The N-(sodium carboxymethylene) N-(carboxymethylene) N,N-ditallow amine betaine, useable in accordance herewith, is prepared by reacting 9.80 grams of ditallow amine (Armeen ZHT marketed by Armour Chemical Div.) with 4.64 grams of sodium chloroacetate and 5.00 grams of sodium bicarbonate in the presence of one crystal of KI (catalyst) in 50 ml. of isopropyl alcohol solvent for 24 hours at the reflux temperature of the solvent. The mixture is then filtered to remove solids and the final product is separated from the filtrate as a semisolid by vacuum distilling to remove solvent. The yield of product is 13 grams.

Example of Preparation (VII) The N-(potassium carboxy l-butylidene) N-(carboxy l-butylidene) N,N-didodecyl amine betaine, useable in accordance herewith, is prepared by reacting 4.1 grams of didodecyl amine with 4.1 grams of potassium a-bromovalerate and 5.0 grams of potassium bicarbonate in the presence of one crystal of K1 in 50 ml. of xylene solvent for 32 hours at the reflux temperature of the solvent. The mixture is then filtered to remove solids and the final product is separated from the filtrate as a semi-solid by vacuum distilling to remove solvent.

Example of Preparation (VIII) The barium di{2-[N-tallow N-methyl N-carhoxymethylene amino] acetate}betaine, useable in accordance herewith is prepared by reacting 7.0 grams of tallow methyl amine with 6.0 grams of sodium chloroacetate and 2.0 grams of barium oxide in the presence of one crystal of K1 in 100 ml. of methanol solvent for 36 hours at the reflux temperature of the solvent. The mixture is then filtered to remove solids and the final product is separated from the filtrate as a semi-solid by vacuum distilling to remove solvent.

Example of preparation (IX) The calcium di{2[N,N-dioleyl N-(carboxymethylene) amino]acetate}betaine, useable in accordance herewith is prepared by reacting 8.3 grams of dioleyl amine with 4.0 grams of sodium chloroacetate and 0.7 gram of calcium oxide in the presence of one crystal of K1 in 100 ml. of n-butanol solvent for 20 hours at the reflux temperature of the solvent. The mixture is then filtered to remove solids and the final product is separated from the filtrate as a semi-solid by vacuum distilling to remove solvent.

HEATING OIL COMPOSITIONS The above described betaines may be used in accordance herewith as distillate heating oil stabilizers.

The distillate heating oil in which the betaines are used in accordance herewith is a hydrocarbon oil, such as for 200 to about 700 F., and preferably in the range of 350 to 650 F. The distillate oil may'contain or consist'of cracked components, such as for "example, those derived from cycle oil or cycle oil cuts boiling heavier than gasoline, usually in the range of from about 450 to about 750 F. and may be derived by catalytic or thermal crack- 7 ing. High-sulfur-containing and low-sulfur-containing oils may also be used. The distillate 'oil may, of course, contain other components such as addition 'agentsused to perform particular functions. e

The preferred heating oils have an initial boiling point in the range of from about 350 to about 475 F. and an end pointin the range of from about500 to about 650. F. The furnace oil may advantageously have an A.P.I. gravity of about at least 30 and a flash point (Tag closed cup) not lower than about Fgand preferably above about F. V

In order to test the etfectiveness of the betaines as heating oil addition agents and more particularly as heating oil stabilizers, various samples of heating oil compositions containing the betaines as addition agents were prepared and tested. Each sample was prepared by mixing the betaine indicated below in very small amounts with a base furnace oil in amounts described below:

' Base furnace oil.A mixture of 50 vol. percent light catalytic cycle oil and 50 vol. percent virgin gas oil.

Sample A.-Tl1e base furnace oil above containing 0.005 weight percent of the N-(carboxymethylene) N-(3- aminopropyl) N,N-ditallow amine betaine prepared as in example of Preparation I.

Sample B.Thebase furnace oil above containing 0.01 weight percent of the N-(sodium carboxymethylene) N- (carboxymethylene) N,N-ditallow amine betaine, prepared'as in example of Preparation VI.

The above base furnace oil and samples were aged in stoppered containers in the dark at 200 F. for 20 hours and then at room temperature (70 F.) for about 48 hours. The aged base furnace oil and samples were each subjected to the following tests with the results reported at the end of each test procedure:

Sediment test-100 mgs. of each aged sample was passed through a fritted glass crucible of fine porosity and the insolubles were collected on the crucible, Washed wtih hexane and the crucible was then evaporated. Weights of 'insolubles collected'from each sample were as follows:

Sample: Mg. of insolubles Base furnace oil 4.6 A 1.4 B 0.5

Sample: Mg. of soluble gum Base furnace oil 37.4 A 18.6 B 14.7

i Filterability test. In this test, 8 successive 50 ml. incre. merits of each sample tested are poured through a one (2111. area of 10 paper. The time in seconds for each increment was noted. Results were as follows:

Time in Seconds, Each Increment Water flocculation test.The increments of filtrate from each of the above filterability tests for each sample were combined and the total filtrate from each sample was mixed with an equal amount (about 400 ml.) of water. Mixing was accomplished by vigorous shaking. The sample and water mixture was then allowed to settle for about 5 to minutes until an interfacial rag appeared. Each mixture was then passed through a medium porosity fritted glass crucible. The appearance of the mat left in the crucible was noted and recorded as a measure of the sludge formed by contact with water. The results were Emulsification test-In this test, the time in minutes required to clear a water-in-oil emulsion (1% water in oil: 3 ml. H O in 300 ml. oil) by blowing with a stream of air is determined.

The results were as follows:

Sample: Time in minutes Base furnace oil 11 The results of the above test procedures demonstrate the efficiency of the betaines of this invention as heating oil stabilizers. With reference to the test results, the sediment test resuits are a measure of the dispersant properties and anti-oxidant properties of the betaine addition agents. The very small amounts of insolubles collected demonstrate excellent dispersant properties as well as antioxidant properties. The soluble gum test is a measure of the anti-oxidant properties of the various samples tested and indicates that the betaines are effective anti-oxidation addition agents even in very small amounts. The filterability test is a measure of dispersant properties of the betaines and the data show greatly improved filterability in comparison with the control. The water flocculation test determines the sludge inhibiting tendencies of an additive and the above results demonstrate an improvement in appearance of the sample compared with the control base furnace oil due to improved sludge inhibition. The NPA color test is well known and indicates the amount of color degradation of each sample due to the aging process. The NPA results show good color for the betaine stabilized composition, better than the non-stabilized control. The emulsification test results demonstrate the emulsion stabilizing tendencies of the betaines as furnace oil addition agents. The emulsions were much more stable than was the emulsion in the control furnace oil.

The betaines may, for convenience, be prepared as addition agent concentrates. Accordingly, the betaine is prepared in or dissolved in a suitable organic solvent therefor in amounts greater than 10% and preferably from about 25% to about 65%. The solvent in such concentrate may conveniently be present in amounts from about 35% to about 75%. The organic solvent preferably boils within the range of from about F. to about 700 F. The preferred organic solvents are hydrocarbon solvents, for example, petroleum fractions such as naphtha, heater oil, mineral spirits and the like, because of their clean burning properties. The solvents selected should, of course, be selected with regard to possible beneficial or adverse effects it may have on the ultimate heating oil composition. Thus, the solvent should preferably burn without leaving a residue and should be non-corrosive with regard to metal, and especially ferrous metals. Other desirable properties are obvious from the intended use of the solvent.

All percentages given herein are percentages by weight unless otherwise indicated.

It is evident from the foregoing that I have provided heating oil compositions containing defined betaines as multi-purpose addition agents effective in very small amounts.

I claim:

1. A heating oil composition comprising a major amount of distillate heating oil and between 0.0001 and 0.1 weight percent of a betaine selected from the class consisting of a betaine containing at least 20 carbon atoms and having the structural formula:

and a his compound thereof, wherein R is an alkylidene group containing from 1 to 4 carbon atoms, R is selected from the class consisting of an amino alkyl group, an alkali metal carboxylate group and an alkaline earth metal carboxylate group, R is an alkyl group having from 10 to 22 carbon atoms, and R is selected from the class consisting of R and R".

2. The composition of claim 1 wherein said distillate heating oil is a mixture of virgin and cracked petroleum distillate heater oils.

3. The composition of claim 2 wherein the cracked component is derived by cracking a cycle oil boiling heavier than gasoline.

4-. The composition of claim 1 wherein said distillate heating oil boils in the range of 3 50 to 650 F.

5. The composition of claim 1 wherein R" is derived from hydrogenated tallow fatty acid.

6. The composition of claim 1 wherein R is a 3-aminopropyl group.

'7. The composition of claim 1 wherein R is a sodium acetate group.

8. The composition of claim 1 wherein R is a methylene group.

9. The composition of claim 1 wherein said betaine has the following structural formula:

wherein R is an alkylidene group having from 1 to 4 carbon atoms, R is an alkyl group having from 10 to 22 car bon atoms, and R is an amino alkyl group having from 1 to 6 carbon atoms.

10. A heating oil composition comprising a major amount of distillate heating oil and between 0.0001 and 0.1 weight percent of a betaine having the following structural formula:

RICO 1 1 wherein R is an alkylidene group having from 1 to 4 carbon atoms, R is an alkyl group having from to 22 carbon atoms, M is a metal selected from the class consisting of alkali metals and alkaline earth metals and n is an integer of from 1 to 2 inclusive corresponding to the valence of said metal.

11. A heating oil composition concentrate containing from about 25% to about of the betaine of claim 1 and from about 35% to about of a hydrocarbon solvent boiling at a temperature in the range of from about F. to about 700 F., said concentrate being capable of dilution with a distillate heating oil to a betaine concentration in the range between 0.0001 and O.=1 Weight percent.

DANIEL E.

Shappirio 252-403 Shappirio 252-401 Shappirio 252403 Stayner et al 4471 Lew 260501 Vitalis 260501 Bartlett 4466 Ebner 4466 WYMAN, Primary Examiner.

Claims

1. A HEATING OIL COMPOSITION COMPRISING A MAJOR AMOUNT OF DISTILLATE HEATING OIL AND BETWEEN 0.0001 AND 0.1 WEIGHT PERCENT OF A BETAINE SELECTED FROM THE CLASS CONSISTING OF A BETAINE CONTAINING AT LEAST 20 CARBON ATOMS AND HAVING THE STRUCTURAL FORMULA